Positioning colored crystal glaze tile and its preparation method

Abstract

The present application belongs to the technical field of building ceramics, and discloses a positioning color crystal polishing glaze brick and a preparation method thereof. The positioning color crystal polishing glaze brick comprises, from bottom to top, a body, a surface glaze layer, a color ink layer, a positioning digital glue layer, a color crystal dry particle layer and a transparent polishing glaze layer; wherein the positioning digital glue layer is formed by digital glue ink jet printing. The present application uses transparent polishing glaze to replace dry particle polishing dry particle, and uses positioning digital glue ink to position the color crystal dry particle. Compared with the traditional positioning color crystal, the present application greatly reduces the production cost and improves the positioning accuracy. At the same time, by using specific surface glaze, transparent polishing glaze and digital glue ink, the compatibility problem between water-based glaze and oil-based ink is overcome, so that the digital glue and the color crystal dry particle can be perfectly combined. After firing and polishing, the product has excellent color development performance, good glaze surface transparency, and no defects on the glaze surface, thereby ensuring the quality stability of the product.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics technology, specifically relating to a positioning colored crystal polished glaze tile and its preparation method. Background Technology

[0002] Positioning crystal technology is a cutting-edge process that precisely controls the distribution of colored crystal particles to achieve a high-precision reproduction of the texture and feel of natural stone crystals. Furthermore, unlike the simple reflection of traditional glossy tiles, positioning crystal technology allows the crystals on the tile surface to produce unique optical effects under light, such as shimmering, refraction, and diffraction, resulting in a more three-dimensional and layered effect, presenting a dynamic and dazzling visual experience.

[0003] Currently, all imitation natural stone products with a positioning crystal effect have a surface glaze layer covered with dry-granulated polished granules. In the field of underglaze positioning crystal dry-granule products, both wet and dry application processes face two major constraints. First, the surface of these products requires a transparent dry-granulated polished granule coating, directly leading to high material costs. Second, it places stringent requirements on glaze line production equipment and supporting processes: the dry positioning crystal dry-granule process requires an additional dedicated dry-granule spreading machine to apply and polish the granules, significantly increasing equipment investment costs. Furthermore, this process involves numerous steps, including spraying a protective glaze to fix the dry granules. The wet positioning crystal process, due to the low specific gravity and high moisture content of the dry-granule polished granule glaze, requires a lengthy drying kiln to ensure drying effectiveness, further increasing production complexity and energy costs. In addition, existing crystal dry granules generally use a dry-granulation machine to apply a fixing agent for positioning, but this positioning method lacks precision.

[0004] Therefore, the existing positioning crystal technology has many technical problems, such as high production process threshold, large equipment investment and high material cost, as well as poor positioning accuracy, which seriously restrict the large-scale promotion and market application of positioning crystal polished glazed tiles. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a positioning colored crystal polished glaze tile and its preparation method. The positioning colored crystal polished glaze tile, while significantly reducing the production cost, ensures the color development, glaze transparency and glaze quality of the product, and the colored crystal is dazzling and eye-catching, which can accurately meet the production needs of high-end positioning colored crystal series products such as luxury stone and black gold flower.

[0006] To solve the above-mentioned technical problems, the first aspect of the present invention provides a positioning colored crystal polished glaze tile, which includes, from bottom to top, a body, a surface glaze layer, a color ink layer, a positioning digital adhesive layer, a colored crystal dry granule layer and a transparent polished glaze layer. The positioning digital adhesive layer is formed by inkjet printing with digital adhesive ink, which contains inorganic materials. The chemical composition of the inorganic materials, by weight percentage, includes: Al2O3 0.3-0.5%, SiO2 51-59%, CaO 35-42%, MgO 0.5-1.5%. The chemical composition of the surface glaze layer, by weight percentage, includes: Al2O3 20-24%, SiO2 60-65%, CaO 1-2%, MgO 0.5-2%, K2O 0.5-2%, Na2O 4-6%, ZrO 4-6%, and loss on ignition 1-3%; The chemical composition of the transparent polished glaze layer, by weight percentage, includes: Al2O3 7-10%, SiO2 48-52%, CaO 12-15%, MgO 1-3%, K2O 2-4%, Na2O 1-2%, BaO 5.5-8%, ZnO 6-10%, B2O3 0-1%, and loss on ignition 6-10%.

[0007] This invention replaces the traditional dry-granule polished glaze in positioning colored crystal glazed tiles with a transparent polished glaze, significantly reducing production costs. It also employs digital adhesive ink for precise positioning of the colored crystal dry granules, solving the problem of poor positioning with traditional fixatives. However, water-based glazes (transparent polished glaze and top glaze) and oil-based digital adhesive inks suffer from interfacial incompatibility; they repel each other, and the ink easily peels off the glaze, leading to glaze defects. Water-based glazes are high surface energy systems, while oil-based digital adhesive inks are low surface energy systems. This mismatch between the surface energy and contact angle of the water and oil phases results in poor interfacial wettability. When they come into contact, the large difference in interfacial tension prevents the formation of a stable interfacial bond, ultimately causing the digital adhesive ink to repel the glaze slurry or even peel off the glaze layer, resulting in glaze defects. To address these technical problems, this invention adjusts the components of the top glaze, transparent polished glaze, and digital adhesive ink to improve their compatibility and bonding, giving the product excellent color development, transparency, and vibrant colors while ensuring the quality of the glaze surface.

[0008] Specifically, the introduction of high-calcium low-temperature inorganic materials into digital adhesive inks allows them to eutecticly fuse with the low-temperature substances in transparent polished glaze and colored crystal dry granules. This facilitates the full melting and leveling of the colored crystal dry granules and transparent polished glaze under high-temperature firing conditions, resulting in a good, smooth, and defect-free glaze surface effect.

[0009] The surface glaze uses a high-silica glaze system. By increasing the content of SiO2 and Al2O3 in the chemical composition, the initial melting temperature of the surface glaze is increased, thereby further promoting the expulsion of bubbles in the transparent polished glaze. At the same time, excessively high Al2O3 content can make it difficult for the colored crystal particles in the transparent polished glaze to be fired evenly, resulting in dense white spots after polishing. Increasing the silica and Na2O content of the surface glaze helps the transparent polished glaze to be fully fired and melted, forming more glass phase, which better combines with digital adhesive ink, transparent polished glaze and colored crystal particles, and reduces pinholes and pores on the product's glaze surface.

[0010] The transparent polished glaze uses a glaze system of low aluminum, low alkali metal oxides and high alkaline earth metal oxides. This glaze system has extremely low high-temperature viscosity and surface tension, which allows the transparent polished glaze to be fully melted and leveled on the colored crystal dry particles. Moreover, the cold-state bubbles generated when the transparent polished glaze is applied to the colored crystal dry particles (where the transparent polished glaze cannot completely wet the colored crystal dry particles) can also be fully melted and leveled.

[0011] In some embodiments of the present invention, the digital adhesive ink further contains an ester solvent, a moisturizing and tackifying agent, and a first dispersant. The digital adhesive ink comprises, by weight, 70-80 parts of ester solvent, 8-10 parts of moisturizing and tackifying agent, 3-5 parts of first dispersant, and 10-15 parts of inorganic material.

[0012] In this invention, digital adhesive ink is printed onto the bright white or crystalline areas of a marble-look product design document using a digital inkjet printer. The digital adhesive ink and color ink can share the same inkjet printer. The digital adhesive ink is loaded into the last 2-3 channels, with a grayscale of 50-100% and a single-channel ink volume of 30-50 g / m³. 2 The digital adhesive ink channel effect mesh and the inkjet color ink channel are precisely interconnected, allowing for precise and rapid positioning and printing of digital adhesive on areas where colored crystals need to be displayed. The positioned digital adhesive then adheres to the colored crystal particles, while any unadhered colored crystal particles are removed by a ventilation system, achieving a precise and rapid positioning effect for colored crystals.

[0013] In some embodiments of the present invention, the ester solvent may be a commonly used ester solvent in the art, such as triethylene glycol diisooctyl ester.

[0014] In some embodiments of the present invention, the moisturizing and tackifying agent may be a C5 copolymer petroleum resin, which serves to moisturize and increase the adhesive viscosity.

[0015] In some embodiments of the present invention, the first dispersant may be a commonly used dispersant in the art, such as Lubrizol Solsperse 13940.

[0016] In some embodiments of the present invention, the raw material components of the glaze layer, by weight, include: 30-45 parts of albite, 5-15 parts of potassium feldspar, 5-10 parts of nepheline, 1-5 parts of wollastonite, 2-5 parts of calcined talc, 5-10 parts of washed clay, 0-5 parts of calcined clay, 20-30 parts of quartz, 5-10 parts of alumina, and 6-10 parts of zirconium silicate. This glaze layer has good bonding properties with the colored crystal dry granule layer. After firing, the surface of the colored crystal dry granules is smooth, and after polishing, there are no white spots and it has good anti-fouling effect.

[0017] In some embodiments of the present invention, the raw material components of the transparent polished glaze layer include, by weight: 3-8 parts of sodium feldspar, 12-20 parts of potassium feldspar, 3-8 parts of washed clay, 0-5 parts of quartz, 5-12 parts of wollastonite, 8-12 parts of calcite, 3-8 parts of calcined talc, 6-10 parts of barium sulfate, 6-10 parts of calcined zinc oxide, and 25-35 parts of low-temperature frit powder.

[0018] In this invention, the CaO in the transparent polished glaze layer is mainly introduced through wollastonite, which helps reduce the source of bubbles in the glaze layer; BaO is mainly introduced through barium sulfate, which helps regulate the surface tension of the glaze melt, promotes the merging and floating of microbubbles, and assists in venting; the low-temperature frit powder serves as the main flux, providing strong fluxing components such as boron, sodium, and potassium to construct a low-temperature glassy phase matrix, promoting the dissolution and reaction of various substances. Therefore, the transparent polished glaze layer of this invention can be produced cleanly without defects such as bubbles and pinholes under high-temperature rapid firing conditions.

[0019] In some embodiments of the present invention, the chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 7-10%, SiO2 62-68%, CaO 12-18%, MgO 1-4%, K2O 2-5%, Na2O 0.1-2%, BaO 3-6%, ZnO 1-3%, and B2O3 1-2%.

[0020] In some embodiments of the present invention, the colored crystal dry granules are selected from those produced by Foshan Digital Technology Co., Ltd., with the serial number V516. These colored crystal dry granules have the following characteristics: 1) few black spots, which do not affect the aesthetics of the ceramic tiles; 2) good compatibility with transparent polished glazes, digital adhesive inks, and after firing and polishing, there are no glaze defects such as pores or white spots.

[0021] In this invention, the colored crystal dry granules are distributed using a dry granule distribution machine, with a distribution amount of 120-250 g / m³. 2 The colored crystal granules are adhered to the digital adhesive layer by positioning, and the colored crystal granules in the unprinted adhesive areas are sucked away by the exhaust equipment to form a positioned colored crystal effect.

[0022] A second aspect of the present invention provides a method for preparing the above-mentioned positioning colored crystal polished glaze tile, comprising the following steps: The ceramic tile is made by sequentially applying a surface glaze slurry, inkjet printing color ink and digital glue ink, applying colored crystal dry granules, and applying a transparent polishing glaze slurry to the body, thereby forming a surface glaze layer, a color ink layer, a positioning digital glue layer, a colored crystal dry granule layer and a transparent polishing glaze layer. After drying, it is fired in a kiln and polished to obtain the ceramic tile.

[0023] In some embodiments of the present invention, the preparation process of the transparent polishing glaze paste includes the following steps: mixing transparent polishing glaze (i.e., each raw material for preparing transparent polishing glaze), water and composite additives in a mass ratio of 100:(10-30):(15-20) to obtain the transparent polishing glaze paste; The composite additive, by weight, comprises: 2-4 parts thickener, 1-3 parts organic amine, 0.5-2 parts bentonite, 1-2 parts secondary dispersant, 0.3-0.5 parts wetting agent, 0.3-1 part defoamer, and 90-95 parts solvent. The composite additive improves the compatibility between transparent polished enamel and digital inks (color inks and digital glue inks) and solves the problems of enamel shrinkage and runners that occur when the two come into contact.

[0024] In some embodiments of the present invention, the thickener is selected as ASE-60, which is used to thicken the glaze paste, prevent the transparent polished glaze paste from flowing on the digital glue, and fix the colored crystal dry particles.

[0025] In some embodiments of the present invention, the second dispersant is selected as ammonium polyacrylate, which is used to stabilize the dispersion of colored crystal dry particles, work synergistically with wetting agents, and is compatible with glaze slurry.

[0026] In some embodiments of the present invention, the wetting agent is AEO-7, which is used to improve the wettability of the glaze paste to the colored crystal dry particles and enhance the bonding of the dry particles, glue ink, and transparent polishing glaze paste.

[0027] In some embodiments of the present invention, the defoamer is selected as a polyether / mineral oil compound defoamer to suppress the generation of bubbles and prevent pinholes.

[0028] In some embodiments of the present invention, the solvent is water, used to dissolve other additives.

[0029] In addition, the organic amine in the composite additive is used to activate the thickener and stabilize the pH of the glaze slurry at 8-9.

[0030] In some embodiments of the present invention, sodium tripolyphosphate and methylcellulose are added during the preparation of the transparent polished glaze slurry. The mass ratio of the transparent polished glaze, sodium tripolyphosphate, and methylcellulose is 100:(0.2-0.5):(0.1-0.3). Sodium tripolyphosphate is mainly used to improve the fluidity of the glaze slurry, reducing moisture while enhancing fluidity and preventing flocculation and sedimentation. Methylcellulose is mainly used for thickening, suspending, water retention, and rheological regulation to prevent glaze particles from settling and stratifying, delay water evaporation after glazing, avoid glaze layer drying and cracking, and control the consistency of the glaze slurry.

[0031] In some embodiments of the present invention, the specific gravity of the surface glaze slurry is 1.85-1.90 g / cm³. 3 The glaze application rate is 400-600g / m². 2 .

[0032] In some embodiments of the present invention, the specific gravity of the transparent polished glaze is 1.85-1.90 g / cm³. 3 The glaze application rate is 600-900g / m². 2 .

[0033] In some embodiments of the present invention, the printing yield of the digital adhesive ink is 100-150 g / m³. 2 .

[0034] In some embodiments of the present invention, the firing temperature is 1180-1220°C, and the firing cycle is 40-60 minutes.

[0035] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages: (1) The present invention uses transparent polished glaze instead of dry granules, and uses positioning digital glue ink to position the colored crystal dry granules. Compared with traditional positioning colored crystals, it not only greatly reduces the production cost, but also greatly improves the positioning accuracy.

[0036] (2) The present invention uses specific surface glaze, transparent polished glaze and digital glue ink to overcome the compatibility problem between water-based glaze and oil-based ink, so that digital glue and colored crystal dry particles can be perfectly combined. After firing and polishing, the product has excellent color performance, good glaze transparency and no defects in the glaze, thus ensuring the quality stability of the product.

[0037] (3) The method for preparing the positioning colored crystal polished glazed tile provided by the present invention effectively reduces the requirements for production equipment and processes. On the one hand, no additional special production equipment is required, and the existing production line can meet the production needs with simple adaptation, which greatly reduces the equipment upgrade investment of enterprises; on the other hand, there is no need to equip with lengthy drying equipment, and the conventional bell jar glazing process and simple drying conditions in the ceramic industry can be used, which simplifies the production process, improves production efficiency, and reduces energy consumption and operation and maintenance costs in the production process. Attached Figure Description

[0038] Figure 1 This is a structural schematic diagram of the positioning colored crystal glazed tile of the present invention; Figure 2 The image shows the actual product of the positioning colored crystal polished glaze tile prepared in Example 1 of the present invention. Figure 3 This is a photograph of the actual product of the positioning colored crystal polished glaze tile prepared in Example 2 of the present invention; Figure 4 This is a physical effect image of the positioning colored crystal polished glaze tile prepared in Comparative Example 1 of the present invention; Figure 5 This is a physical effect image of the positioning colored crystal polished glaze tile prepared in Comparative Example 2 of the present invention; Figure 6 This is a physical effect image of the positioning colored crystal polished glaze tile prepared in Comparative Example 3 of the present invention; Figure 7 This is a physical effect image of the positioning colored crystal polished glaze tile prepared in Comparative Example 5 of the present invention; Figure 8 This is a physical effect image of the positioning colored crystal polished glaze tile prepared in Comparative Example 6 of the present invention; Figure 9 This is a physical image of the positioning colored crystal polished glaze tile prepared in Comparative Example 7 of the present invention. Detailed Implementation

[0039] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0040] like Figure 1 As shown, the positioning colored crystal polished glaze tile of the present invention comprises, from bottom to top, a body (not shown), a surface glaze layer and a color ink layer, a positioning digital adhesive layer, a colored crystal dry granule layer and a transparent polished glaze layer.

[0041] The raw materials used in the various embodiments and comparative examples of the present invention are as follows: C5 copolymer petroleum resin: C5-100 from Shandong Yuhuang Chemical Co., Ltd.; Ammonium polyacrylate: Jiangsu Fumiao Technology Co., Ltd. PA-30; Polyether / mineral oil compound defoamer: Guangzhou Keao Chemical Co., Ltd. KA-220.

[0042] The following will refer to Figure 1 The positioning colored crystal glazed tiles and their preparation methods in the examples and comparative examples are described. Some raw materials... Example 1 A type of positioning colored crystal polished glazed tile, from bottom to top, includes a body, a surface glaze layer, a color ink layer, a positioning digital adhesive layer, a colored crystal dry granule layer, and a transparent polished glaze layer.

[0043] The chemical composition of the glaze layer, by weight percentage, includes: Al2O3 22.33%, SiO2 62.02%, CaO 1.79%, MgO 0.87%, K2O 1.26%, Na2O 4.48%, ZrO 24.89%, and loss on ignition 2.00%. The raw material components of the glaze layer, by weight, include: albite 32 parts, potassium feldspar 10 parts, nepheline 5 parts, wollastonite 4 parts, calcined talc 3 parts, washed clay 8 parts, calcined clay 3 parts, quartz 25 parts, alumina 9 parts, and zirconium silicate 8 parts.

[0044] The positioning digital adhesive layer is formed by inkjet printing with digital adhesive ink. The raw material components of the digital adhesive ink, by weight, include: 75 parts triethylene glycol diisooctyl ester, 8 parts C5 copolymer petroleum resin, 5 parts Lubrizol Solsperse 13940, and 12 parts inorganic materials. The chemical composition of the inorganic materials, by weight percentage, includes: 0.35% Al₂O₃, 58.02% SiO₂, 40.53% CaO, and 0.82% MgO.

[0045] The colored crystal granule layer is made of colored crystal granule fabric, which is produced by Foshan Digital Technology Co., Ltd., with the serial number V516.

[0046] The chemical composition of the transparent polished glaze layer, by weight percentage, includes: Al₂O₃ 8.14%, SiO₂ 49.21%, CaO 12.79%, MgO 2.55%, K₂O 2.87%, Na₂O 1.19%, BaO 7.33%, ZnO 7.48%, B₂O 30.45%, and loss on ignition 7.65%. The raw material components of the transparent polished glaze layer, by weight, include: albite 5 parts, potassium feldspar 15 parts, washed clay 5 parts, quartz 2 parts, wollastonite 8 parts, calcite 8 parts, calcined talc 5 parts, barium sulfate 8 parts, calcined zinc oxide 7 parts, and low-temperature frit powder 35 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 8.26%, SiO2 65.48%, CaO 12.05%, MgO 2.05%, K2O 4.02%, Na2O 1.17%, BaO 3.82%, ZnO 2.01%, and B2O3 0.89%.

[0047] The above-mentioned method for preparing the positioning colored crystal polished glazed tile includes the following steps: (1) Weigh the raw materials for preparing the glaze layer according to the mass ratio, add water and ball mill (mass ratio of material to water is 100:40) to obtain the glaze slurry (specific gravity is 1.86 g / cm³). 3 The surface glaze is applied to the upper surface of the body using a bell-shaped glazing device (glaze application amount is 520g / m²). 2 A surface glaze layer is formed; then, inkjet printing of colored ink is performed on the surface of the surface glaze layer to form a colored ink layer with a black and gold marble pattern.

[0048] (2) Weigh the raw materials for preparing digital glue ink according to the mass ratio, mix them evenly, and process them to obtain digital glue ink; then print it on the surface of the color ink layer (printing amount is 110g / m). 2 This forms a digital adhesive layer for positioning.

[0049] (3) A dry granule cloth is used to apply the colored crystal dry granules. The colored crystal dry granules in the areas where digital glue has been printed are fixed on the surface glaze, while the colored crystal dry granules in the remaining areas are removed by a vacuum device to form a colored crystal dry granule layer.

[0050] (4) Weigh the raw materials for preparing the transparent polished glaze layer (i.e., transparent polished glaze) according to the mass ratio, add water, composite additives, sodium tripolyphosphate, and methylcellulose, and ball mill to obtain a transparent polished glaze slurry with a pH of 8.3 (specific gravity of 1.87 g / cm³). 3 The transparent polished glaze is applied to the surface of the brick using a bell-shaped glazing device (glaze application rate: 680g / m²). 2 This process involves covering the surface glaze layer, the positioning digital adhesive layer, and the colored crystal dry granule layer with a transparent polished glaze, forming a transparent polished glaze layer. After drying, it is fired in a kiln at a maximum temperature of 1200℃ for a firing cycle of 55 minutes. After polishing, the positioning colored crystal polished glaze tile of this embodiment is obtained, as shown in the following figure. Figure 2 As shown.

[0051] The mass ratio of transparent polished glaze, water, composite additives, sodium tripolyphosphate, and methylcellulose is 100:20:20:0.3:0.1. The raw material components of the composite additives, by weight, include: 3 parts thickener ASE-60, 3 parts organic amine, 1.5 parts bentonite, 1 part ammonium polyacrylate, 0.3 parts wetting agent AEO-7, 0.5 parts polyether / mineral oil compound defoamer, and 90 parts water.

[0052] Example 2 A type of positioning colored crystal polished glazed tile, from bottom to top, includes a body, a surface glaze layer, a color ink layer, a positioning digital adhesive layer, a colored crystal dry granule layer, and a transparent polished glaze layer.

[0053] The chemical composition of the glaze layer, by weight percentage, includes: Al2O3 23.16%, SiO2 61.26%, CaO 1.23%, MgO 0.95%, K2O 0.94%, Na2O 5.09%, ZrO2 4.98%, and loss on ignition 1.96%. The raw material components of the glaze layer, by weight, include: albite 48 parts, potassium feldspar 5 parts, nepheline 8 parts, wollastonite 2 parts, calcined talc 3 parts, washed clay 8 parts, calcined clay 3 parts, quartz 23 parts, alumina 9 parts, and zirconium silicate 8 parts.

[0054] The positioning digital adhesive layer is formed by inkjet printing with digital adhesive ink. The raw material components of the digital adhesive ink, by weight, include: 78 parts triethylene glycol diisooctyl ester, 8 parts C5 copolymer petroleum resin, 4 parts Lubrizol Solsperse 13940, and 10 parts inorganic materials. The chemical composition of the inorganic materials, by weight percentage, includes: Al₂O₃ 0.42%, SiO₂ 56.67%, CaO 41.89%, and MgO 0.63%.

[0055] The colored crystal granule layer is made of colored crystal granule fabric, which is produced by Foshan Digital Technology Co., Ltd., with the serial number V516.

[0056] The chemical composition of the transparent polished glaze layer, by weight percentage, includes: Al₂O₃ 8.51%, SiO₂ 48.42%, CaO 14.04%, MgO 1.92%, K₂O 2.47%, Na₂O 1.49%, BaO 5.92%, ZnO 7.73%, B₂O 30.4%, and loss on ignition 8.53%. The raw material components of the transparent polished glaze layer, by weight, include: albite 8 parts, potassium feldspar 12 parts, washed clay 6 parts, quartz 4 parts, wollastonite 6 parts, calcite 12 parts, calcined talc 3 parts, barium sulfate 6 parts, calcined zinc oxide 7 parts, and low-temperature frit powder 30 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 9.42%, SiO2 62.05%, CaO 14.64%, MgO 1.86%, K2O 3.84%, Na2O 1.08%, BaO 4.32%, ZnO 1.28%, and B2O3 1.02%.

[0057] The above-mentioned method for preparing the positioning colored crystal polished glazed tile includes the following steps: (1) Weigh each raw material for preparing the glaze layer according to the mass ratio, add water and ball mill (mass ratio of material to water is 100:40) to obtain the glaze slurry (specific gravity is 1.88 g / cm³). 3 The surface glaze is applied to the upper surface of the body using a bell-shaped glazing device (glaze application rate: 500g / m²). 2 A surface glaze layer is formed; then, colored ink is sprayed onto the surface of the surface glaze layer to form a colored ink layer with a yellow marble pattern.

[0058] (2) Weigh the raw materials for preparing digital glue ink according to the mass ratio, mix them evenly, and process them to obtain digital glue ink; then print it on the surface of the color ink layer (printing amount is 100g / m). 2 This forms a digital adhesive layer for positioning.

[0059] (3) A dry granule cloth is used to apply the colored crystal dry granules. The colored crystal dry granules in the areas where digital glue has been printed are fixed on the surface glaze, while the colored crystal dry granules in the remaining areas are removed by a vacuum device to form a colored crystal dry granule layer.

[0060] (4) Weigh the raw materials for preparing the transparent polished glaze layer (i.e., transparent polished glaze) according to the mass ratio, add water, composite additives, sodium tripolyphosphate, and methylcellulose, and ball mill to obtain a transparent polished glaze slurry with a pH of 8.7 (specific gravity of 1.88 g / cm³). 3 A transparent polished glaze is applied to the surface of the brick using a bell-shaped glazing device (glaze application rate: 800g / m²). 2This process involves covering the surface glaze layer, the positioning digital adhesive layer, and the colored crystal dry granule layer with a transparent polished glaze, forming a transparent polished glaze layer. After drying, it is fired in a kiln at a maximum temperature of 1210℃ for a firing cycle of 45 minutes. After polishing, the positioning colored crystal polished glaze tile of this embodiment is obtained, as shown in the following image. Figure 3 As shown.

[0061] The mass ratio of transparent polished glaze, water, composite additives, sodium tripolyphosphate, and methylcellulose is 100:20:16:0.3:0.1. The raw material components of the composite additives, by weight, include: 3 parts thickener ASE-60, 2 parts organic amine, 1 part bentonite, 1 part ammonium polyacrylate, 0.5 parts wetting agent AEO-7, 0.8 parts polyether / mineral oil compound defoamer, and 92 parts water.

[0062] Example 3 A type of positioning colored crystal polished glazed tile, from bottom to top, includes a body, a surface glaze layer, a color ink layer, a positioning digital adhesive layer, a colored crystal dry granule layer, and a transparent polished glaze layer.

[0063] The chemical composition of the glaze layer, by weight percentage, includes: Al2O3 22.72%, SiO2 61.52%, CaO 1.16%, MgO 0.90%, K2O 1.08%, Na2O 5.40%, ZrO2 4.92%, and loss on ignition 2.05%. The raw material components of the glaze layer, by weight, include: albite 43 parts, potassium feldspar 6 parts, nepheline 6 parts, wollastonite 2 parts, calcined talc 3 parts, washed clay 8 parts, calcined clay 3 parts, quartz 20 parts, alumina 9 parts, and zirconium silicate 8 parts.

[0064] The positioning digital adhesive layer is formed by inkjet printing with digital adhesive ink. The raw material components of the digital adhesive ink, by weight, include: 72 parts triethylene glycol diisooctyl ester, 8 parts C5 copolymer petroleum resin, 5 parts Lubrizol Solsperse 13940, and 15 parts inorganic materials. The chemical composition of the inorganic materials, by weight percentage, includes: Al₂O₃ 0.38%, SiO₂ 58.46%, CaO 39.39%, and MgO 1.22%.

[0065] The colored crystal granule layer is made of colored crystal granule fabric, which is produced by Foshan Digital Technology Co., Ltd., with the serial number V516.

[0066] The chemical composition of the transparent polished glaze layer, by weight percentage, includes: Al₂O₃ 8.35%, SiO₂ 48.15%, CaO 13.68%, MgO 1.75%, K₂O 2.94%, Na₂O 1.38%, BaO 6.29%, ZnO 8.47%, B₂O₃ 0.56%, and loss on ignition 7.83%. The raw material components of the transparent polished glaze layer, by weight, include: albite 6 parts, potassium feldspar 18 parts, washed clay 5 parts, quartz 0 parts, wollastonite 10 parts, calcite 10 parts, calcined talc 3 parts, barium sulfate 7 parts, calcined zinc oxide 8 parts, and low-temperature frit powder 28 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 7.65%, SiO2 62.82%, CaO 16.48%, MgO 1.52%, K2O 3.92%, Na2O 0.89%, BaO 3.72%, ZnO 1.34%, and B2O3 1.32%.

[0067] The above-mentioned method for preparing the positioning colored crystal polished glazed tile includes the following steps: (1) Weigh each raw material for preparing the glaze layer according to the mass ratio, add water and ball mill (mass ratio of material to water is 100:40) to obtain the glaze slurry (specific gravity is 1.89 g / cm³). 3 The glaze slurry is applied to the upper surface of the body using a bell-shaped glazing device (glaze application amount is 480g / m²). 2 A surface glaze layer is formed; then, inkjet printing of colored ink is performed on the surface of the surface glaze layer to form a colored ink layer with a black and gold marble pattern.

[0068] (2) Weigh the raw materials for preparing digital glue ink according to the mass ratio, mix them evenly, and process them to obtain digital glue ink; then print it on the surface of the color ink layer (printing amount is 120g / m). 2 This forms a digital adhesive layer for positioning.

[0069] (3) A dry granule cloth is used to apply the colored crystal dry granules. The colored crystal dry granules in the areas where digital glue has been printed are fixed on the surface glaze, while the colored crystal dry granules in the remaining areas are removed by a vacuum device to form a colored crystal dry granule layer.

[0070] (4) Weigh the raw materials for preparing the transparent polished glaze layer (i.e., transparent polished glaze) according to the mass ratio, add water, composite additives, sodium tripolyphosphate, and methylcellulose, and ball mill to obtain a transparent polished glaze slurry with a pH of 8.8 (specific gravity of 1.85 g / cm³). 3 The transparent polished glaze is applied to the surface of the brick using a bell-shaped glazing device (glaze application rate: 750g / m²). 2 The process involves covering the surface glaze layer, the positioning digital adhesive layer, and the colored crystal dry granule layer with a transparent polished glaze, forming a transparent polished glaze layer. After drying, the tile is fired in a kiln at a maximum temperature of 1195℃ for a firing cycle of 55 minutes. After polishing, the positioned colored crystal polished glaze tile of this embodiment is obtained.

[0071] The mass ratio of transparent polished glaze, water, composite additives, sodium tripolyphosphate, and methylcellulose is 100:20:18:0.3:0.1. The raw material components of the composite additives, by weight, include: 2 parts thickener ASE-60, 1 part organic amine, 1.5 parts bentonite, 2 parts ammonium polyacrylate, 0.5 parts wetting agent AEO-7, 1 part polyether / mineral oil compound defoamer, and 92 parts water.

[0072] Comparative Example 1 The difference between Comparative Example 1 and Example 2 lies in the different raw material components and chemical composition of the glaze layer.

[0073] The chemical composition of the glaze layer in Comparative Example 1, by weight percentage, includes: Al2O3 30.06%, SiO2 52.32%, CaO 2.06%, MgO 0.29%, K2O 1.87%, Na2O 5.87%, ZrO2 4.59%, and loss on ignition 2.1%. The raw material components of the glaze layer, by weight, include: albite 45 parts, potassium feldspar 15 parts, nepheline 10 parts, wollastonite 6 parts, calcined talc 1 part, washed clay 8 parts, calcined clay 2 parts, quartz 5 parts, alumina 17 parts, and zirconium silicate 8 parts.

[0074] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the raw material components and chemical composition of the glaze layer are different.

[0075] The chemical composition of the glaze layer in Comparative Example 2, by weight percentage, includes: Al2O3 28.52%, SiO2 54.52%, CaO 1.69%, MgO 0.63%, K2O 2.47%, Na2O 4.72%, ZrO2 4.98%, and loss on ignition 1.98%. The raw material components of the glaze layer, by weight, include: albite 28 parts, potassium feldspar 20 parts, nepheline 10 parts, wollastonite 3 parts, calcined talc 2 parts, washed clay 8 parts, calcined clay 2 parts, quartz 12 parts, alumina 15 parts, and zirconium silicate 8 parts.

[0076] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that the raw material components and chemical composition of the transparent polished glaze layer are different.

[0077] The chemical composition of the transparent polished glaze layer in Comparative Example 3, by weight percentage, includes: Al₂O₃ 8.93%, SiO₂ 41.72%, CaO 11.88%, MgO 2.60%, K₂O 3.28%, Na₂O 0.77%, BaO 10.84%, ZnO 7.57%, B₂O₃ 0.39%, and loss on ignition 11.42%. The raw material components of the transparent polished glaze layer, by weight, include: albite 0 parts, potassium feldspar 20 parts, washed clay 8 parts, quartz 0 parts, wollastonite 0 parts, calcite 13 parts, calcined talc 5 parts, barium sulfate 13 parts, calcined zinc oxide 7 parts, and low-temperature frit powder 30 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 7.47%, SiO2 64.90%, CaO 14.38%, MgO 1.84%, K2O 3.50%, Na2O 0.40%, BaO 4.74%, ZnO 1.13%, and B2O3 1.25%.

[0078] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that the raw material components and chemical composition of the transparent polished glaze layer are different.

[0079] The chemical composition of the transparent polished glaze layer in Comparative Example 4, by weight percentage, includes: Al₂O₃ 9.64%, SiO₂ 45.82%, CaO 10.68%, MgO 4.84%, K₂O 2.84%, Na₂O 0.69%, BaO 5.33%, ZnO 10.18%, B₂O₃ 0.31%, and loss on ignition 8.92%. The raw material components of the transparent polished glaze layer, by weight, include: albite 0 parts, potassium feldspar 19 parts, washed clay 8 parts, calcined clay 3 parts, quartz 4 parts, wollastonite 0 parts, calcite 13 parts, calcined talc 12 parts, barium sulfate 6 parts, calcined zinc oxide 10 parts, and low-temperature frit powder 25 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 13.60%, SiO2 59.08%, CaO 8.11%, MgO 2.56%, K2O 3.51%, Na2O 1.78%, BaO 6.77%, ZnO 3.16%, and B2O3 0.77%.

[0080] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that the raw material components and chemical composition of the transparent polished glaze layer are different, and the inks used for inkjet printing are different.

[0081] The chemical composition of the transparent polished glaze layer in Comparative Example 5, by weight percentage, includes: Al₂O₃ 8.34%, SiO₂ 41.22%, CaO 16.16%, MgO 1.52%, K₂O 2.88%, Na₂O 1.24%, BaO 4.78%, ZnO 12.20%, B₂O₃ 0.35%, and loss on ignition 10.86%. The raw material components of the transparent polished glaze layer, by weight, include: albite 5 parts, potassium feldspar 18 parts, washed clay 6 parts, quartz 0 parts, wollastonite 6 parts, calcite 18 parts, calcined talc 2 parts, barium sulfate 5 parts, calcined zinc oxide 12 parts, and low-temperature frit powder 28 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 7.36%, SiO2 66.83%, CaO 12.78%, MgO 2.45%, K2O 3.67%, Na2O 0.48%, BaO 4.21%, ZnO 1.05%, and B2O3 1.06%.

[0082] Comparative Example 6 The difference between Comparative Example 6 and Example 2 is that the raw material components and chemical composition of the transparent polished glaze layer are different, and the inks used for inkjet printing are different.

[0083] The chemical composition of the transparent polished glaze layer in Comparative Example 6, by weight percentage, includes: Al₂O₃ 8.06%, SiO₂ 46.33%, CaO 14.19%, MgO 2.26%, K₂O 2.80%, Na₂O 1.05%, BaO 9.24%, ZnO 5.18%, B₂O₃ 0.25%, and loss on ignition 10.36%. The raw material components of the transparent polished glaze layer, by weight, include: albite 3 parts, potassium feldspar 20 parts, washed clay 7 parts, quartz 3 parts, wollastonite 15 parts, calcite 10 parts, calcined talc 5 parts, barium sulfate 12 parts, calcined zinc oxide 5 parts, and low-temperature frit powder 20 parts. The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 7.02%, SiO2 63.02%, CaO 16.83%, MgO 1.06%, K2O 3.45%, Na2O 0.78%, BaO 4.82%, ZnO 1.05%, and B2O3 1.43%.

[0084] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is that no composite additives were added during the preparation of the transparent polished glaze paste, and the inks used for inkjet printing are different.

[0085] Product Effects Figure 2 and Figure 3 The images show actual photos of the positioning colored crystal glazed tiles prepared in Examples 1 and 2, respectively. Figure 2-3It can be seen that the products all have good color development, good transparency, precise positioning of the colored crystal dry particles, and good glaze quality with no obvious glaze defects.

[0086] Figure 4 and Figure 5 The images show actual photos of the positional colored crystal polished glazed tiles prepared in Comparative Examples 1 and 2, respectively. The surface glaze layer of Comparative Examples 1 and 2 uses a conventional high-alumina fully polished glaze formulation system. Figure 4 It can be seen that the bonding performance between the surface glaze layer and the transparent polished glaze layer is poor, resulting in more pores in the darker areas, and the colored crystal dry particles are uneven after firing, showing numerous white spots after polishing. Figure 5 It can be seen that the colored crystal particles on the surface glaze layer show signs of overfiring, and after polishing, there are dense white spots.

[0087] Figure 6-8 The images show actual photos of the positional colored crystal glazed tiles prepared in Comparative Examples 3, 5, and 6. The raw material components and chemical composition of the transparent glazed tiles in Comparative Examples 3-6 differ from those in the examples. Figure 6 It is evident that noticeable microcracks appear in the dry crystalline particles. During polishing, wax seeps into these cracks, trapping wax and affecting the glaze quality of the product. Figure 7 It is evident that the transparent polished glaze layer contains numerous air bubbles, resulting in many white spots after polishing, thus affecting the glaze surface quality. Figure 8 It can be seen that white crystal flowers appear locally in the transparent glaze layer, and cannot be removed after polishing. In addition, the iridescent effect of the positioning colored crystal polished glaze tile prepared in Comparative Example 4 is very weak, and it cannot achieve the ideal iridescent and sparkling colored crystal effect. No corresponding physical pictures are provided.

[0088] Figure 9 The image shows a physical photograph of the positioning colored crystal glazed tile prepared in Comparative Example 7. Figure 9 It can be seen that, since no composite additives were added during the preparation of the transparent polished glaze, the glaze surface exhibits obvious glaze shrinkage.

[0089] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.

Claims

1. A type of positioning colored crystal glazed tile, characterized in that, From bottom to top, it includes the body, the surface glaze layer, the color ink layer, the positioning digital adhesive layer, the color crystal dry granule layer, and the transparent polished glaze layer; The positioning digital adhesive layer is formed by inkjet printing with digital adhesive ink, which contains inorganic materials. The chemical composition of the inorganic materials, by weight percentage, includes: Al2O3 0.3-0.5%, SiO2 51-59%, CaO 35-42%, MgO 0.5-1.5%. The chemical composition of the surface glaze layer, by weight percentage, includes: Al2O3 20-24%, SiO2 60-65%, CaO 1-2%, MgO 0.5-2%, K2O 0.5-2%, Na2O 4-6%, ZrO 4-6%, and loss on ignition 1-3%; The chemical composition of the transparent polished glaze layer, by weight percentage, includes: Al2O3 7-10%, SiO2 48-52%, CaO 12-15%, MgO 1-3%, K2O 2-4%, Na2O 1-2%, BaO 5.5-8%, ZnO 6-10%, B2O3 0-1%, and loss on ignition 6-10%.

2. The positioning colored crystal polished glazed tile according to claim 1, characterized in that, The digital adhesive ink also contains ester solvents, moisturizing and tackifying agents, and a first dispersant. The digital adhesive ink comprises, by weight, 70-80 parts of ester solvents, 8-10 parts of moisturizing and tackifying agents, 3-5 parts of the first dispersant, and 10-15 parts of inorganic materials.

3. The positioning colored crystal polished glazed tile according to claim 1, characterized in that, The raw material components of the surface glaze layer, by weight, include: 30-45 parts of sodium feldspar, 5-15 parts of potassium feldspar, 5-10 parts of nepheline, 1-5 parts of wollastonite, 2-5 parts of calcined talc, 5-10 parts of washed clay, 0-5 parts of calcined clay, 20-30 parts of quartz, 5-10 parts of alumina, and 6-10 parts of zirconium silicate.

4. The positioning colored crystal polished glazed tile according to claim 1, characterized in that, The raw material components of the transparent polished glaze layer, by weight, include: 3-8 parts of sodium feldspar, 12-20 parts of potassium feldspar, 3-8 parts of washed clay, 0-5 parts of quartz, 5-12 parts of wollastonite, 8-12 parts of calcite, 3-8 parts of calcined talc, 6-10 parts of barium sulfate, 6-10 parts of calcined zinc oxide, and 25-35 parts of low-temperature frit powder.

5. The positioning colored crystal polished glazed tile according to claim 4, characterized in that, The chemical composition of the low-temperature frit powder, by weight percentage, includes: Al2O3 7-10%, SiO2 62-68%, CaO 12-18%, MgO 1-4%, K2O 2-5%, Na2O 0.1-2%, BaO 3-6%, ZnO 1-3%, and B2O3 1-2%.

6. The method for preparing positioning colored crystal polished glazed tiles according to any one of claims 1-5, characterized in that, Includes the following steps: The ceramic tile is made by sequentially applying a surface glaze slurry, inkjet printing color ink and digital glue ink, applying colored crystal dry granules, and applying a transparent polishing glaze slurry to the body, thereby forming a surface glaze layer, a color ink layer, a positioning digital glue layer, a colored crystal dry granule layer and a transparent polishing glaze layer. After drying, it is fired in a kiln and polished to obtain the ceramic tile.

7. The method for preparing positioning colored crystal glazed tiles according to claim 6, characterized in that, The preparation process of the transparent polishing glaze includes the following steps: mixing transparent polishing glaze, water and composite additives in a mass ratio of 100:(10-30):(15-20) to obtain the transparent polishing glaze; The composite additive comprises, by weight, 2-4 parts thickener, 1-3 parts organic amine, 0.5-2 parts bentonite, 1-2 parts secondary dispersant, 0.3-0.5 parts wetting agent, 0.3-1 parts defoamer, and 90-95 parts solvent.

8. The method for preparing positioning colored crystal polished glazed tiles according to claim 6, characterized in that, The specific gravity of the surface glaze slurry is 1.85-1.90 g / cm³. 3 The glaze application rate is 400-600g / m². 2 ; And / or, the specific gravity of the transparent polished glaze is 1.85-1.90 g / cm³. 3 The glaze application rate is 600-900g / m². 2 .

9. The method for preparing a positioning colored crystal polished glazed tile according to claim 6, characterized in that, The printing yield of the digital adhesive ink is 100-150 g / m³. 2 .

10. The method for preparing a positioning colored crystal polished glazed tile according to claim 6, characterized in that, The firing temperature is 1180-1220℃, and the firing cycle is 40-60 minutes.

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