Ceramic tile with velvet texture and replica stone effect and preparation method thereof

Abstract

The present invention relates to the field of ceramic technology, and discloses a ceramic tile with a velvet texture and a replica of an original stone effect, and a preparation method thereof; the ceramic tile comprises a body layer, a surface glaze layer, a pattern texture layer, a digital engraving ink layer, and a dry granular glaze layer, which are sequentially arranged from bottom to top; the digital engraving ink layer is composed of digital matte engraving ink; the dry granular glaze layer is composed of dry granular glaze; a surface tension difference is formed between the digital matte engraving ink and the dry granular glaze. By improving the digital matte engraving ink, it can be combined with the dry granular glaze and form a matte three-dimensional non-collapse effect on the glaze surface; by improving the dry granular glaze, it has better physical properties; by improving the suspending agent, the suspending agent can produce a stronger binding ability with the dry granular particles, so that the dry granular glaze has a stronger polarity, and when combined with the highly hydrophobic digital matte engraving ink, it can form sufficient repulsive force to form a more delicate three-dimensional concave and convex effect.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramics, and in particular to a ceramic tile having a velvet texture and a replica of an original stone effect, and a preparation method thereof. Background Art

[0002] The development of ceramic tiles primarily utilizes natural stone as a base material. With advancements in inkjet technology, the clarity and texture of patterns are increasingly approaching that of natural stone. With the development of new ceramic materials, advancements in glazes, dry granular glazes, and production processes, the production technology of ceramic wall and floor tiles has been greatly improved. Not only do the pattern and layering effects rival those of natural marble, but ceramic tiles also offer superior performance, with far superior wear resistance, acid and alkali resistance, and stain resistance compared to natural stone. Ceramic tiles have essentially achieved the goal of being derived from natural stone and yet surpassing it.

[0003] Replicating natural marble is a major research area in ceramic production, with highly realistic textures currently achieved. Driven by consumer demand for high-quality products and the need for extreme product refinement by R&D professionals, the naturally occurring concave and convex textures of matte natural marble are being replicated on ceramic tiles, adding a more three-dimensional quality. Currently, this effect is primarily achieved by reacting a sinking ink with the surface glaze, primarily in glossy marble products. With the rise of matte products, ceramic products that replicate the natural concave and convex textures of the stone are also a major research area. Advances in production processes and materials have led to significant advancements in digital molds and glue-based positioning products for simulating natural marble. These products utilize a combination of digital and glaze materials to create a more three-dimensional concave texture. Glue-based positioning achieves this undulating effect by printing glue patterns on dry particles with an inkjet printer.

[0004] Currently, marble-based ceramic tiles primarily include glossy finishes with a textured surface created by sinking ink. This early generation of marble products utilizes the shrinkage caused by the reaction of sinking ink with the glaze. This results in less detailed, coarse, and less realistic texture. Digital molded products utilize digitally laid out base glaze to create a textured surface, but this type is too coarse and deep, easily leading to problems such as dirt lurking in the crevices. Glue-set marble products, created using inkjet printing glue, can achieve deep, large-scale textured surfaces and are suitable for marble products with a more coarse texture. Currently, finer marble textures require refined file processing. This fine textured surface is created by spreading the surface glaze. After fine polishing, the surface becomes smooth and refined, resembling the texture of natural marble after years of use. Currently, surface glazes require the use of ordinary raw glazes and digital matte engraving inks to create fine textures. However, ordinary protective glazes have numerous pores in the glaze layer after firing, which damages the surface structure after fine polishing, resulting in poor anti-fouling properties. With the development of dry-granular glazes, their dense structure, formed after calcination, offers improved anti-fouling and wear resistance when applied to products. However, dry-granular glazes currently require a suspending agent to form a glaze slurry. Conventional suspending agents are highly hydrophobic. When dry-granular glazes containing suspending agents and digital matte engraving inks meet, the digital matte engraving inks struggle to generate sufficient repulsion against the dry-granular glazes, making it difficult to create fine concave and convex textures, limiting the development of this product type.

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

[0006] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a ceramic tile with a velvet texture and a replica of the original stone effect and a preparation method thereof, and the matte inorganic glaze in the developed digital matte engraving ink is used, which has a relatively matte texture effect formed after reacting with the surface dry granular glaze, achieving a replica effect that is relatively close to the surface of natural marble; the developed dry granular glaze has high transparency and low high-temperature deformation, ensuring that the fine concave and convex texture remains relatively intact after firing, and the glaze surface has good physical properties, ensuring a wide range of applications for the product; the development of the suspending agent in the dry granular glaze can be dissolved in water at a large ratio, avoiding the problem that conventional suspending agents need to use ethylene glycol with high hydrophobicity as a solvent, and the inorganic suspending agent provided by the present invention contains more electrolyte Na +Ions make the dry granular glaze have greater polarity, which can form a greater repulsive force with digital matte deep ink, thereby producing a fine three-dimensional concave and convex texture effect.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A ceramic tile with a velvet texture and a replica of an original stone, comprising a body layer, a surface glaze layer, a pattern texture layer, a digital engraving ink layer, and a dry granular glaze layer, arranged in order from bottom to top; the digital engraving ink layer is composed of digital matte engraving ink; the dry granular glaze layer is composed of dry granular glaze; a surface tension difference is formed between the digital matte engraving ink and the dry granular glaze; the surface tension of the digital matte engraving ink is 1.25×10 -2 N / m~2.27×10 -2 N / m, the surface tension of the dry granular glaze is 6.50×10 -2 N / m~6.80×10 -2 N / m. When the subsequently applied dry granular glaze combines with the digital matte engraving ink, the digital matte engraving ink has a smaller surface tension, while the dry granular glaze has a larger surface tension. This physical repulsion between the two forms a fine concave and convex texture on the digital matte engraving ink.

[0009] Preferably, the digital matte engraving ink comprises 60-65 parts of organic solvent and 35-40 parts of matte inorganic glaze, calculated by weight; the organic solvent comprises the following components: 40%-55% of isooctyl laurate, 40%-55% of ethyl acetate, 3%-6% of dispersant, 0.1%-0.2% of suspending agent, 0.2%-0.3% of defoaming agent, 0.3%-0.6% of leveling agent, and 0.15%-0.3% of pH regulator; the matte inorganic The chemical composition of the glaze is: Al2O3: 18.45% to 21.54%, SiO2: 45.68% to 50.24%, K2O: 1.24% to 3.25%, Na2O: 1.25% to 2.58%, CaO: 4.37% to 6.58%, ZnO: 3.24% to 5.58%, BaO: 8.57% to 10.24%, SrO: 6.35% to 8.54%, with the remainder being trace impurities and loss on ignition. A suitable digital matte engraving ink is prepared. Since the present invention requires the dry granular glaze to be spread to form a fine texture, and dry granular glaze is more difficult to spread than conventional glazes due to the use of a suspending agent, the present invention requires the preparation of a digital matte engraving ink with greater hydrophobicity. To ensure that the present invention has a natural marble luster, the portion of the digital matte engraving ink in contact with the dry granular glaze must have a matte luster after firing. The use of organic solvents in the digital matte engraving ink of the present invention imparts low surface tension and high hydrophobicity to the ink. This allows for sufficient repulsion when combined with the high-surface-tension and hydrophilic dry granular glaze, enabling the dry granular glaze to repel the printed digital matte engraving ink, creating a fine texture and a concave-convex effect. The digital matte engraving ink also primarily comprises a matte inorganic glaze. Al2O3 is incorporated primarily to achieve matte effect, reacting with SiO2 in the dry granular glaze to form a mullite crystal phase, which prevents the formation of an excessive glass phase and increases the gloss of the glaze. Furthermore, the use of polyvalent divalent oxides such as CaO, ZnO, BaO, and SrO not only promotes high-temperature fluxing but also aids in matte removal. Consequently, the product produced by the present invention can achieve a fine, undulating texture while maintaining the natural luster of natural marble, enabling this product to perfectly replicate the effect of natural marble.

[0010] Preferably, the dry granular glaze comprises 30-40 parts of dry granules and 60-70 parts of suspending agent in parts by weight; 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%, and the rest are trace impurities and loss on ignition; 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, which is then ground and added to the suspending agent to form the dry granule glaze with a particle size range of 80-120 μm. The dry granule glaze has a suitable particle size and is not easy to settle, so that the powdered dry granules can be evenly dispersed in the suspending agent under the action of the suspending agent. While achieving the goal of replicating natural marble, the present invention also needs to ensure that the dry granule glaze on the pattern texture layer and the digital engraving ink layer has good transparency to ensure the clarity of the printed pattern details. Therefore, the dry granule glaze needs to have good high-temperature viscosity so that the fine concave and convex effect formed after firing does not melt and collapse. Furthermore, the dry granular glaze layer must be dense, mature after firing, and possess excellent acid and alkali resistance and stain resistance, enabling multi-area application of ceramic wall and floor tiles. Specifically, the calcined kaolin in the dry granules primarily provides aluminum oxide and silicon dioxide, which increase the high-temperature viscosity of the dry granules, ensuring that the glaze surface does not collapse after firing and imparts a three-dimensional texture. Waste glass is primarily used to provide sufficient silicon dioxide, enabling the dry granular glaze to more easily form a glass phase after firing, thereby increasing its transparency. Fluorite, primarily composed of calcium fluoride, decomposes during the production of dry granular glaze, allowing the dry granules to react more fully during firing. The CaO it provides, along with divalent oxides such as BaO and SrO from barium carbonate and strontium sulfate, impart a matte sheen to the dry granular glaze after firing, resembling the effect of natural marble.

[0011] 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 aspects of the present invention lies in the development of a suspending agent for dry granular glaze. Conventional suspending agents have a relatively high hydrophobicity, and the dry granules have a relatively large mass. When the highly hydrophobic dry granular glaze meets the digital matte engraving ink, the digital matte engraving ink has difficulty forming a sufficiently large repulsive force on the dry granular glaze, resulting in a less than fine repelling effect. Compared with conventional suspending agents currently formed by mainly using sodium methylcellulose and dissolving it in ethylene glycol, the suspending agent provided by the present invention has a relatively high hydrophobicity. When the conventional suspending agent is combined with the digital matte engraving ink having a relatively high hydrophobicity, it is difficult to form a mutual repulsion effect between the two, that is, it is difficult to form a relatively fine, three-dimensional concave and convex texture. The suspension agent developed by the present invention mainly uses sodium methylcellulose combined with highly water-soluble sodium polyacrylate, sodium alginate and water-soluble biopolysaccharides. Sodium polyacrylate has strong viscosity and suspension properties, has a large solubility in water, and forms a relatively active Na + Sodium alginate has a large solubility in water. After dissolving, it can increase the suspending properties of the suspending agent. At the same time, the electrolyte Na + , can increase the fluidity of the suspension, making it easier to implement the spraying process of the dry granular glaze. The water-soluble biopolysaccharide improves the viscosity of the suspension after dissolving in water. Its strong intermolecular bond force can make the granular dry particles form a more compact and evenly dispersed dry granular glaze. The use of this composition increases the Na in the suspension + The content of suspending agent makes it have strong hydrophobicity and large surface tension. When the dry granular glaze containing suspending agent with high polarity and high surface tension meets the digital matte deep-cut ink with low surface tension and high hydrophobicity, the repulsive force between the two causes the dry granular glaze tightly adhering to the suspending agent to be pushed away, thus forming a relatively fine, uneven glaze effect. The present invention can form fine textures with a minimum range of 0.01 to 0.05mm on the brick surface, and can also form large-scale uneven textures with a maximum area of ​​8 to 10 square centimeters. The multi-dimensional uneven textures combining points, lines and surfaces make the product have a more realistic replica of natural marble.

[0012] Another object of the present invention is to provide a method for preparing a ceramic tile having a velvet texture and a replica of an original stone, comprising the following steps:

[0013] S1, pressing the powder to form a green body layer;

[0014] S2, applying a glaze on the body layer to form a glaze layer;

[0015] S3. First, print the color texture on the surface glaze layer to form the pattern texture layer. The color pattern mainly selects the pattern material with natural marble effect; then print the digital matte deep-engraving ink on the pattern texture layer to form a digital deep-engraving ink layer; the digital matte deep-engraving ink forms different grayscale value textures through the texture setting. When the subsequent digital matte deep-engraving ink is combined with the dry granular glaze, the digital matte deep-engraving ink has greater hydrophobicity and smaller surface tension, while the dry granular glaze has greater polarity and greater surface tension. The two form physical mutual repulsion after meeting, thereby forming concave and convex textures of different depths and shapes according to the different printed digital grayscales, that is, forming a fine concave and convex texture on the surface of the fired brick.

[0016] S4. Applying dry granular glaze on the formed digital engraving ink layer to form a dry granular glaze layer. Preferably, the dry granular glaze is applied by spraying. The dry granular glaze, dispersed by the suspending agent, encounters the digital matte engraving ink. Due to the significant surface tension difference between the two, the dry granular glaze is dispersed according to the different spray volumes of the digital matte engraving ink. This forms a concave and convex texture of varying depths and shapes, based on the different pixels and depths of the design file.

[0017] S5. The green body layer coated with the dry granular glaze is fired and formed to obtain the ceramic tile having the texture of golden velvet and the effect of replicating the original stone.

[0018] Preferably, the powder in step S1 is pressed into bricks of the desired thickness and size using a brick press and then dried. After drying, the moisture content of the bricks is controlled to be below 0.5%, and the strength of the bricks is controlled to be above 1.8 MPa. The above restrictions ensure that the bricks have a certain strength, which is convenient for the subsequent glazing process.

[0019] Preferably, the chemical composition of the topcoat in step S2 is: Al2O3: 23.24% to 25.67%, SiO2: 51.24% to 53.65%, ZrO2: 6.32% to 8.58%, K2O: 2.45% to 3.68%, Na2O: 1.67% to 2.69%, CaO: 1.17% to 2.56%, MgO: 2.30% to 3.65%, Fe2O3: 0.56% to 0.89%, TiO2: 0.35% to 0.68%, and the remainder is loss on ignition. The topcoat has high high-temperature viscosity and hiding power.

[0020] More preferably, the specific gravity of the glaze is 1.85-1.90 g / ml, and the glaze amount is 300-400 g / m 2 .

[0021] Preferably, the firing temperature in step S5 is 1180-1190°C, and the firing time is 60-65 minutes. This firing temperature is compatible with the melting temperature of the digital matte engraving ink and the dry granular glaze, and can form a fine, concave and convex texture effect on the tile surface without causing the concave and convex texture to be filled due to melting caused by the firing temperature being too high.

[0022] Beneficial effects:

[0023] The present invention provides a ceramic tile having a velvet texture and a replica of an original stone effect and a preparation method thereof, which has the following advantages:

[0024] 1. Conventional dry granular glaze products often struggle to create a delicate, three-dimensional, undulating texture when using digital matte engraving ink. The present invention utilizes a suspending agent, which, on the one hand, allows the powdered dry particles to be more evenly dispersed within the suspending agent. Furthermore, this novel suspending agent exhibits a high polarity, creating a strong repulsive force between the hydrophobic digital matte engraving ink and the pre-printed texture. Furthermore, this suspending agent exhibits a strong bonding ability with the dry granular particles, enabling the dry granular glaze to create a fine, three-dimensional undulating texture by following the repulsive force between the two.

[0025] 2. The matte marble products prepared using the developed dry granular glaze as the surface glaze have better physical properties than conventional water glaze, which is mainly manifested in better transparency of the glaze layer, clearer patterns, and more prominent texture details; at the same time, the glaze layer also has better wear resistance, acid and alkali resistance, and anti-fouling properties, giving ceramic tiles a wider application space.

[0026] 3. Research and development of digital matte engraving ink. Compared with conventional sinking ink and fine carving ink, the digital matte engraving ink of the present invention can react with the dry granular glaze of the present invention during the firing process to form a matte luster and a relatively three-dimensional non-collapse effect through the research and development of matte inorganic glaze in the digital matte engraving ink and the adjustment of the formula. In addition, the digital matte engraving ink can react with the oxides in the dry granular glaze during the firing process to form a variety of crystals with different reflectivities, forming a matte luster, which can perfectly replicate the effect of natural marble from a visual perspective. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of the ceramic tile with velvet texture and replica of original stone effect prepared in Example 1.

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

[0029] Figure 3Schematic diagram of the ceramic tile with velvet texture and replica of original stone effect prepared in Example 2.

[0030] Figure 4 Schematic diagram of the ceramic tile prepared in Comparative Example 2. DETAILED DESCRIPTION

[0031] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples. Its purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention are all conventional common reagents and instruments unless otherwise specified.

[0032] Example 1

[0033] A ceramic tile with a velvet texture and a replica of original stone effect includes a body layer, a surface glaze layer, a pattern texture layer, a digital engraving ink layer, and a dry granular glaze layer, which are arranged in sequence from bottom to top; the digital engraving ink layer is composed of digital matte engraving ink; the dry granular glaze layer is composed of dry granular glaze; a surface tension difference is formed between the digital matte engraving ink and the dry granular glaze.

[0034] Calculated by weight, the digital matte engraving ink comprises 62 parts of an organic solvent and 38 parts of a 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%, and the remainder is trace impurities and loss on ignition;

[0035] Calculated by weight, the dry granule glaze comprises 35 parts of dry granules and 65 parts of a suspending agent; the raw materials of the dry granules are: 20 parts of calcined kaolin, 20 parts of potassium feldspar, 23 parts of sodium feldspar, 6.5 parts of waste glass, 4.5 parts of corundum, 10 parts of sodium borate, 5 parts of fluorite, 5 parts of barium carbonate, and 6 parts of strontium sulfate; 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%, and the remainder is trace impurities and loss on ignition; the suspending agent comprises the following components: 2 parts of sodium methylcellulose, 7.5 parts of sodium polyacrylate, 5.5 parts of sodium alginate, 7.5 parts of water-soluble biopolysaccharide, and 77.5 parts of water. The particle size of the dry granular glaze is 80 to 90 μm.

[0036] The chemical composition of the glaze in the glaze layer is: 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%, and the rest is loss on ignition. The specific gravity of the glaze is 1.85 g / ml, and the glaze amount is 320 g / m 2 .

[0037] The firing temperature of the ceramic tile is 1180-1190° C., and the firing time is 60-65 minutes.

[0038] Example 2

[0039] Compared with Example 1, Example 2 is different in that:

[0040] The dry granular glaze has an aluminum oxide content of 16.25%. The 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 loss on ignition. The particle size of the dry granular glaze is 100-110 μm. This study was used to investigate the effect of a low aluminum content in the dry granular glaze on the glaze's gloss and three-dimensional effect.

[0041] 2. The chemical composition of the top glaze layer is: 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%, and the rest is loss on ignition. The specific gravity of the top glaze is 1.89 g / ml, and the glaze amount is 380 g / m 2 .

[0042] Example 3

[0043] Example 3 differs from Example 1 in that the aluminum oxide content in the dry granule glaze is 20.10%. The chemical composition of the dry granule is as follows: 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 loss on ignition. This is used to examine the effect of a high aluminum content in the dry granule on the glaze gloss and the effect on the glaze's three-dimensional effect.

[0044] Example 4

[0045] Example 4 differs from Example 1 in that the dry granule raw material contains 5 parts of waste glass. The chemical composition of the dry granules is as follows: 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 loss on ignition. This was used to examine 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 dry granule raw material contains 8 parts of waste glass. The chemical composition of the dry granules is as follows: 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 loss on ignition. This was used to investigate the effect of the transparency of the dry granule glaze on pattern clarity and the three-dimensional effect of the glaze surface.

[0048] Example 6

[0049] Example 6 differs from Example 1 in that the BaO and SrO contents in the dry granular glaze are both at the lower limit. The 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 loss on ignition. This was used to investigate the effects of divalent oxides on glaze gloss and three-dimensional effect.

[0050] Example 7

[0051] Example 7 differs from Example 1 in that the BaO and SrO contents in the dry granular glaze are both upper limits. The 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 loss on ignition. This was used to investigate the effects of divalent oxides on glaze gloss and three-dimensional effect.

[0052] Example 8

[0053] Example 8 differs from Example 1 in that the Al2O3 content in the matte inorganic glaze used in the digital matte engraving ink is 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 loss on ignition. This was used to examine the effects of digital matte engraving ink on the brightness of the glaze's concave and convex effects and the three-dimensional effect.

[0054] Example 9

[0055] Example 9 differs from Example 1 in that the Al2O3 content in the matte inorganic glaze used in the digital matte engraving ink is the 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 loss on ignition. This was used to examine the effects of digital matte engraving ink on the brightness of the glaze's concave and convex positions and the three-dimensional effect.

[0056] Example 10

[0057] Example 10 differs from Example 1 in that the contents of divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze in the digital matte deep engraving ink are all 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 loss on ignition. This was used to examine the effect of the lower limit divalent oxide content on the brightness and three-dimensional effect of the glaze's concave-convex effect areas.

[0058] Example 11

[0059] Example 11 differs from Example 1 in that the contents of the divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze in the digital matte deep engraving ink are all at the 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 loss on ignition. This was used to examine the effects of the divalent oxide content at the upper limit on the brightness and three-dimensional effect of the glaze's concave-convex effect.

[0060] Example 12

[0061] Example 12 is different from Example 1 in that the composition of the suspending agent in the dry granular glaze is different, that is, the content of sodium polyacrylate in the suspending agent in Example 12 is the lower limit: 5 parts. This is used to examine the suspension effect of the dry granular glaze and the glaze surface concave-convex effect.

[0062] Example 13

[0063] Example 13 is different from Example 1 in that the composition of the suspending agent in the dry granular glaze is different, that is, the content of sodium polyacrylate in the suspending agent in Example 13 is the upper limit: 10 parts. This is used to examine the suspension effect of the dry granular glaze and the convex-concave effect of the glaze surface.

[0064] Example 14

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

[0066] Example 15

[0067] Example 15 differs from Example 1 in that the composition of the suspending agent in the dry granular glaze is different, i.e., the content of sodium alginate in the suspending agent in Example 15 is the upper limit of 8 parts. This is used to examine the suspension effect of the dry granular glaze and the concave-convex effect of the glaze surface.

[0068] Example 16

[0069] Example 16 differs from Example 1 in that the composition of the suspending agent in the dry granular glaze is different, i.e., the content of the water-soluble biopolysaccharide in the suspending agent in Example 16 is the lower limit of 5 parts. This is used to examine the suspension effect of the dry granular glaze and the glaze surface concave-convex effect.

[0070] Example 17

[0071] Example 17 differs from Example 1 in that the composition of the suspending agent in the dry granular glaze is different, i.e., the content of the water-soluble biopolysaccharide in the suspending agent in Example 17 is limited to 10 parts. This is used to investigate the suspension effect of the dry granular glaze and the convex-concave effect of the glaze surface.

[0072] Comparative Example 1

[0073] Compared with Example 1, the difference is that the Al2O3 content in the dry particles is lower than the lower limit, and the chemical composition of the dry particles is specifically: Al2O3: 15.25%, SiO2: 65.73%, B2O3: 3.90%, K2O: 1.98%, Na2O: 2.05%, CaO: 3.34%, BaO: 3.88%, SrO: 2.92%, and the rest are trace impurities and loss on ignition.

[0074] Comparative Example 2

[0075] Compared with Example 1, the difference is that the Al2O3 content in the dry particles is higher than the upper limit, and the chemical composition of the dry particles is specifically: Al2O3: 22.10%, SiO2: 56.77%, B2O3: 5.80%, K2O: 1.86%, Na2O: 2.04%, CaO: 3.39%, BaO: 3.83%, SrO: 2.97%, and the rest are trace impurities and loss on ignition.

[0076] Comparative Example 3

[0077] Compared with Example 1, the difference is that the content of waste glass in the dry granular raw material is 4 parts, which is lower than the lower limit. The chemical composition of the dry granules is specifically: Al2O3: 20.15%, SiO2: 55.71%, B2O3: 5.56%, K2O: 1.87%, Na2O: 2.55%, CaO: 3.39%, BaO: 4.31%, SrO: 3.94%, and the rest are trace impurities and loss on ignition.

[0078] Comparative Example 4

[0079] Compared with Example 1, the difference is that the content of waste glass in the dry granular raw material is 9 parts, which is higher than the upper limit. The chemical composition of the dry granules is specifically: 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 rest are trace impurities and loss on ignition.

[0080] Comparative Example 5

[0081] Compared with Example 1, the difference is that the contents of BaO and SrO in the dry granule glaze are both lower than the lower limit, and the chemical composition of the dry granules is specifically: Al2O3: 19.13%, SiO2: 64.24%, B2O3: 4.97%, K2O: 2.17%, Na2O: 1.85%, CaO: 3.48%, BaO: 1.80%, SrO: 1.07%, and the rest are trace impurities and loss on ignition.

[0082] Comparative Example 6

[0083] Compared with Example 1, the difference is that the contents of BaO and SrO in the dry granular glaze are all 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 rest are trace impurities and loss on ignition.

[0084] Comparative Example 7

[0085] Compared with Example 1, the difference is that the content of Al2O3 in the matte inorganic glaze in the digital matte deep engraving ink is lower than the lower limit, and 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 rest are trace impurities and loss on ignition.

[0086] Comparative Example 8

[0087] Compared with Example 1, the difference is that the content of Al2O3 in the matte inorganic glaze in the digital matte deep engraving ink is higher than the upper limit, and 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 rest are trace impurities and loss on ignition.

[0088] Comparative Example 9

[0089] Compared with Example 1, the difference is that the contents of divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze in the digital matte deep engraving ink are all lower than the lower limit, and 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 rest are trace impurities and loss on ignition.

[0090] Comparative Example 10

[0091] Compared with Example 1, the difference is that the contents of divalent oxides ZnO, BaO, and SrO in the matte inorganic glaze in the digital matte deep engraving ink are all higher than the upper limit, and the 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%, and the rest are trace impurities and loss on ignition.

[0092] Comparative Example 11

[0093] Compared with Example 1, the difference is that the composition of the suspending agent in the dry granular glaze is different, that is, 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 is that the composition of the suspending agent in the dry granular glaze is different, that is, 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 is that the composition of the suspending agent in the dry granular glaze is different, that is, 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] Compared with Example 1, the difference is that the composition of the suspending agent in the dry granular glaze is different, that is, 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 is that the composition of the suspending agent in the dry granular glaze is different, that is, the content of the water-soluble polysaccharide 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 is that the composition of the suspending agent in the dry granular glaze is different, that is, the content of the water-soluble polysaccharide 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 granular glaze used in Comparative Example 17 is conventional dry granular, and its composition is: Al2O3: 15.24%, SiO2: 67.57%, K2O: 3.68%, Na2O: 4.67%, CaO: 1.48%, MgO: 1.57%, B2O3: 4.65%, and the rest is loss on ignition and trace impurities.

[0106] Comparative Example 18

[0107] Comparative Example 18 differs from Example 1 in that it uses conventional digital engraving ink, whose composition is: 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 loss on ignition. This was used to examine the effect of conventional ink on the brightness of the concave and convex textures and the three-dimensional effect of the texture.

[0108] Comparative Example 19

[0109] Compared with Example 1, the difference is that: Comparative Example 19 uses a common suspending agent, whose ingredients are: sodium methyl cellulose: 5 parts, ethylene glycol: 83 parts, glycerin: 10 parts, and bentonite: 2 parts, as the main suspending agent for dry particles, to examine the effect of the common suspending agent on the formation of the convex and concave texture effect on the glaze surface.

[0110] Performance Testing

[0111] Glossiness of ceramic tile glaze: The specific glossiness of the glaze can be measured by using a digital photometer.

[0112] Glaze acid and alkali resistance and anti-fouling performance: The test basis is GB / T4100-2015, "Ceramic Tiles" Appendix G Dry-pressed Ceramic Tiles (E≤0.5 Bia Class).

[0113] Glaze concave and convex texture effect: based on visual inspection of the layout effect.

[0114] Glossiness of concave and convex textures: The specific glossiness of the glaze surface can be measured by a digital photometer.

[0115] Pattern clarity: Mainly through visual inspection, observing texture details and pattern layering effects.

[0116] The results are shown in Table 1.

[0117]

[0118]

[0119]

[0120]

[0121] from Figure 1 and Figure 3 It can be seen from the appearance of the ceramic tiles that the ceramic tiles prepared by the present invention have a natural texture like natural marble, and the overall glaze surface presents a clearly visible concave-convex effect, and the concave-convex effect is three-dimensional and has rich texture. Figure 2 The optical microscope diagram shows that the glaze surface has micro cracks with a fineness of 50μm. Figure 1 As can be seen from the performance tests in the above table, the glaze is matte, with a soft light feeling and good transparency. It is also acid and alkali resistant, dirt resistant, and has excellent physical properties, which can ensure that the product has a wide range of applications.

[0122] In comparative example 1, due to the low Al2O3 content in the dry granular glaze, the glaze surface of the tile collapsed after firing and was not three-dimensional enough. In comparative example 2, due to the high Al2O3 content in the dry granular glaze, the glaze surface of the tile was relatively rough after firing. Figure 4 It can be seen that the glaze pattern of the tile prepared in Comparative Example 2 is fuzzy and not clear enough. Figure 3 Compared with the pattern clarity of the ceramic tile prepared in Example 2, there is a significant difference.

[0123] In Comparative Example 3, due to the use of less waste glass, the glaze transparency is poor and the pattern is not clear enough. In Comparative Example 4, due to the use of more waste glass, the glaze collapses and is not three-dimensional enough.

[0124] In Comparative Example 5, the low content of divalent barium and strontium oxides in the dry granular glaze resulted in a less three-dimensional glaze surface, a high level of crystallization, and poor glaze transparency. In Comparative Example 6, the high content of divalent barium and strontium oxides in the dry granular glaze resulted in unqualified acid and alkali resistance of the tile, with the glaze layer easily reacting with acid and poor glaze transparency.

[0125] In Comparative Example 7, due to the low Al₂O₃ content in the digital matte engraving ink, the glossiness of the concave and convex areas formed after the reaction with the dry granular glaze was bright, resulting in a poor texture. In Comparative Example 8, due to the high Al₂O₃ content in the digital matte engraving ink, the glossiness of the concave and convex areas formed after the reaction with the dry granular glaze was matte and dry.

[0126] In Comparative Example 9, the low content of zinc, barium, and strontium divalent oxides in the digital matte engraving ink resulted in a sunken glaze surface with a bright glossiness. In Comparative Example 10, the high content of zinc, barium, and strontium divalent oxides in the digital matte engraving ink resulted in a matte finish in the glaze surface due to their reaction with the dry granular glaze. This resulted in a dry, dull, and textureless finish in the glaze surface.

[0127] In Comparative Example 11, due to the low amount of sodium polyacrylate used in the suspending agent for the dry granular glaze, the adsorption force of the suspending agent on the dry granules was insufficient, making it difficult to achieve a fine dispersing effect. In Comparative Example 12, due to the high amount of sodium polyacrylate used in the suspending agent, the suspending agent was highly viscous, making it difficult to achieve a dispersing effect.

[0128] In Comparative Example 13, the low amount of sodium alginate in the suspending agent resulted in a low hydrophilicity, making it difficult to achieve a displacing effect. In Comparative Example 14, the high amount of sodium alginate in the suspending agent resulted in an excessively high viscosity. When this highly viscous suspending agent encountered digital matte engraving ink, it was difficult to achieve a fine displacing effect.

[0129] In Comparative Example 15, the low amount of water-soluble polysaccharide in the suspending agent formula resulted in a low electrolyte content in the dry granular glaze. This made it difficult to achieve a repelling effect when the suspending agent encountered the digital matte engraving ink. In Comparative Example 16, the high amount of water-soluble polysaccharide in the suspending agent formula increased the viscosity of the suspending agent. When the suspending agent encountered the digital matte engraving ink, the repulsive force generated by the suspending agent made it difficult to effectively repel the dry granular glaze, thus hindering the formation of a fine, concave-convex texture.

[0130] In Comparative Example 17, conventional dry particles were selected. Since the formula did not match this process, the glaze surface collapsed and the texture pattern was unclear.

[0131] In Comparative Example 18, conventional digital engraving ink is used instead of the digital matte engraving ink of the present invention. Due to the lack of barium strontium components in the conventional digital engraving ink, the glossiness at the concave and convex positions is brighter, the natural effect is poor, and the effect at the concave and convex positions collapses.

[0132] In Comparative Example 19, conventional suspending agents were used as the suspension medium for dry granular glaze. Since conventional dry granular glaze contains a large amount of organic components, it is difficult to form a mutually repulsive force when it encounters digital matte deep ink, making it difficult to form a fine concave-convex effect.

[0133] 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 the technical solutions of the present invention may be modified or replaced by equivalents 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 the original stone effect, characterized in that: The invention comprises a body layer, a surface glaze layer, a pattern texture layer, a digital engraving ink layer, and a dry granular glaze layer arranged in sequence from bottom to top; the digital engraving ink layer is composed of digital matte engraving ink; the dry granular glaze layer is composed of dry granular glaze; a surface tension difference is formed between the digital matte engraving ink and the dry granular glaze; Calculated by weight, the digital matte engraving ink includes 60-65 parts of an organic solvent and 35-40 parts of a 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%, and the remainder is trace impurities and loss on ignition; The dry granular glaze comprises 30 to 40 parts of dry granules and 60 to 70 parts of a suspending agent, calculated by weight. The chemical composition of the dry granules is as follows: Al2O3: 16.21% to 20.14%, SiO2: 58.12% to 63.34%, B2O3: 4.27% to 7.54%, K2O: 1.34% to 2.34%, Na2O: 1.56% to 2.54%, CaO: 2.14% to 4.57%, BaO: 2.10% to 5.65%, SrO: 1.87% to 3.98%, and the remainder is trace impurities and loss on ignition. The suspending agent comprises the following components: 1.5 to 3.5 parts of sodium methylcellulose, 5 to 10 parts of sodium polyacrylate, 3 to 8 parts of sodium alginate, 5 to 10 parts of water-soluble biopolysaccharide, and 70 to 85 parts of water.

2. The ceramic tile with a velvet texture and a replica of an original stone according to claim 1, characterized in that: The surface tension of the digital matte deep ink is 1.25×10 -2 N / m~2.27×10 -2 N / m, the surface tension of the dry granular glaze is 6.50×10 -2 N / m~6.80×10 -2 N / m.

3. The ceramic tile with a velvet texture and a replica of an original stone according to claim 1, characterized in that: Calculated by mass percentage, the organic solvent includes the following components: 40% to 55% of isooctyl laurate, 40% to 55% of ethyl acetate, 3% to 6% of dispersant, 0.1% to 0.2% of suspending agent, 0.2% to 0.3% of defoaming agent, 0.3% to 0.6% of leveling agent, and 0.15% to 0.3% of pH regulator.

4. The ceramic tile with a velvet texture and a replica of an original stone according to claim 1, characterized in that: The raw materials of the dry particles 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 an original stone according to claim 4, characterized in that: The raw materials constituting the dry particles are calcined and melted to form a frit, and then the frit is ground and the suspending agent is added to form the dry particle glaze with a particle size ranging from 80 to 120 μm.

6. A method for preparing a ceramic tile having a velvet texture and a replica of an original stone according to any one of claims 1 to 5, characterized in that: The steps are as follows: S1, pressing the powder to form a green body layer; S2, applying a glaze on the body layer to form a glaze layer; S3. First, color texture is printed on the glaze layer to form a pattern texture layer; then, digital matte deep ink is printed on the pattern texture layer to form a digital deep ink layer; S4, applying dry granular glaze on the formed digital deep ink layer to form a dry granular glaze layer; S5. The green body layer coated with the dry granular glaze is fired and formed to obtain the ceramic tile having the texture of gold velvet and the effect of replicating the original stone.

7. The method for preparing a ceramic tile having a velvet texture and a replica of an original stone according to claim 6, characterized in that: The powder in step S1 is pressed into bricks by a brick press and dried. After drying, the moisture content of the bricks is controlled below 0.5%, and the strength of the bricks is controlled above 1.8 MPa.

8. The method for preparing a ceramic tile having a velvet texture and a replica of an original stone according to claim 6, characterized in that: The chemical composition of the glaze in step S2 is: Al2O3: 23.24% to 25.67%, SiO2: 51.24% to 53.65%, ZrO2: 6.32% to 8.58%, K2O: 2.45% to 3.68%, Na2O: 1.67% to 2.69%, CaO: 1.17% to 2.56%, MgO: 2.30% to 3.65%, Fe2O3: 0.56% to 0.89%, TiO2: 0.35% to 0.68%, and the rest is loss on ignition.

9. The method for preparing a ceramic tile having a golden velvet texture and replicating an original 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 amount is 300-400 g / m 2 .

10. The method for preparing ceramic tiles having a velvet texture and replicating the original stone effect according to claim 6, characterized in that: The firing temperature of the sintering molding in the step S5 is 1180-1190° C., and the firing time is 60-65 minutes.

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