High-stain-resistance glazed ceramic tile and preparation method thereof

Abstract

The invention discloses a high-stain-resistance glazed ceramic tile and a preparation method thereof, and belongs to the technical field of ceramic tile preparation. The preparation method comprises the following steps: glazing the surface of a ceramic green body with a mixed glaze, controlling the glazing thickness to be 0.8-0.9 mm, standing at 25 + / -2 DEG C for 20-24 hours, drying at 110-120 DEG C for 50 minutes, calcining at 1200-1250 DEG C for 2-3 hours, cooling, and polishing to obtain the high-stain-resistance glazed ceramic tile. According to the invention, the glaze used by the ceramic tile is innovatively modified, so that the antifouling property of the ceramic tile is realized.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic tile preparation, and particularly relates to a highly stain-resistant glazed ceramic tile and a preparation method thereof. Background Art

[0002] Ceramic tiles are a variety of building decoration materials, often used for indoor and outdoor decoration, including indoor and outdoor floors and walls. Although the use of ceramic tiles can greatly improve the aesthetics of buildings, the surface of traditional ceramic tiles is easily contaminated by various dust, sewage, etc., which produces dirt on the surface, affecting the aesthetics. Therefore, improving the stain resistance of ceramic tiles has important development prospects. As an important branch of modern building decoration materials, stain-resistant ceramic tiles have solved the pain point of traditional ceramic tiles being easy to harbor dirt and become the preferred material for homes, public spaces and special environments. The main preparation routes of existing stain-resistant ceramic tiles include: (1) Adjustment of formula ingredients: Adjusting the composition ratio of ceramic tile body and glaze to improve the stain resistance of ceramic tiles; (2) Waxing or spraying protective base on the surface of ceramic tiles to improve the anti-fouling effect of ceramic tiles; (3) Adjusting the calcination process of ceramic tiles to improve the anti-fouling performance of ceramic tiles.

[0003] Patent CN118702508A discloses an anti-slip and anti-fouling ceramic tile and its production process. The invention immerses the pretreated substrate in a composite sol, immerses and pulls it, dries and sinters it, and finally immerses it in a heptadecafluorodecyltrimethoxysilane solution to produce the anti-slip and anti-fouling ceramic tile. After the pretreated substrate is immersed and pulled in the composite sol, a glaze will be formed on the surface during sintering. However, due to the presence of cyclodextrin, the cyclodextrin will be carbonized and fall off, causing small holes in the glaze on the surface. The siloxane on the heptadecafluorodecyltrimethoxysilane will hydrolyze and graft with the hydroxyl groups on the glaze surface, and at the same time enter the surface holes to form a long-chain fluorocarbon film, which can reduce the surface energy and avoid stain adsorption.

[0004] Patent CN116751030A discloses a super-fouling-resistant ceramic tile and its production process. The invention uses high-quality kaolin, high-purity silica sand and other materials in an optimized ratio, and combines them with a special high-pressure water flow or acid treatment process to form a microscopic concave-convex structure on the surface of the ceramic tile, and then a coating is applied on the surface to form a foul-resistant protective layer; this special structure and protective layer effectively prevent the adhesion of stains, so that the ceramic tile has excellent fouling resistance, can be easily cleaned, and maintains long-term beauty; this coating agent can maintain the original brightness and color of the ceramic tile after long-term use, and is not easy to fade, yellow or be damaged, thereby maintaining the long-term beauty of the ceramic tile.

[0005] The above-mentioned improvement of the anti-fouling performance of ceramic tiles is mainly achieved by modifying the surface treatment process of the ceramic tiles. There are few methods to improve the density of the ceramic tiles and thus improve the anti-fouling performance by improving the ceramic tile glaze. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention innovatively proposes to modify the glaze used for ceramic tiles, thereby achieving the anti-fouling performance of the ceramic tiles, in order to solve the technical problems raised in the background art. Specifically, the technical solution of the present invention includes the following:

[0007] A method for preparing highly stain-resistant glazed ceramic tiles, the method comprising the following steps:

[0008] The mixed glaze is applied on the surface of the ceramic body, and the glaze thickness is controlled to be 0.8mm~0.9mm. It is then allowed to stand at 25℃±2℃ for 20h~24h, then dried at 110℃~120℃ for 50min, and then calcined at 1200℃~1250℃ for 2h~3h. After cooling, it is polished and ground to obtain highly stain-resistant glazed ceramic tiles.

[0009] Furthermore, the preparation method of the mixed glaze comprises the following steps:

[0010] Quartz sand, calcite, dolomite and magnesite are mixed and crushed in a weight ratio of 20-25:6-10:12-15:5-8 to obtain a mixture, and the mixture, grinding beads and water are wet-ground in a weight ratio of 1:2-3:0.5-0.8 to obtain a mixed slurry;

[0011] The mixed slurry and the metal ion chelated levodopa mixed solution are mixed in a weight ratio of 1:1-2, and the pH value is adjusted to 8-9. The mixed glaze is then protected and stored under nitrogen to obtain a mixed glaze.

[0012] Furthermore, the grinding beads are made of zirconium oxide.

[0013] Furthermore, the method for preparing the metal ion chelated levodopa mixed solution comprises the following steps:

[0014] Levodopa, a metal chelating agent, and anhydrous ethylene glycol are mixed in a weight ratio of 1:1-1.5:2-3, followed by ultrasonic dispersion to obtain a dispersion liquid. The dispersion liquid is mixed with p-toluenesulfonic acid in a weight ratio of 1:0.01-0.015, and heated in a nitrogen atmosphere for reaction to obtain an ethylenediaminetetraacetic acid-modified levodopa mixture liquid.

[0015] The ethylenediaminetetraacetic acid modified levodopa mixed solution and the aluminum chloride aqueous solution are mixed and stirred in a weight ratio of 1:1-1.2, and then heated to 40°C-50°C for reaction for 8h-12h to obtain a metal ion chelated levodopa mixed solution.

[0016] Furthermore, the metal chelator includes ethylenediaminetetraacetic acid, and the metal chelator needs to have a reactive carboxyl group, so that it can be introduced into levodopa through an esterification reaction.

[0017] Furthermore, the conditions for the heating reaction in the nitrogen atmosphere include a reaction temperature of 80° C. to 90° C. and a reaction time of 3 h to 4 h.

[0018] Furthermore, the mass fraction of the aluminum chloride aqueous solution is 40% to 50%.

[0019] Furthermore, the method for preparing the ceramic body comprises the following steps:

[0020] Kaolin, potassium feldspar, fly ash, cerium oxide and silicon dioxide are mixed and crushed in a weight ratio of 30-36:18-22:17-20:1-3:5-8 to obtain a crushed material, and the crushed material, water and grinding beads are mixed and wet-milled in a weight ratio of 1:0.8:1.5 to obtain a green body material;

[0021] The green body material and liquid paraffin are mixed and stirred in a weight ratio of 1:0.03-0.05, aged for 24 hours, and then dried at 140° C. to constant weight and crushed to obtain green body powder. The green body powder is pressed and formed into a ceramic green body.

[0022] Furthermore, the pressing conditions include a pressure strength of 20 MPa to 30 MPa and a pressing time of 2 min.

[0023] A method for preparing highly stain-resistant glazed ceramic tiles provides highly stain-resistant glazed ceramic tiles.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The present invention uses levodopa as a carrier and ethylene glycol as a bridging structure. The metal chelator ethylenediaminetetraacetic acid is introduced into the levodopa structure through an esterification reaction to form an ethylenediaminetetraacetic acid-modified levodopa mixed solution. The ethylenediaminetetraacetic acid-modified levodopa mixed solution is mixed and chelated with an aqueous solution of aluminum chloride to obtain a metal ion chelated levodopa mixed solution. Levodopa can self-polymerize in an alkaline aerobic environment to form polylevodopa with strong adhesion, thereby improving the bonding strength of the mixed glaze and the body. The improvement in bonding strength helps the glaze to fully penetrate the pores on the body surface, enhancing density and mechanical properties. The role of ethylenediaminetetraacetic acid is to increase the sites for levodopa to chelate metal ions and aluminum ions, thereby increasing the content of metal ions and aluminum ions. The metal ion chelated levodopa mixed solution and the mixed slurry are mixed in an alkaline oxygen-free environment. The alkaline environment helps the metal ions and aluminum ions form hydroxide deposits, thereby preparing a mixed glaze. The mixed glaze is applied to the surface of the ceramic body to a specific thickness and then allowed to stand in an alkaline, oxygen-rich environment. This facilitates the oxidation and self-crosslinking of L-dopa to form a highly adhesive poly-L-dopa structure, thereby improving the mixed glaze's adhesion to the ceramic body. During high-temperature calcination, polydopamine is released through pyrolysis, producing gases such as carbon dioxide. The resulting aluminum hydroxide forms a dense oxide film, which increases the density of the ceramic tile surface, thereby blocking the penetration of stains and improving stain resistance. This increased density also contributes to the increased hardness and wear resistance of the ceramic tile. DETAILED DESCRIPTION

[0026] The following will clearly and completely describe the technical solutions of the present invention through the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0027] Unless otherwise specified, the raw materials and reagents used in the present invention are commercially available or can be prepared by known methods.

[0028] Preparation Example 1:

[0029] The preparation method of the metal ion chelated levodopa mixed solution specifically includes the following steps:

[0030] 1 part by weight of levodopa, 1 part by weight of ethylenediaminetetraacetic acid, and 2 parts by weight of anhydrous ethylene glycol were mixed in a reactor, then placed in an ultrasonic disperser and subjected to ultrasonic mixing at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was then mixed with 0.01 part by weight of p-toluenesulfonic acid and heated to 80°C under a nitrogen atmosphere for a reaction time of 4 hours. After the reaction, the extract was extracted with ethyl acetate, and the ethyl acetate was removed by evaporation under reduced pressure to obtain an ethylenediaminetetraacetic acid-modified levodopa mixture. 1 part by weight of the ethylenediaminetetraacetic acid-modified levodopa mixture was then mixed with 1 part by weight of an aqueous solution of aluminum chloride (40% by mass) and stirred for 10 minutes. The mixture was then heated to 40°C for 8 hours. After the reaction, the mixture was cooled to room temperature to obtain a metal ion-chelated levodopa mixture.

[0031] Preparation Example 2:

[0032] The preparation method of the metal ion chelated levodopa mixed solution specifically includes the following steps:

[0033] 1 part by weight of levodopa, 1.3 parts by weight of ethylenediaminetetraacetic acid, and 2.5 parts by weight of anhydrous ethylene glycol were mixed in a reactor, then placed in an ultrasonic disperser and subjected to ultrasonic mixing at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was then mixed with 0.013 parts by weight of p-toluenesulfonic acid and heated to 85°C under a nitrogen atmosphere for a reaction time of 3.5 hours. After the reaction, the extract was extracted with ethyl acetate, and the ethyl acetate was removed by evaporation under reduced pressure to obtain an ethylenediaminetetraacetic acid-modified levodopa mixture. 1 part by weight of the ethylenediaminetetraacetic acid-modified levodopa mixture was then mixed with 1.1 parts by weight of an aqueous solution of aluminum chloride (45% by mass) and stirred for 10 minutes. The mixture was then heated to 45°C for 10 hours. After the reaction, the mixture was cooled to room temperature to obtain a metal ion-chelated levodopa mixture.

[0034] Preparation Example 3:

[0035] The preparation method of the metal ion chelated levodopa mixed solution specifically includes the following steps:

[0036] 1 part by weight of levodopa, 1.5 parts by weight of ethylenediaminetetraacetic acid, and 3 parts by weight of anhydrous ethylene glycol were mixed in a reactor, then placed in an ultrasonic disperser and subjected to ultrasonic mixing at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was then mixed with 0.015 parts by weight of p-toluenesulfonic acid and heated to 90°C under a nitrogen atmosphere for a timed reaction time of 3 hours. After the reaction, the extract was extracted with ethyl acetate, and the ethyl acetate was removed by evaporation under reduced pressure to obtain an ethylenediaminetetraacetic acid-modified levodopa mixture. 1 part by weight of the ethylenediaminetetraacetic acid-modified levodopa mixture was then mixed with 1.2 parts by weight of an aqueous solution of aluminum chloride (50% by mass) and stirred for 10 minutes. The mixture was then heated to 50°C for 12 hours and cooled to room temperature to obtain a metal ion-chelated levodopa mixture.

[0037] Preparation Example 4:

[0038] The preparation method of the metal ion chelated levodopa mixed solution specifically includes the following steps:

[0039] 2 parts by weight of levodopa, 1.5 parts by weight of ethylenediaminetetraacetic acid, and 3 parts by weight of anhydrous ethylene glycol were mixed in a reactor, then placed in an ultrasonic disperser and subjected to ultrasonic mixing at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was mixed with 0.015 parts by weight of p-toluenesulfonic acid and then heated to 90°C under a nitrogen atmosphere for a reaction time of 3 hours. After the reaction, the extract was extracted with ethyl acetate, and the ethyl acetate was removed by evaporation under reduced pressure to obtain an ethylenediaminetetraacetic acid-modified levodopa mixture. 2 parts by weight of the ethylenediaminetetraacetic acid-modified levodopa mixture was mixed with 1.2 parts by weight of an aqueous solution of aluminum chloride (50% by mass) and stirred for 10 minutes. The mixture was then heated to 50°C for 12 hours. After the reaction, the mixture was cooled to room temperature to obtain a metal ion-chelated levodopa mixture.

[0040] Preparation Example 5:

[0041] The preparation method of the metal ion chelated levodopa mixed solution specifically includes the following steps:

[0042] 0.5 parts by weight of levodopa, 1.5 parts by weight of ethylenediaminetetraacetic acid, and 3 parts by weight of anhydrous ethylene glycol were weighed and mixed in a reactor. The mixture was then placed in an ultrasonic disperser and ultrasonically mixed at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was then mixed with 0.015 parts by weight of p-toluenesulfonic acid and heated to 90°C under a nitrogen atmosphere for a reaction time of 3 hours. After the reaction, the mixture was extracted with ethyl acetate to obtain an extract. The extract was then evaporated under reduced pressure to remove the ethyl acetate, resulting in an ethylenediaminetetraacetic acid-modified levodopa mixture. 0.5 parts by weight of the ethylenediaminetetraacetic acid-modified levodopa mixture was then mixed with 1.2 parts by weight of an aqueous solution of aluminum chloride (50% by mass) and stirred for 10 minutes. The mixture was then heated to 50°C for 12 hours. After the reaction, the mixture was cooled to room temperature to obtain a metal ion-chelated levodopa mixture.

[0043] Preparation Example 6:

[0044] The preparation method of the metal ion chelated dopamine mixed solution specifically includes the following steps:

[0045] 1 part by weight of dopamine hydrochloride, 1.5 parts by weight of ethylenediaminetetraacetic acid, and 3 parts by weight of anhydrous ethylene glycol were mixed in a reactor, then placed in an ultrasonic disperser and subjected to ultrasonic mixing at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was then mixed with 0.015 parts by weight of p-toluenesulfonic acid and heated to 90°C under a nitrogen atmosphere for a timed reaction time of 3 hours. After the reaction, the extract was extracted with ethyl acetate, and the ethyl acetate was removed by evaporation under reduced pressure to obtain an EDTA-modified dopamine mixture. 1 part by weight of the EDTA-modified dopamine mixture was then mixed with 1.2 parts by weight of an aqueous solution of aluminum chloride (50% by mass) and stirred for 10 minutes. The mixture was then heated to 50°C for 12 hours. After the reaction, the mixture was cooled to room temperature to obtain a metal ion-chelated dopamine mixture.

[0046] Preparation Example 7:

[0047] The preparation method of the metal ion chelated levodopa mixed solution specifically includes the following steps:

[0048] 1 part by weight of levodopa, 1.5 parts by weight of sodium hexametaphosphate, and 3 parts by weight of anhydrous ethylene glycol were mixed in a reactor, then placed in an ultrasonic disperser and subjected to ultrasonic mixing at 400 W for 20 minutes to obtain a dispersion. 1 part by weight of the dispersion was then mixed with 0.015 parts by weight of p-toluenesulfonic acid and heated to 90°C under a nitrogen atmosphere for a reaction time of 3 hours. After the reaction, the extract was extracted with ethyl acetate, and the ethyl acetate was removed by evaporation under reduced pressure to obtain an EDTA-modified levodopa mixture. 1 part by weight of the EDTA-modified levodopa mixture was then mixed with 1.2 parts by weight of an aqueous solution of aluminum chloride (50% by mass) and stirred for 10 minutes. The mixture was then heated to 50°C for 12 hours and cooled to room temperature to obtain a metal ion-chelated levodopa mixture.

[0049] Preparation Example 8:

[0050] The preparation method of the mixed glaze specifically includes the following steps:

[0051] 20 parts by weight of quartz sand, 6 parts by weight of calcite, 12 parts by weight of dolomite, and 5 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.5 times the weight of the mixture was added with water. Then, grinding beads made of zirconium oxide were added in an amount of 2 times the weight of the mixture. Subsequently, wet ball milling was performed at a speed of 600 r / min for 30 minutes to obtain a mixed slurry. 1 part by weight of the mixed slurry and 1 part by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 1 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 8. Subsequently, the air in the reactor was completely replaced with nitrogen. The mixture was stirred for 30 minutes to obtain a mixed glaze, which was stored for later use.

[0052] Preparation Example 9:

[0053] The preparation method of the mixed glaze specifically includes the following steps:

[0054] 22 parts by weight of quartz sand, 8 parts by weight of calcite, 14 parts by weight of dolomite and 6 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.6 times the weight of the mixture was added with water. 2.5 times the weight of the mixture was added with grinding beads made of zirconium oxide. The mixture was then wet-milled at a speed of 600 r / min for 30 min to obtain a mixed slurry. 1 part by weight of the mixed slurry and 1.5 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 2 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 8.5. The air in the reactor was then completely replaced with nitrogen. The mixture was stirred for 30 min to obtain a mixed glaze, which was stored for later use.

[0055] Preparation Example 10:

[0056] The preparation method of the mixed glaze specifically includes the following steps:

[0057] 25 parts by weight of quartz sand, 10 parts by weight of calcite, 15 parts by weight of dolomite, and 8 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added with water. Then, 3 times the weight of the mixture was added with grinding beads made of zirconium oxide. The mixture was then wet-milled at a speed of 600 r / min for 30 min to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 3 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. The air in the reactor was then completely replaced with nitrogen. The mixture was stirred for 30 min to obtain a mixed glaze, which was stored for later use.

[0058] Preparation Example 11:

[0059] The preparation method of the mixed glaze specifically includes the following steps:

[0060] 25 parts by weight of quartz sand, 10 parts by weight of calcite, 15 parts by weight of dolomite, and 8 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added with water. Then, 3 times the weight of the mixture was added with grinding beads made of zirconium oxide. The mixture was then wet-milled at a speed of 600 r / min for 30 min to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 4 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. The air in the reactor was then completely replaced with nitrogen. The mixture was stirred for 30 min to obtain a mixed glaze, which was stored for later use.

[0061] Preparation Example 12:

[0062] The preparation method of the mixed glaze specifically includes the following steps:

[0063] 25 parts by weight of quartz sand, 10 parts by weight of calcite, 15 parts by weight of dolomite and 8 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added with water. Then, grinding beads made of zirconium oxide were added in an amount of 3 times the weight of the mixture. Subsequently, wet ball milling was performed at a speed of 600 r / min for 30 minutes to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 5 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. Subsequently, the air in the reactor was completely replaced with nitrogen. The mixture was stirred for 30 minutes to obtain a mixed glaze, which was stored for later use.

[0064] Preparation Example 13:

[0065] The preparation method of the mixed glaze specifically includes the following steps:

[0066] 25 parts by weight of quartz sand, 10 parts by weight of calcite, 15 parts by weight of dolomite and 8 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added to water. Then, grinding beads made of zirconium oxide were added in an amount of 3 times the weight of the mixture. The mixture was then wet-milled at a speed of 600 r / min for 30 min to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated dopamine mixed solution obtained in Preparation Example 6 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. The air in the reactor was then completely replaced with nitrogen. The mixture was stirred for 30 min to obtain a mixed glaze, which was stored for later use.

[0067] Preparation Example 14:

[0068] The preparation method of the mixed glaze specifically includes the following steps:

[0069] 25 parts by weight of quartz sand, 10 parts by weight of calcite, 15 parts by weight of dolomite, and 8 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added with water. Then, 3 times the weight of the mixture was added with grinding beads made of zirconium oxide. The mixture was then wet-milled at a speed of 600 r / min for 30 min to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 7 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. The air in the reactor was then completely replaced with nitrogen. The mixture was stirred for 30 min to obtain a mixed glaze, which was stored for later use.

[0070] Preparation Example 15:

[0071] The preparation method of the mixed glaze specifically includes the following steps:

[0072] 20 parts by weight of quartz sand, 3 parts by weight of calcite, 10 parts by weight of dolomite, and 3 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added with water. Then, grinding beads made of zirconium oxide were added in an amount of 3 times the weight of the mixture. Subsequently, wet ball milling was performed at a speed of 600 r / min for 30 minutes to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 3 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. Subsequently, the air in the reactor was completely replaced with nitrogen. The mixture was stirred for 30 minutes to obtain a mixed glaze, which was stored for later use.

[0073] Preparation Example 16:

[0074] The preparation method of the mixed glaze specifically includes the following steps:

[0075] 25 parts by weight of quartz sand, 12 parts by weight of calcite, 18 parts by weight of dolomite, and 10 parts by weight of magnesite were weighed and added to a crusher for crushing. After crushing, the mixture was passed through a 20-mesh sieve to obtain a mixture. 1 part by weight of the mixture was weighed and added to a ball mill. 0.8 times the weight of the mixture was added with water. Then, 3 times the weight of the mixture was added with grinding beads made of zirconium oxide. The mixture was then wet-milled at a speed of 600 r / min for 30 min to obtain a mixed slurry. 1 part by weight of the mixed slurry and 2 parts by weight of the metal ion chelated levodopa mixed solution obtained in Preparation Example 3 were added to a reactor. Sodium carbonate solution was added to adjust the pH to 9. The air in the reactor was then completely replaced with nitrogen. The mixture was stirred for 30 min to obtain a mixed glaze, which was stored for later use.

[0076] Preparation Example 17:

[0077] The preparation method of the ceramic body specifically includes the following steps:

[0078] 30 parts by weight of kaolin, 18 parts by weight of potassium feldspar, 17 parts by weight of fly ash, 1 part by weight of cerium oxide and 5 parts by weight of silicon dioxide are weighed and mixed in a crusher. After the potassium feldspar is crushed, the mixture is passed through a 20-mesh sieve to obtain a crushed material. 1 part by weight of the crushed material is weighed and added to a ball mill. Subsequently, 0.8 times the weight of water of the crushed material is added and mixed. Finally, grinding beads made of zirconium oxide are added according to 1.5 times the weight of the crushed material. The mixture is then wet-milled at a speed of 800 r / min for 40 minutes to obtain a green body material. 1 part by weight of the green body material and 0.03 parts by weight of liquid paraffin are weighed and mixed, stirred and aged for 24 hours, then dried at 140°C to constant weight and crushed to obtain a green body powder. The green body powder is placed in a press and pressed for 2 minutes in a pressure environment of 20 MPa to obtain a ceramic green body.

[0079] Preparation Example 18:

[0080] The preparation method of the ceramic body specifically includes the following steps:

[0081] 34 parts by weight of kaolin, 20 parts by weight of potassium feldspar, 19 parts by weight of fly ash, 2 parts by weight of cerium oxide and 6 parts by weight of silicon dioxide are weighed and mixed in a crusher. After the potassium feldspar is crushed, the mixture is passed through a 20-mesh sieve to obtain a crushed material. 1 part by weight of the crushed material is weighed and added to a ball mill. Subsequently, 0.8 times the weight of water of the crushed material is added and mixed. Finally, grinding beads made of zirconium oxide are added according to 1.5 times the weight of the crushed material. The mixture is then wet-milled at a speed of 800 r / min for 40 minutes to obtain a green body material. 1 part by weight of the green body material and 0.04 part by weight of liquid paraffin are weighed, mixed, stirred, and aged for 24 hours. The mixture is then dried at 140°C to constant weight and crushed to obtain a green body powder. The green body powder is placed in a press and pressed for 2 minutes in a pressure environment of 25 MPa to obtain a ceramic green body.

[0082] Preparation Example 19:

[0083] The preparation method of the ceramic body specifically includes the following steps:

[0084] 36 parts by weight of kaolin, 22 parts by weight of potassium feldspar, 20 parts by weight of fly ash, 3 parts by weight of cerium oxide and 8 parts by weight of silicon dioxide are weighed and mixed in a crusher. After the potassium feldspar is crushed, the mixture is passed through a 20-mesh sieve to obtain a crushed material. 1 part by weight of the crushed material is weighed and added to a ball mill. Subsequently, 0.8 times the weight of water of the crushed material is added and mixed. Finally, grinding beads made of zirconium oxide are added according to 1.5 times the weight of the crushed material. The mixture is then wet-milled at a speed of 800 r / min for 40 minutes to obtain a green body material. 1 part by weight of the green body material and 0.05 parts by weight of liquid paraffin are weighed and mixed, stirred, and aged for 24 hours. The mixture is then dried at 140°C to constant weight and crushed to obtain a green body powder. The green body powder is placed in a press and pressed for 2 minutes in a pressure environment of 30 MPa to obtain a ceramic green body.

[0085] Example 1:

[0086] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0087] The mixed glaze obtained in Preparation Example 8 was glazed on the surface of the ceramic body obtained in Preparation Example 17 using a glaze scraper, and the glaze thickness was controlled to be 0.8 mm. The ceramic body was then placed in a natural environment at 25±2°C for 20 hours. After the standing period, the ceramic body was placed in a dryer and dried at 110°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1200°C, and fired for 2 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.1 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0088] Example 2:

[0089] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0090] The mixed glaze obtained in Preparation Example 9 was glazed on the surface of the ceramic body obtained in Preparation Example 18 by a glaze scraper, and the glaze thickness was controlled to be 0.8 mm. Then, the ceramic body was placed in a natural environment at 25±2°C for 22 hours. After standing, the ceramic body was placed in a dryer and dried at 110°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1230°C, and fired for 2.5 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.1 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0091] Example 3:

[0092] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0093] The mixed glaze obtained in Preparation Example 10 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0094] Comparative Example 1:

[0095] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0096] The mixed glaze obtained in Preparation Example 11 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0097] Comparative Example 2:

[0098] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0099] The mixed glaze obtained in Preparation Example 12 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0100] Comparative Example 3:

[0101] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0102] The mixed glaze obtained in Preparation Example 13 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0103] Comparative Example 4:

[0104] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0105] The mixed glaze obtained in Preparation Example 14 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0106] Comparative Example 5:

[0107] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0108] The mixed glaze obtained in Preparation Example 15 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0109] Comparative Example 6:

[0110] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0111] The mixed glaze obtained in Preparation Example 16 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.9 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0112] Comparative Example 7:

[0113] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0114] The mixed glaze obtained in Preparation Example 10 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 0.6 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0115] Comparative Example 8:

[0116] A method for preparing highly stain-resistant glazed ceramic tiles, specifically comprising the following steps:

[0117] The mixed glaze obtained in Preparation Example 10 was glazed on the surface of the ceramic body obtained in Preparation Example 19 using a glaze scraper, and the glaze thickness was controlled to be 1.2 mm. The ceramic body was then placed in a natural environment at 25±2°C for 24 hours. After the standing period, the ceramic body was placed in a dryer and dried at 120°C for 50 minutes. After the drying process, the ceramic body was placed in a high-temperature electric furnace, heated by 10°C to 1250°C, and fired for 3 hours. After the firing process, the ceramic body was naturally cooled to room temperature, and a 0.2 mm glaze layer was removed by polishing with a polishing machine to obtain a highly stain-resistant glazed ceramic tile.

[0118] According to GB / T 3810.7-2016 Test methods for ceramic tiles Part 3: Determination of water absorption, apparent porosity, apparent relative density and bulk density, the apparent porosity of the ceramic tiles obtained in Examples 1 to 3 and Comparative Examples 1 to 7 was measured. The results are shown in Table 1 below.

[0119] Table 1 Apparent porosity

[0120]

[0121] The Vickers hardness of the ceramic tiles obtained in Examples 1 to 3 and Comparative Examples 1 to 7 was tested using a micro Vickers hardness tester. The results are shown in Table 2 below.

[0122] Table 2 Vickers hardness

[0123]

[0124] Simulated soil pollution prevention test: Dry soil passed through a 100-mesh sieve was evenly sprinkled on the surfaces of the ceramic tiles obtained in Examples 1-3 and Comparative Examples 1-7. Water was then added until the soil was completely moistened and no water flowed out. After standing for 12 hours, the tiles were cleaned according to the cleaning method specified in "GB / T 3810.14-2016 Ceramic Tiles Test Methods Part 14: Determination of Pollution Resistance". The pollution resistance level was recorded. The results are shown in Table 3 below.

[0125] Simulated test for resistance to vegetable oil and pigment contamination: Soybean oil was evenly applied to the surfaces of the ceramic tiles obtained in Examples 1-3 and Comparative Examples 1-7, and then Solvent Yellow 33 was dropped on the surfaces. The tiles were then allowed to stand for 12 hours and then cleaned according to the cleaning method specified in "GB / T 3810.14-2016 Ceramic Tile Test Methods Part 14: Determination of Contamination Resistance". The contamination resistance level was recorded. The results are shown in Table 3 below.

[0126] Table 3 Antifouling performance

[0127]

[0128] The following conclusions can be drawn from the structures in Tables 1 to 3 above:

[0129] (1) It can be found from Examples 1 to 3 that the present invention, by modifying the glaze used for ceramic tiles, makes the prepared ceramic tiles have low apparent porosity, good stain resistance and high hardness.

[0130] (2) It can be found from Comparative Examples 1 and 2 that the apparent porosity of the prepared ceramic tiles is high, the stain resistance is poor, and the hardness of the ceramic tiles is poor. This may be because the modification of levodopa by ethylenediaminetetraacetic acid can improve the chelation of aluminum ions and thus improve the density by forming a dense oxide film through high-temperature calcination. However, due to excessive use of levodopa, the fluidity of the mixed glaze may be deteriorated, and the distribution of the mixed glaze on the surface of the ceramic body may be uneven, thereby affecting the performance of the ceramic tiles; and when the usage amount is low, the oxide film may be less formed due to fewer sites for adsorbing aluminum ions, and when the usage amount is low, the adhesion may be poor, and then the bonding force between the mixed glaze and the ceramic body may be poor during high-temperature calcination, and the density improvement is poor, thereby causing poor stain resistance, apparent porosity and hardness.

[0131] (3) It can be found from Comparative Example 3 that the apparent porosity of the prepared ceramic tiles is high, the stain resistance is poor, and the hardness of the ceramic tiles is poor. This may be because although dopamine hydrochloride can be oxidized and self-polymerized to form polydopamine with adhesiveness, it does not contain carboxyl groups in its structure, resulting in a low loading of EDTA and less aluminum ion chelation, which in turn weakens the formation of the oxide film, resulting in poor performance of the ceramic tiles.

[0132] (4) Comparative Example 4 shows that the apparent porosity of the prepared ceramic tiles is high, the stain resistance is poor, and the hardness of the ceramic tiles is poor. This may be because sodium hexametaphosphate cannot be condensed onto the levodopa structure through esterification reaction, which makes it difficult to chelate aluminum ions, and thus makes it difficult to form an oxide film, resulting in poor performance of the ceramic tiles.

[0133] (5) Comparative Examples 5 and 6 show that the apparent porosity of the prepared ceramic tiles is high, the stain resistance is poor, and the hardness of the ceramic tiles is poor. This may be because although alumina can improve the density of the ceramic tile surface, the sintering temperature of ceramics containing alumina is high. Although silica in quartz sand can increase hardness, when there is not enough calcite, dolomite and magnesite containing calcium oxide and magnesium oxide active ingredients to assist in calcination, which can reduce the sintering temperature of alumina, the calcination temperature of this system may be unfavorable for the formation of ceramic tiles, resulting in poor performance of the ceramic tiles. When the amount of calcite, dolomite and magnesite is further increased, although it helps the sintering of alumina, excessive calcite, dolomite and magnesite are prone to release a large amount of carbon dioxide and other gases. In this system, due to the untimely and poor discharge of gases, microcracks or pores may form, which reduces the performance of the ceramic tiles.

[0134] (6) It can be found from Comparative Examples 7 and 8 that the prepared ceramic tiles have a high apparent porosity, poor stain resistance, and poor hardness. This may be because when the mixed glaze used in this system has a low glazing thickness, the glaze protective layer becomes too thin after polishing, which easily leads to glaze denaturation and is not conducive to improving the performance of the ceramic tiles; when the glazing thickness is too high, the glaze surface may easily crack and warp, and the performance of the ceramic tiles is poor at the firing temperature in this system.

[0135] The embodiments described above provide a detailed description of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. A method for preparing highly stain-resistant glazed ceramic tiles, characterized in that: The preparation method comprises the following steps: The mixed glaze is applied on the surface of the ceramic body, and the glaze thickness is controlled to be 0.8mm~0.9mm. It is then allowed to stand at 25℃±2℃ for 20h~24h, then dried at 110℃~120℃ for 50min, and then calcined at 1200℃~1250℃ for 2h~3h. After cooling, it is polished and ground to obtain highly stain-resistant glazed ceramic tiles.

2. The method for preparing a highly stain-resistant glazed ceramic tile according to claim 1, characterized in that: The preparation method of the mixed glaze comprises the following steps: Quartz sand, calcite, dolomite and magnesite are mixed and crushed in a weight ratio of 20-25:6-10:12-15:5-8 to obtain a mixture, and the mixture, grinding beads and water are wet-ground in a weight ratio of 1:2-3:0.5-0.8 to obtain a mixed slurry; The mixed slurry and the metal ion chelated levodopa mixed solution are mixed in a weight ratio of 1:1-2, and the pH value is adjusted to 8-9. The mixed glaze is then protected and stored under nitrogen to obtain a mixed glaze.

3. The method for preparing a highly stain-resistant glazed ceramic tile according to claim 2, wherein: The preparation method of the metal ion chelated levodopa mixed solution comprises the following steps: Levodopa, a metal chelating agent, and anhydrous ethylene glycol are mixed in a weight ratio of 1:1-1.5:2-3, followed by ultrasonic dispersion to obtain a dispersion liquid. The dispersion liquid is mixed with p-toluenesulfonic acid in a weight ratio of 1:0.01-0.015, and heated in a nitrogen atmosphere for reaction to obtain an ethylenediaminetetraacetic acid-modified levodopa mixture liquid. The ethylenediaminetetraacetic acid modified levodopa mixed solution and the aluminum chloride aqueous solution are mixed and stirred in a weight ratio of 1:1-1.2, and then heated to 40°C-50°C for reaction for 8h-12h to obtain a metal ion chelated levodopa mixed solution.

4. The method for preparing a highly stain-resistant glazed ceramic tile according to claim 3, wherein: The metal chelating agent includes ethylenediaminetetraacetic acid.

5. The method for preparing a highly stain-resistant glazed ceramic tile according to claim 3, characterized in that: The conditions for the heating reaction in the nitrogen atmosphere include a reaction temperature of 80° C. to 90° C. and a reaction time of 3 h to 4 h.

6. The method for preparing a highly stain-resistant glazed ceramic tile according to claim 3, characterized in that: The mass fraction of the aluminum chloride aqueous solution is 40% to 50%.

7. The method for preparing a highly stain-resistant glazed ceramic tile according to claim 1, characterized in that: The preparation method of the ceramic body comprises the following steps: Kaolin, potassium feldspar, fly ash, cerium oxide and silicon dioxide are mixed and crushed in a weight ratio of 30-36:18-22:17-20:1-3:5-8 to obtain a crushed material, and the crushed material, water and grinding beads are mixed and wet-milled in a weight ratio of 1:0.8:1.5 to obtain a green body material; The green body material and liquid paraffin are mixed and stirred in a weight ratio of 1:0.03-0.05, aged for 24 hours, and then dried at 140° C. to constant weight and crushed to obtain green body powder. The green body powder is pressed and formed into a ceramic green body.

8. A highly stain-resistant glazed ceramic tile prepared by the method for preparing a highly stain-resistant glazed ceramic tile according to any one of claims 1 to 7.

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