Ceramic tile having velvety texture and replicated natural stone effect and preparation method therefor

Abstract

The present invention relates to the technical field of ceramics. Disclosed are a ceramic tile having a velvety texture and a replicated natural stone effect and a preparation method therefor. The ceramic tile comprises a green body layer, a surface glaze layer, a pattern texture layer, a digital deep-engraving ink layer, and a dry grain glaze layer which are sequentially arranged from bottom to top. The digital deep-engraving ink layer is composed of a digital matte deep-engraving ink. The dry grain glaze layer is composed of a dry grain glaze. A surface tension difference is formed between the digital matte deep-engraving ink and the dry grain glaze. By means of the improvement of the digital matte deep-engraving ink, the digital matte deep-engraving ink can bind with the dry grain glaze and achieve a matte three-dimensional non-collapse effect on the glaze surface. By means of the improvement of the dry grain glaze, the dry grain glaze exhibits better physical properties. By means of the improvement of a suspending agent, the suspending agent can achieve relatively strong binding affinity with dry grains, thereby imparting stronger polarity to the dry grain glaze, and when the dry grain glaze binds with the digital matte deep-engraving ink having high hydrophobicity, sufficient repulsive forces can be formed, resulting in the formation of a more refined and three-dimensional relief effect.

Description

A ceramic tile with a velvet texture and a replica of natural stone effect, and its preparation method. Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to a ceramic tile with a velvet texture and a replica of natural stone effect, and its preparation method. Background Technology

[0002] The development of ceramic tiles primarily utilizes natural stone as its material. With the advancement of inkjet technology, the clarity and texture of patterns are increasingly approaching the quality of natural stone. As research and development of new ceramic materials, glazes, dry-granule glazes, and production processes have progressed, the production technology of ceramic wall and floor tiles has been greatly improved. Not only do they achieve patterns and textures comparable to natural marble, but they also surpass natural marble in performance. Their wear resistance, acid and alkali resistance, and stain resistance are far superior to natural stone. Ceramic tiles have essentially achieved a superior result compared to natural stone, derived from it.

[0003] The replication of natural marble is a major research direction in ceramic production. Currently, the texture and layering have been made very realistically. With increasing consumer demands for product effects and researchers' pursuit of perfection, replicating the naturally formed textures of matte natural marble on ceramic tiles makes the products more three-dimensional. Currently, this is mainly achieved by creating the recessed effect through the reaction of ink with the surface glaze, primarily in glossy marble products. With the rise of matte products, ceramic products featuring the natural textures of stone are also a major research direction. With advancements in production processes and materials, digital molds and adhesive positioning products have made significant progress in simulating natural marble. Digital molds utilize the stacking of digital inks and glazes to create relatively three-dimensional recessed textures. Adhesive positioning uses an inkjet printer to print adhesive patterns and then applies dry granules to achieve the product's undulating effect.

[0004] Currently, ceramic tiles produced using marble-like materials mainly fall into two categories: glossy and textured. Early marble-like products used a combination of ink-based coatings to create raised textures. These tiles achieved their marble effect through the reaction of ink and glaze, resulting in shrinkage and unevenness. However, the raised textures were not refined enough, and the overall texture was coarse and unrealistic. Digital mold-based products used digitally applied base glazes to create raised textures, but this type was too coarse and the deep raised textures could trap dirt in the crevices. Adhesive-based marble products, created using inkjet printing, could achieve deeper and larger raised textures, suitable for coarser marble textures. More refined marble textures require meticulous document processing. This involves spreading the surface glaze to create a fine raised texture, followed by polishing to achieve a smooth, natural marble finish acquired over many years of use. Currently, surface glazes require the use of ordinary raw material glazes combined with digital matte engraving inks to create fine textures. However, ordinary protective glazes have numerous capillaries after firing, which damages the surface structure after polishing, resulting in poor stain resistance. With the development of dry granule glazes, their dense structure, after firing, allows for better stain resistance and abrasion resistance when applied to products. However, current dry granule glazes require suspending agents to form a glaze slurry. Conventional suspending agents are highly hydrophobic, and when dry granule glazes containing suspending agents and with high hydrophobicity encounter digital matte engraving inks, the inks struggle to generate sufficient repulsion, making it difficult to create fine textures and limiting the development of such products.

[0005] Therefore, it is necessary to develop a relatively simple production process that can replicate the surface effect of natural marble through fine processing of the texture, and then combine it with glaze to form the desired surface texture effect.

[0006] Summary of the Invention

[0007] In view of the shortcomings of the prior art, the purpose of this invention is to provide a ceramic tile with a velvet texture and a replica of natural stone effect, and its preparation method. This invention utilizes a matte inorganic glaze in a specially developed digital matte ink, which reacts with the surface dry granule glaze to form a relatively matte texture, achieving a replica effect closely resembling the surface of natural marble. The developed dry granule glaze has high transparency and low high-temperature deformation, ensuring that the fine texture remains relatively intact after firing, and the glaze surface has good physical properties, guaranteeing a wide range of applications for the product. Furthermore, the development of a suspending agent in the dry granule glaze allows for high water solubility, avoiding the problem of conventional suspending agents requiring highly hydrophobic ethylene glycol as a solvent. The inorganic suspending agent provided by this invention contains a relatively high amount of the electrolyte Na. +The ions give the dry granule glaze a high degree of polarity, which can create a strong repulsive force with digital matte inks, thus producing a fine and three-dimensional textured effect.

[0008] To achieve the above objectives, the present invention adopts the following technical solution:

[0009] A ceramic tile with a velvety texture and a replica of natural stone effect comprises, from bottom to top, a body layer, a glaze layer, a pattern texture layer, a digitally engraved ink layer, and a dry-granule glaze layer; the digitally engraved ink layer is composed of digital matte engraved ink; the dry-granule glaze layer is composed of dry-granule glaze; a surface tension difference exists between the digitally matte engraved ink and the dry-granule glaze; the surface tension of the digitally matte engraved ink is 1.25 × 10⁻⁶. -2 N / m~2.27×10 -2 N / m, the surface tension of the dry granular glaze is 6.50 × 10 N / m. -2 N / m~6.80×10 -2 N / m. When the subsequently applied dry granule enamel is combined with digital matte embossing ink, the digital matte embossing ink has a lower surface tension while the dry granule enamel has a higher surface tension. This causes the two to physically repel each other when they meet, thus creating a fine textured surface on the digital matte embossing ink.

[0010] Preferably, by weight, the digital matte deep-dark ink comprises 60-65 parts of organic solvent and 35-40 parts of matte inorganic enamel; the organic solvent comprises the following components: 40%-55% isooctyl laurate, 40%-55% ethyl acetate, 3%-6% dispersant, 0.1%-0.2% suspending agent, 0.2%-0.3% defoamer, 0.3%-0.6% leveling agent, and 0.15%-0.3% pH adjuster; the matte inorganic enamel comprises... The chemical composition of the glaze is as follows: Al2O3: 18.45%–21.54%, SiO2: 45.68%–50.24%, K2O: 1.24%–3.25%, Na2O: 1.25%–2.58%, CaO: 4.37%–6.58%, ZnO: 3.24%–5.58%, BaO: 8.57%–10.24%, SrO: 6.35%–8.54%, with the remainder being trace impurities and adjusted accordingly. To prepare a suitable digital matte deep-etching ink, since this invention requires the dry granule glaze to be dispersed to form fine textures, and dry granule glaze is more difficult to disperse than conventional glazes due to the use of suspending agents, this invention requires the preparation of a digital matte deep-etching ink with higher hydrophobicity. Furthermore, to ensure that this invention has a natural marble-like luster, the portion of the digital matte deep-etching ink in contact with the dry granule glaze must have a matte finish after firing. The use of organic solvents in the digital matte engraving ink of this invention gives it low surface tension and high hydrophobicity. This provides sufficient repulsion when it combines with dry granular glaze, which has high surface tension and hydrophilicity, allowing the dry granular glaze to repel the printed digital matte engraving ink and create a fine texture and embossed effect. Another major component of the digital matte engraving ink is matte inorganic glaze. The use of Al2O3 mainly serves to matte the surface. Al2O3 can react with SiO2 in the dry granular glaze to form a mullite crystal phase, preventing the formation of excessive glass phase and thus reducing the gloss of the glaze surface. Furthermore, the use of divalent oxides CaO, ZnO, BaO, and SrO serves both as a high-temperature flux and as a means of matting. Therefore, the product obtained by this invention can form a fine, undulating texture while maintaining the natural luster of natural marble, allowing the product to perfectly replicate the effect of natural marble.

[0011] Preferably, by weight, the dry granule glaze comprises 30-40 parts dry granules and 60-70 parts suspending agent; the chemical composition of the dry granules is: Al2O3: 16.21%-20.14%, SiO2: 58.12%-63.34%, B2O3: 4.27%-7.54%, K2O: 1.34%-2.34%, Na2O: 1.56%-2.54%, CaO: 2.14%-4.57%, BaO: 2.10%-5.65%, SrO: 1.87%-3.98%, with the remainder being trace impurities and adjusted accordingly; preferably, the... The raw materials for the dry granules are: calcined kaolin: 18-22 parts, potassium feldspar: 15-25 parts, sodium feldspar: 18-28 parts, waste glass: 5-8 parts, corundum: 3-6 parts, sodium borate: 8-12 parts, fluorite: 3-7 parts, barium carbonate: 3-7 parts, and strontium sulfate: 4-8 parts. The raw materials constituting the dry granules are calcined and melted to form a frit. The frit is then ground, and the suspending agent is added to form the dry granule glaze with a particle size range of 80-120 μm. This ensures the dry granule glaze has a suitable particle size, is not prone to sedimentation, and is easily dispersed uniformly in the suspending agent. This invention, while replicating natural marble, also needs to ensure good transparency of the dry granule glaze on the pattern texture layer and the digital ink layer to guarantee the clarity of the printed pattern details. Therefore, the dry granule glaze needs to have good high-temperature viscosity to prevent the fine textured effect formed after firing from melting and collapsing. In addition, the dry-granule glaze layer needs to be dense, mature after firing, resistant to acids and alkalis, and have excellent stain resistance, enabling multi-area application of ceramic wall and floor tiles. Specifically, the calcined kaolin in the dry granules mainly provides alumina and silica, which can be used to increase the high-temperature viscosity of the dry granules, ensuring that the glaze surface does not collapse after firing and has a three-dimensional texture effect. The application of waste glass is mainly to provide sufficient silica, making it easier for the dry-granule glaze to form a glassy phase after firing, thereby increasing the transparency of the dry-granule glaze layer. The main component of fluorite is calcium fluoride. During the production of dry-granule glaze, due to the decomposition characteristics of calcium fluoride, the dry granules can react more fully during firing. At the same time, the CaO provided, as well as the divalent oxides such as BaO and SrO provided by barium carbonate and strontium sulfate, can give the dry-granule glaze layer a matte gloss after firing, achieving a replica of natural marble.

[0012] Preferably, the suspending agent comprises the following components: sodium methylcellulose: 1.5-3.5 parts, sodium polyacrylate: 5-10 parts, sodium alginate: 3-8 parts, water-soluble biopolysaccharide: 5-10 parts, and water: 70-85 parts. One of the inventive points of this invention lies in the development of a suspending agent for dry-granule glazes. Conventional suspending agents have significant hydrophobicity, and dry granules have a large mass. When the highly hydrophobic dry-granule glaze encounters digital matte embossing ink, the ink struggles to generate a sufficiently strong repulsive force, resulting in a less refined separation effect. Compared to conventional suspending agents that primarily utilize sodium methylcellulose dissolved in ethylene glycol, the suspending agent provided by this invention, due to the significant hydrophobicity of ethylene glycol, makes it difficult for conventional suspending agents to repel the highly hydrophobic digital matte embossing ink, thus hindering the formation of a fine, three-dimensional textured surface. The suspending agent developed in this invention mainly utilizes sodium methylcellulose combined with highly water-soluble sodium polyacrylate, sodium alginate, and water-soluble biological polysaccharides. Sodium polyacrylate has strong viscosity and suspending properties, and high solubility in water, forming highly active Na+ after dissolution. + Sodium alginate has high solubility in water, which increases the suspension properties of suspending agents after dissolution. Simultaneously, the formed electrolyte Na... + This increases the fluidity of the suspending agent, making it easier to apply dry granule glaze using a spraying process. The water-soluble biopolysaccharide, after dissolving in water, enhances the viscosity of the suspending agent; its stronger intermolecular bonds allow the granular dry particles to form a more compact and uniformly dispersed dry granule glaze. The use of this composition increases the Na content in the suspending agent. + The content of [specific ingredient] gives the suspending agent strong hydrophobicity and high surface tension. When the dry granule glaze containing the suspending agent, which has high polarity and high surface tension, encounters the digital matte deep-dark ink with low surface tension and high hydrophobicity, the repulsive force between the two causes the dry granule glaze, which is tightly adhered to the suspending agent, to be pushed away, thereby forming a finer, more textured glaze surface. This invention can form micro-textures on the brick surface with a minimum thickness of 0.01 to 0.05 mm, as well as larger block-shaped textures, with a maximum size of 8 to 10 square centimeters. The multi-dimensional three-dimensional texture combining points, lines, and surfaces gives the product a more realistic replica of natural marble.

[0013] Another objective of this invention is to provide a method for preparing ceramic tiles with a velvet texture and a replica of natural stone effect, comprising the following steps:

[0014] S1. Pressing the powder to form a green body layer;

[0015] S2. Apply a surface glaze to the body layer to form a surface glaze layer;

[0016] S3. First, print the color texture on the glaze layer to form a pattern texture layer. The color pattern is mainly selected from natural marble effect pattern materials. Then, print digital matte deep ink on the pattern texture layer to form a digital deep ink layer. The digital matte deep ink forms textures with different gray values ​​through texture settings. When the digital matte deep ink is combined with dry granule glaze, the digital matte deep ink has greater hydrophobicity and lower surface tension, while the dry granule glaze has greater polarity and higher surface tension. When the two meet, they form a physical mutual repulsion. Thus, different depths and shapes of concave and convex textures can be formed according to different printed digital gray values. That is, a fine concave and convex texture is formed on the surface of the brick after firing.

[0017] S4. Apply dry granule glaze to the formed digital deep-engraving ink layer to form a dry granule glaze layer; preferably, the dry granule glaze is applied by spraying. Under the dispersion of the suspending agent, when the dry granule glaze encounters the digital matte deep-engraving ink, due to the large surface tension difference between the two, the dry granule glaze, according to different ink spray volumes of digital matte deep-engraving ink, is dispersed and, according to different pixels and depths in the design file, can form textures of different depths and shapes.

[0018] S5. The body layer covered with dry granule glaze is fired and shaped to obtain the ceramic tile with the texture of gold velvet and the effect of replicating the original stone.

[0019] Preferably, in step S1, the powder is pressed into brick blanks of the required thickness and size using a brick press, and then dried. After drying, the moisture content of the brick blanks is controlled below 0.5%, and the strength of the brick blanks is controlled above 1.8 MPa. These limitations ensure that the brick blanks have a certain strength, facilitating subsequent glazing processes.

[0020] Preferably, the chemical composition of the glaze in step S2 is as follows: Al2O3: 23.24%–25.67%, SiO2: 51.24%–53.65%, ZrO2: 6.32%–8.58%, K2O: 2.45%–3.68%, Na2O: 1.67%–2.69%, CaO: 1.17%–2.56%, MgO: 2.30%–3.65%, Fe2O3: 0.56%–0.89%, TiO2: 0.35%–0.68%, with the remainder to be reduced as needed. The above-mentioned glaze has high high-temperature viscosity and covering power.

[0021] More preferably, the specific gravity of the glaze is 1.85–1.90 g / ml, and the glaze application amount is 300–400 g / ml. 2 .

[0022] Preferably, the firing temperature in step S5 is 1180–1190°C, and the firing time is 60–65 min. This firing temperature is compatible with the melting temperature of digital matte ink and dry granule glaze, allowing for the formation of fine, textured effects on the brick surface without the texture being filled in by melting due to excessively high firing temperatures. Beneficial effects:

[0023] This invention provides a ceramic tile with a velvet texture and a replica of natural stone effect, and its preparation method, with the following advantages:

[0024] 1. For conventional dry granule enamel products, it is often difficult to achieve a delicate and three-dimensional textured effect when using digital matte engraving ink. This invention utilizes a specially developed suspending agent. On the one hand, this agent allows the powdered dry granules to be more evenly dispersed within the suspending agent. On the other hand, this novel suspending agent has high polarity. When it encounters highly hydrophobic digital matte engraving ink, it can create a strong repulsive force between the granules according to the pre-set texture. Furthermore, this suspending agent has a strong binding ability with the dry granule particles, allowing the dry granule enamel to form a finer, three-dimensional textured effect through this repulsive force.

[0025] 2. Matte marble products prepared using the developed dry granule glaze as the surface glaze have superior physical properties compared to conventional water-based glazes. These properties are mainly reflected in better glaze transparency, clearer patterns, and more prominent texture details. At the same time, the glaze also has better wear resistance, acid and alkali resistance, and stain resistance, giving ceramic tiles a wider range of applications.

[0026] 3. The development of digital matte deep-carving ink: Compared with conventional sinking ink and fine carving ink, the digital matte deep-carving ink of this invention, through the development of matte inorganic glaze and the adjustment of the formula, can react with the dry granule glaze in this invention during the firing process to form a matte gloss and a more three-dimensional, non-collapsed effect; in addition, the digital matte deep-carving ink can react with the oxides in the dry granule glaze during the firing process to form a variety of crystals with different reflectivities, forming a matte gloss, which can perfectly replicate the effect of natural marble in terms of visual effect. Attached Figure Description

[0027] Figure 1 is a schematic diagram of the ceramic tile with a velvet texture and a replica of the original stone effect obtained in Example 1.

[0028] Figure 2 is an optical microscope magnification of the ceramic tile with a velvet texture and a replica of the original stone effect obtained in Example 1.

[0029] Figure 3 is a schematic diagram of the ceramic tile with a velvet texture and a replica of the original stone effect obtained in Example 2.

[0030] Figure 4 is a schematic diagram of the ceramic tile prepared in Comparative Example 2. Detailed Implementation

[0031] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments.

[0032] Example 1

[0033] A ceramic tile with a velvet texture and a replica of natural stone effect includes, from bottom to top, a body layer, a glaze layer, a pattern texture layer, a digital deep-ink layer, and a dry granule glaze layer; the digital deep-ink layer is composed of digital matte deep-ink; the dry granule glaze layer is composed of dry granule glaze; a surface tension difference is formed between the digital matte deep-ink and the dry granule glaze.

[0034] By weight, the digital matte deep-dark ink comprises 62 parts of organic solvent and 38 parts of matte inorganic glaze; the organic solvent comprises the following components: 47.5% isooctyl laurate, 47% ethyl acetate, 4.5% dispersant, 0.2% suspending agent, 0.2% defoamer, 0.4% leveling agent, and 0.2% pH adjuster; the chemical composition of the matte inorganic glaze is: Al2O3: 19.99%, SiO2: 47.96%, K2O: 2.24%, Na2O: 1.91%, CaO: 5.47%, ZnO: 4.41%, BaO: 9.40%, SrO: 7.44%, with the remainder being trace impurities and adjusted accordingly;

[0035] By weight, the dry granule glaze comprises 35 parts dry granules and 65 parts suspending agent; the raw materials of the dry granules are: calcined kaolin: 20 parts, potassium feldspar: 20 parts, sodium feldspar: 23 parts, waste glass: 6.5 parts, corundum: 4.5 parts, sodium borate: 10 parts, fluorite: 5 parts, barium carbonate: 5 parts, strontium sulfate: 6 parts; the chemical composition of the dry granules is: Al2O3: 18.17%, SiO2: 60.73%, B2O3: 5.90%, K2O: 1.84%, Na2O: 2.05%, CaO: 3.35%, BaO: 3.87%, SrO: 2.92%, with the remainder being trace impurities and reduced as appropriate; the suspending agent comprises the following components: sodium methylcellulose: 2 parts, sodium polyacrylate: 7.5 parts, sodium alginate: 5.5 parts, water-soluble biological polysaccharide: 7.5 parts, and water: 77.5 parts. The particle size of the dry granule glaze is 80–90 μm.

[0036] The chemical composition of the surface glaze is as follows: Al₂O₃: 24.67%, SiO₂: 51.65%, ZrO₂: 7.34%, K₂O: 3.48%, Na₂O: 1.88%, CaO: 1.86%, MgO: 3.05%, Fe₂O₃: 0.59%, TiO₂: 0.45%, with the remainder adjusted accordingly. The specific gravity of the surface glaze is 1.85 g / ml, and the application rate is 320 g / ml. 2 .

[0037] The ceramic bricks are fired at a temperature of 1180–1190°C for 60–65 minutes.

[0038] Example 2

[0039] The difference between Example 2 and Example 1 is that:

[0040] 1. The alumina content in the dry granule glaze is 16.25%. The specific chemical composition of the dry granules is as follows: Al2O3: 16.25%, SiO2: 61.93%, B2O3: 5.95%, K2O: 1.93%, Na2O: 2.15%, CaO: 3.24%, BaO: 3.90%, SrO: 2.87%, with the remainder being trace impurities and adjusted accordingly. The particle size of the dry granule glaze is 100–110 μm. This is used to investigate the effect of low aluminum content in the dry granule glaze on the glaze gloss and the three-dimensional effect of the glaze surface.

[0041] 2. The chemical composition of the surface glaze is as follows: Al2O3: 25.24%, SiO2: 52.42%, ZrO2: 6.85%, K2O: 2.86%, Na2O: 2.43%, CaO: 2.03%, MgO: 2.75%, Fe2O3: 0.74%, TiO2: 0.56%, with the remainder adjusted accordingly. The specific gravity of the surface glaze is 1.89 g / ml, and the application rate is 380 g / ml. 2 .

[0042] Example 3

[0043] Example 3 differs from Example 1 in that the alumina content in the dry granule glaze is 20.10%. The specific chemical composition of the dry granules is: Al₂O₃: 20.10%, SiO₂: 58.43%, B₂O₃: 5.93%, K₂O: 1.94%, Na₂O: 2.08%, CaO: 3.29%, BaO: 3.88%, SrO: 3.57%, with the remainder being trace impurities and adjusted accordingly. This was used to investigate the effect of a higher aluminum content in the dry granules on the glaze's gloss and its three-dimensional effect.

[0044] Example 4

[0045] Example 4 differs from Example 1 in that the content of waste glass in the dry granule raw material is 5 parts. The specific chemical composition of the dry granules is: Al2O3: 19.30%, SiO2: 58.13%, B2O3: 5.69%, K2O: 1.93%, Na2O: 2.38%, CaO: 2.99%, BaO: 3.78%, SrO: 3.58%, with the remainder being trace impurities and adjusted accordingly. This was used to investigate the effect of the transparency of the dry granule glaze on the clarity of the pattern.

[0046] Example 5

[0047] Example 5 differs from Example 1 in that the content of waste glass in the dry granule raw material is 8 parts. The specific chemical composition of the dry granules is: Al2O3: 19.31%, SiO2: 63.33%, B2O3: 4.99%, K2O: 1.95%, Na2O: 2.48%, CaO: 3.69%, BaO: 3.78%, SrO: 2.18%, with the remainder being trace impurities and adjusted accordingly. This was used to investigate the effect of the transparency of the dry granule glaze on the clarity of the pattern and the three-dimensional effect of the glaze surface.

[0048] Example 6

[0049] Example 6 differs from Example 1 in that the contents of BaO and SrO in the dry granule glaze are both at the lower limit. The specific chemical composition of the dry granules is as follows: Al2O3: 19.43%, SiO2: 60.33%, B2O3: 4.29%, K2O: 1.55%, Na2O: 2.39%, CaO: 3.79%, BaO: 2.10%, SrO: 1.87%, with the remainder being trace impurities and reduced as needed. This was used to investigate the influence of divalent oxides on the gloss and three-dimensional effect of the glaze surface.

[0050] Example 7

[0051] Example 7 differs from Example 1 in that the contents of BaO and SrO in the dry granule glaze are at their upper limits. The specific chemical composition of the dry granules is as follows: Al2O3: 19.43%, SiO2: 60.33%, B2O3: 4.29%, K2O: 1.55%, Na2O: 2.28%, CaO: 3.79%, BaO: 5.65%, SrO: 3.98%, with the remainder being trace impurities and adjusted accordingly. This was used to investigate the influence of divalent oxides on the gloss and three-dimensional effect of the glaze surface.

[0052] Example 8

[0053] Example 8 differs from Example 1 in that the Al2O3 content in the matte inorganic glaze of the digital matte engraving ink is at the lower limit. Its specific chemical composition is: Al2O3: 18.45%, SiO2: 50.16%, K2O: 2.11%, Na2O: 1.27%, CaO: 4.45%, ZnO: 5.42%, BaO: 9.38%, SrO: 7.22%, with the remainder being trace impurities and adjusted amounts. This was used to investigate the effect of the digital matte engraving ink on the brightness and three-dimensional effect of the glaze surface's unevenness.

[0054] Example 9

[0055] Example 9 differs from Example 1 in that the Al2O3 content in the matte inorganic glaze of the digital matte engraving ink is at its upper limit. Its specific chemical composition is: Al2O3: 21.54%, SiO2: 45.96%, K2O: 2.21%, Na2O: 1.87%, CaO: 4.47%, ZnO: 5.40%, BaO: 9.36%, SrO: 7.31%, with the remainder being trace impurities and adjusted accordingly. This was used to investigate the effect of the digital matte engraving ink on the brightness and three-dimensional effect of the glaze surface's unevenness.

[0056] Example 10

[0057] Example 10 differs from Example 1 in that the content of divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze of the digital matte engraving ink is at the lower limit. Its specific chemical composition is: Al2O3: 19.54%, SiO2: 48.96%, K2O: 2.12%, Na2O: 1.99%, CaO: 5.77%, ZnO: 3.24%, BaO: 8.58%, SrO: 6.39%, with the remainder being trace impurities and reduced as needed. This was used to investigate the effect of the divalent oxide content at the lower limit on the brightness and three-dimensional effect of the glaze surface's unevenness.

[0058] Example 11

[0059] Example 11 differs from Example 1 in that the content of divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze of the digital matte engraving ink is at its upper limit. Its specific chemical composition is: Al2O3: 21.54%, SiO2: 45.96%, K2O: 2.21%, Na2O: 1.87%, CaO: 4.47%, ZnO: 5.58%, BaO: 10.24%, SrO: 8.54%, with the remainder being trace impurities and reduced as needed. This was used to investigate the effect of the upper limit of divalent oxide content on the brightness and three-dimensional effect of the glaze surface's unevenness.

[0060] Example 12

[0061] Example 12 differs from Example 1 in that the composition of the suspending agent in the dry granule glaze is different; specifically, the content of sodium polyacrylate in the suspending agent in Example 12 is the lower limit: 5 parts. This was used to examine the suspension effect and surface texture of the dry granule glaze.

[0062] Example 13

[0063] The difference between Example 13 and Example 1 is that the composition of the suspending agent in the dry granule glaze is different; that is, the content of sodium polyacrylate in the suspending agent in Example 13 is at the upper limit of 10 parts. This was used to examine the suspension effect and surface texture of the dry granule glaze.

[0064] Example 14

[0065] Example 14 differs from Example 1 in that the composition of the suspending agent in the dry granule glaze is different; specifically, the content of sodium alginate in the suspending agent of Example 14 is the lower limit: 3 parts. This was used to examine the suspension effect and surface texture of the dry granule glaze.

[0066] Example 15

[0067] Example 15 differs from Example 1 in that the composition of the suspending agent in the dry granule glaze is different; specifically, the content of sodium alginate in the suspending agent in Example 15 is at an upper limit of 8 parts. This was used to examine the suspension effect and surface texture of the dry granule glaze.

[0068] Example 16

[0069] The difference between Example 16 and Example 1 is that the composition of the suspending agent in the dry granule glaze is different; specifically, the content of water-soluble biopolysaccharides in the suspending agent of Example 16 is the lower limit: 5 parts. This was used to examine the suspension effect and surface texture of the dry granule glaze.

[0070] Example 17

[0071] Example 17 differs from Example 1 in that the composition of the suspending agent in the dry granule glaze is different; specifically, the content of water-soluble biopolysaccharides in the suspending agent of Example 17 is capped at 10 parts. This was used to examine the suspension effect and surface texture of the dry granule glaze.

[0072] Comparative Example 1

[0073] Compared with Example 1, the difference is that the content of Al2O3 in the dry granules is lower than the lower limit. The specific chemical composition of the dry granules is as follows: Al2O3: 15.25%, SiO2: 65.73%, B2O3: 3.90%, K2O: 1.98%, Na2O: 2.05%, CaO: 3.34%, BaO: 3.88%, SrO: 2.92%, with the remainder being trace impurities and reduced as appropriate.

[0074] Comparative Example 2

[0075] Compared with Example 1, the difference is that the content of Al2O3 in the dry granules is higher than the upper limit. The specific chemical composition of the dry granules is as follows: Al2O3: 22.10%, SiO2: 56.77%, B2O3: 5.80%, K2O: 1.86%, Na2O: 2.04%, CaO: 3.39%, BaO: 3.83%, SrO: 2.97%, with the remainder being trace impurities and reduced accordingly.

[0076] Comparative Example 3

[0077] Compared with Example 1, the difference is that the content of waste glass in the dry granule raw material is 4 parts, which is lower than the lower limit. The specific chemical composition of the dry granules is as follows: Al2O3: 20.15%, SiO2: 55.71%, B2O3: 5.56%, K2O: 1.87%, Na2O: 2.55%, CaO: 3.39%, BaO: 4.31%, SrO: 3.94%, with the remainder being trace impurities and reduced as appropriate.

[0078] Comparative Example 4

[0079] Compared with Example 1, the difference is that the content of waste glass in the dry granule raw material is 9 parts, which is higher than the upper limit. The specific chemical composition of the dry granules is as follows: Al2O3: 20.15%, SiO2: 64.17%, B2O3: 5.57%, K2O: 1.97%, Na2O: 2.65%, CaO: 3.41%, BaO: 4.32%, SrO: 3.14%, and the remainder are trace impurities and reduced accordingly.

[0080] Comparative Example 5

[0081] Compared with Example 1, the difference is that the content of BaO and SrO in the dry granule glaze is lower than the lower limit. The specific chemical composition of the dry granules is as follows: Al2O3: 19.13%, SiO2: 64.24%, B2O3: 4.97%, K2O: 2.17%, Na2O: 1.85%, CaO: 3.48%, BaO: 1.80%, SrO: 1.07%, with the remainder being trace impurities and reduced as appropriate.

[0082] Comparative Example 6

[0083] Compared with Example 1, the difference is that the content of BaO and SrO in the dry granule glaze is higher than the upper limit: Al2O3: 18.55%, SiO2: 60.27%, B2O3: 4.67%, K2O: 1.77%, Na2O: 1.89%, CaO: 3.43%, BaO: 6.25%, SrO: 4.56%, and the remainder are trace impurities and reduced accordingly.

[0084] Comparative Example 7

[0085] Compared with Example 1, the difference is that the content of Al2O3 in the matte inorganic glaze of the digital matte deep ink is lower than the lower limit. Its specific chemical composition is: Al2O3: 17.45%, SiO2: 50.36%, K2O: 3.27%, Na2O: 2.57%, CaO: 5.57%, ZnO: 5.45%, BaO: 9.46%, SrO: 7.37%, and the remainder are trace impurities and reduced accordingly.

[0086] Comparative Example 8

[0087] Compared with Example 1, the difference is that the content of Al2O3 in the matte inorganic glaze of the digital matte deep ink is higher than the upper limit. Its specific chemical composition is: Al2O3: 22.54%, SiO2: 45.16%, K2O: 1.28%, Na2O: 1.89%, CaO: 4.17%, ZnO: 5.44%, BaO: 9.06%, SrO: 6.92%, and the remainder are trace impurities and reduced accordingly.

[0088] Comparative Example 9

[0089] Compared with Example 1, the difference is that the content of divalent oxides ZnO, BaO and SrO in the matte inorganic glaze of the digital matte ink is lower than the lower limit. Its specific chemical composition is: Al2O3: 21.55%, SiO2: 49.18%, K2O: 2.27%, Na2O: 1.44%, CaO: 4.57%, ZnO: 2.84%, BaO: 7.57%, SrO: 5.45%, and the remainder are trace impurities and reduced accordingly.

[0090] Comparative Example 10

[0091] Compared with Example 1, the difference is that the content of divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze of the digital matte ink is higher than the upper limit. Its specific chemical composition is: Al2O3: 21.55%, SiO2: 47.14%, K2O: 1.98%, Na2O: 2.39%, CaO: 4.96%, ZnO: 5.98%, BaO: 10.94%, SrO: 9.24%, with the remainder being trace impurities and reduced accordingly.

[0092] Comparative Example 11

[0093] Compared with Example 1, the difference lies in the composition of the suspending agent in the dry granule glaze. Specifically, the content of sodium polyacrylate in the suspending agent of Comparative Example 11 is lower than the lower limit, which is 3 parts.

[0094] Comparative Example 12

[0095] Compared with Example 1, the difference lies in the composition of the suspending agent in the dry granule glaze. Specifically, the content of sodium polyacrylate in the suspending agent of Comparative Example 12 is higher than the upper limit, which is 12 parts.

[0096] Comparative Example 13

[0097] Compared with Example 1, the difference lies in the composition of the suspending agent in the dry granule glaze. Specifically, the content of sodium alginate in the suspending agent of Comparative Example 13 is lower than the lower limit, which is 2 parts.

[0098] Comparative Example 14

[0099] The difference compared to Example 1 is that the composition of the suspending agent in the dry granule glaze is different. Specifically, the content of sodium alginate in the suspending agent of Comparative Example 14 is higher than the upper limit, which is 10 parts.

[0100] Comparative Example 15

[0101] Compared with Example 1, the difference lies in the composition of the suspending agent in the dry granule glaze. Specifically, the content of water-soluble polysaccharides in the suspending agent of Comparative Example 15 is lower than the lower limit, which is 3 parts.

[0102] Comparative Example 16

[0103] Compared with Example 1, the difference lies in the composition of the suspending agent in the dry granule glaze. Specifically, the content of water-soluble polysaccharides in the suspending agent of Comparative Example 16 is higher than the upper limit, which is 12 parts.

[0104] Comparative Example 17

[0105] Compared with Example 1, the difference is that the dry granule glaze used in Comparative Example 17 is a conventional dry granule with the following composition: Al2O3: 15.24%, SiO2: 67.57%, K2O: 3.68%, Na2O: 4.67%, CaO: 1.48%, MgO: 1.57%, B2O3: 4.65%, with the remainder being reduced and trace impurities.

[0106] Comparative Example 18

[0107] Compared to Example 1, the difference lies in that Comparative Example 18 uses ordinary digital deep-drilling ink with the following composition: Al2O3: 21.24%, SiO2: 56.56%, K2O: 4.65%, Na2O: 5.77%, CaO: 2.88%, MgO: 2.97%, B2O3: 4.05%, with the remainder being trace impurities and adjusted amounts. This was used to investigate the effect of ordinary ink on the brightness and three-dimensional effect of the raised / undrilled texture.

[0108] Comparative Example 19

[0109] Compared with Example 1, the difference is that Comparative Example 19 uses a common suspending agent with the following composition: sodium methylcellulose: 5 parts, ethylene glycol: 83 parts, glycerin: 10 parts, and bentonite: 2 parts. As the main suspending agent for dry particles, the effect of the common suspending agent on the formation of uneven texture on the glaze surface was investigated.

[0110] Performance testing

[0111] The gloss of ceramic tile glaze can be measured using a digital photometer.

[0112] Glaze acid and alkali resistance and stain resistance: The test is based on GB / T4100-2015, Appendix G of "Ceramic Tiles" for dry-pressed ceramic tiles (E≤0.5Bia class).

[0113] Glazed texture effect: based on visual inspection of the surface.

[0114] Gloss level at textured surfaces: The specific gloss level of the glaze can be measured using a digital photometer.

[0115] Pattern clarity: This is mainly achieved through visual inspection, observing the texture details and pattern layering effects.

[0116] The results are shown in Table 1.

[0117] As can be seen from the appearance of the ceramic tiles in Figures 1 and 3, the ceramic tiles prepared by this invention have a natural texture similar to natural marble. The glaze surface exhibits a clearly visible uneven surface effect, which is three-dimensional and rich in texture. Combined with the optical microscope diagram in Figure 2, it can be seen that the glaze surface has micro-gaps with a fineness of 50μm. Furthermore, as shown in Figure 1 and the performance test results in the table above, the glaze surface is matte, with a soft light feel, good transparency, and is resistant to acids and alkalis, as well as dirt, exhibiting excellent physical properties that ensure a wide range of applications for the product.

[0118] In Comparative Example 1, the low Al2O3 content in the prepared dry granule glaze caused the glaze surface to collapse and lack three-dimensionality after firing. In Comparative Example 2, the high Al2O3 content in the prepared dry granule glaze resulted in a rougher glaze surface after firing. As can be seen from Figure 4, the glaze pattern of the tile prepared in Comparative Example 2 is blurry and unclear, showing a significant difference compared to the clarity of the pattern of the ceramic tile prepared in Example 2 in Figure 3.

[0119] In Comparative Example 3, the limited use of waste glass resulted in poor glaze transparency and unclear patterns. In Comparative Example 4, the excessive use of waste glass caused the glaze to collapse and lack three-dimensionality.

[0120] In Comparative Example 5, the dry granule glaze contained relatively low levels of barium and strontium divalent oxides, resulting in a less three-dimensional glaze surface, more crystallization, and poor transparency. In Comparative Example 6, the dry granule glaze contained excessive levels of barium and strontium divalent oxides, causing the ceramic tile to fail acid and alkali resistance tests, making the glaze layer prone to reaction with acid, and also resulting in poor transparency.

[0121] In Comparative Example 7, the low Al2O3 content in the digital matte engraving ink resulted in a brighter gloss and poorer texture at the uneven areas formed after its reaction with the dry granular glaze. In Comparative Example 8, the high Al2O3 content in the digital matte engraving ink resulted in a duller and drier gloss at the uneven areas formed after its reaction with the dry granular glaze.

[0122] In Comparative Example 9, the low content of divalent oxides zinc, barium, and strontium in the digital matte engraving ink caused the uneven areas of the glaze to collapse, and the gloss was too bright. In Comparative Example 10, the excessive content of divalent oxides zinc, barium, and strontium in the digital matte engraving ink caused the uneven areas of the glaze to be too matte after reacting with the dry granule glaze, resulting in a dry, dull, and textureless appearance.

[0123] In Comparative Example 11, the amount of sodium polyacrylate in the suspending agent of the dry granule glaze was too small, resulting in insufficient adsorption of the suspending agent on the dry granules, making it difficult to achieve a fine dispersing effect. In Comparative Example 12, the amount of sodium polyacrylate in the suspending agent was too large, resulting in high viscosity of the suspending agent, making it difficult to achieve a dispersing effect.

[0124] In Comparative Example 13, the amount of sodium alginate used in the suspending agent was relatively small, resulting in low hydrophilicity and difficulty in achieving a dispersing effect. In Comparative Example 14, the amount of sodium alginate used in the suspending agent was relatively large, resulting in excessive viscosity. When this excessively viscous suspending agent came into contact with digital matte ink, it was difficult to achieve a fine dispersing effect.

[0125] In Comparative Example 15, the low amount of water-soluble polysaccharide in the suspending agent formulation resulted in a low electrolyte content in the dry granular glaze, making it difficult for the suspending agent to achieve a repulsion effect when it encountered digital matte deep-dark ink. In Comparative Example 16, the high amount of water-soluble polysaccharide in the suspending agent formulation increased the viscosity of the suspending agent, making it difficult to achieve a good repulsion force against the dry granular glaze when it encountered digital matte deep-dark ink, thus hindering the formation of a fine, textured effect.

[0126] In Comparative Example 17, conventional dry granules were used. Due to the formula not matching this process, the glaze collapsed and the texture pattern was unclear.

[0127] In Comparative Example 18, conventional digital embossing ink was used instead of the digital matte embossing ink of the present invention. Due to the lack of barium and strontium components in the conventional digital embossing ink, the gloss at the uneven areas was too bright, resulting in a poor natural effect and a collapsed effect at the uneven areas.

[0128] In Comparative Example 19, a conventional suspending agent was used as the suspension medium for the dry granule glaze. Because the conventional dry granule glaze contains a large amount of organic components, it is difficult to form a repulsive force when it encounters digital matte deep ink, resulting in difficulty in forming a fine embossed effect.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A ceramic tile with a velvet texture and a replica of natural stone effect, characterized in that, It includes, from bottom to top, a body layer, a surface glaze layer, a pattern texture layer, a digital deep-engraving ink layer, and a dry granule glaze layer; the digital deep-engraving ink layer is composed of digital matte deep-engraving ink; the dry granule glaze layer is composed of dry granule glaze; a surface tension difference is formed between the digital matte deep-engraving ink and the dry granule glaze; By weight, the digital matte deep-dark ink comprises 60-65 parts of organic solvent and 35-40 parts of matte inorganic glaze; the chemical composition of the matte inorganic glaze is: Al2O3: 18.45%-21.54%, SiO2: 45.68%-50.24%, K2O: 1.24%-3.25%, Na2O: 1.25%-2.58%, CaO: 4.37%-6.58%, ZnO: 3.24%-5.58%, BaO: 8.57%-10.24%, SrO: 6.35%-8.54%, with the remainder being trace impurities and adjusted accordingly; By weight, the dry granule glaze comprises 30-40 parts dry granules and 60-70 parts suspending agent; the chemical composition of the dry granules is: Al2O3: 16.21%-20.14%, SiO2: 58.12%-63.34%, B2O3: 4.27%-7.54%, K2O: 1.34%-2.34%, Na2O: 1.56%-2.54%, CaO: 2.14%-4.57%, BaO: 2.10%-5.65%, SrO: 1.87%-3.98%, with the remainder being trace impurities and adjusted accordingly; The suspending agent comprises the following components: sodium methylcellulose: 1.5-3.5 parts, sodium polyacrylate: 5-10 parts, sodium alginate: 3-8 parts, water-soluble biopolysaccharide: 5-10 parts, and water: 70-85 parts.

2. The ceramic tile with a velvet texture and a replica of natural stone effect as described in claim 1, characterized in that, The surface tension of the digital matte deep-engraving ink is 1.25 × 10⁻⁶. -2 N / m~2.27×10 -2 N / m, the surface tension of the dry granular glaze is 6.50 × 10 N / m. -2 N / m~6.80×10 -2 N / m.

3. The ceramic tile with a velvet texture and a replica of natural stone effect as described in claim 1, characterized in that, The organic solvent comprises, by mass percentage, the following components: 40%–55% isooctyl laurate, 40%–55% ethyl acetate, 3%–6% dispersant, 0.1%–0.2% suspending agent, 0.2%–0.3% defoamer, 0.3%–0.6% leveling agent, and 0.15%–0.3% pH adjuster.

4. The ceramic tile with a velvet texture and a replica of natural stone effect as described in claim 1, characterized in that, The raw materials for the dry granules are: calcined kaolin: 18-22 parts, potassium feldspar: 15-25 parts, sodium feldspar: 18-28 parts, waste glass: 5-8 parts, corundum: 3-6 parts, sodium borate: 8-12 parts, fluorite: 3-7 parts, barium carbonate: 3-7 parts, and strontium sulfate: 4-8 parts.

5. The ceramic tile with a velvet texture and a replica of natural stone effect according to claim 4, characterized in that, The raw materials constituting the dry granules are calcined and melted to form a frit, and then the frit is ground and the suspending agent is added to form the dry granule glaze with a particle size range of 80 to 120 μm.

6. A method for preparing a ceramic tile with a velvet texture and a replica of natural stone effect, characterized in that, The following steps are required: S1. Pressing the powder to form a green body layer; S2. Apply a surface glaze to the body layer to form a surface glaze layer; S3. First, print the color texture on the surface glaze layer to form the pattern texture layer; then print the digital matte deep ink on the pattern texture layer to form the digital deep ink layer. S4. Apply dry granule glaze onto the formed digital deep ink layer to form a dry granule glaze layer. S5. The body layer covered with dry granule glaze is fired and shaped to obtain a ceramic tile with a velvet texture and a replica of the original stone effect as described in any one of claims 1-5.

7. The method for preparing ceramic tiles with a velvet texture and a replica of natural stone effect according to claim 6, characterized in that, In step S1, the powder is pressed into brick blanks by a brick press and then dried. After drying, the moisture content of the brick blanks is controlled below 0.5%, and the strength of the brick blanks is controlled above 1.8 MPa.

8. The method for preparing ceramic tiles with a velvet texture and a replica of natural stone effect according to claim 6, characterized in that, The chemical composition of the glaze in step S2 is as follows: Al2O3: 23.24%–25.67%, SiO2: 51.24%–53.65%, ZrO2: 6.32%–8.58%, K2O: 2.45%–3.68%, Na2O: 1.67%–2.69%, CaO: 1.17%–2.56%, MgO: 2.30%–3.65%, Fe2O3: 0.56%–0.89%, TiO2: 0.35%–0.68%, with the remainder to be reduced as appropriate.

9. The method for preparing ceramic tiles with a velvet texture and a replica of natural stone effect according to claim 8, characterized in that, The specific gravity of the glaze is 1.85–1.90 g / ml, and the glaze application amount is 300–400 g / ml. 2 .

10. The method for preparing ceramic tiles with a velvet texture and a replica of natural stone effect according to claim 6, characterized in that, The firing temperature for the molding process in step S5 is 1180–1190°C, and the firing time is 60–65 min.

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