Environment-friendly concave-convex embossment colored ceramic tile and preparation method thereof

Abstract

The invention discloses an environment-friendly concave-convex embossed colored ceramic tile and a preparation method thereof. The ceramic tile sequentially comprises a green body, a cover glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer and a second protective glaze layer from bottom to top, the raw material components for preparing the composite dry particle layer comprise hydrophobic high-zirconium colorful dry particles and hydrophilic transparent dry particles, and the content of ZrO2 in the chemical composition of the hydrophobic high-zirconium colorful dry particles is greater than or equal to 65wt%; the particle size range D97 of the hydrophobic high-zirconium colorful dry particles is 250-300 [mu] m, and the particle size range D97 of the hydrophilic transparent dry particles is 125-150 [mu] m. According to the invention, strong specular reflection is generated by using the high refractive index of ZrO2, and light scattering is initiated at the grain boundary to form a colorful effect; hydrophobic large-particle-size high-zirconium colorful dry particles and hydrophilic small-particle-size transparent dry particles can form a composite gradient structure surface of high-reflection protrusions and high-light-transmission recesses, and transparent gradual change and multicolor layering sense like natural stone are achieved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building ceramics, and particularly relates to an environment-friendly concave-convex relief color ceramic tile and a preparation method thereof. BACKGROUND

[0002] The ceramic tile with concave-convex texture of traditional natural stone imitation generally forms the concave texture through the hydrophobic mold ink and the hydrophilic face glaze, and the convex depends on the positioning of the adhesive dry powder glaze, but the color is only printed by the pattern layer ink, and lacks the natural penetration and gradient of the glaze layer, and it is difficult to realize the rich level and multi-color gradient effect of natural stone. And due to the process difference, such as the volatilization of organic matter in the adhesive ink during firing, the glaze layer in the convex region is prone to have voids, thereby causing orange peel, glaze peeling and falling, and poor ceramic tile stain resistance and wear resistance.

[0003] In the prior art, the three-dimensional relief effect of the ceramic tile is generally realized by applying dry particles, and the color pattern is added by a protective glaze layer. This process is easily blocked by the dry particle layer, and has technical problems such as color turbidity, lack of three-dimensional effect and color fusion. And the difference in the thermal expansion coefficient of the dry particle layer and the protective glaze layer easily leads to poor combination of the dry particle and the protective glaze, and a narrow firing temperature range, such as using dry particles with different firing temperatures, which easily leads to relief collapse or overfiring.

[0004] In addition, the existing concave-convex texture relief effect color ceramic tile needs to be printed by multiple inkjet printers, and needs to go through multiple processes such as inkjet, glazing, adhesive printing, powder suction, and dry powder application, which requires large equipment investment, high energy consumption, and is greatly affected by environmental temperature.

[0005] Therefore, it is urgent to develop a ceramic tile that can further simplify the preparation process, reduce production costs, improve the fusion of concave-convex texture and color effect, and enhance the physical properties and quality 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 proposes an environment-friendly concave-convex relief color ceramic tile and a preparation method thereof, which has the natural stone-like permeability, gradient and multi-color level, and the glaze surface has good wear resistance, stain resistance and glaze surface quality.

[0007] To solve the above technical problems, the first aspect of the present application provides a ceramic tile, which comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer and a second protective glaze layer; the raw material components for preparing the composite dry particle layer include hydrophobic high-zirconium fancy dry particles and hydrophilic transparent dry particles, the content of ZrO2 in the chemical composition of the hydrophobic high-zirconium fancy dry particles is ≥65wt%; the particle size range of the hydrophobic high-zirconium fancy dry particles is D97 between 250-300μm, and the particle size range of the hydrophilic transparent dry particles is D97 between 125-150μm.

[0008] Specifically, the composite dry particle layer of the present application uses hydrophobic high-zirconium fancy dry particles and hydrophilic transparent dry particles as raw materials, wherein: the content of ZrO2 in the chemical composition of the high-zirconium fancy dry particles is ≥65wt%, and the high refractive index (about 2.2) of ZrO2 is much higher than the refractive index (about 1.5-1.6) of traditional quartz-based dry particles. When light is incident on the surface of the dry particles, the high refractive index will cause strong specular reflection (reflectivity > 85%), and at the same time, light scattering will be induced at the grain boundaries, forming a “fire color” effect similar to natural diamond (i.e. multi-color flashing fancy phenomenon). At the same time, the hydrophobic large-particle-size high-zirconium fancy dry particles and the hydrophilic small-particle-size transparent dry particles can form a composite structure surface of “high-reflective protrusions-high-transmittance depressions”. The high-zirconium fancy dry particles in the protrusion area highlight the texture profile through strong reflection light, and the transparent dry particles in the depression area can make the light penetrate to the underlying pattern layer or body, reflecting the base color or gradient light and shadow, and the combination of the two forms a fusion effect of three-dimensional light and shadow and color.

[0009] In some embodiments of the present application, the raw material components for preparing the hydrophobic high-zirconium fancy dry particles include high-zirconium fancy dry particles and a hydrophobic agent; the chemical composition of the high-zirconium fancy dry particles includes, by weight percentage: ZrO2 65-68%, SiO2 15-20%, Al2O3 8-12%, Y2O3 3-5%; and the hydrophobic agent includes zinc stearate.

[0010] Specifically, in the high-zirconium fancy dry particles, ZrO2 as the main crystal phase has high refractive index and wear resistance; SiO2 forms a glass phase matrix to adjust the melting temperature; Al2O3 is beneficial to improve the chemical stability and mechanical strength; Y2O3 as a stabilizer can inhibit the transformation of ZrO2 from monoclinic phase to tetragonal phase during sintering, avoid uneven light scattering caused by crystal type disorder, and reduce the volume change after firing, thereby maintaining the stability of the protrusion shape. The stable monoclinic phase ZrO2 crystal structure makes the reflection and scattering path of light in the dry particle layer more regular, thereby realizing a uniform “fancy” effect. At the same time, the hydrophobic agent zinc stearate is beneficial to reduce the agglomeration of high-zirconium fancy dry particles during storage and application, ensure uniform particle size distribution during sintering, and avoid the collapse of the protrusion area caused by agglomeration.

[0011] In some embodiments of the present application, the amount of the hydrophobic agent is 0.2-0.4wt% of the high-zirconium color glaze dry particles.

[0012] In some embodiments of the present application, the composite dry particle layer is attached to the surface of the pattern layer by glue, and the glue is a hydrophilic glue.

[0013] In some embodiments of the present application, the hydrophilic glue is a water-based polyurethane glue.

[0014] Specifically, there is a surface energy repulsion between the hydrophobic zinc stearate and the water-based polyurethane glue, and the hydrophobic high-zirconium color glaze dry particles are difficult to attach outside the glue printing area and are only fixed by glue bonding in the glue-coated area. The large-particle-size high-zirconium dry particles are accumulated in the glue area, and form obvious protrusions after sintering. At the same time, the hydrophobicity of the high-zirconium color glaze dry particles avoids accidental attachment in the non-glue printing area, which is conducive to improving the clarity of the protrusion edges.

[0015] In some embodiments of the present application, the raw material components for preparing the hydrophilic transparent dry particles include transparent dry particles and a hydrophilic agent; the chemical composition of the transparent dry particles includes, in terms of weight percentage, SiO2 57-63%, Al2O3 10-12%, CaO 11-14%, ZnO 13-16%, and Li2O 1-2%, and the SiO2 contains 2-3% of nano-SiO2; and the hydrophilic agent includes a silane coupling agent.

[0016] Specifically, the addition of a small amount of nano-SiO2 in the transparent dry particles is conducive to enhancing the density and wear resistance of the glaze surface, filling the glass phase gap, improving the transparency of the recessed area, making the light penetrate the dry particle layer to the pattern layer or the body, reflecting the body color or the lower pattern layer, and forming a transparent gradient effect from the inside to the outside. Li2O is conducive to adjusting the melting temperature of the transparent dry particles and widening the sintering range, so as to match the thermal expansion coefficient with the protective glaze, and at the same time, avoid the decrease of the light transmittance caused by overburning. The silane coupling agent has good compatibility with the hydrophilic protective glaze layer, and the hydrophilic transparent dry particles are more easily penetrated and adsorbed by the protective glaze in the recessed area without glue coating, forming recessed textures and filling the uncovered area of the hydrophobic high-zirconium color glaze dry particles. At the same time, the small-particle-size transparent dry particles are uniformly distributed in the recessed area, filling the gap between the hydrophobic high-zirconium color glaze dry particles, and cooperating with the penetration of the protective glaze, so that the surface of the recessed area is more flat and forms a clear height difference with the protrusion area. At the same time, the silane coupling agent is conducive to enhancing the chemical bonding (Si-O bond) between the transparent dry particles and the first protective glaze, forming a tight interface after sintering, and avoiding the glaze peeling in the recessed area.

[0017] In some embodiments of the present application, the amount of the hydrophilic agent is 0.4-0.6wt% of the transparent dry particles.

[0018] In some embodiments of the present application, the mass ratio of the hydrophobic high-zirconium color dry particles and the hydrophilic transparent dry particles is 1:(0.55-0.65).

[0019] In some embodiments of the present application, the thickness of the composite dry particle layer is 0.8-1.2 mm.

[0020] In some embodiments of the present application, the preparation process of the hydrophobic high-zirconium color dry particles comprises the following steps:

[0021] First, the raw materials for preparing high-zirconium color dry particles are mixed, and then the mixture is poured into water for quenching after melting, the melting temperature is 1400-1450℃, the holding time is 2-4 hours, and the clinker particles are obtained; then the clinker particles are crushed to obtain high-zirconium color dry particles; finally, the high-zirconium color dry particles are mixed with zinc stearate to form a hydrophobic surface, and the hydrophobic high-zirconium color dry particles are obtained.

[0022] In some embodiments of the present application, the preparation process of the hydrophilic transparent dry particles comprises the following steps:

[0023] First, the raw materials for preparing hydrophilic transparent dry particles are mixed, and then the mixture is poured into water for quenching after melting, the melting temperature is 1500-1550℃, the holding time is 1-3 hours, and the clinker particles are obtained; then the clinker particles are crushed to obtain transparent dry particles; finally, the transparent dry particles are mixed with a silane coupling agent to form a hydrophilic surface, and the hydrophilic transparent dry particles are obtained.

[0024] In some embodiments of the present application, the raw material components for preparing the first protective glaze layer include, by weight: 86-90 parts of first transparent glaze, 2-4 parts of acrylic glue, 1-3 parts of nano-SiO2, and 0.5-1 part of dispersant.

[0025] In some embodiments of the present application, the raw material components for preparing the second protective glaze layer include, by weight: 80-84 parts of second transparent glaze, 6-10 parts of acrylic glue, 2-4 parts of nano-SiO2, and 0.3-0.8 part of dispersant.

[0026] In some embodiments of the present application, the dispersant is selected from at least one of sodium tripolyphosphate and sodium hexametaphosphate.

[0027] In some embodiments of the present application, the molecular weight of the acrylic glue is 30000-50000.

[0028] In some embodiments of the present application, the first transparent glaze and the second transparent glaze have the same chemical composition, including, by weight percentage, SiO2 60-65%, Al2O3 12-15%, K2O 2-3%, Na2O 2-3%, CaO 8-10%, MgO 3-5%, ZnO 5-8%, Li2O 1-2%.

[0029] Specifically, the present application adds acrylic glue into the protective glaze (including the first protective glaze and the second protective glaze), which on the one hand helps to reduce the volatilization of organic matter and improve the density of the glaze. The acrylic glue in the protective glaze is an aqueous system, which gradually decomposes during the firing process as the water evaporates. The residual acrylic ester monomer forms a chemical bond (C-O-Si bond) with SiO2 and Al2O3 in the transparent glaze, filling the gaps in the composite dry particle layer, and forming a pinhole-free glass phase after sintering, making the glaze smooth and free of orange peel defects. Moreover, the acrylic glue as a bonding medium improves the adhesion of the protective glaze to the composite dry particle layer, reducing the shedding of dry particles in the raised area. On the other hand, it helps the gradient penetration and coverage of the protective glaze, further optimizing the concave-convex structure of the product. The acrylic glue content in the first layer of protective glaze is relatively low, and the low-viscosity glue promotes the penetration of the glaze into the transparent dry particle layer, fixing the dry particle arrangement in the concave area and forming a flat base. The acrylic glue content in the second layer of protective glaze is relatively high, and the high-viscosity glue forms a thick glass phase in the raised area, covering the surface of the high-zircon fancy dry particles, improving the height of the raised area and enhancing the gloss, making the relief edges clearer. At the same time, the present application uses acrylic glue to adjust the protective glaze, which forms a gradient melting with the composite dry particle layer, effectively avoiding the collapse or overfiring caused by the inconsistent melting of traditional glue ink and dry powder glaze.

[0030] In some embodiments of the present application, the particle size range of the first transparent glaze and the second transparent glaze is the same, both being D97 between 21-25 μm.

[0031] The present application does not have special requirements for the body and the surface glaze layer, and can be prepared using ordinary ceramic tile body and surface glaze.

[0032] The second aspect of the present application provides a preparation method of the above-mentioned ceramic tile, comprising the following steps:

[0033] The surface of the body is sequentially applied with a surface glaze, inkjet printed with a pattern, positioned and applied with a composite dry particle through glue, applied with a first protective glaze and a second protective glaze, sequentially forming a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer and a second protective glaze layer, and after drying, the ceramic tile is obtained by firing in a kiln.

[0034] In some embodiments of the present application, the raw material components for preparing the glue include, by weight parts: 15-25 parts of water-based polyurethane, 12-18 parts of propylene glycol, 3-8 parts of nano-bentonite, 40-60 parts of water, and 0.1-0.4 parts of defoaming agent.

[0035] In some embodiments of the present application, the molecular weight of the water-based polyurethane is 100000-150000, and the solid content is 25-45wt%. Compared with low molecular weight acrylic polymers, high molecular weight water-based polyurethane can form a high-strength continuous film layer, improve adhesion, and form chemical adsorption (hydrogen bond combination) with the hydrophobic surface of high-zirconium color dry particles after sintering, thereby ensuring that the dry particles do not shift during application and sintering.

[0036] In some embodiments of the present application, the cation exchange capacity of the nano-bentonite is 80-120 meq / 100g, and the lamellar structure of the nano-bentonite adsorbs the hydroxyl groups (-OH) on the surface of the dry particles to form a "glue-bentonite-dry particle" bonding system, thereby improving the adhesion stability of the dry particles.

[0037] In some embodiments of the present application, the defoaming agent is selected from at least one of a polyether defoaming agent and a silicone defoaming agent.

[0038] In some embodiments of the present application, the pH value of the glue is 7.5-8.5, and a suitable pH value can ensure the stability of the water-based polyurethane colloid and solve the flocculation and stratification problems caused by pH fluctuations in traditional methods.

[0039] In some embodiments of the present application, the glue is positioned using a three-channel gray-scale inkjet printing process.

[0040] Specifically, traditional single-channel or double-channel inkjet printing can only achieve "on / off" glue control, so at least three inkjet printers are required to print mold ink, pattern layer, and glue ink, respectively, and cannot accurately adjust the gradient of glue coverage, thereby limiting the delicacy of the concave-convex texture. The present application uses a piezoelectric inkjet machine equipped with three independent gray-scale control channels to support continuous adjustment of 0-100% glue coverage, and can achieve multi-layer glue superposition in the same area through different channel combinations to meet the three-dimensional effect of "high-low staggered" in natural stone texture. At the same time, the three-channel design can simultaneously jet glue with different viscosities, and is suitable for various adhesives such as water-based polyurethane and acrylic glue.

[0041] In some embodiments of the present application, the composite dry particles are applied using a two-layer screen.

[0042] In some embodiments of the present application, the mesh size of the screen is 40 mesh.

[0043] Specifically, the application installs a two-layer screen on a dry particle distributor, the upper layer of the screen preliminarily filters large-particle impurities and pre-distributes dry particles, and the lower layer of the screen ensures uniform distribution of dry particles according to a designed pattern through high-frequency vibration and accurate angle control, thereby reducing agglomeration.

[0044] In some embodiments of the application, the specific gravity of the first protective glaze is 1.05-1.08 g / cm 3 , and the glazing amount is 170-180 g / m 2 .

[0045] In some embodiments of the application, the specific gravity of the second protective glaze is 1.10-1.13 g / cm 3 , and the glazing amount is 280-290 g / m 2 .

[0046] In some embodiments of the application, the maximum temperature of the firing is 1150-1220 DEG C.

[0047] The above technical solution of the application has at least the following technical effects or advantages relative to the prior art:

[0048] (1) The application uses hydrophobic high-zirconium color-changing dry particles and hydrophilic transparent dry particles as raw materials to prepare a composite dry particle layer, uses the high refractive index of ZrO2 to produce strong mirror reflection, and uses the light scattering at the grain boundaries to form a multicolor flashing color-changing effect. At the same time, the hydrophobic high-zirconium color-changing dry particles with a large particle size and the hydrophilic transparent dry particles with a small particle size can form a composite gradient structure surface of "high-reflection protrusions-high-transparency depressions", so as to achieve the fusion effect of stereoscopic light and color, and realize the natural stone-like permeability gradient and multicolor gradation.

[0049] (2) The application adds acrylic glue to the protective glaze (including the first protective glaze and the second protective glaze), which is beneficial to reducing the volatilization of organic matter, improving the denseness of the glaze surface and the adhesion between the protective glaze and the composite dry particle layer, reducing the falling and collapse of dry particles in the protrusion area. On the other hand, it is beneficial to the gradient penetration and coverage of the protective glaze, further optimizes the concave-convex structure of the product, makes the edge of the relief clearer, and improves the wear resistance, stain resistance and glaze quality of the glaze surface.

[0050] (3) The ceramic tile of the application is prepared by using a one-step synchronous glazing-inkjet technology, positioning through a three-channel gray-scale inkjet process, and distributing the composite dry particles through a two-layer screen, which simplifies the preparation process, reduces the production cost, and provides a feasible way for the production of the environment-friendly concave-convex relief color ceramic tile. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 A product physical map of the ceramic tile prepared in Example 1 of the application;

[0052] Figure 2 Product physical picture of the ceramic tile prepared for the present application comparative example 1;

[0053] Figure 3 Product physical picture of the ceramic tile prepared for the present application comparative example 2;

[0054] Figure 4 Product physical picture of the ceramic tile prepared for the present application comparative example 4. DETAILED DESCRIPTION

[0055] 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 the person 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. The non-essential improvements and adjustments of the present application made by the person skilled in the art according to the above-mentioned content of the present application shall still belong to the protection scope of the present application. Meanwhile, the raw materials mentioned below which are not described in detail are all commercially available products; the process steps or preparation methods which are not mentioned in detail are all known process steps or preparation methods by the person skilled in the art.

[0056] The raw material components of the body used in the following examples and comparative examples include, in parts by weight: 45 parts of kaolin, 25 parts of quartz, 20 parts of feldspar, and 10 parts of dolomite.

[0057] The chemical composition of the surface glaze includes, in percentage by weight: 62% of SiO2, 14% of Al2O3, 2% of K2O, 3% of Na2O, 9% of CaO, 4% of MgO, and 6% of ZnO.

[0058] Example 1

[0059] A ceramic tile sequentially includes, from bottom to top, a body, a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer, and a second protective glaze layer.

[0060] The raw material components for preparing the composite dry particle layer include hydrophobic high-zirconium color-changing dry particles and hydrophilic transparent dry particles in a mass ratio of 1:0.6.

[0061] The raw material components for preparing the hydrophobic high-zirconium color-changing dry particles include high-zirconium color-changing dry particles and a hydrophobic agent zinc stearate, and the amount of zinc stearate accounts for 0.3% of the high-zirconium color-changing dry particles by weight; the chemical composition of the high-zirconium color-changing dry particles includes, in percentage by weight: 66% of ZrO2, 18% of SiO2, 12% of Al2O3, and 4% of Y2O3; the particle size distribution of the high-zirconium color-changing dry particles is D97=280 μm.

[0062] The raw material components for preparing the transparent dry particles include the transparent dry particles and a hydrophilic agent, the hydrophilic agent is a silane coupling agent KH-550, the amount of the KH-550 accounts for 0.5wt% of the transparent dry particles; the chemical composition of the transparent dry particles includes, in percentage by weight: SiO261%, Al2O311%, CaO 12.5%, ZnO 14.5%, Li2O 1%, wherein the SiO2 contains 2.5% of nano-SiO2; the particle size distribution of the transparent dry particles is D97=135μm.

[0063] The raw material components for preparing the first protective glaze layer include, in parts by weight: the first transparent glaze 88, acrylic glue 3 (molecular weight 30000-50000), nano-SiO2 2, and sodium tripolyphosphate 0.8.

[0064] The raw material components for preparing the second protective glaze layer include, in parts by weight: the second transparent glaze 82, acrylic glue 8 (molecular weight 30000-50000), nano-SiO2 3, and sodium tripolyphosphate 0.5.

[0065] The chemical composition of the first transparent glaze and the second transparent glaze is the same, including, in percentage by weight: SiO263%, Al2O314%, K2O 2%, Na2O 1%, CaO 9%, MgO 4%, ZnO 5%, and Li2O 2%. The particle size distribution of the first transparent glaze and the second transparent glaze is D97=21-25μm.

[0066] The method for preparing the ceramic tile includes the following steps:

[0067] (1) According to the raw material ratio, the raw materials for preparing the high-zirconium color dry particles are mixed, melted at 1450℃ for 3 hours, and then poured into water for quenching to obtain the fused block particles; then the fused block particles are crushed to obtain the high-zirconium color dry particles; finally, the high-zirconium color dry particles are mixed with zinc stearate to form a hydrophobic surface, thereby obtaining the hydrophobic high-zirconium color dry particles.

[0068] (2) According to the raw material ratio, the raw materials for preparing the hydrophilic transparent dry particles are mixed, melted at 1550℃ for 2 hours, and then poured into water for quenching to obtain the fused block particles; then the fused block particles are crushed to obtain the transparent dry particles; finally, the transparent dry particles are mixed with the silane coupling agent KH-550 to form a hydrophilic surface, thereby obtaining the hydrophilic transparent dry particles.

[0069] (3) The hydrophobic high-zirconium color dry particles prepared in step (1) and the hydrophilic transparent dry particles are mixed according to the mass ratio to obtain the composite dry particles.

[0070] (4) The raw materials for preparing the water-based polyurethane adhesive are weighed according to the proportion: 20 parts of water-based polyurethane (molecular weight 100000-150000, solid content 40wt%), 15 parts of propylene glycol, 5 parts of nano-bentonite, 50 parts of deionized water, and 0.3 parts of defoaming agent dimethyl silicone oil. First, the deionized water is mixed with propylene glycol, then the nano-bentonite is dispersed, and then the water-based polyurethane and the defoaming agent are added. The pH is adjusted to 7.5-8.5, and the viscosity is controlled to 15-20s (4-cup, 25℃). The water-based polyurethane adhesive is prepared.

[0071] (5) The raw materials of the first protective glaze are weighed according to the proportion, ball-milled with water (mass ratio of material to water 1:0.4), and sieved through a 250-mesh screen to obtain a first protective glaze slurry with a specific gravity of 1.07 g / cm 3 .

[0072] (6) The raw materials of the second protective glaze are weighed according to the proportion, ball-milled with water (mass ratio of material to water 1:0.4), and sieved through a 250-mesh screen to obtain a second protective glaze slurry with a specific gravity of 1.11 g / cm 3 .

[0073] (7) The surface of the body is sequentially applied with a face glaze, inkjet-printed with a pattern, positioned with the adhesive prepared in step (4) using a three-channel gray-scale inkjet printing process, applied with the composite dry particles prepared in step (3) using a two-layer screen cloth, applied with the first protective glaze prepared in step (5) (glaze application amount 175 g / m 2 ), which penetrates into the hydrophilic transparent dry particles to form a "dry particle-glaze layer" interlocking structure, and applied with the second protective glaze prepared in step (6) (glaze application amount 285 g / m 2 ), which covers the surface of the high-zirconia color-changing dry particles in the raised area to form a 0.4mm-thick glass phase. The face glaze layer, pattern layer, composite dry particle layer, first protective glaze layer, and second protective glaze layer are sequentially formed. After drying, the ceramic rock plate of the present embodiment is prepared by firing in a kiln (maximum firing temperature 1220℃).

[0074] Among them: three-channel gray-scale inkjet printing positioning uses a piezoelectric inkjet printer (Xaar 128 nozzle, nozzle diameter 50μm), three-channel gray-scale control (0-100% coverage), inkjet printing resolution 600dpi, positioning accuracy ±2mm. The adhesive temperature is 25±2℃, the nozzle pressure is 2.5bar, and the inkjet printing speed is 12m / min.

[0075] The screen cloth parameters for two-layer screen cloth application are: upper layer 40-mesh coarse screen + lower layer 40-mesh fine screen, installation angle 18°, vibration frequency 50Hz, and vibration amplitude 0.8mm.

[0076] Example 2

[0077] A ceramic tile comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer and a second protective glaze layer.

[0078] Among them: the raw material components for preparing the composite dry particle layer include hydrophobic high-zirconium colorful dry particles and hydrophilic transparent dry particles in a mass ratio of 1:0.55.

[0079] The raw material components for preparing the hydrophobic high-zirconium colorful dry particles include high-zirconium colorful dry particles and a hydrophobic agent, zinc stearate, with the amount of zinc stearate accounting for 0.2wt% of the high-zirconium colorful dry particles. The chemical composition of the high-zirconium colorful dry particles, by weight percentage, includes: ZrO2 65%, SiO2 20%, Al2O3 10%, Y2O3 5%; the particle size distribution of the high-zirconium colorful dry particles is D97 = 270μm.

[0080] The raw materials for preparing transparent dry granules include transparent dry granules and a hydrophilic agent. The hydrophilic agent is a silane coupling agent KH-550, and the amount of KH-550 accounts for 0.4wt% of the transparent dry granules. The chemical composition of the transparent dry granules, by weight percentage, includes: SiO2 60%, Al2O3 12%, CaO 13%, ZnO 14%, and Li2O 1%, wherein the SiO2 contains 3% nano-SiO2. The particle size distribution of the transparent dry granules is D97 = 150 μm.

[0081] The raw material components for preparing the first protective glaze layer include, by weight: 86 parts of the first transparent glaze, 4 parts of acrylic glue (molecular weight 30,000-50,000), 1 part of nano-SiO2, and 0.8 part of sodium tripolyphosphate.

[0082] The raw material components for preparing the second protective glaze layer include, by weight, 80 parts of the second transparent glaze, 10 parts of acrylic glue (molecular weight 30,000-50,000), 4 parts of nano-SiO2, and 0.4 parts of sodium tripolyphosphate.

[0083] The first and second transparent glazes have the same chemical composition, comprising, by weight, 62% SiO2, 13% Al2O3, 3% K2O, 2% Na2O, 8% CaO, 4% MgO, 6% ZnO, and 2% Li2O. The particle size distribution of the first and second transparent glazes is D97 = 21-25 μm.

[0084] The method for preparing the ceramic tile comprises the following steps:

[0085] (1) According to the raw material ratio, the raw materials for preparing high-zirconium colorful dry particles are mixed, melted at 1500°C for 2 hours, and then poured into water for quenching to obtain frit particles; the frit particles are then crushed to obtain high-zirconium colorful dry particles; finally, the high-zirconium colorful dry particles are mixed with zinc stearate to form a hydrophobic surface to obtain hydrophobic high-zirconium colorful dry particles.

[0086] (2) According to the raw material ratio, the hydrophilic transparent dry particles are prepared by mixing the raw materials, melting at 1500℃ for 3 hours, pouring into water for quenching, crushing the melt particles to obtain transparent dry particles, and mixing the transparent dry particles with silane coupling agent KH-550 to form a hydrophilic surface.

[0087] (3) The hydrophobic high-zirconium color-changing dry particles prepared in step (1) are mixed with the hydrophilic transparent dry particles according to the mass ratio to obtain composite dry particles.

[0088] (4) The raw materials for preparing water-based polyurethane glue are weighed according to the ratio: water-based polyurethane (molecular weight 100000-150000, solid content 40wt%) 25 parts, propylene glycol 18 parts, nano-bentonite 8 parts, deionized water 60 parts, and defoaming agent dimethyl silicone oil 0.4 parts. The deionized water and propylene glycol are mixed first, then the nano-bentonite is dispersed, and then the water-based polyurethane and the defoaming agent are added. The pH is adjusted to 7.5-8.5, and the viscosity is controlled to 15-20s (4 cups, 25℃). The water-based polyurethane glue is prepared.

[0089] (5) The raw materials of the first protective glaze are weighed according to the ratio, and water is added for ball milling (the mass ratio of material to water is 1:0.4). The slurry is sieved through a 250 mesh screen to obtain a first protective glaze slurry with a specific gravity of 1.08g / cm 3 .

[0090] (6) The raw materials of the second protective glaze are weighed according to the ratio, and water is added for ball milling (the mass ratio of material to water is 1:0.4). The slurry is sieved through a 250 mesh screen to obtain a second protective glaze slurry with a specific gravity of 1.12g / cm 3 .

[0091] (7) The surface of the body is coated with face glaze, inkjet printed with a pattern, and positioned with the glue prepared in step (4) using a three-channel gray-scale inkjet printing process to form a raised area positioning pattern. The composite dry particles prepared in step (3) are applied using a two-layer screen cloth. The first protective glaze prepared in step (5) is applied (the amount of glaze applied is 180g / m 2 ), and penetrates into the hydrophilic transparent dry particles to form a "dry particle-glaze layer" interlocking structure. The second protective glaze prepared in step (6) is applied (the amount of glaze applied is 290g / m 2 ), covering the surface of the high-zirconium color-changing dry particles in the raised area to form a 0.4mm thick glass phase. The face glaze layer, pattern layer, composite dry particle layer, first protective glaze layer and second protective glaze layer are formed in sequence. After drying, the ceramic rock plate of the present embodiment is obtained by firing in a kiln (the maximum firing temperature is 1200℃).

[0092] The three-channel gray-scale inkjet positioning adopts a piezoelectric inkjet machine (Xaar 128 nozzle, nozzle diameter 50 μm), three-channel gray-scale control (0-100% coverage), inkjet resolution 600 dpi, positioning accuracy ±2 mm. The glue temperature is 25±2℃, the nozzle pressure is 2.5 bar, and the inkjet speed is 12 m / min.

[0093] The screen parameters of the two-layer screen cloth are: upper layer 40-mesh coarse screen + lower layer 40-mesh fine screen, installation angle 18°, vibration frequency 50 Hz, and vibration amplitude 0.8 mm.

[0094] Example 3

[0095] A ceramic tile sequentially comprises, from bottom to top, a body, a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer, and a second protective glaze layer.

[0096] The raw material components for preparing the composite dry particle layer include hydrophobic high-zirconium color-changing dry particles and hydrophilic transparent dry particles in a mass ratio of 1:0.65.

[0097] The raw material components for preparing the hydrophobic high-zirconium color-changing dry particles include high-zirconium color-changing dry particles and a hydrophobic agent zinc stearate, and the amount of zinc stearate accounts for 0.3 wt% of the high-zirconium color-changing dry particles; the chemical composition of the high-zirconium color-changing dry particles includes, by weight percentage, ZrO268%, SiO216%, Al2O311%, and Y2O35%; the particle size distribution of the high-zirconium color-changing dry particles is D97=300 μm.

[0098] The raw material components for preparing the transparent dry particles include transparent dry particles and a hydrophilic agent, and the hydrophilic agent is silane coupling agent KH-550, and the amount of KH-550 accounts for 0.5 wt% of the transparent dry particles; the chemical composition of the transparent dry particles includes, by weight percentage, SiO264%, Al2O310%, CaO 12%, ZnO 14%, and Li2O 2%, wherein SiO2 contains 3% of nano-SiO2; the particle size distribution of the transparent dry particles is D97=140 μm.

[0099] The raw material components for preparing the first protective glaze layer include, by weight, 87 parts of first transparent glaze, 3 parts of acrylic glue (molecular weight 30000-50000), 1.5 parts of nano-SiO2, and 0.6 parts of sodium tripolyphosphate.

[0100] The raw material components for preparing the second protective glaze layer include, by weight, 80 parts of second transparent glaze, 6 parts of acrylic glue (molecular weight 30000-50000), 2 parts of nano-SiO2, and 0.4 parts of sodium tripolyphosphate.

[0101] The first transparent glaze and the second transparent glaze have the same chemical composition, including, by weight percentage, SiO2 62%, Al2O3 15%, K2O 3%, Na2O 1%, CaO 8%, MgO 3%, ZnO 7%, Li2O 1%. The particle size distribution of the first transparent glaze and the second transparent glaze is D97 = 21-25 μm.

[0102] The method for preparing the ceramic tile comprises the following steps:

[0103] (1) According to the raw material ratio, the raw materials for preparing high-zirconium color dry particles are mixed, and then the mixture is melted at 1450℃ for 3 hours and poured into water for quenching to obtain frit particles. Then the frit particles are crushed to obtain high-zirconium color dry particles. Finally, the high-zirconium color dry particles are mixed with zinc stearate to form a hydrophobic surface, thereby obtaining hydrophobic high-zirconium color dry particles.

[0104] (2) According to the raw material ratio, the raw materials for preparing hydrophilic transparent dry particles are mixed, and then the mixture is melted at 1550℃ for 2 hours and poured into water for quenching to obtain frit particles. Then the frit particles are crushed to obtain transparent dry particles. Finally, the transparent dry particles are mixed with silane coupling agent KH-550 to form a hydrophilic surface, thereby obtaining hydrophilic transparent dry particles.

[0105] (3) The hydrophobic high-zirconium color dry particles prepared in step (1) and the hydrophilic transparent dry particles are mixed according to the mass ratio to obtain composite dry particles.

[0106] (4) According to the raw material ratio, the raw materials for preparing water-based polyurethane glue are weighed: water-based polyurethane (molecular weight 100000-150000, solid content 40wt%) 15 parts, propylene glycol 12 parts, nano-bentonite 3 parts, deionized water 40 parts, and defoaming agent dimethyl silicone oil 0.2 parts. First, the deionized water and propylene glycol are mixed, then the nano-bentonite is dispersed, and then the water-based polyurethane and the defoaming agent are added. The pH is adjusted to 7.5-8.5, and the viscosity is controlled to 15-20 s (4 cups, 25℃), thereby obtaining the water-based polyurethane glue.

[0107] (5) The raw materials of the first protective glaze are weighed according to the raw material ratio, and then ball milled with water (the mass ratio of material to water is 1:0.4), and then sieved through a 250 mesh screen to obtain the first protective glaze slurry with a specific gravity of 1.06 g / cm 3 .

[0108] (6) The raw materials of the second protective glaze are weighed according to the raw material ratio, and then ball milled with water (the mass ratio of material to water is 1:0.4), and then sieved through a 250 mesh screen to obtain the second protective glaze slurry with a specific gravity of 1.10 g / cm 3 .

[0109] (7) applying a surface glaze on the surface of the body, inkjet printing a pattern, and using the three-channel gray-scale inkjet printing to position the glue prepared in step (4) to form a raised area positioning pattern; using the two-layer screen cloth to apply the composite dry particles prepared in step (3); applying the first protective glaze prepared in step (5) (the amount of glaze applied is 170 g / m 2 ), which penetrates into the hydrophilic transparent dry particles to form a "dry particle-glaze layer" interlocking structure; applying the second protective glaze prepared in step (6) (the amount of glaze applied is 280 g / m 2 ), which covers the surface of the raised area high-zirconium color-changing dry particles to form a 0.4 mm thick glass phase, sequentially forming a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer, and a second protective glaze layer, and after drying, firing in a kiln (the maximum firing temperature is 1180℃) to prepare the ceramic rock plate of the present embodiment.

[0110] Among them: the three-channel gray-scale inkjet printing positioning uses a piezoelectric inkjet printer (Xaar 128 nozzle, nozzle diameter 50 μm), three-channel gray-scale control (0-100% coverage), inkjet printing resolution 600 dpi, positioning accuracy ±2 mm. The glue temperature is 25±2℃, the nozzle pressure is 2.5 bar, and the inkjet printing speed is 12 m / min.

[0111] The screen parameters of the two-layer screen cloth application are: upper layer 40 mesh coarse screen + lower layer 40 mesh fine screen, installation angle 18°, vibration frequency 50 Hz, and vibration amplitude 0.8 mm.

[0112] Comparative Example 1

[0113] The difference between Comparative Example 1 and Example 1 is only that the chemical composition of the high-zirconium color-changing dry particles is different. Comparative Example 1 uses a silicon-based dry particle to replace the high-zirconium color-changing dry particle of Example 1, and the chemical composition thereof includes, by weight percentage: ZrO230%, SiO254%, Al2O3 12%, and Y2O3 4%.

[0114] Comparative Example 2

[0115] The difference between Comparative Example 2 and Example 1 is only that the raw material components for preparing the composite dry particle layer are different. The raw material components for preparing the composite dry particle layer of Comparative Example 2 include high-zirconium color-changing dry particles and transparent dry particles, i.e., the high-zirconium color-changing dry particles are not subjected to hydrophobic treatment, and the transparent dry particles are not subjected to hydrophilic treatment.

[0116] Comparative Example 3

[0117] The difference between Comparative Example 3 and Example 1 is only that the particle size range of the hydrophilic transparent dry particles is different. The particle size range of the hydrophilic transparent dry particles of Comparative Example 3 is the same as that of the hydrophobic high-zirconium color-changing dry particles, i.e., D97 is between 250-300 μm.

[0118] Comparative Example 4

[0119] The difference between Comparative Example 4 and Example 1 is only that the chemical composition of the transparent dry granules does not contain nano-SiO2 and Li2O, and the chemical composition of the transparent dry granules of Comparative Example 4 includes, in percentage by weight: SiO261%, Al2O311%, CaO 12.5%, ZnO 14.5%, Na2O 1%.

[0120] Comparative Example 5

[0121] The difference between Comparative Example 5 and Example 1 is only that the layer structure of the ceramic tile is different, and the ceramic of Comparative Example 5 does not contain a second protective glaze layer.

[0122] Comparative Example 6

[0123] The difference between Comparative Example 6 and Example 1 is only that the raw material components of the glue are different, and the raw material components of the glue of Comparative Example 6 use an equal amount of acrylic polymer (molecular weight 50000) to replace the water-based polyurethane of Example 1.

[0124] Comparative Example 7

[0125] The difference between Comparative Example 7 and Example 1 is only that the preparation method of the ceramic tile is different, and Comparative Example 7 uses single-channel spray printing of glue and uses a single layer of 30-mesh screen cloth to apply the composite dry granules.

[0126] Performance test

[0127] The ceramic tile samples prepared in Examples 1-3 and Comparative Examples 1-7 were subjected to relevant performance tests and the glaze surface concave-convex and relief effects, flash effects and glaze surface quality were observed, and the results are shown in Table 1.

[0128] Among them, the light transmittance is tested according to GB / T 3810.18-2020 "Ceramic Tile Test Methods Part 18: Determination of Gloss, Specular Gloss and Haze of Glazed Tile Surfaces".

[0129] The abrasion resistance is detected according to GB / T3810.7-2016 "Determination of Surface Abrasion Resistance of Ceramic Glazed Tiles", and the grinding amount is tested; the stain resistance grade is tested according to GB / T3810.14-2016 "Ceramic Tile Test Methods Part 14: Determination of Stain Resistance", and the stain resistance performance is divided into grades, with grade 1 indicating the worst stain resistance and grade 5 indicating the best stain resistance.

[0130] Table 1:

[0131]

[0132] As can be seen from Table 1, the ceramic tiles prepared in Examples 1-3 have high light transmittance, up to 32.5-35.1%; the glaze surface is dense and fine, without obvious defects; the concave-convex is obvious, the texture is clear, the relief has strong three-dimensional effect, and has multi-color flash and dazzling effect, realizing the integration effect of three-dimensional light and color (see Figure 1 ); and has excellent wear resistance and stain resistance.

[0133] In Comparative Example 1, relative to Example 1, the ZrO2 content is insufficient due to the use of low-zirconium dry particles, the refractive index decreases significantly, the light scattering is disordered, and the light transmittance decreases obviously; at the same time, the dry particles collapse due to the softening of the glass phase at high temperature; the glaze surface has dense pinholes and serious orange peel, and has no obvious dazzling effect (see Figure 2 ), and the wear resistance and stain resistance also decrease significantly.

[0134] In Comparative Example 2, relative to Example 1, the high-zirconium dazzling dry particles are not subjected to hydrophobic treatment, and are accidentally attached in the non-glue area, destroying the concave-convex boundary; and the transparent dry particles are not subjected to hydrophilic treatment, and have no Si-O bond with the protective glaze interface, resulting in glaze peeling and dull color (see Figure 3 ), and the wear resistance and stain resistance decrease slightly.

[0135] In Comparative Example 3, relative to Example 1, the transparent dry particles have a larger particle size, and the absence of small particle sizes leads to the blocking of the light transmission path, the light transmission in the concave area is blocked by large particles, the light transmittance decreases, the protective glaze cannot penetrate, resulting in a rough glaze surface, many pores, poor flatness, and dull color.

[0136] In Comparative Example 4, relative to Example 1, the transparent dry particles do not contain nano-SiO2 and Li2O in the chemical composition, the absence of nano-SiO2 leads to the decrease of the density of the transparent dry particles, and the light transmission is turbid; the absence of Li2O narrows the melting temperature, and the thermal expansion is not matched, resulting in local overfiring during firing, and microcracks appear on the glaze surface (see Figure 4 ).

[0137] In Comparative Example 5, relative to Example 1, the first protective glaze cannot cover the high-zirconium dry particles protrusions, and the surface is exposed to dry particles which are easy to wear. At the same time, the absence of the gradient coverage of the second protective glaze flattens the protrusions of the glaze surface, and the dazzling intensity is weak; and the glaze surface has uneven thickness, and the gloss difference is obvious.

[0138] In Comparative Example 6, relative to Example 1, the acrylic glue is used instead of the water-based polyurethane, the acrylic glue has low molecular weight and cannot form a continuous bonding film; and the bonding force is insufficient, the dry particle positioning has deviation, and the dazzling area is misaligned. At the same time, due to the increase in the amount of organic matter volatilized during sintering, the glaze surface has more pores and poor flatness.

[0139] Comparative Example 7, relative to Example 1, adopts single-channel inkjet printing and single-layer screen, and the single-channel can only spray glue in "all or nothing", which cannot realize gray gradient, resulting in rough concave-convex texture; and the glaze thickness is uneven, and the gloss difference is obvious. Single-layer screen leads to dry particle aggregation and uneven distribution of iridescence.

[0140] For those skilled in the art of the present application, 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 scope of protection 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 scope of protection of the present application.

Claims

1. A ceramic tile, characterized by, From bottom to top, the ceramic tile comprises a body, a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer and a second protective glaze layer; the raw material components for preparing the composite dry particle layer comprise hydrophobic high-zirconium color-changing dry particles and hydrophilic transparent dry particles, the content of ZrO2 in the chemical composition of the hydrophobic high-zirconium color-changing dry particles is ≥65wt%; the particle size range of the hydrophobic high-zirconium color-changing dry particles is D97 between 250-300μm, and the particle size range of the hydrophilic transparent dry particles is D97 between 125-150μm.

2. The ceramic tile according to claim 1, characterized in that, The raw material components for preparing the hydrophobic high-zirconium color-changing dry particles comprise high-zirconium color-changing dry particles and a hydrophobic agent; the chemical composition of the high-zirconium color-changing dry particles comprises, by weight percentage, ZrO2 65-68%, SiO2 15-20%, Al2O3 8-12%, and Y2O3 3-5%; the hydrophobic agent comprises zinc stearate.

3. The ceramic tile according to claim 1 or 2, characterized in that, The raw material components for preparing the hydrophilic transparent dry particles comprise transparent dry particles and a hydrophilic agent; the chemical composition of the transparent dry particles comprises, by weight percentage, SiO2 57-63%, Al2O3 10-12%, CaO 11-14%, ZnO 13-16%, and Li2O 1-2%, and the SiO2 contains 2-3% of nano-SiO2; the hydrophilic agent comprises a silane coupling agent.

4. The ceramic tile according to claim 1, characterized in that, The mass ratio of the hydrophobic high-zirconium color-changing dry particles to the hydrophilic transparent dry particles is 1:(0.55-0.65).

5. The ceramic tile according to claim 1, characterized in that, The raw material components for preparing the first protective glaze layer comprise, by weight parts, first transparent glaze 86-90 parts, acrylic glue 2-4 parts, nano-SiO2 1-3 parts, and dispersant 0.5-1 part; And / or, the raw material components for preparing the second protective glaze layer comprise, by weight parts, second transparent glaze 80-84 parts, acrylic glue 6-10 parts, nano-SiO2 2-4 parts, and dispersant 0.3-0.8 part.

6. The ceramic tile according to claim 5, characterized in that, The chemical composition of the first transparent glaze and the second transparent glaze is the same, comprising, by weight percentage, SiO2 60-65%, Al2O3 12-15%, K2O 2-3%, Na2O 2-3%, CaO 8-10%, MgO 3-5%, ZnO 5-8%, and Li2O 1-2%.

7. A method of producing a ceramic tile according to any one of claims 1 to 6, characterized in that, The method comprises the following steps: The surface of the body is sequentially applied with a surface glaze, inkjet-printed with a pattern, positioned and applied with the composite dry particles by glue, applied with a first protective glaze and a second protective glaze, sequentially forming a surface glaze layer, a pattern layer, a composite dry particle layer, a first protective glaze layer and a second protective glaze layer, dried, and fired in a kiln to obtain the ceramic tile.

8. The method of manufacturing a ceramic tile according to claim 7, characterized in that, The raw material components for preparing the glue comprise, by weight parts, water-based polyurethane 15-25 parts, propylene glycol 12-18 parts, nano-bentonite 3-8 parts, water 40-60 parts, and defoaming agent 0.1-0.4 part.

9. The method of manufacturing ceramic tiles according to claim 7 or 8, characterized in that, The glue is positioned by a three-channel gray-scale printing process.

10. The method of claim 7, wherein the ceramic tile is prepared by the steps of: The composite dry particles are applied by a two-layer screen.

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