Ceramic tile with imitation natural stone texture and method for manufacturing the same

Abstract

The application discloses a kind of ceramic tiles of imitating natural stone texture and preparation method thereof, belong to building material field, the preparation raw material of protective glaze layer is optimized in the application, can form stable three-dimensional network structure by specific suspension system, effectively prevent protective glaze slurry from depositing and delaminating, ensure uniform and stable of protective glaze slurry in storage and glazing process;Then, the dispersibility and fluidity of protective glaze slurry are significantly improved by combining composite dispersant, further reduce particle agglomeration and flocculation, so that protective glaze slurry is easy to apply, form uniform protective glaze layer, in combination with the leveling performance of leveling agent, avoid the appearance of orange peel, pinhole and other defects, the interaction of spherical fine dry particles and functional auxiliary dry particles of protective glaze layer makes the glaze surface have the visual aesthetic sense of imitating natural stone texture and the touch of warm and delicate.

Description

Technical Field

[0001] This invention relates to the field of building materials technology, and more specifically, to a ceramic tile that imitates the texture of natural stone and its preparation method. Background Technology

[0002] Natural stone, with its unique texture, elegant feel, and durability, has long been widely used in high-end architecture and home decoration. However, natural stone has inherent drawbacks such as limited resources, high mining costs, heavy weight, uncertain radioactive element content, susceptibility to staining, and complex maintenance. Therefore, ceramic tiles that mimic the texture of natural stone have emerged. Existing stone-like ceramic tiles typically achieve this by applying a base glaze layer to the tile body, then using inkjet printing technology to print a stone-like pattern, and finally covering it with a transparent protective glaze layer. The main functions of this protective glaze layer are to protect the pattern, provide wear and stain resistance, and give the tile a specific surface texture. For example, Chinese patent application number CN201811138891.1 discloses a production process for imitation natural stone ceramic tiles, including the following steps: S1 feeding; S2 ball milling; S3 iron removal and sieving; S4 spray drying; S5 homogenization; S6 mixing and kneading; S7 primary drying; S8 cutting; S9 spreading; S10 pressing and molding; S11 secondary drying; S12 sintering; and S13 polishing, resulting in imitation natural stone ceramic tiles with a texture structure without layering and a pattern without breakage. Another example is Chinese patent application number CN200710002485.8, which discloses an imitation natural stone ceramic tile that uses a secondary granulation process, increasing the density of the body by approximately 60%, resulting in good stain resistance, aging resistance, and corrosion resistance. For example, Chinese patent application number CN201710595984.6 discloses a preparation process for imitation natural stone texture tiles with natural superposition and mixing. Through the preparation process of imitation natural stone texture tiles with natural superposition and mixing, the degree of fusion between different slurry layers can be higher, and the resulting patterns and textures are more realistic and richer.

[0003] However, existing technologies still have the following shortcomings in achieving highly realistic artistic effects and excellent tactile feel when preparing stone-like ceramic tiles: 1. Insufficient slurry stability: As the size of the grinding particles in the glaze slurry used to form the protective layer decreases, their shape becomes closer to flakes or strips, making them prone to settling at the bottom. This leads to uneven glaze dispersion or even layering, resulting in defects such as pinholes on the glaze surface, and even noticeable pitting, failing to achieve a warm and smooth effect and damaging the overall visual integrity of the tile. 2. The dry granules used in traditional protective glazes are usually large in diameter (D50 is often above 20μm) and irregular in shape. Irregular large particles make the glaze surface rough to the touch, making it difficult to simulate the warm and delicate touch of high-end natural stone. 3. The problem of balancing composition and performance: Conventional glaze compositions, in pursuit of high hardness or low melting point, often fail to balance visual aesthetics and tactile feel. The glaze surface is either too glossy and looks cheap, or too dry and lacks a warm and smooth feel. Therefore, optimizing the design of glaze composition to achieve visual transparency, clear texture, warm feel, and soft and delicate touch while ensuring the performance of ceramic tiles is currently a challenge for technological innovation in the industry. Summary of the Invention

[0004] In order to solve one of the above problems, the present invention provides a ceramic tile with a texture similar to natural stone and a method for preparing the same, the specific technical solution of which is as follows:

[0005] A ceramic tile with a texture resembling natural stone, the ceramic tile comprising a tile blank and a base glaze layer, a pattern layer, and a protective glaze layer sequentially disposed on the surface of the tile blank, the protective glaze layer being prepared from a protective glaze slurry, and the protective glaze slurry comprising the following raw materials in parts by weight:

[0006] Spherical fine dry granules: 50-70 parts, functional auxiliary dry granules: 3-10 parts, suspending agent: 0.5-3 parts, leveling agent: 0.3-2 parts, composite dispersant: 0.2-3 parts, and surfactant: 0.5-5 parts;

[0007] The spherical fine dry particles comprise the following components by mass percentage: SiO2: 55%~60%, Al2O3: 12%~16%, K2O: 3%~9%, Na2O: 1%~5%, CaO: 3%~8%, MgO: 1%~4%, ZnO: 1%~3%, BaO: 0.5%~2.5%;

[0008] The functional auxiliary dry granules comprise the following components by mass percentage: SiO2: 45%~55%, Bi2O3: 20%~25%, ZnO: 5%~12%, MgO: 2%~5%, Na2O: 10%~15%, K2O: 5%~10%, Li2O: 1%~5%, ZrO2: 1%~2%.

[0009] Preferably, the melting temperature of the functional auxiliary dry granules is 400℃~800℃, and the melting temperature of the spherical fine dry granules is 1120℃~1250℃.

[0010] Preferably, the D50 particle size of the functional auxiliary dry granules is 1μm to 5μm; the D50 particle size of the spherical fine dry granules is 5μm to 15μm, and the sphericity is greater than 0.9.

[0011] Preferably, the preparation method of the suspending agent is as follows: lithium saponite is added to the silane coupling agent and stirred at a speed of 20 r / min to 50 r / min for 10 min to 20 min, then polyethylene glycol-400 and polymethylsiloxane are added, and the stirring is continued for 30 min to 45 min to obtain the suspending agent.

[0012] Preferably, the weight ratio of lithium saponite, silane coupling agent, polyethylene glycol-400 and polymethylsiloxane is (20~35):(9~15):(1~5):(5~15).

[0013] Preferably, the leveling agent is N-dodecylpyrrolidone.

[0014] Preferably, the composite dispersant is obtained by mixing sodium carboxymethyl cellulose and sodium silicate in a mass ratio of (5~7):(3~5).

[0015] Preferably, the surfactant is at least one of dodecyltrimethylammonium bromide and N,N-dimethyldodecylamine-N-oxide.

[0016] In addition, the present invention also provides a method for preparing ceramic tiles with imitation natural stone texture, the method comprising the following steps:

[0017] S1. Preparing brick blanks;

[0018] S2. Apply a base glaze to the surface of the brick blank to form a base glaze layer;

[0019] S3. A pattern is printed on the base glaze layer using inkjet printing technology to form a pattern layer;

[0020] S4. Preparation of protective glaze slurry: Add functional auxiliary dry granules, suspending agent, leveling agent, composite dispersant and surfactant to an appropriate amount of water, mix evenly, and then slowly add spherical fine dry granules. Under stirring conditions, continue stirring until a uniform and stable glaze slurry is formed. Let stand for 3h~8h to obtain the protective glaze slurry.

[0021] S5. Apply the protective glaze to the pattern layer, dry it to form a protective glaze layer, heat it to 600℃~1000℃ at a heating rate of 3℃ / min~5℃ / min, hold it for 5min~15min, and then heat it to 1180℃~1220℃ at a heating rate of 10℃ / min~15℃ / min for firing. The firing cycle is 40min~70min to obtain a ceramic tile with a texture similar to natural stone.

[0022] Preferably, the thickness of the protective glaze layer is 0.3mm to 0.8mm.

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

[0024] 1. This invention optimizes the raw materials for preparing the protective glaze layer. Through a specific suspension system, a stable three-dimensional network structure can be formed, effectively preventing the protective glaze slurry from settling and separating. This ensures that the protective glaze slurry remains uniform and stable during storage and glazing, avoiding sedimentation. Then, combined with a composite dispersant, the dispersibility and flowability of the protective glaze slurry are significantly improved, further reducing particle agglomeration and flocculation, making the protective glaze slurry easy to apply and forming a uniform protective glaze layer. Combined with the leveling agent's leveling properties, defects such as orange peel and pinholes are avoided, resulting in a smooth and even glaze surface.

[0025] 2. The spherical fine dry particles used in the protective glaze slurry of this invention are small and round, and have better resistance to disturbance after application and before drying. This helps to form a protective glaze layer with a softer and more delicate feel, and the texture is clearer, more natural, warmer, and has a better artistic effect.

[0026] 3. The functional auxiliary dry particles of the present invention have a lower melting temperature. After heating, they will melt and fill the gaps in the skeleton formed by the spherical fine dry particles. The particle size of the functional auxiliary dry particles is limited to be smaller than that of the spherical fine dry particles to ensure that they can fully fill the gaps. The crystalline phase and glass are mixed with each other, which also makes it easier for the gas inside the protective glaze to be discharged, which helps to obtain a protective glaze layer with a better degree of densification.

[0027] 4. After optimizing the composition, the present invention adopts a staged heating process to fully melt and spread the functional auxiliary dry particles, so as to achieve gradient melting and good bonding of the protective glaze during the firing process, ensuring that the glaze surface is dense and defect-free, and has both the visual beauty of imitating natural stone texture and a warm and delicate touch. Detailed Implementation

[0028] 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.

[0029] This invention discloses a ceramic tile with a texture resembling natural stone. The ceramic tile comprises a tile blank and a base glaze layer, a pattern layer, and a protective glaze layer sequentially disposed on the surface of the tile blank. The protective glaze layer is prepared from a protective glaze slurry, and the protective glaze slurry comprises the following raw materials in parts by weight:

[0030] Spherical fine dry granules: 50-70 parts, functional auxiliary dry granules: 3-10 parts, suspending agent: 0.5-3 parts, leveling agent: 0.3-2 parts, composite dispersant: 0.2-3 parts, and surfactant: 0.5-5 parts;

[0031] The spherical fine dry particles comprise the following components by mass percentage: SiO2: 55%~60%, Al2O3: 12%~16%, K2O: 3%~9%, Na2O: 1%~5%, CaO: 3%~8%, MgO: 1%~4%, ZnO: 1%~3%, BaO: 0.5%~2.5%;

[0032] The functional auxiliary dry granules comprise the following components by mass percentage: SiO2: 45%~55%, Bi2O3: 20%~25%, ZnO: 5%~12%, MgO: 2%~5%, Na2O: 10%~15%, K2O: 5%~10%, Li2O: 1%~5%, ZrO2: 1%~2%.

[0033] In one embodiment, the melting temperature of the functional auxiliary dry granules is 400°C to 800°C, and the melting temperature of the spherical fine dry granules is 1120°C to 1250°C.

[0034] In one embodiment, the D50 particle size of the functional auxiliary dry granules is 1μm to 5μm; the D50 particle size of the spherical fine dry granules is 5μm to 15μm, and the sphericity is greater than 0.9.

[0035] In one embodiment, the suspension is prepared by adding lithium saponite to a silane coupling agent and stirring at a speed of 20 r / min to 50 r / min for 10 min to 20 min, then adding polyethylene glycol-400 and polymethylsiloxane, and continuing to stir for 30 min to 45 min to obtain the suspension.

[0036] In one embodiment, the weight ratio of lithium saponite, silane coupling agent, polyethylene glycol-400 and polymethylsiloxane is (20~35):(9~15):(1~5):(5~15).

[0037] In one embodiment, the lithium saponite is in the form of flakes, with a thickness of 1 nm and a diameter of 20 nm to 50 nm. This invention uses lithium saponite as a raw material to prepare a suspension system that can form a stable three-dimensional network structure with strong thixotropy. It can interact with silane coupling agents, polyethylene glycol-400, and polymethylsiloxane to form a stable suspending agent system. Through long-chain entanglement and hydrogen bonding, it effectively prevents glaze precipitation, ensuring clear texture and a warm, smooth surface finish in the patterned layer.

[0038] In one embodiment, the silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0039] In one embodiment, the leveling agent is N-dodecylpyrrolidone.

[0040] In one embodiment, the composite dispersant is obtained by mixing sodium carboxymethyl cellulose and sodium silicate in a mass ratio of (5~7):(3~5). Sodium silicate forms a double electric layer in the solid-liquid mixture. When charged particles with the same charge collide with it, a repulsive force is generated, thereby achieving a dispersion effect. The repulsive forces are mutually inverse, and the fluidity is not easily coagulated, resulting in good suspension, fluidity, and dispersibility. Van der Waals attraction is reduced, and combined with the mutual repulsion of the high molecular chains of sodium carboxymethyl cellulose, particle aggregation is prevented, thereby reducing glaze agglomeration and flocculation, thus improving the dispersibility and stability of the protective glaze slurry.

[0041] In one embodiment, the surfactant is at least one of dodecyltrimethylammonium bromide and N,N-dimethyldodecylamine-N-oxide.

[0042] In addition, the present invention also provides a method for preparing ceramic tiles with imitation natural stone texture, the method comprising the following steps:

[0043] S1. Preparing brick blanks;

[0044] S2. Apply a base glaze to the surface of the brick blank to form a base glaze layer;

[0045] S3. A pattern is printed on the base glaze layer using inkjet printing technology to form a pattern layer;

[0046] S4. Preparation of protective glaze slurry: Add functional auxiliary dry granules, suspending agent, leveling agent, composite dispersant and surfactant to an appropriate amount of water, mix evenly, and then slowly add spherical fine dry granules. Under stirring conditions, continue stirring until a uniform and stable glaze slurry is formed. Let stand for 3h~8h to obtain the protective glaze slurry.

[0047] S5. Apply the protective glaze to the pattern layer, dry it to form a protective glaze layer, heat it to 600℃~1000℃ at a heating rate of 3℃ / min~5℃ / min, hold it for 5min~15min, and then heat it to 1180℃~1220℃ at a heating rate of 10℃ / min~15℃ / min for firing. The firing cycle is 40min~70min to obtain a ceramic tile with a texture similar to natural stone.

[0048] In one embodiment, the thickness of the base glaze layer is 1 mm to 2 mm.

[0049] In one embodiment, in step S3, different colored pigments are added to the base slurry to create glaze slurries of different colors. These glaze slurries are then sprayed onto the base glaze layer using inkjet printing technology, forming a pattern layer with natural stone texture. In this invention, the pattern layer can be customized with different colored glaze slurries using inkjet printing technology according to market demand. This allows for precise replication of the complex textures of natural stone, resulting in rich colors, natural transitions, and a realistic decorative effect, meeting the needs of high-end personalized decoration.

[0050] In one embodiment, in step S4, the stirring conditions are: a rotation speed of 20 r / min to 100 r / min.

[0051] In one embodiment, the specific gravity of the protective glaze is 1.56 g / cm³. 3 ~1.80g / cm 3 .

[0052] In one embodiment, the drying process is carried out at a temperature of 65°C to 70°C for a time of 10 min to 20 min.

[0053] In one embodiment, the thickness of the protective glaze layer is 0.3 mm to 0.8 mm.

[0054] The ceramic tiles prepared using the above method have clear imitation natural stone textures, a warm and delicate touch, and superior artistic effect.

[0055] To make the technical problems solved by the present invention, the technical solutions adopted, and the technical effects achieved clearer, the present invention will be further described below in conjunction with embodiments. Example 1:

[0056] A method for preparing ceramic tiles with imitation natural stone texture includes the following steps:

[0057] S1. Preparing brick blanks;

[0058] S2. Apply a base glaze to the surface of the brick blank to form a base glaze layer with a thickness of 1 mm;

[0059] S3. By adding different colored pigments to the base slurry, glaze slurries of different colors are made. The different colored glaze slurries are then sprayed onto the base glaze layer by inkjet printing technology to form a pattern layer with natural stone texture.

[0060] S4. Preparation of protective glaze slurry: According to weight, add 7 parts of functional auxiliary dry granules, 2 parts of suspending agent, 1 part of N-dodecylpyrrolidone, 3 parts of composite dispersant (obtained by mixing 1.8 parts of sodium carboxymethyl cellulose and 1.2 parts of sodium silicate), and 3 parts of dodecyltrimethylammonium bromide to an appropriate amount of water, mix thoroughly, then slowly add 55 parts of spherical fine dry granules, stirring continuously at 20 r / min until a uniform and stable glaze slurry is formed. Let stand for 6 hours to obtain a specific gravity of 1.62 g / cm³. 3 Protective glaze;

[0061] The functional auxiliary dry granules comprise the following components by mass percentage: SiO2: 45.4%, Bi2O3: 21.4%, ZnO: 5.1%, MgO: 4.1%, Na2O: 12.7%, K2O: 7.8%, Li2O: 2.3%, ZrO2: 1.2%; the D50 particle size of the functional auxiliary dry granules is 3 μm.

[0062] The spherical fine dry particles comprise the following components by mass percentage: SiO2: 59.3%, Al2O3: 15.5%, K2O: 7.2%, Na2O: 2.7%, CaO: 7.0%, MgO: 3.7%, ZnO: 2.5%, BaO: 2.1%; the spherical fine dry particles have a D50 particle size of 15 μm and a sphericity greater than 0.9.

[0063] Add 30 parts by weight of lithium saponite to 12 parts by weight of vinyltriethoxysilane, stir at 50 r / min for 15 min, then add 3 parts by weight of polyethylene glycol-400 and 12 parts by weight of polymethylsiloxane, and continue stirring for 30 min to obtain a suspending agent.

[0064] S5. Apply the protective glaze to the pattern layer and dry it at 65°C for 10 minutes to form a protective glaze layer with a thickness of 0.5 mm. Heat the layer to 950°C at a heating rate of 5°C / min and hold it for 10 minutes. Then heat the layer to 1210°C at a heating rate of 10°C / min and fire it for 50 minutes to obtain a ceramic tile with a texture similar to natural stone. Example 2:

[0065] A method for preparing ceramic tiles with imitation natural stone texture includes the following steps:

[0066] S1. Preparing brick blanks;

[0067] S2. Apply a base glaze to the surface of the brick blank to form a base glaze layer with a thickness of 1 mm;

[0068] S3. By adding different colored pigments to the base slurry, glaze slurries of different colors are made. The different colored glaze slurries are then sprayed onto the base glaze layer by inkjet printing technology to form a pattern layer with natural stone texture.

[0069] S4. Preparation of protective glaze slurry: According to weight, add 8 parts of functional auxiliary dry granules, 3 parts of suspending agent, 1 part of N-dodecylpyrrolidone, 3 parts of composite dispersant (obtained by mixing 1.8 parts of sodium carboxymethyl cellulose and 1.2 parts of sodium silicate), and 2 parts of dodecyltrimethylammonium bromide to an appropriate amount of water, mix thoroughly, then slowly add 58 parts of spherical fine dry granules, stirring continuously at 20 r / min until a uniform and stable glaze slurry is formed. Let stand for 7 hours to obtain a specific gravity of 1.64 g / cm³. 3 Protective glaze;

[0070] The functional auxiliary dry granules comprise the following components by mass percentage: SiO2: 45.8%, Bi2O3: 21.7%, ZnO: 5.3%, MgO: 3.8%, Na2O: 11.9%, K2O: 8.0%, Li2O: 2.2%, ZrO2: 1.3%; the D50 particle size of the functional auxiliary dry granules is 3 μm.

[0071] The spherical fine dry particles comprise the following components by mass percentage: SiO2: 58.9%, Al2O3: 15.8%, K2O: 6.7%, Na2O: 2.1%, CaO: 7.7%, MgO: 3.8%, ZnO: 2.9%, BaO: 2.1%; the spherical fine dry particles have a D50 particle size of 10 μm and a sphericity greater than 0.9.

[0072] By weight ratio, 32 parts of lithium saponite were added to 15 parts of vinyltriethoxysilane and stirred at 50 r / min for 12 min. Then, 2 parts of polyethylene glycol-400 and 13 parts of polymethylsiloxane were added and stirred for another 30 min to obtain a suspension.

[0073] S5. Apply the protective glaze to the pattern layer and dry it at 65°C for 12 minutes to form a protective glaze layer with a thickness of 0.5 mm. Heat the layer to 950°C at a heating rate of 5°C / min and hold it for 10 minutes. Then heat the layer to 1220°C at a heating rate of 12°C / min and fire it for 45 minutes to obtain a ceramic tile with a texture similar to natural stone. Example 3:

[0074] A method for preparing ceramic tiles with imitation natural stone texture includes the following steps:

[0075] S1. Preparing brick blanks;

[0076] S2. Apply a base glaze to the surface of the brick blank to form a base glaze layer with a thickness of 1 mm;

[0077] S3. By adding different colored pigments to the base slurry, glaze slurries of different colors are made. The different colored glaze slurries are then sprayed onto the base glaze layer by inkjet printing technology to form a pattern layer with natural stone texture.

[0078] S4. Preparation of protective glaze slurry: According to weight, add 10 parts of functional auxiliary dry granules, 3 parts of suspending agent, 2 parts of N-dodecylpyrrolidone, 3 parts of composite dispersant (a mixture of 1.8 parts of sodium carboxymethyl cellulose and 1.2 parts of sodium silicate), and 4 parts of dodecyltrimethylammonium bromide to an appropriate amount of water, mix thoroughly, then slowly add 60 parts of spherical fine dry granules, stirring continuously at 50 r / min until a uniform and stable glaze slurry is formed. Let stand for 8 hours to obtain a specific gravity of 1.65 g / cm³. 3 Protective glaze;

[0079] The functional auxiliary dry granules comprise the following components by mass percentage: SiO2: 45.7%, Bi2O3: 22.2%, ZnO: 5.3%, MgO: 3.7%, Na2O: 12.9%, K2O: 7.5%, Li2O: 1.4%, ZrO2: 1.3%; the D50 particle size of the functional auxiliary dry granules is 3 μm.

[0080] The spherical fine dry particles comprise the following components by mass percentage: SiO2: 58.7%, Al2O3: 15.2%, K2O: 8.2%, Na2O: 2.6%, CaO: 7.3%, MgO: 3.5%, ZnO: 2.7%, BaO: 1.8%; the spherical fine dry particles have a D50 particle size of 12μm and a sphericity greater than 0.9.

[0081] According to the weight ratio, 35 parts of lithium saponite were added to 15 parts of vinyltriethoxysilane and stirred at 50 r / min for 10 min. Then, 3 parts of polyethylene glycol-400 and 15 parts of polymethylsiloxane were added and stirred for another 35 min to obtain a suspension.

[0082] S5. Apply the protective glaze to the pattern layer and dry it at 70°C for 10 minutes to form a protective glaze layer with a thickness of 0.5 mm. Heat the glaze to 950°C at a heating rate of 5°C / min and hold it for 10 minutes. Then heat the glaze to 1220°C at a heating rate of 15°C / min and fire it for 45 minutes to obtain a ceramic tile with a texture similar to natural stone.

[0083] Comparative Example 1:

[0084] Compared with Example 3, Comparative Example 1 uses a high melting point frit to replace the functional auxiliary dry granules, and the melting point of the high melting point frit is 1100°C. Otherwise, it is the same as Example 3.

[0085] The high-temperature molten metal in Comparative Example 1 has the following chemical composition by mass percentage: SiO2: 52.3%, Al2O3: 25.6%, K2O: 1.4%, CaCO3: 14.0%, MgO: 5.3%, ZnO: 1.4%.

[0086] Comparative Example 2:

[0087] The difference between Comparative Example 2 and Example 3 is that the functional auxiliary dry granules of the present invention were not added in Comparative Example 2, but otherwise the same as in Example 3.

[0088] Comparative Example 3:

[0089] The difference between Comparative Example 3 and Example 3 is that the D50 particle size of the functional auxiliary dry granules in Comparative Example 3 is 50 μm; the D50 particle size of the spherical fine dry granules is 50 μm and the sphericity is 0.6; the rest is the same as Example 3.

[0090] Comparative Example 4:

[0091] The difference between Comparative Example 4 and Example 3 is that the suspending agent in Comparative Example 4 is a conventional single polymethylsiloxane, while the rest is the same as in Example 3.

[0092] Comparative Example 5:

[0093] The difference between Comparative Example 5 and Example 3 is that no suspending agent was added in Comparative Example 5, but otherwise it is the same as Example 3.

[0094] Comparative Example 6:

[0095] The difference between Comparative Example 6 and Example 3 is that Comparative Example 6 uses sodium carboxymethyl cellulose as a single dispersant and does not add sodium silicate; otherwise, it is the same as Example 3.

[0096] Comparative Example 7:

[0097] The difference between Comparative Example 7 and Example 3 is that no dodecyltrimethylammonium bromide (surfactant) was added in Comparative Example 7, but otherwise it was the same as Example 3.

[0098] Comparative Example 8:

[0099] The difference between Comparative Example 8 and Example 3 is that step S5 in Comparative Example 8 is different, while the rest is the same as in Example 3.

[0100] Step S5 in Comparative Example 8 is as follows: S5. Apply the protective glaze to the pattern layer, dry it at 70°C for 10 minutes to form a protective glaze layer with a thickness of 0.5 mm, heat it to 1220°C at a heating rate of 15°C / min, and fire it for 70 minutes to obtain a ceramic tile with a texture similar to natural stone.

[0101] The apparent performance of the ceramic tile samples prepared in Examples 1-3 and the comparative ceramic tile samples prepared in Comparative Examples 1-8 was tested. The results were observed and recorded by those skilled in the art with the naked eye. If necessary, auxiliary means such as microscopes or magnifying glasses could be used. The results are shown in Table 1 below.

[0102] Table 1: Apparent Status

[0103] Group Glaze condition Line texture Glazed surface texture Example 1 Smooth and flat, without obvious defects The natural stone texture is clearly visible. Warm, soft, and delicate Example 2 Smooth and flat, without obvious defects The natural stone texture is clearly visible. Warm, soft, and delicate Example 3 Smooth and flat, without obvious defects The natural stone texture is clearly visible. Warm, soft, and delicate Comparative Example 1 Local unevenness Natural stone texture clarity is generally low It has a grainy texture Comparative Example 2 The glaze is not hard enough and has scratches. Natural stone texture clarity is generally low dry Comparative Example 3 Minor pinholes and bubbles in the glaze The clarity of natural stone texture is blurred. rough Comparative Example 4 The glaze surface is flat and has poor uniformity. Natural stone textures generally lack clarity, with some areas appearing blurry. The warm and smooth feel is worse than in Example 3. Comparative Example 5 Uneven glaze surface with localized build-up Natural stone has poor texture clarity and loses detail. rough Comparative Example 6 Slight glaze buildup Natural stone has poor texture clarity and loses detail. rough Comparative Example 7 The glaze is smooth with slight pinholes. Natural stone texture clarity is generally low The warm and smooth feel is worse than in Example 3. Comparative Example 8 minor cracks Natural stone textures generally lack clarity, with some areas appearing blurry. dry

[0104] As shown in Table 1, this invention optimizes the composition of the protective glaze layer and improves process parameters, ensuring the natural stone texture of the ceramic tile while also providing an excellent warm, soft, and delicate touch. The overall glaze quality, texture effect, and feel are all improved. In Comparative Example 1, a high-melting-point frit was used to replace the functional auxiliary dry particles, resulting in poor glaze melting and affecting flatness and texture clarity. In Comparative Example 2, without the functional auxiliary dry particles of this invention, the glaze hardness and texture decreased, and the texture lacked three-dimensionality. In Comparative Example 3, the functional auxiliary dry particles had a D50 particle size of 50 μm; the spherical fine dry particles also had a D50 particle size of 50 μm and a sphericity of 0.6. The excessively large particle size and low sphericity resulted in a rough glaze surface and poor texture detail. In Comparative Example 4, the suspending agent was a single component, leading to poor suspension and affecting the uniformity of the protective glaze and the final glaze quality. This demonstrates that this invention, through its optimized suspension system, can significantly improve the glaze quality of ceramic tiles. Comparative Example 5, without the addition of a suspending agent, resulted in poor stability of the protective glaze slurry, leading to glaze defects and unclear textures. Comparative Example 6 used sodium carboxymethyl cellulose as a single dispersant, and Comparative Example 7 did not add dodecyltrimethylammonium bromide (a surfactant), but the glaze quality was not as good as in Example 3, indicating that the compounded dispersant and added surfactant in this invention can both promote glaze quality. In Comparative Example 8, the temperature was directly raised to 1220°C at a heating rate of 15°C / min. Although both the functional auxiliary dry particles and the spherical fine dry particles could melt, the resulting glaze effect was not as good as that obtained by staged heating. The staged heating of this invention can ensure that the functional auxiliary dry particles melt and spread fully first, achieving gradient melting and good bonding of the protective glaze layer during firing, which helps to promote glaze performance.

[0105] In addition, performance tests were conducted on the ceramic tile samples of Examples 1-3 and the comparative ceramic tile samples of Comparative Examples 1-8, and the results are shown in Table 2 below.

[0106] Table 2: Performance Data

[0107] Group Stain resistance abrasion resistance Mohs hardness Example 1 Level 5 ≥4 levels (2000 RPM) 7 Example 2 Level 5 ≥4 levels (2000 RPM) 7 Example 3 Level 5 ≥4 levels (2000 RPM) 7 Comparative Example 1 Level 4 Level 3 or higher (750 RPM) 5 Comparative Example 2 Level 3 Level 2 or higher (500 RPM) 4 Comparative Example 3 Level 2 Level 3 or higher (750 RPM) 5 Comparative Example 4 Level 4 Level 3 or higher (750 RPM) 6 Comparative Example 5 Level 2 Level 3 or higher (750 RPM) 6 Comparative Example 6 Level 3 ≥4 levels (2000 RPM) 6 Comparative Example 7 Level 3 Level 3 or higher (750 RPM) 6 Comparative Example 8 Level 3 Level 2 or higher (500 RPM) 5

[0108] Stain Resistance Rating: Level 5 (Excellent): Extremely dense and smooth glaze. Common stains such as ink, soy sauce, and vinegar can be easily wiped away with a damp cloth after prolonged exposure, leaving no residue. Level 4 (Good): Very dense glaze. Most stains can be easily wiped away. A few strong staining substances (such as ink) may leave slight marks after prolonged exposure, but this does not affect the overall appearance. Level 3 (Average): Microscopic unevenness exists in the glaze. Everyday stains (such as juice) can be wiped away promptly, but vinegar, dyes, etc., may leave visible marks if left for a slightly longer period. Level 2 (Poor): Obvious defects in the glaze, such as high roughness or the presence of micropores. Liquid stains easily penetrate, usually leaving noticeable residue after wiping, requiring detergent for barely removal. Level 1 (Poor): Porous or loosely structured glaze. Any stain will quickly penetrate, making thorough cleaning impossible and leaving permanent stains.

[0109] As can be seen from the data in Table 2, the optimized composition and process of this invention result in better surface density, which in turn helps to improve stain resistance. Furthermore, the addition of functional auxiliary dry particles significantly improves the hardness of the glaze. In Comparative Example 1, the high-temperature frit failed to pre-melt and combine with the spherical fine dry particles, resulting in slightly poorer wear resistance and stain resistance. In Comparative Example 2, the lack of functional auxiliary dry particles led to poor high-temperature fluidity of the glaze, preventing the formation of a dense glaze surface and thus affecting stain resistance. In Comparative Example 3, the excessively large particle size and low sphericity of the dry particles resulted in a rough glaze surface after firing, providing adhesion points for contaminants. In Comparative Examples 4 and 5, the poor suspension system led to uneven protective glaze slurry and inconsistent microstructure of the glaze surface after firing, resulting in decreased stain resistance. In Comparative Examples 6 and 7, the poor glaze quality resulted in lower stain resistance compared to Example 3. In Comparative Example 8, internal stress in the glaze layer caused microcracks, reducing both wear resistance and stain resistance. This invention demonstrates that the ceramic tiles prepared by this invention, through the optimization of the raw materials for the preparation of the protective glaze, can possess both the warm and delicate touch of natural stone and the surface properties of stain resistance and wear resistance, thus exhibiting excellent artistic effects and remarkable performance.

[0110] 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 ceramic tile with a texture resembling natural stone, the ceramic tile comprising a tile blank and a base glaze layer, a pattern layer, and a protective glaze layer sequentially disposed on the surface of the tile blank, characterized in that, The protective glaze layer is prepared from a protective glaze slurry, and the protective glaze slurry comprises the following raw materials in parts by weight: Spherical fine dry granules: 50-70 parts, functional auxiliary dry granules: 3-10 parts, suspending agent: 0.5-3 parts, leveling agent: 0.3-2 parts, composite dispersant: 0.2-3 parts, and surfactant: 0.5-5 parts; The spherical fine dry particles comprise the following components by mass percentage: SiO2: 55%~60%, Al2O3: 12%~16%, K2O: 3%~9%, Na2O: 1%~5%, CaO: 3%~8%, MgO: 1%~4%, ZnO: 1%~3%, BaO: 0.5%~2.5%; The functional auxiliary dry granules comprise the following components by mass percentage: SiO2: 45%~55%, Bi2O3: 20%~25%, ZnO: 5%~12%, MgO: 2%~5%, Na2O: 10%~15%, K2O: 5%~10%, Li2O: 1%~5%, ZrO2: 1%~2%; The melting temperature of the functional auxiliary dry granules is 400℃~800℃, and the melting temperature of the spherical fine dry granules is 1120℃~1250℃. The functional auxiliary dry granules have a D50 particle size of 1μm to 5μm; the spherical fine dry granules have a D50 particle size of 5μm to 15μm and a sphericity greater than 0.

9. The preparation method of the suspension is as follows: lithium saponite is added to the silane coupling agent and stirred at a speed of 20 r / min to 50 r / min for 10 min to 20 min. Then, polyethylene glycol-400 and polymethylsiloxane are added and stirred at a speed of 20 r / min to 50 r / min for 30 min to 45 min to obtain the suspension. The composite dispersant is obtained by mixing sodium carboxymethyl cellulose and sodium silicate in a mass ratio of (5~7):(3~5); The surfactant is at least one of dodecyltrimethylammonium bromide and N,N-dimethyldodecylamine-N-oxide.

2. The ceramic tile according to claim 1, characterized in that, The weight ratio of lithium saponite, silane coupling agent, polyethylene glycol-400 and polymethylsiloxane is (20~35):(9~15):(1~5):(5~15).

3. The ceramic tile according to claim 1, characterized in that, The leveling agent is N-dodecylpyrrolidone.

4. A method for preparing ceramic tiles with imitation natural stone texture, characterized in that, The preparation method is used to prepare ceramic tiles with imitation natural stone texture as described in any one of claims 1 to 3, and the preparation method includes the following steps: S1. Preparing brick blanks; S2. Apply a base glaze to the surface of the brick blank to form a base glaze layer; S3. A pattern is printed on the base glaze layer using inkjet printing technology to form a pattern layer; S4. Preparation of protective glaze slurry: Add functional auxiliary dry granules, suspending agent, leveling agent, composite dispersant and surfactant to an appropriate amount of water, mix evenly, and then slowly add spherical fine dry granules. Under stirring conditions, continue stirring until a uniform and stable glaze slurry is formed. Let stand for 3h~8h to obtain the protective glaze slurry. S5. Apply the protective glaze to the pattern layer, dry it to form a protective glaze layer, heat it to 600℃~1000℃ at a heating rate of 3℃ / min~5℃ / min, hold it for 5min~15min, and then heat it to 1180℃~1220℃ at a heating rate of 10℃ / min~15℃ / min for firing. The firing cycle is 40min~70min to obtain a ceramic tile with a texture similar to natural stone.

5. The preparation method according to claim 4, characterized in that, The thickness of the protective glaze layer is 0.3mm to 0.8mm.