Ceramic tile with three-dimensional embossment effect and preparation method

Abstract

The invention relates to the field of architectural ceramics, and discloses a ceramic tile with a three-dimensional embossment effect and a preparation method thereof. The method comprises the steps that digital carving ink is printed on a green body layer through multiple channels in a layered mode to form a pattern layer, multiple relief glaze layers are overlaid in a matched mode, three-dimensional textures are formed, bionic concave-convex textures are constructed, the concave-convex depth difference of the glaze surface reaches 2 mm, and natural and smooth texture veins of natural stone are finely restored. In addition, the ceramic tile glaze is good in physical performance and has high wear resistance, skid resistance and antifouling property.

Description

Technical Field

[0001] This invention relates to the field of architectural ceramics, and in particular to a ceramic tile with a three-dimensional relief effect and its preparation method. Background Technology

[0002] Ceramic tiles, with their excellent physical and chemical properties and rich decorative effects, have become an indispensable material in modern home and architectural decoration, and their applications are extremely widespread. However, with the continuous improvement of consumers' aesthetic tastes and the diversification of lifestyles, the market has placed higher demands on the decorative properties of ceramic tile products. Traditional flat printed decorative tiles, with their monotonous visual effects and insufficient sense of layering, can no longer meet consumers' growing demands for spatial three-dimensionality, realistic texture, and personalized expression.

[0003] To achieve a three-dimensional decorative effect, the industry adds special carving ink to the glaze, hoping to create raised textures during firing. However, this technique has significant limitations: the final three-dimensional effect (usually a shallow relief) is highly dependent on the precise control of the glaze formula and the glazing process (glaze amount, uniformity). In actual production, factors such as the rheological properties of the glaze and the firing regime often result in a weak three-dimensional effect, blurred boundaries, and poor layering, making it difficult to achieve a clear, full, and tactile relief texture. Consequently, the industry uses molds with raised textures to directly press three-dimensional shapes into the brick blank during the forming stage. While this method can achieve a relatively obvious raised effect, its drawbacks are equally prominent: the mold itself has a limited texture and low design freedom; changing the texture requires re-molding, leading to long development cycles and extremely high costs. More importantly, limited by the carving precision of the mold and the pressing process, it is difficult to accurately and delicately reproduce the complex, varied, naturally flowing textures and subtle layers of natural stone, resulting in limited simulation and a lack of the vividness and artistic expression of natural materials.

[0004] In summary, existing technologies face significant and insurmountable technical bottlenecks in achieving a substantial, clear, low-cost, and highly realistic three-dimensional relief effect on ceramic tile surfaces. Therefore, the market urgently needs to develop a new ceramic tile manufacturing technology that can effectively overcome these limitations, creating a richly layered, clearly textured, and tactilely immersive three-dimensional relief decorative effect on the tile surface in a cost-effective manner. This would fill a market gap and meet consumers' pressing demand for high-end, personalized decorative tiles. Summary of the Invention

[0005] The main objective of this invention is to propose a method for preparing ceramic tiles with a three-dimensional relief effect, which can achieve a three-dimensional relief glaze effect close to the texture of the mold, with good stability and high production efficiency.

[0006] To achieve the above objectives, this invention proposes a method for preparing ceramic tiles with a three-dimensional relief effect, comprising the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials according to the base glaze, mix them thoroughly, and then ball mill them to obtain the base glaze material. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; S4. Prepare the materials according to the raw materials of the relief glaze, mix them thoroughly and then ball mill to obtain the relief glaze. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a drying kiln, use digital engraving ink to print a pattern on the second relief glaze layer to form a third pattern layer. S8. The relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then fired in a kiln to obtain a three-dimensional relief effect.

[0007] This invention breaks through the limitations of traditional planar printing. By printing pattern layers in multiple channels and superimposing multiple layers of relief glaze, a three-dimensional texture is formed, creating a biomimetic concave-convex texture with a depth difference of up to 2mm on the glaze surface. It delicately restores the natural and smooth texture of natural stone.

[0008] Preferably, the raw material components of the base glaze, by weight, include: 5-13 parts alumina, 12-25 parts zirconium silicate, 35-57 parts albite, 5-10 parts quartz, 5-15 parts limestone, and 5-10 parts kaolin.

[0009] Preferably, the raw material components of the digital engraving ink, by weight, include: 16-45 parts of titanium blue dispersion, 25-43 parts of acrylic resin, 15-18 parts of propylene glycol phenyl ether, 0.5-1.5 parts of aluminum-carbon modified polymer, 0.5-0.8 parts of triethanolamine, 0.15-0.32 parts of antibacterial agent, and 1-1.4 parts of ultrapure water; wherein the conductivity of the ultrapure water is ≤4μs / cm.

[0010] Preferably, the raw material components of the relief glaze, by weight, include: 10-35 parts potassium feldspar, 10-16 parts wollastonite, 6-11 parts kaolinite, 7-11 parts zinc oxide, 11-16 parts modified lithium carbonate frit, 7-11 parts limestone, 6-14 parts barium carbonate, and 15-25 parts sodium feldspar. The raw material components of the modified lithium carbonate frit, by weight, include: 10-15 parts quartz, 6-9 parts lithium carbonate, 13-18 parts limestone, 4-11 parts talc, 4-7 parts wollastonite, 5-15 parts calcined kaolin, 2-7 parts alumina, 3-7 parts borax, 11-14 parts diopside, 6-8 parts clay, 12-15 parts lithium ceramic stone, and 1-4 parts sodium carbonate.

[0011] Preferably, the preparation process of the modified lithium carbonate frit includes: preparing frit dry granules from raw material components other than lithium carbonate and lithium ceramic stone according to the specified ratio, mixing them evenly with lithium carbonate, calcining them at 1100~1200℃, soaking them in lithium ceramic stone suspension for 2~3 hours, drying them at 100~150℃, and passing them through a 200-mesh sieve to obtain the modified lithium carbonate frit.

[0012] The relief glaze formula provided by this invention gives the surface of the ceramic tile good anti-slip and anti-fouling effects after firing, and excellent wear resistance.

[0013] Preferably, in step S4, the fineness of the relief glaze is 100-120 mesh, and the moisture content is controlled at 10-13%.

[0014] Preferably, in step S7, the drying kiln is 100 meters long and the drying temperature is 150~180℃.

[0015] Preferably, in step S9, the firing temperature is 1190~1210℃ and the firing time is 55~65min.

[0016] The present invention also provides a ceramic tile with a three-dimensional relief effect, which is prepared by any of the preparation methods described above.

[0017] Compared with the prior art, the present invention has at least the following advantages: 1. The preparation method provided by the present invention has a texture similar to that of the mold. It uses a fractal algorithm combined with high-precision digital inkjet to generate three-dimensional texture data with a self-similar structure, which can create a delicate and realistic texture of natural stone with a height difference of up to 2 mm.

[0018] 2. By using the base glaze, engraving ink, and relief glaze formula provided by this invention, combined with a multi-layer gradient relief glaze structure, zero glaze shrinkage is achieved, resulting in a significant improvement in the flexural strength of the glazed tiles.

[0019] 3. The ceramic tile glaze prepared by this invention has excellent physical properties, with a Vickers hardness of 5, good anti-slip and anti-fouling properties, and is easy to clean; it also has excellent optical properties, with a metamerism index (CMF) ≥ 0.95 (industry standard ≥ 0.85). Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a photograph of the ceramic tile prepared in Example 3.

[0022] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of this application can be combined with each other. At the same time, the raw materials mentioned below, unless otherwise specified, are all commercially available products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0024] This invention provides a method for preparing ceramic tiles with a three-dimensional relief effect, comprising the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials according to the base glaze, mix them thoroughly, and then ball mill them to obtain the base glaze material. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; S4. Prepare the materials according to the raw materials of the relief glaze, mix them thoroughly and then ball mill to obtain the relief glaze. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a 100-meter drying kiln at a temperature of 150~180℃, use digital engraving ink to print a pattern on the second relief glaze layer to form the third pattern layer. S8. The relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then placed in a kiln for firing at a temperature of 1190~1210℃ for 55~65 minutes to obtain a three-dimensional relief effect.

[0025] In step S2, the raw material components of the base glaze, by weight, include: 5-13 parts alumina, 12-25 parts zirconium silicate, 35-57 parts albite, 5-10 parts quartz, 5-15 parts limestone, and 5-10 parts kaolin. The above raw materials are mixed evenly with 0.10-0.25 parts methylcellulose and 0.25-0.45 parts sodium tripolyphosphate in the specified proportions. Water, accounting for 58% of the total weight of the base glaze, is added. The mixture is ball-milled for 15 minutes per 100g and then passed through a 100-mesh sieve to obtain the base glaze material.

[0026] Steps S3, S5, and S7 all use the same digital engraving ink, whose raw material components, by weight, include: 16-45 parts of titanium cyanine blue dispersion, 25-43 parts of acrylic resin, 15-18 parts of propylene glycol phenyl ether, 0.5-1.5 parts of aluminum-carbon modified polymer, 0.5-0.8 parts of triethanolamine, 0.15-0.32 parts of antibacterial agent, and 1-1.4 parts of ultrapure water; the conductivity of the ultrapure water is ≤4μs / cm. Plasma activation treatment of the blank surface using this ink material results in a surface energy ≥66 mN / m, which is superior to conventional ultrasonic cleaning technology (surface energy ≤56 mN / m). Among them, the aluminum-carbon modified polymer is Ts005 purchased from Shanghai Yuyu New Material Technology Co., Ltd., which can improve the stability and solvent resistance of ink, making the printing effect more three-dimensional, less prone to collapse, and less prone to dissolution; the antibacterial agent is Kj547 purchased from Shenzhen Lvtai Environmental Protection Technology Co., Ltd. This invention uses a six-axis linkage digital engraving inkjet equipment for inkjet printing, with a positioning accuracy of ±0.01mm, and can complete dual-channel synchronous printing of the underlying texture (grayscale value 0~128) and the surface light and shadow (grayscale value 129~255).

[0027] Steps S4, S6, and S8 all use the same relief glaze, whose raw material components, by weight, include: 10-35 parts potassium feldspar, 10-16 parts wollastonite, 6-11 parts kaolin, 7-11 parts zinc oxide, 11-16 parts modified lithium carbonate frit, 7-11 parts limestone, 6-14 parts barium carbonate, and 15-25 parts sodium feldspar. The above raw materials are mixed with 52-75 parts printing paste, 12-20 parts printing oil, and 6-10 parts water in the specified proportions and ball-milled to produce a relief glaze with a fineness of 100-200 mesh, with the moisture content controlled at 10-13%.

[0028] The raw material components of the modified lithium carbonate briquettes, by weight, include: 10-15 parts quartz, 6-9 parts lithium carbonate, 13-18 parts limestone, 4-11 parts talc, 4-7 parts wollastonite, 5-15 parts calcined kaolin, 2-7 parts alumina, 3-7 parts borax, 11-14 parts diopside, 6-8 parts clay, 12-15 parts lithium ceramic stone, and 1-4 parts sodium carbonate.

[0029] The preparation process of modified lithium carbonate frit includes: mixing raw materials other than lithium carbonate and lithium ceramic stone in proportion, preparing frit dry granules according to conventional frit preparation process, then mixing with lithium carbonate and coating, calcining at 1100~1200℃, soaking in lithium ceramic stone suspension for 2~3 hours, drying at 100~150℃, and passing through a 200-mesh sieve to obtain the modified lithium carbonate frit.

[0030] Understandably, in the above-mentioned preparation process of modified lithium carbonate frit, when preparing the frit dry granules, the raw material components excluding lithium carbonate and lithium ceramic stone are mixed in proportion and calcined at 1350~1450℃ to prepare frit dry granules. These granules are then mixed with 6-9 parts of lithium carbonate, coated, calcined at 1100~1200℃, soaked in a suspension prepared with 12-15 parts of lithium ceramic stone for 2-3 hours, dried at 100-150℃, and passed through a 200-mesh sieve to obtain the modified lithium carbonate frit.

[0031] This invention employs a three-dimensional fractal digital imaging system to create high-precision digital raised and recessed textures through alternating layers of pattern and relief glaze. The height difference is significant, comparable to conventional mold production. The three-dimensional relief texture is natural, smooth, delicate, and realistic, vividly reproducing the texture and feel of the original stone.

[0032] The relief glaze provided by this invention, through precise control of its formula components, results in a significant difference in relief depth after firing. Simultaneously, the glaze layer possesses high hardness, high wear resistance, and excellent anti-slip and anti-fouling properties. The formula utilizes modified lithium carbonate frit. The preparation process involves encapsulating lithium carbonate during calcination, followed by immersion in lithium ceramic stone, achieving double lithium strengthening. During ceramic firing, lithium carbonate decomposes into active lithium oxide, and the lithium ions in the encapsulated lithium ceramic stone further replace the surface structure of the frit, lowering the overall melting point of the glaze, increasing low-temperature fluidity, and enhancing the elasticity of the glaze layer, thus enhancing the relief effect. The compounding of wollastonite, limestone, and barium carbonate improves the glaze surface hardness and enhances chemical stability, resulting in a dense and smooth glaze layer, reducing pinhole defects, and achieving a glaze layer with high wear resistance and anti-fouling properties. The high-calcium components such as limestone and diopside enhance the rigidity of the glaze surface, while alumina increases the high-temperature viscosity of the glaze, controls flowability, balances the transitional flow of lithium, and further maintains the clarity of the relief outline.

[0033] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters in the following examples are merely one example within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply.

[0034] It should be noted that the green body layer in the preparation method of the present invention can adopt a conventional green body formula in the ceramic field. Exemplarily, the formula components of the green body layer in the following embodiments and comparative examples of the present invention are as follows (parts by weight): 10 parts potassium feldspar, 30 parts clay, 10 parts white mud, 5 parts black mud, 20 parts quartz sand, 10 parts sodium feldspar powder, 5 parts low-temperature sand, and 10 parts aluminum sand.

[0035] Example 1 The modified lithium carbonate frit is prepared by means of the following raw material components by weight: 15 parts quartz, 9 parts lithium carbonate, 18 parts limestone, 5 parts talc, 4 parts wollastonite, 5 parts calcined kaolin, 7 parts alumina, 7 parts borax, 11 parts diopside, 6 parts ball clay, 12 parts lithium ceramic stone, and 1 part sodium carbonate.

[0036] The above raw material components, excluding lithium carbonate and lithium ceramic stone, are mixed in proportion, calcined and melted at 1350℃, water-quenched and ground into dry frit particles, mixed with lithium carbonate and coated, calcined at 1120℃, soaked in lithium ceramic stone suspension for 2 hours, dried at 130℃, and passed through a 200-sieve to obtain modified lithium carbonate frit powder.

[0037] The preparation of ceramic tiles with a three-dimensional relief effect includes the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials for the base glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the base glaze material. The raw material components of the base glaze, by weight, include: 8 parts alumina, 12 parts zirconium silicate, 45 parts albite, 10 parts quartz, 15 parts limestone, and 10 parts kaolin. Mix the above raw materials with 0.15 parts methylcellulose and 0.23 parts sodium tripolyphosphate in the specified proportions, add water equal to 58% of the total weight of the base glaze, ball mill for 15 minutes per 100g, and pass through a 100-mesh sieve. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; the raw material components of the digital engraving ink, by weight, include: 44 parts of titanium blue dispersion, 37.75 parts of acrylic resin, 15 parts of propylene glycol phenyl ether, 1.5 parts of aluminum carbon modified polymer, 0.5 parts of triethanolamine, 0.15 parts of antibacterial agent, and 1 part of ultrapure water; the conductivity of ultrapure water is ≤4μs / cm; S4. Prepare the raw materials for the relief glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the relief glaze. The raw material components, by weight, include: 35 parts potassium feldspar, 10 parts wollastonite, 6 parts kaolin, 7 parts zinc oxide, 14 parts modified lithium carbonate frit, 7 parts limestone, 6 parts barium carbonate, and 15 parts sodium feldspar. Mix the above raw materials with 52 parts printing paste, 12 parts printing oil, and 6 parts of other materials in the specified proportions, and ball mill to obtain a relief glaze with a fineness of 100-200 mesh, and control the moisture content at 10-13%. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use the above-mentioned digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the above-mentioned relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a 100-meter drying kiln at a drying temperature of 180°C, the above-mentioned digital engraving ink is used to inkjet print a pattern on the second relief glaze layer to form the third pattern layer. S8. The above-mentioned relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then placed in a kiln and fired at a temperature of 1190℃ for 55 minutes to obtain a three-dimensional relief effect.

[0038] Example 2 The modified lithium carbonate frit is prepared by means of the following raw material components by weight: 10 parts quartz, 8 parts lithium carbonate, 18 parts limestone, 6 parts talc, 4 parts wollastonite, 10 parts calcined kaolin, 7 parts alumina, 7 parts borax, 11 parts diopside, 6 parts ball clay, 12 parts lithium ceramic stone, and 1 part sodium carbonate.

[0039] The above raw material components, excluding lithium carbonate and lithium ceramic stone, are mixed in proportion, calcined and melted at 1350℃, water-quenched and ground into frit dry particles, mixed with lithium carbonate and coated, calcined at 1100℃, soaked in lithium ceramic stone suspension for 2.5 hours, dried at 150℃, and passed through a 200-sieve to obtain modified lithium carbonate frit powder.

[0040] The preparation of ceramic tiles with a three-dimensional relief effect includes the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials for the base glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the base glaze material. The raw material components of the base glaze, by weight, include: 12 parts alumina, 13 parts zirconium silicate, 40 parts albite, 10 parts quartz, 15 parts limestone, and 10 parts kaolin. Mix the above raw materials with 0.16 parts methylcellulose and 0.25 parts sodium tripolyphosphate in the specified proportions, add water equal to 58% of the total weight of the base glaze, ball mill for 15 minutes per 100g, and pass through a 100-mesh sieve. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; the raw material components of the digital engraving ink, by weight, include: 45 parts of titanium blue dispersion, 37.75 parts of acrylic resin, 16 parts of propylene glycol phenyl ether, 1.5 parts of aluminum carbon modified polymer, 0.5 parts of triethanolamine, 0.15 parts of antibacterial agent, and 1 part of ultrapure water; the conductivity of ultrapure water is ≤4μs / cm; S4. Prepare the raw materials for the relief glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the relief glaze. The raw material components, by weight, include: 33 parts potassium feldspar, 12 parts wollastonite, 6 parts kaolin, 7 parts zinc oxide, 14 parts modified lithium carbonate frit, 7 parts limestone, 6 parts barium carbonate, and 15 parts sodium feldspar. Mix the above raw materials with 55 parts printing paste, 15 parts printing oil, and 7 parts of other materials in the specified proportions, and ball mill to obtain a relief glaze with a fineness of 100-200 mesh, and control the moisture content at 10-13%. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use the above-mentioned digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the above-mentioned relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a 100-meter drying kiln at a drying temperature of 165°C, the above-mentioned digital engraving ink is used to inkjet print a pattern on the second relief glaze layer to form the third pattern layer. S8. The above-mentioned relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then placed in a kiln and fired at a temperature of 1195℃ for 56 minutes to obtain a three-dimensional relief effect.

[0041] Example 3 The modified lithium carbonate frit is prepared by means of the following raw material components by weight: 13 parts quartz, 9 parts lithium carbonate, 18 parts limestone, 5 parts talc, 4 parts wollastonite, 7 parts calcined kaolin, 7 parts alumina, 7 parts borax, 11 parts diopside, 6 parts clay, 12 parts lithium ceramic stone, and 1 part sodium carbonate.

[0042] The above raw material components, excluding lithium carbonate and lithium ceramic stone, are mixed in proportion, calcined and melted at 1350℃, water-quenched and ground into frit dry particles, mixed with lithium carbonate and coated, calcined at 1110℃, soaked in lithium ceramic stone suspension for 2.4 hours, dried at 130℃, and passed through a 200-sieve to obtain modified lithium carbonate frit powder.

[0043] The preparation of ceramic tiles with a three-dimensional relief effect includes the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials for the base glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the base glaze material. The raw material components of the base glaze, by weight, include: 12 parts alumina, 18 parts zirconium silicate, 38 parts albite, 10 parts quartz, 10 parts limestone, and 8 parts kaolin. Mix the above raw materials with 0.17 parts methylcellulose and 0.26 parts sodium tripolyphosphate in the specified proportions, add water equal to 58% of the total weight of the base glaze, ball mill for 15 minutes per 100g, and pass through a 100-mesh sieve. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; the raw material components of the digital engraving ink, by weight, include: 44 parts of titanium blue dispersion, 38.75 parts of acrylic resin, 17 parts of propylene glycol phenyl ether, 1.5 parts of aluminum carbon modified polymer, 0.5 parts of triethanolamine, 0.15 parts of antibacterial agent, and 1 part of ultrapure water; the conductivity of ultrapure water is ≤4μs / cm; S4. Prepare the raw materials for the relief glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the relief glaze. The raw material components, by weight, include: 34 parts potassium feldspar, 11 parts wollastonite, 6 parts kaolin, 7 parts zinc oxide, 14 parts modified lithium carbonate frit, 7 parts limestone, 6 parts barium carbonate, and 15 parts sodium feldspar. Mix the above raw materials with 57 parts printing paste, 17 parts printing oil, and 6 parts of other materials in the specified proportions, and ball mill evenly to obtain a relief glaze with a fineness of 100-200 mesh, with the moisture content controlled at 10-13%. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use the above-mentioned digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the above-mentioned relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a 100-meter drying kiln at a drying temperature of 160°C, the above-mentioned digital engraving ink is used to inkjet print a pattern on the second relief glaze layer to form the third pattern layer. S8. The above-mentioned relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then placed in a kiln and fired at a temperature of 1200℃ for 60 minutes to obtain a three-dimensional relief effect.

[0044] Example 4 The modified lithium carbonate frit is prepared by means of the following raw material components by weight: 14 parts quartz, 7 parts lithium carbonate, 18 parts limestone, 5 parts talc, 4 parts wollastonite, 7 parts calcined kaolin, 7 parts alumina, 7 parts borax, 12 parts diopside, 6 parts clay, 13 parts lithium ceramic stone, and 4 parts sodium carbonate.

[0045] The above raw material components, excluding lithium carbonate and lithium ceramic stone, are mixed in proportion, calcined and melted at 1450℃, water-quenched and ground into frit dry particles, mixed with lithium carbonate and coated, calcined at 1100℃, soaked in lithium ceramic stone suspension for 2 hours, dried at 100℃, and passed through a 200-sieve to obtain modified lithium carbonate frit powder.

[0046] The preparation of ceramic tiles with a three-dimensional relief effect includes the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials according to the specifications of the base glaze, mix them thoroughly, and then ball mill to obtain the base glaze material. The raw material components of the base glaze, by weight, include: 38 parts potassium feldspar, 13 parts lithium feldspar, 12 parts quartz, 10 parts limestone, 8 parts talc, 7 parts corundum, and 12 parts zirconium silicate. Mix the above raw materials with 0.13 parts methylcellulose and 0.30 parts sodium tripolyphosphate in the specified proportions, add water equal to 58% of the total weight of the base glaze, ball mill for 15 minutes per 100g, and pass through a 100-mesh sieve. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; the raw material components of the digital engraving ink, by weight, include: 43 parts of titanium blue dispersion, 37.75 parts of acrylic resin, 18 parts of propylene glycol phenyl ether, 1.5 parts of aluminum carbon modified polymer, 0.5 parts of triethanolamine, 0.15 parts of antibacterial agent, and 1 part of ultrapure water; the conductivity of ultrapure water is ≤4μs / cm; S4. Prepare the raw materials for the relief glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the relief glaze. The raw material components, by weight, include: 32 parts potassium feldspar, 10 parts wollastonite, 6 parts kaolin, 10 parts zinc oxide, 15 parts modified lithium carbonate frit, 7 parts limestone, 6 parts barium carbonate, and 14 parts sodium feldspar. Mix the above raw materials with 60 parts printing paste, 15 parts printing oil, and 6 parts of other materials in the specified proportions, and ball mill to obtain a relief glaze with a fineness of 100-200 mesh, with the moisture content controlled at 10-13%. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use the above-mentioned digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the above-mentioned relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a 100-meter drying kiln at a drying temperature of 150°C, the above-mentioned digital engraving ink is used to inkjet print a pattern on the second relief glaze layer to form the third pattern layer. S8. The above-mentioned relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then placed in a kiln and fired at a temperature of 1210℃ for 65 minutes to obtain a three-dimensional relief effect.

[0047] Comparative Example 1 The modified lithium carbonate frit is prepared by means of the following raw material components by weight: 13 parts quartz, 9 parts lithium carbonate, 18 parts limestone, 5 parts talc, 4 parts wollastonite, 7 parts calcined kaolin, 7 parts alumina, 7 parts borax, 11 parts diopside, 6 parts clay, 12 parts lithium ceramic stone, and 1 part sodium carbonate.

[0048] The above raw material components, excluding lithium carbonate and lithium ceramic stone, are mixed in proportion, calcined and melted at 1350℃, water-quenched and ground into frit dry particles, mixed with lithium carbonate and coated, calcined at 1110℃, soaked in lithium ceramic stone suspension for 2.4 hours, dried at 130℃, and passed through a 200-sieve to obtain modified lithium carbonate frit powder.

[0049] The preparation of ceramic tiles with a three-dimensional relief effect includes the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials for the base glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the base glaze material. The raw material components of the base glaze, by weight, include: 12 parts alumina, 18 parts zirconium silicate, 38 parts albite, 10 parts quartz, 10 parts limestone, and 8 parts kaolin. Mix the above raw materials with 0.17 parts methylcellulose and 0.26 parts sodium tripolyphosphate in the specified proportions, add water equal to 58% of the total weight of the base glaze, ball mill for 15 minutes per 100g, and pass through a 100-mesh sieve. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; the raw material components of the digital engraving ink, by weight, include: 44 parts of titanium blue dispersion, 38.75 parts of acrylic resin, 16 parts of propylene glycol phenyl ether, 1.5 parts of aluminum carbon modified polymer, 0.5 parts of triethanolamine, 0.15 parts of antibacterial agent, and 1 part of ultrapure water; the conductivity of ultrapure water is ≤4μs / cm; S4. Prepare the raw materials for the relief glaze according to the instructions, mix them thoroughly, and then ball mill to obtain the relief glaze. The raw material components, by weight, include 33 parts potassium feldspar, 11 parts wollastonite, 6 parts kaolin, 7 parts zinc oxide, 15 parts modified lithium carbonate frit, 7 parts limestone, 6 parts barium carbonate, and 15 parts sodium feldspar. Mix the above raw materials with 57 parts printing paste, 17 parts printing oil, and 6 parts of other materials in the specified proportions, and ball mill to obtain a relief glaze with a fineness of 100-200 mesh, with the moisture content controlled at 10-13%. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. After drying in a 100-meter drying kiln at a drying temperature of 160°C, the above-mentioned digital engraving ink is used to inkjet print a pattern on the first relief glaze layer to form a second pattern layer. S6. The above-mentioned relief glaze is screen-printed onto the second pattern layer to form the second relief glaze layer; S7. The ceramic tile is then placed in a kiln and fired at a temperature of 1200℃ for 60 minutes to obtain a three-dimensional relief effect.

[0050] Comparative Example 2 This comparative example uses the same preparation method and process parameters as in Example 3, the only difference being the preparation process of the modified lithium carbonate frit as follows: The modified lithium carbonate frit powder is obtained by mixing the raw material components other than lithium carbonate and lithium ceramic stone in a certain proportion, calcining at 1050℃, water quenching and grinding through a 200-sieve.

[0051] Comparative Example 3 This comparative example uses the same preparation method and process parameters as in Example 3, except that the raw material composition of the relief glaze is adjusted to (parts by weight): 34 parts potassium feldspar, 10 parts wollastonite, 10 parts kaolin, 10 parts zinc oxide, 7 parts limestone, 6 parts barium carbonate, and 15 parts sodium feldspar.

[0052] The performance parameters of the ceramic tiles prepared in Examples 1-4 and Comparative Examples 1-3 were tested using the following standards and methods: 1. Height difference of glaze texture: The thickness h1 is measured from the bottom of the ceramic tile to the highest point of the raised part of the surface, and the thickness h2 is measured from the bottom of the ceramic tile to the lowest point of the groove on the surface. The height difference of the texture is ΔH=h1-h2.

[0053] 2. Gloss: In accordance with the national standard GB / T 4100-2015, the gloss of different locations on the surface of the tile was measured using a photometer at a 60° angle.

[0054] 3. Vickers hardness: Referring to industry standard JC / T 2531-2019, the hardness of the brick surface is measured by indentation depth method (instrumented indentation) and traditional diagonal measurement method.

[0055] 4. Slip resistance: The slip resistance performance is tested in accordance with the national standard GB / T 37798-2019. The slope method (wearing shoes and applying oil) is used to test the slip resistance of the tile surface. The grades are marked as "-, R9, R10, R11, R12, R13". Among them, R12-R13 is high slip resistance, R10-R11 is medium slip resistance, and R9 and below is low slip resistance.

[0056] 5. Stain resistance: The stain resistance of the tile surface is tested in accordance with the national standard GB / T 3810.14-2016. The stain agent is brought into contact with the tile surface and allowed to act for a period of time. The tile surface is then cleaned according to the prescribed cleaning method. The changes on the tile surface are observed to determine the stain resistance level of the tile, which is divided into 1 to 5 levels, with level 5 being the highest stain resistance.

[0057] 6. Flexural strength of ceramic tiles: The flexural strength of glazed tiles shall be tested in accordance with the national standard GB / T 4740-2024. The flexural strength shall be ≥35MPa.

[0058] 7. Metamerism Index: The metamerism index is tested according to the method for visual evaluation of metamerism and estimation of color difference specified in the national standard GB / T 15610-2008.

[0059] The test results are shown in Table 1.

[0060] Table 1 As shown in Table 1, the height difference of the uneven texture on the ceramic tile glaze prepared in Examples 1-4 can reach up to 2mm. Figure 1 As shown in Example 3, the three-dimensional relief effect is remarkable. The glaze has good physical properties, with a Vickers hardness of 5, slip resistance of R13, stain resistance of 5, high flexural strength, and a metamerism index of 0.95. It also has good gloss.

[0061] In Comparative Example 1, the second pattern layer and embossed glaze layer were not sprayed, the texture was not significant, the height difference was 0.5mm, and the gloss was low, with a significant decrease in various physical properties.

[0062] The modified lithium carbonate frit used in Comparative Example 2 was prepared using only conventional frit preparation methods, without mixing with lithium carbonate or immersion in a lithium ceramic stone suspension. The height difference of the glaze's uneven texture was only 0.5 mm, resulting in a less pronounced three-dimensional effect. The glaze's physical properties declined, with a Vickers hardness of 2, slip resistance of R9, and stain resistance of 3. It also exhibited low gloss and a decreased metamerism index.

[0063] In Comparative Example 3, without the addition of modified lithium carbonate frit, the height difference of the glaze's uneven texture was only 0.5 mm, resulting in a poor three-dimensional relief effect. The physical properties of the glaze were significantly reduced, with a Vickers hardness of 1, slip resistance of R9, and stain resistance of 3. The gloss was low, and the metamerism index decreased.

[0064] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A method for preparing ceramic tiles with a three-dimensional relief effect, characterized in that, Includes the following steps: S1. Press the ceramic powder into shape and dry it to obtain a green body layer; S2. Prepare the raw materials according to the base glaze, mix them thoroughly, and then ball mill them to obtain the base glaze material. Apply the base glaze material to the body layer to form the base glaze layer. S3. Use digital engraving ink to inkjet print a pattern on the base glaze layer to form the first pattern layer; S4. Prepare the materials according to the raw materials of the relief glaze, mix them thoroughly and then ball mill to obtain the relief glaze. Spray the relief glaze onto the first pattern layer to form the first relief glaze layer. S5. Use digital engraving ink to inkjet print a pattern on the first relief glaze layer to form a second pattern layer; S6. Spray the relief glaze onto the second pattern layer to form the second relief glaze layer; S7. After drying in a drying kiln, use digital engraving ink to print a pattern on the second relief glaze layer to form a third pattern layer. S8. The relief glaze is screen-printed onto the third pattern layer to form the third relief glaze layer; S9. The ceramic tile is then fired in a kiln to obtain a three-dimensional relief effect.

2. The preparation method according to claim 1, characterized in that, The raw material components of the base glaze, by weight, include: 5-13 parts alumina, 12-25 parts zirconium silicate, 35-57 parts albite, 5-10 parts quartz, 5-15 parts limestone, and 5-10 parts kaolin.

3. The preparation method according to claim 1, characterized in that, The raw material components of the digital engraving ink, by weight, include: 16-45 parts of titanium blue dispersion, 25-43 parts of acrylic resin, 15-18 parts of propylene glycol phenyl ether, 0.5-1.5 parts of aluminum-carbon modified polymer, 0.5-0.8 parts of triethanolamine, 0.15-0.32 parts of antibacterial agent, and 1-1.4 parts of ultrapure water; wherein the conductivity of the ultrapure water is ≤4μs / cm.

4. The preparation method according to claim 1, characterized in that, The raw material components of the relief glaze, by weight, include: 10-35 parts potassium feldspar, 10-16 parts wollastonite, 6-11 parts kaolinite, 7-11 parts zinc oxide, 11-16 parts modified lithium carbonate frit, 7-11 parts limestone, 6-14 parts barium carbonate, and 15-25 parts sodium feldspar. The raw material components of the modified lithium carbonate frit, by weight, include: 10-15 parts quartz, 6-9 parts lithium carbonate, 13-18 parts limestone, 4-11 parts talc, 4-7 parts wollastonite, 5-15 parts calcined kaolin, 2-7 parts alumina, 3-7 parts borax, 11-14 parts diopside, 6-8 parts clay, 12-15 parts lithium ceramic stone, and 1-4 parts sodium carbonate.

5. The preparation method according to claim 4, characterized in that, The preparation process of the modified lithium carbonate frit includes: preparing frit dry granules from raw material components other than lithium carbonate and lithium ceramic stone according to the specified ratio, mixing them evenly with lithium carbonate, calcining them at 1100~1200℃, soaking them in lithium ceramic stone suspension for 2~3 hours, drying them at 100~150℃, and passing them through a 200-mesh sieve to obtain the modified lithium carbonate frit.

6. The preparation method according to claim 1, characterized in that, In step S4, the fineness of the relief glaze is 100-120 mesh, and the moisture content is controlled at 10-13%.

7. The preparation method according to claim 1, characterized in that, In step S7, the drying kiln is 100 meters long and the drying temperature is 150~180℃.

8. The preparation method according to claim 1, characterized in that, In step S9, the firing temperature is 1190~1210℃ and the firing time is 55~65min.

9. A type of ceramic tile with a three-dimensional relief effect, characterized in that, The ceramic tile with a three-dimensional relief effect is prepared by any one of the preparation methods described in claims 1 to 8.

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