Ceramic tile with bright sub-combination effect on the surface and method for manufacturing the same

Abstract

The present application belongs to the field of ceramic tiles, and particularly relates to a ceramic tile with bright and matt combined effects on the surface and a preparation method thereof. The ceramic tile comprises a body layer, a bottom glaze layer, an inkjet functional ink layer comprising bright and matt ink, and a surface glaze layer comprising dry particles, which are sequentially stacked. The dry particles with a particle size of 250-400 mesh comprise, in terms of mass percentage, Al2O3 17%-20%, SrO 4.5%-6.5%, and BaO 14%-17%. The gray scale of the matt ink is 30%-60%, and the gray scale of the bright ink is 50%-100%. After the specific dry particle glaze and the bright and matt functional ink are interacted at high temperature, the obtained ceramic tile has good bright and matt effects and multi-dimensional three-dimensional gloss effects, and also has good surface flatness, color development ability, friction coefficient, anti-skid, wear resistance, stain resistance and other characteristics. The preparation method is simple and easy to implement, stable in production, and has great popularization value.

Description

Technical Field

[0001] This invention belongs to the field of ceramic tiles, specifically relating to a ceramic tile with a glossy-matte surface effect and its preparation method. Background Technology

[0002] As living standards improve, people's taste in interior decoration is also rising, and their requirements for ceramic tiles are becoming increasingly stringent. Currently, the ceramic tile industry offers a wide variety of tiles: polished tiles, antique tiles, fully polished glazed tiles, dry-granule glazed tiles, microcrystalline stone, and more. Each category has its own unique characteristics, satisfying diverse consumer needs to a certain extent. Among these, tiles with a three-dimensional effect are particularly popular due to their special visual appeal. Existing three-dimensional tiles generally achieve this effect through physical carving to create an uneven structure on the tile surface, or by using the repulsive effect of organic solvents in carving ink on the water-based glaze layer. However, while this uneven structure produces a three-dimensional effect, its surface roughness makes it prone to accumulating dirt and grime, making it difficult to clean and, over time, affecting the decorative effect. Summary of the Invention

[0003] The purpose of this invention is to address the shortcomings of existing ceramic tiles with three-dimensional effects, which rely on a textured surface and suffer from complex manufacturing methods and poor stain resistance. This invention provides a ceramic tile with a glossy / matte finish, comprising a body layer, a base glaze layer, an inkjet functional ink layer, and a top glaze layer stacked sequentially. The top glaze layer comprises a dry granule glaze, which consists of dry granules comprising, by mass percentage: Al₂O₃ 17%-20%, SrO 4.5%-6.5%, and BaO 14%-17%; the particle size of the dry granules is 250-400 mesh. The inkjet functional ink layer comprises matte ink and glossy ink, with the matte ink having a gray content of 30%-60% and the glossy ink having a gray content of 50%-100%.

[0004] The dry granules proposed in this invention can interact with the functional inks, including matte and glossy inks, after high-temperature firing. This ensures good flatness and strong color development of the tile glaze, while also promoting the stability of the gloss of the glossy and matte inks. This results in a better combination of gloss and matte effects on the tile, achieving a multi-dimensional gloss effect with multiple gloss levels (matte 3-10 degrees, glaze 15-25 degrees, gloss 50-80 degrees), thus enhancing the product's delicate and high-end feel.

[0005] This invention, through exploration and the formulation of the aforementioned dry granules among numerous ceramic raw materials, effectively achieves the aforementioned effects. The key lies in limiting the BaO content to 14%-17% (different from the commonly used 0.05%-2%). Barium oxide, primarily introduced through the form of barium carbonate, has a significant fusion-enhancing effect, helping to lower the melting temperature and high-temperature viscosity of the glaze, thereby improving glaze fluidity and gloss. Limiting its content to an appropriate amount of 14%-17% in this invention significantly enhances the refractive index and gloss of the glaze, achieving a multi-dimensional gloss presentation for both glossy and matte inks. If the BaO content in the dry granule composition is below 14%, it will affect the gloss of glossy inks and also somewhat affect the gloss of matte inks. If the content exceeds 17%, barium silicate crystals are more likely to precipitate during high-temperature processes, similarly affecting the loss of gloss in glossy inks. Both ultimately lead to the tile losing its gloss-matte combination effect and multi-dimensional gloss effect. Furthermore, the gloss-matte combination effect and multi-dimensional gloss effect of ceramic tiles are also affected by factors such as the smoothness of the glaze surface. This invention controls the Al2O3 content between 17% and 20% because Al2O3 can regulate the firing temperature. Higher Al2O3 content results in a higher firing temperature and a decrease in glaze smoothness; conversely, lower Al2O3 content results in a lower firing temperature and a decrease in the glaze's matte finish / feel. Both of these factors prevent the ceramic tiles from achieving the gloss-matte combination effect and multi-dimensional gloss effect. Only within this range can a good glaze smoothness and matte finish / feel be guaranteed, thus ensuring the achievement of the gloss-matte combination effect and multi-dimensional gloss effect. This invention controls the SrO content to 4.5%-6.5% because SrO only within this range can better ensure the color stability of the glaze and reduce the cracking rate. This invention controls the particle size of the dry granules to 250-400 mesh. This is because if the mesh size is too large, it will severely affect the flatness of the tile surface; if the mesh size is too small, the surface will feel rough, attract dirt easily, and the color will be weak, making it impossible to achieve the aforementioned gloss-matte combination effect and multi-dimensional three-dimensional gloss effect. Furthermore, this invention also requires limiting the gray content of the matte ink to 30%-60% and the gloss content of the gloss ink to 50%-100%. If the gray content of the matte ink is too high, i.e., its content is too excessive, the final product will easily attract dirt, affecting the clarity of any printed patterns. If the gray content of the gloss ink is below 50%, the final product will have a poor gloss effect.

[0006] It should be noted that the biggest technical challenge in the research of this invention is to explore specific materials among the many raw materials of ceramics and to match them with specific content ranges when there are still unknown interactions between them. Moreover, the above-mentioned dry granule composition not only has its own interaction, but also needs to be designed to interact with glossy ink and matte ink to stabilize its ink gloss, thereby achieving a glossy and matte combined effect and a multi-dimensional three-dimensional gloss effect.

[0007] In addition, the dry granules used in this invention can make the tiles have the characteristics of not hiding dirt, wear resistance, and excellent friction coefficient. Its frosted texture allows light shining on the glaze surface to form uniform diffuse reflection, creating a more comfortable and warm living environment. It effectively solves the problems of existing "three-dimensional effect" tiles that hide dirt seriously and have glaring light reflection.

[0008] In some preferred embodiments, the aforementioned dry granules, by mass percentage, comprise: SiO2 40%-45%, Al2O3 17%-20%, CaO 1.5%-3.5%, Na2O 4.5%-6.5%, K2O 1.5%-3.5%, ZrO2 0.1%-0.5%, Fe2O3

[0009] 0.05%-0.15%, ZnO 5.5%-7.5%, P2O5 0.1%-0.2%, BaO 14%-17%, SrO4.5%-6.5%, MgO 0.5%-2.0%, TiO2 0.01%-0.1%, CuO 0.01%-0.1%, HfO2 0.01%-0.03%, PbO 0.01%-0.08%, Mn3O40.01%-0.05%, SO3 0.01%-0.05%, ignition reduction 0.1%-1.5%.

[0010] In some preferred embodiments, the aforementioned dry granule glaze comprises, by mass percentage: 15%-25% dry granules, 70%-80% suspending agent, and 5%-15% protective glaze slurry. The aforementioned protective glaze slurry may include, by mass percentage: SiO2 45%-50%, Al2O3 14%-17%, CaO 4.0%-6.0%, Na2O 1.0%-3.0%, K2O 3.5%-5.5%, Fe2O3 0.15%-0.25%, ZnO 3.5%-5.5%, P2O5 0.1%-0.3%, BaO 4.5%-6.5%, SrO 1.5%-3.0%, MgO 3.0%-5.0% (with excellent fluxing effect), TiO2 0.05%-0.15%, HfO2 0.0%-0.05%, SO3 0.01%-0.05%, V2O5

[0011] 0.02-0.08%, loss on ignition 5.5%-8.5%.

[0012] This invention discovers that introducing a protective glaze slurry into dry granule glaze can further ensure the smoothness and flatness of the glaze surface without affecting the color development ability, better achieve the combination of gloss and matte finish and multi-dimensional three-dimensional gloss effect, further improve the stain resistance of the ceramic tile, and ensure that the firing temperature is controlled within a wide range, thereby enabling stable mass production through temperature adjustment.

[0013] The suspending agent can be HB-818A, which, by mass parts, may include: 28-38 parts deionized water, 15-25 parts methyl ethylene glycol, 15-25 parts sodium carboxymethyl cellulose, 15-25 parts polymethylsiloxane, 3-6 parts sodium dodecylbenzenesulfonate (dispersant), and 2-4 parts sodium hydroxide pH adjuster. Sodium dodecylbenzenesulfonate (dispersant) helps improve overall suspension and flowability. The combination of polymethylsiloxane and sodium carboxymethyl cellulose enhances the viscosity and suspension dispersion properties of the suspending agent. Deionized water serves as a common solvent, methyl ethylene glycol adjusts the suspension viscosity, and sodium hydroxide pH adjuster acts as an acid-base regulator.

[0014] In some preferred embodiments, the above-mentioned matte ink comprises, by weight parts: 4-6 parts high-temperature frit, 9-11 parts fused silica, 2-3 parts calcined zinc oxide, 13-16 parts zirconium silicate, 3-7 parts gibbsite, 2-4 parts bismuth oxide, 4-6 parts polyurethane dispersant, and 45-60 parts methyl oleate; the above-mentioned high-temperature frit comprises, by weight percentage: 45%-55% SiO2, 28%-35% Al2O3, 3.5%-6.5% K2O, 3.5%-6.5% Na2O, 3.5%-5.5% ZnO, and 4%-6% CaO.

[0015] The above-mentioned glossy ink, by mass parts, comprises: 4-6 parts of medium-temperature frit, 9-11 parts of fused silica, 2-3 parts of calcined zinc oxide, 13-16 parts of zirconium silicate, 3-7 parts of gibbsite, 2-4 parts of bismuth oxide, 4-6 parts of polyurethane dispersant, and 45-60 parts of methyl oleate; the above-mentioned medium-temperature frit, by mass percentage, comprises: 49%-59% SiO2, 16%-22% Al2O3, 3.5%-7.5% K2O, 3.5%-7% Na2O, 4.5%-7.5% ZnO, and 4%-7% CaO.

[0016] In some preferred embodiments, an inkjet printing layer is also provided between the base glaze layer and the inkjet functional ink layer.

[0017] The base glaze forming the aforementioned base glaze layer may, by mass percentage, comprise: 15%-25% potassium feldspar, 20%-30% sodium feldspar, 6%-14% air-knife clay, 7%-14% nepheline, 5%-10% quartz, 3%-9% wollastonite, 2%-8% zinc oxide, 5%-10% alumina, and 10%-15% zirconium silicate. More preferably, the aforementioned base glaze may, by mass percentage, comprise: 20% potassium feldspar, 25% sodium feldspar, 10% air-knife clay, 10% nepheline, 7% quartz, 5% wollastonite, 3% zinc oxide, 8% alumina, and 12% zirconium silicate.

[0018] The raw material used to prepare the above-mentioned green body layer may, by mass percentage, include: 67.5% silicon dioxide, 18.8% aluminum oxide, 2.5% potassium oxide, 2.5% sodium oxide, 0.5% calcium oxide, and 1.5% magnesium oxide, with the remainder to be reduced as needed and containing trace impurities. The fineness of the above powder is controlled to be 1.0% on a 250-mesh sieve, followed by spray granulation, with the gradation controlled as follows: less than 5% on 30-mesh, 30% on 40-mesh, 62% on 60-mesh, and no more than 5% on 100-mesh.

[0019] By using the aforementioned base glaze, dry-granule glaze, and body material, the bonding between the ceramic tile body, base glaze, and top glaze can be improved. Furthermore, the combined effect of this base glaze, functional ink layer, and dry-granule glaze achieves a multi-dimensional, three-dimensional glossy-matte finish. In particular, the formulation of the dry granules in this invention was developed through numerous formula experiments, optimizing the temperature and content range of each raw material to ensure better interaction and fusion with glossy and matte inks during high-temperature firing, thus achieving a superior multi-dimensional, three-dimensional glossy-matte finish.

[0020] The present invention also provides a method for preparing a ceramic tile with a glossy-matte bonding effect on the surface, comprising the following steps:

[0021] Prepare the above-mentioned blank layer (specifically, this can involve powder preparation, fabrication, and drying);

[0022] A base glaze is applied to the surface of the above-mentioned body layer to form the above-mentioned base glaze layer;

[0023] Subsequently, the above-mentioned matte ink and glossy ink are sprayed to form the above-mentioned inkjet functional ink layer;

[0024] The aforementioned dry granule glaze is applied to the surface of the aforementioned inkjet functional ink layer to form the aforementioned surface glaze layer;

[0025] The above-mentioned ceramic tiles were obtained by firing.

[0026] When an inkjet printing layer is also provided, the step of forming the inkjet printing layer by inkjet printing on the aforementioned base glaze layer is also included.

[0027] In some preferred embodiments, the fired product is subjected to a brush polishing treatment to obtain the aforementioned ceramic tile. The brush polishing treatment includes the following steps: sequentially brush polishing with a 2000-mesh resin film for 25-35 seconds, fine polishing with a 240-mesh fiber module for 45-55 seconds, and fine polishing with a 240-mesh plastic silicon carbide abrasive brush for 25-35 seconds. The pressure during the resin abrasive brush polishing is 1.0 MPa-1.5 MPa; the pressure during the fiber module and plastic silicon carbide abrasive brush fine polishing is 1.0 MPa-1.5 MPa. After the brush polishing treatment, the surface smoothness of the ceramic tile is further improved.

[0028] In some preferred embodiments, when forming the inkjet functional ink layer, the matte ink and the glossy ink are sprayed, causing a gradient change in the grayscale values ​​of the matte ink and the glossy ink. That is, by spraying the matte ink and the glossy ink onto the surface to be inkjetized according to the gradient grayscale values, this method can produce a more natural color transition.

[0029] In some preferred embodiments, the specific gravity of the base glaze is 1.80 g / mL to 1.86 g / mL, and the glaze application rate is 450 g / mL. 2 -550g / m 2 The flow rate is 35s-45s; applying the base glaze under these conditions ensures a smoother surface and more stable structure for the resulting ceramic tile. The specific gravity of the aforementioned dry granule glaze is 1.35g / mL-1.5g / mL, and the glaze application rate is 300g / m³. 2 -400g / m 2 The flow rate is 30s-40s. The above dry granules can be prepared by the following steps: mixing raw materials that meet the conditions, melting them at high temperature, pouring them into water for quenching, obtaining dry granule flocs, and then crushing and classifying them to obtain the above dry granules.

[0030] The firing conditions mentioned above include a firing temperature of 1180℃-1210℃ and a firing time of 45min-65min. Using this firing temperature can improve the surface finish of the fired ceramic tiles.

[0031] The beneficial effects of this invention are as follows: After the specific dry granule glaze proposed in this invention interacts with the glossy and matte functional ink at high temperature, the resulting ceramic tile has a good glossy and matte effect and a multi-dimensional three-dimensional gloss effect. It also has good surface flatness, color development ability, friction coefficient, anti-slip, wear resistance, and stain resistance. Its preparation method is simple and easy to implement, and the production is stable, which has significant promotional value. Attached Figure Description

[0032] Figure 1 The image shown is a photograph of a ceramic tile produced using the method of Example 1, excluding the inkjet ink step.

[0033] Figure 2 The image shown is a photograph of the ceramic tile prepared in Example 1. Detailed Implementation

[0034] The following will provide a clear and complete description of the concept and technical effects of the present invention in conjunction with the embodiments and accompanying drawings, so as to fully understand the purpose, solution and effects of the present invention. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0035] Example 1

[0036] A ceramic tile with a glossy / matte finish, comprising, in sequence, a body layer, a base glaze layer, an inkjet printing layer, an inkjet functional ink layer, and a top glaze layer; the top glaze layer comprises a dry granule glaze, which includes dry granules, and the dry granules, by mass percentage, comprise: SiO2 42.89%, Al2O3 18.5%, CaO 2.04%, Na2O 5.20%, K2O 1.86%, ZrO2 0.12%, Fe2O3 0.09%, ZnO 6.11%, P2O5 0.14%, BaO 15.74%, SrO 5.76%, MgO 0.9%, TiO2 0.04%, CuO 0.01%, PbO 0.04%, HfO2 0.03%, SO3 0.02%, and Mn3O4. 0.01%, loss on ignition 0.5%; dry particle size is 250-320 mesh. Inkjet functional ink layers include matte ink 131-8 (ash content 30%-60%) and glossy ink CZN00045 (ash content 50%-100%).

[0037] The above-mentioned method for preparing ceramic tiles includes the following steps:

[0038] (1) Preparation of ceramic body layer: After powdering, spreading, and drying, a ceramic body layer is obtained with a water absorption rate ≤0.5%; the ceramic body powder is composed of the following components by mass percentage: silicon dioxide 67.5%, aluminum oxide 18.8%, potassium oxide 2.5%, sodium oxide 2.5%, calcium oxide 0.5%, magnesium oxide 1.5%, and the rest are reduced and trace impurities. The fineness of the powder is controlled at 1.0% on a 250-mesh sieve, and then spray granulation is performed, with the gradation controlled at: 30 mesh less than 5%, 40 mesh 30%, 60 mesh 62%, and 100 mesh not more than 5%;

[0039] (2) Apply a base glaze to the surface of the ceramic body to form a base glaze layer; the specific gravity of the base glaze is 1.84 g / mL, the flow rate is 40 s, and the application amount is 450 g / mL. 2 ;

[0040] The base glaze is composed of the following components by mass percentage: 20% potassium feldspar, 25% sodium feldspar, 10% air-knife clay, 10% nepheline, 7% quartz, 5% wollastonite, 3% zinc oxide, 8% aluminum oxide, and 12% zirconium silicate.

[0041] (3) Print an inkjet printing layer on the surface of the base glaze layer;

[0042] (4) Print functional ink layers on the inkjet printing layer (where: matte ink 131-8 has a gray content of 30%-60%, and glossy ink CZN00045 has a gray content of 50%-100%); the matte ink and glossy ink are inkjet printed according to the gradient gray content, so that the matte ink and glossy ink on the surface of the inkjet printing layer have a gradient gray content distribution.

[0043] The matte ink, by weight parts, comprises: 5 parts high-temperature frit, 10 parts fused silica, 3 parts calcined zinc oxide, 14 parts zirconium silicate, 5 parts gibbsite, 3 parts bismuth oxide, 5 parts Foshan Kening polyurethane dispersant UV-531, and 55 parts methyl oleate; the high-temperature frit, by weight percentage, comprises: 51% SiO2, 30% Al2O3, 5% K2O, 4% Na2O, 4% ZnO, and 6% CaO;

[0044] The glossy ink, by weight parts, comprises: 5 parts medium-temperature frit, 10 parts fused silica, 2 parts calcined zinc oxide, 15 parts zirconium silicate, 6 parts gibbsite, 2 parts bismuth oxide, 6 parts Foshan Koning polyurethane dispersant UV-531, and 54 parts methyl oleate; the medium-temperature frit, by weight percentage, comprises: 55% SiO2, 20% Al2O3, 6.5% K2O, 6.5% Na2O, 6% ZnO, and 6% CaO;

[0045] (5) Apply dry granule glaze to the surface of the functional ink layer to form a surface glaze layer; wherein the dry granule glaze is composed of the following components by mass percentage: 20% dry granules, 75% suspending agent, and 5% protective glaze paste;

[0046] The protective glaze paste is composed of the following chemical components by mass percentage: SiO2 49%, Al2O3 16.57%, CaO 5.26%, Na2O 1.68%, K2O 4.03%, Fe2O3 0.19%, ZnO 4.25%, P2O5 0.23%, BaO 5.02%, SrO

[0047] 2.36%, MgO 3.89%, TiO2 0.09%, HfO2 0.05%, SO3 0.04%, V2O5 0.04%, loss on ignition 7.30%;

[0048] The suspending agent is HB-818A, which includes the following components by mass: 32 parts deionized water, 20 parts methyl ethylene glycol, 20 parts sodium carboxymethyl cellulose, 20 parts polymethylsiloxane, 5 parts sodium dodecylbenzene sulfonate (dispersant), and 3 parts sodium hydroxide (pH adjuster).

[0049] The specific gravity of the dry granule glaze is 1.4 g / mL, the flow rate is 35 s, the residue on a 325-mesh sieve is 1.2%, and the glaze application rate is 300 g / mL. 2 ;

[0050] (6) Firing is carried out to obtain the initial finished ceramic tile; the firing temperature is 1200℃ and the firing time is 50min;

[0051] (7) Use a 2000-mesh resin grinding disc for micro-brush polishing for 30 seconds, where the pressure of the resin grinding disc on the initial ceramic tile product is 1.0 MPa. Then, use 8 sets of 240-mesh fiber modules for fine polishing for 50 seconds and 5 sets of 240-mesh plastic silicon carbide abrasive brushes for fine polishing for 30 seconds, where the pressure of the fiber modules and plastic silicon carbide abrasive brushes on the initial ceramic tile product is 1.5 MPa. After applying anti-fouling wax, the finished ceramic tile product is obtained.

[0052] Example 2

[0053] A ceramic tile with a glossy / matte finish, comprising, in sequence, a body layer, a base glaze layer, an inkjet printing layer, an inkjet functional ink layer, and a top glaze layer; the top glaze layer comprises a dry-granule glaze, which includes dry granules, and the dry granules, by mass percentage, comprise: SiO2 41.79%, Al2O3 20%, CaO 1.54%, Na2O 4.7%, K2O 1.96%, ZrO2 0.12%, and Fe2O3.

[0054] The composition is as follows: 0.09%, ZnO 6.11%, P2O5 0.14%, BaO 16.24%, SrO 5.76%, MgO 0.9%, TiO2 0.04%, CuO 0.01%, PbO 0.04%, HfO2 0.03%, SO3 0.02%, Mn3O4 0.01%, with a loss on ignition of 0.5%; the dry particle size is 250-320 mesh. The inkjet functional ink layer includes matte ink 131-8 (ash content 30%-60%) and glossy ink CZN00045 (ash content 50%-100%).

[0055] The above-mentioned method for preparing ceramic tiles includes the following steps:

[0056] (1) Preparation of ceramic body layer: After powdering, spreading, and drying, a ceramic body layer is obtained with a water absorption rate ≤0.5%; the ceramic body powder is composed of the following components by mass percentage: silicon dioxide 67.5%, aluminum oxide 18.8%, potassium oxide 2.5%, sodium oxide 2.5%, calcium oxide 0.5%, magnesium oxide 1.5%, and the rest are reduced and trace impurities. The fineness of the powder is controlled at 1.0% on a 250-mesh sieve, and then spray granulation is performed, with the gradation controlled at: 30 mesh less than 5%, 40 mesh 30%, 60 mesh 62%, and 100 mesh not more than 5%;

[0057] (2) Apply a base glaze to the surface of the ceramic body to form a base glaze layer; the specific gravity of the base glaze is 1.84 g / mL, the flow rate is 40 s, and the application amount is 450 g / mL. 2 ;

[0058] The base glaze is composed of the following components by mass percentage: 20% potassium feldspar, 25% sodium feldspar, 10% air-knife clay, 10% nepheline, 7% quartz, 5% wollastonite, 3% zinc oxide, 8% aluminum oxide, and 12% zirconium silicate.

[0059] (3) Print an inkjet printing layer on the surface of the base glaze layer;

[0060] (4) Print functional ink layers on the inkjet printing layer (where: matte ink 131-8 has a gray content of 30%-60%, and glossy ink CZN00045 has a gray content of 50%-100%); the matte ink and glossy ink are inkjet printed according to the gradient gray content, so that the matte ink and glossy ink on the surface of the inkjet printing layer have a gradient gray content distribution.

[0061] The matte ink, by weight parts, comprises: 4 parts high-temperature frit, 9 parts fused silica, 2 parts calcined zinc oxide, 15 parts zirconium silicate, 5 parts gibbsite, 4 parts bismuth oxide, 6 parts Foshan Koning polyurethane dispersant UV-531, and 55 parts methyl oleate; the high-temperature frit, by weight percentage, comprises: 49% SiO2, 28% Al2O3, 6% K2O, 5.5% Na2O, 5.5% ZnO, and 6% CaO;

[0062] The glossy ink, by weight parts, comprises: 4 parts medium-temperature frit, 9 parts fused silica, 2 parts calcined zinc oxide, 15 parts zirconium silicate, 5 parts gibbsite, 3 parts bismuth oxide, 4 parts Foshan Koning polyurethane dispersant UV-531, and 58 parts methyl oleate; the medium-temperature frit, by weight percentage, comprises: 58% SiO2, 20% Al2O3, 4.5% K2O, 5.5% Na2O, and 10% ZnO.

[0063] 6.5% CaO 5.5%;

[0064] (5) Apply dry granule glaze to the surface of the functional ink layer to form a surface glaze layer; wherein the dry granule glaze is composed of the following components by mass percentage: 20% dry granules, 75% suspending agent, and 5% protective glaze paste;

[0065] The protective glaze paste is composed of the following chemical components by mass percentage: SiO2 49%, Al2O3 16.57%, CaO 5.26%, Na2O 1.68%, K2O 4.03%, Fe2O3 0.19%, ZnO 4.25%, P2O5 0.23%, BaO 5.02%, SrO

[0066] 2.36%, MgO 3.89%, TiO2 0.09%, ZrO2 0.05%, SO3 0.04%, V2O5 0.04%, ignition loss 7.30%;

[0067] The suspending agent is HB-818A, which includes the following components by mass: 32 parts deionized water, 20 parts methyl ethylene glycol, 20 parts sodium carboxymethyl cellulose, 20 parts polymethylsiloxane, 5 parts sodium dodecylbenzene sulfonate (dispersant), and 3 parts sodium hydroxide (pH adjuster).

[0068] The specific gravity of the dry granule glaze is 1.4 g / mL, the flow rate is 35 s, the residue on a 325-mesh sieve is 1.2%, and the glaze application rate is 300 g / mL. 2 ;

[0069] (6) Firing is carried out to obtain the initial finished ceramic tile; the firing temperature is 1200℃ and the firing time is 50min;

[0070] (7) Use a 2000-mesh resin grinding disc for micro-brush polishing for 30 seconds, where the pressure of the resin grinding disc on the initial ceramic tile product is 1.0 MPa. Then, use 8 sets of 240-mesh fiber modules for fine polishing for 50 seconds and 5 sets of 240-mesh plastic silicon carbide abrasive brushes for fine polishing for 30 seconds, where the pressure of the fiber modules and plastic silicon carbide abrasive brushes on the initial ceramic tile product is 1.5 MPa. After applying anti-fouling wax, the finished ceramic tile product is obtained.

[0071] Example 3

[0072] A ceramic tile with a glossy / matte finish, comprising, in sequence, a body layer, a base glaze layer, an inkjet printing layer, an inkjet functional ink layer, and a top glaze layer; the top glaze layer comprises a dry-granule glaze, which includes dry granules, and the dry granules, by mass percentage, comprise: SiO2 42.79%, Al2O3 17%, CaO 2.04%, Na2O 4.7%, K2O 2.96%, ZrO2 0.12%, and Fe2O3.

[0073] The composition is as follows: 0.09%, ZnO 6.11%, P2O5 0.14%, BaO 16.74%, SrO 5.76%, MgO 0.9%, TiO2 0.04%, CuO 0.01%, PbO 0.04%, HfO2 0.03%, SO3 0.02%, Mn3O4 0.01%, with a loss on ignition of 0.5%; the dry particle size is 250-320 mesh. The inkjet functional ink layer includes matte ink 131-8 (ash content 30%-60%) and glossy ink CZN00045 (ash content 50%-100%).

[0074] The above-mentioned method for preparing ceramic tiles includes the following steps:

[0075] (1) Preparation of ceramic body layer: After powdering, spreading, and drying, a ceramic body layer is obtained with a water absorption rate ≤0.5%; the ceramic body powder is composed of the following components by mass percentage: silicon dioxide 67.5%, aluminum oxide 18.8%, potassium oxide 2.5%, sodium oxide 2.5%, calcium oxide 0.5%, magnesium oxide 1.5%, and the rest are reduced and trace impurities. The fineness of the powder is controlled at 1.0% on a 250-mesh sieve, and then spray granulation is performed, with the gradation controlled at: 30 mesh less than 5%, 40 mesh 30%, 60 mesh 62%, and 100 mesh not more than 5%;

[0076] (2) Apply a base glaze to the surface of the ceramic body to form a base glaze layer; the specific gravity of the base glaze is 1.84 g / mL, the flow rate is 40 s, and the application amount is 450 g / mL. 2 ;

[0077] The base glaze is composed of the following components by mass percentage: 20% potassium feldspar, 25% sodium feldspar, 10% air-knife clay, 10% nepheline, 7% quartz, 5% wollastonite, 3% zinc oxide, 8% aluminum oxide, and 12% zirconium silicate.

[0078] (3) Print an inkjet printing layer on the surface of the base glaze layer;

[0079] (4) Print functional ink layers on the inkjet printing layer (where: matte ink 131-8 has a gray content of 30%-60%, and glossy ink CZN00045 has a gray content of 50%-100%); the matte ink and glossy ink are inkjet printed according to the gradient gray content, so that the matte ink and glossy ink on the surface of the inkjet printing layer have a gradient gray content distribution.

[0080] The matte ink, by weight parts, comprises: 6 parts high-temperature frit, 11 parts fused silica, 3 parts calcined zinc oxide, 15 parts zirconium silicate, 5 parts gibbsite, 3 parts bismuth oxide, 4 parts Foshan Koning polyurethane dispersant UV-531, and 53 parts methyl oleate; the high-temperature frit, by weight percentage, comprises: 49% SiO2, 33% Al2O3, 4.5% K2O, 4% Na2O, 4.5% ZnO, and 5% CaO.

[0081] The glossy ink, by weight parts, comprises: 5 parts medium-temperature frit, 10 parts fused silica, 2 parts calcined zinc oxide, 13 parts zirconium silicate, 4 parts gibbsite, 2 parts bismuth oxide, 6 parts Foshan Koning polyurethane dispersant UV-531, and 58 parts methyl oleate; the medium-temperature frit, by weight percentage, comprises: 59% SiO2, 17% Al2O3, 5.5% K2O, 6.5% Na2O, 6.5% ZnO, and 5.5% CaO;

[0082] (5) Apply dry granule glaze to the surface of the functional ink layer to form a surface glaze layer; wherein the dry granule glaze is composed of the following components by mass percentage: 20% dry granules, 75% suspending agent, and 5% protective glaze paste;

[0083] The protective glaze slurry is composed of the following chemical components by mass percentage: SiO2 49%, Al2O3 16.57%, CaO 5.26%, Na2O 1.68%, K2O 4.03%, Fe2O3 0.19%, ZnO 4.25%, P2O5 0.23%, BaO 5.02%, SrO 2.36%, MgO 3.89%, TiO2 0.09%, HfO2 0.05%, SO3 0.04%, V2O5 0.04%, with a loss on ignition of 7.30%.

[0084] The suspending agent is HB-818A, which includes the following components by mass: 32 parts deionized water, 20 parts methyl ethylene glycol, 20 parts sodium carboxymethyl cellulose, 20 parts polymethylsiloxane, 5 parts sodium dodecylbenzene sulfonate (dispersant), and 3 parts sodium hydroxide (pH adjuster).

[0085] The specific gravity of the dry granule glaze is 1.4 g / mL, the flow rate is 35 s, the residue on a 325-mesh sieve is 1.2%, and the glaze application rate is 300 g / mL. 2 ;

[0086] (6) Firing is carried out to obtain the initial finished ceramic tile; the firing temperature is 1200℃ and the firing time is 50min;

[0087] (7) Use a 2000-mesh resin grinding disc for micro-brush polishing for 30 seconds, where the pressure of the resin grinding disc on the initial ceramic tile product is 1.0 MPa. Then, use 8 sets of 240-mesh fiber modules for fine polishing for 50 seconds and 5 sets of 240-mesh plastic silicon carbide abrasive brushes for fine polishing for 30 seconds, where the pressure of the fiber modules and plastic silicon carbide abrasive brushes on the initial ceramic tile product is 1.5 MPa. After applying anti-fouling wax, the finished ceramic tile product is obtained.

[0088] Figure 2 The image shown is a rendering of the tile produced in this embodiment. Tiles produced using non-printing functional ink (otherwise the same as in this embodiment) would look like this. Figure 1 As shown; by Figure 2 It can be seen that the produced tiles have an ultra-flat surface, a combination of gloss and matte finish, and a multi-dimensional three-dimensional luster, giving them a very high-end feel.

[0089] Comparative Example 1

[0090] A type of ceramic tile with a glossy-matte combined effect differs from Example 1 in that: the functional inks include matte ink 131-8 (gray content 30%-60%) and glossy ink CZN00045 (gray content 1%-49%); otherwise, it is the same as Example 1.

[0091] Comparative Example 2

[0092] A type of ceramic tile with a glossy-matte combined effect differs from Example 1 in that: the functional inks include matte ink 131-8 (gray content 61%-100%) and glossy ink CZN00045 (gray content 50%-100%); otherwise, it is the same as Example 1.

[0093] Comparative Example 3

[0094] A type of ceramic tile differs from Example 1 in that the content of Al2O3 in the dry granules is 24% and the content of SrO is 0.26%; otherwise, it is the same as Example 1.

[0095] Comparative Example 4

[0096] A type of ceramic tile differs from Example 1 in that: the dry granules contain 13% Al2O3, 8.2% Na2O, and 4.36% K2O; otherwise, it is the same as Example 1.

[0097] Comparative Example 5

[0098] A ceramic tile differs from Example 1 in that the dry granules contain 13.74% BaO and 40.89% SiO2; otherwise, it is the same as Example 1.

[0099] Comparative Example 6

[0100] A ceramic tile differs from Example 1 in that the SrO content in the dry granules is 0.63% and the SiO2 content is 48.02%; otherwise, it is the same as Example 1.

[0101] Comparative Example 7

[0102] A type of ceramic tile differs from Example 1 in that no protective glaze slurry is added to the dry granule glaze; otherwise, it is the same as Example 1.

[0103] Comparative Example 8

[0104] A type of ceramic tile differs from Example 1 in that the dry granules have a particle size of 30-120 mesh; otherwise, it is the same as Example 1.

[0105] Comparative Example 9

[0106] A ceramic tile differs from Example 1 in that the dry granules contain 17.74% BaO and 44.89% SiO2; otherwise, it is the same as Example 1.

[0107] Comparative Example 10

[0108] A type of ceramic tile differs from Example 1 in that the dry granules contain 0.2% BaO and 0.2% TiO2; otherwise, it is the same as Example 1.

[0109] The ceramic tiles prepared in Examples 1-3 and Comparative Examples 1-10 were tested. Surface stain resistance was tested using the method in GB / T 3810.14; the coefficient of friction was tested using the GB / 4100 method; surface flatness was measured using a Type 1000 flatness measuring ruler from Keneng Ceramics Testing Equipment Co., Ltd.; and average gloss was measured using GB / T 13891-2006 (gloss meter). The results are shown in Table 1.

[0110] Table 1

[0111]

[0112]

[0113] As shown in Table 1:

[0114] Examples 1-3 showed excellent results: stain resistance, Mohs hardness, and flexural strength all met the standards, and the glaze surface was smooth and delicate, with a glossy-matte combination effect. In Comparative Example 1, compared to the examples, the glossy ink had a lower gray content and a smoother, more delicate glaze surface, but the glossy-matte combination effect felt weaker. In Comparative Example 2, compared to the examples, the matte ink had a higher gray content, resulting in slight stain absorption in the matte ink area (due to the high temperature of matte ink 131-8, ink penetration and stain absorption occur at a certain peak ink volume), but the glaze surface was smooth and delicate, with a glossy-matte combination effect.

[0115] Compared to Example 1, Comparative Example 3, due to its excessively high Al2O3 content (greater than 20%), was fired at a high-temperature molten state, resulting in a rough, gritty surface after firing. It also exhibited severe dirt absorption and accumulation, weak color development, low gloss, and a rough, uneven glaze surface without a gloss-matte finish. Compared to Example 1, Comparative Example 4, due to its excessively low Al2O3 content (less than 17%), was fired at a low-temperature molten state, resulting in a surface with no finish after firing. It was not wear-resistant, lacked anti-slip properties, and the glaze surface was smooth but not fine, uneven, and without a gloss-matte finish.

[0116] Compared to Example 1, Comparative Example 5 showed poor surface hardness, abrasion resistance, and glaze brightness due to excessively low BaO content (less than 14%). The surface was uneven and lacked a gloss-matte finish. Compared to Example 1, Comparative Example 10 showed poor surface stain resistance and glaze brightness due to the use of TiO2 as the core control component instead of BaO, set at 0.2%. The surface was uneven and lacked a gloss-matte finish. Compared to Example 1, Comparative Example 9 showed poor surface hardness, abrasion resistance, and glaze brightness due to excessively high BaO content (greater than 17%). The surface was uneven and lacked a gloss-matte finish.

[0117] Compared with Example 1, Comparative Example 6 shows that due to the low SrO content (less than 4.5%), the glaze surface is slightly cracked and has poor color development, resulting in an uneven surface and no gloss-matte bonding effect.

[0118] Compared with Example 1, Comparative Example 7 has a narrower firing temperature range due to the lack of protective glaze, making it difficult to control high and low temperatures. This results in unstable quality of the ceramic tiles produced, as well as an unstable and narrow range of surface flatness and gloss-matte bonding effect.

[0119] Compared to Example 1, Example 8 uses dry granules with a smaller mesh size. Although the surface has a certain anti-slip effect, the coarse mesh size of the granules leads to serious dirt accumulation, and the surface feels rough and prickly. Although it has a textured feel, the glaze is uneven and lacks a delicate and high-end feel and a combination of gloss and matte finish.

[0120] The above description is merely a preferred embodiment of the present invention. The present invention is not limited to the above-described embodiments. Any embodiment that achieves the technical effects of the present invention using the same means should fall within the protection scope of the present invention. Within the protection scope of the present invention, various modifications and variations can be made to the technical solutions and / or implementation methods.

Claims

1. A ceramic tile with a surface exhibiting a combination of gloss and matte finish, characterized in that, The ceramic tile comprises a body layer, a base glaze layer, an inkjet functional ink layer, and a top glaze layer stacked sequentially. The top glaze layer comprises dry granule glaze, which includes dry granules and a protective glaze slurry. The dry granules, by mass percentage, comprise: Al2O3 17%-20%, SrO 4.5%-6.5%, and BaO 14%-17%. The particle size of the dry granules is 250-400 mesh. The inkjet functional ink layer comprises matte ink and glossy ink. The matte ink has a gray content of 30%-60%, and the glossy ink has a gray content of 50%-100%. The matte ink comprises, by weight parts: 4-6 parts high-temperature frit, 9-11 parts fused silica, 2-3 parts calcined zinc oxide, 13-16 parts zirconium silicate, 3-7 parts gibbsite, 2-4 parts bismuth oxide, 4-6 parts polyurethane dispersant, and 45-60 parts methyl oleate; the high-temperature frit comprises, by weight percentage: 45%-55% SiO2, 28%-35% Al2O3, 3.5%-6.5% K2O, 3.5%-6.5% Na2O, 3.5%-5.5% ZnO, and 4%-6% CaO; The glossy ink comprises, by weight parts: 4-6 parts of medium-temperature frit, 9-11 parts of fused silica, 2-3 parts of calcined zinc oxide, 13-16 parts of zirconium silicate, 3-7 parts of gibbsite, 2-4 parts of bismuth oxide, 4-6 parts of polyurethane dispersant, and 45-60 parts of methyl oleate; the medium-temperature frit comprises, by weight percentage: 49%-59% SiO2, 16%-22% Al2O3, 3.5%-7.5% K2O, 3.5%-7% Na2O, 4.5%-7.5% ZnO, and 4%-7% CaO.

2. The ceramic tile according to claim 1, characterized in that, The dry granules, by mass percentage, comprise: SiO2 40%-45%, Al2O3 17%-20%, CaO 1.5%-3.5%, Na2O 4.5%-6.5%, K2O 1.5%-3.5%, ZrO2 0.1%-0.5%, Fe2O3 0.05%-0.15%, ZnO 5.5%-7.5%, P2O5 0.1%-0.2%, BaO 14%-17%, SrO 4.5%-6.5%, MgO 0.5%-2.0%, TiO2 0.01%-0.1%, CuO 0.01%-0.1%, HfO2 0.01%-0.03%, PbO 0.01%-0.08%, Mn3O4 0.01%-0.05%, SO3 0.01%-0.05%, loss on ignition 0.1%-1.5%.

3. The ceramic tile according to claim 1, characterized in that, The dry granule glaze comprises, by weight percentage: 15%-25% dry granules, 70%-80% suspending agent, and 5%-15% protective glaze slurry.

4. The ceramic tile according to claim 3, characterized in that, The protective glaze slurry comprises, by mass percentage: 45%-50% SiO2, 14%-17% Al2O3, 4.0%-6.0% CaO, 1.0%-3.0% Na2O, 3.5%-5.5% K2O, 0.15%-0.25% Fe2O3, 3.5%-5.5% ZnO, 0.1%-0.3% P2O5, 4.5%-6.5% BaO, 1.5%-3.0% SrO, 3.0%-5.0% MgO, 0.05%-0.15% TiO2, 0.0%-0.05% HfO2, 0.01%-0.05% SO3, 0.02-0.08% V2O5, with a loss on ignition of 5.5%-8.5%.

5. The ceramic tile according to any one of claims 1 to 4, characterized in that, An inkjet printing layer is also provided between the base glaze layer and the inkjet functional ink layer.

6. A method for preparing a ceramic tile according to any one of claims 1 to 5, comprising the following steps: Prepare the preform layer; A base glaze is applied to the surface of the blank layer to form the base glaze layer; Subsequently, the matte ink and the glossy ink are inkjet-sprayed to form the inkjet functional ink layer; The dry granule glaze is applied to the surface of the inkjet functional ink layer to form the surface glaze layer; The ceramic tile is obtained by firing.

7. The preparation method according to claim 6, characterized in that, The fired product is then brushed and polished to obtain the ceramic tile; the brushing and polishing process... The process includes the following steps: sequentially polishing with a 2000-mesh resin grinding wheel for 25-35 seconds, fine polishing with a 240-mesh fiber module for 45-55 seconds, and fine polishing with a 240-mesh plastic silicon carbide abrasive brush for 25-35 seconds.

8. The preparation method according to claim 6, characterized in that, When forming the inkjet functional ink layer, the matte ink and the glossy ink are inkjet-sprayed, causing the grayscale values ​​of the matte ink and the glossy ink to exhibit a gradient change.

9. The preparation method according to claim 6, characterized in that, The specific gravity of the base glaze is 1.80 g / mL-1.86 g / mL, and the glaze application amount is 450 g / mL. 2 -550 g / m 2 ; and / or, The specific gravity of the dry granular glaze is 1.35 g / mL-1.5 g / mL, and the glaze application amount is 300 g / mL. 2 -400 g / m 2 ; And / or, The firing conditions include: a firing temperature of 1180 ℃-1210 ℃ and a firing time of 45 min-65 min.

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