Antiskid antifouling glazed tile and preparation method thereof

Abstract

The invention relates to the field of glazed tiles, in particular to an antiskid antifouling glazed tile and a preparation method thereof. The anti-skid and anti-fouling glazed tile sequentially comprises an anti-skid and anti-fouling layer, a glaze layer and a ceramic tile blank from top to bottom, wherein the glaze layer is prepared from the following components in parts by weight: 40 to 50 parts of quartz sand, 6 to 12 parts of calcined magnesium oxide, 10 to 15 parts of magnesium aluminate spinel, 7 to 15 parts of calcium carbonate, 10 to 20 parts of strontium-boron glass powder, 2 to 5 parts of yttrium-stabilized zirconium oxide and 1 to 3 parts of hydroxyapatite nanorods. The glaze layer and the anti-skid and anti-fouling layer are sequentially arranged on the surface of the green brick, the glaze layer is arranged through multiple high-strength and wear-resistant components, high hardness, wear resistance and thermal shock resistance of the glaze surface are guaranteed, the anti-skid and anti-fouling layer takes fluorosilicone resin as a base material, multiple additives are added, intelligent balance of skid resistance and self-cleaning is achieved, and the anti-skid and anti-fouling green brick is good in anti-skid and self-cleaning performance. The paint is especially suitable for high-humidity and high-oil-stain scenes such as bathrooms and kitchens.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glazed tiles, in particular to a kind of antiskid and antifouling glazed tile and preparation method thereof. BACKGROUND

[0002] Glazed tiles are widely used in the field of construction due to their excellent decorative properties, but in humid environment (such as bathroom, kitchen, swimming pool), it is easy to cause safety accidents due to slippery surface. According to the statistics of WHO, about 400,000 falling accidents occur worldwide every year, which are directly related to the slip of floor tiles. At the same time, the micro-porous structure on the surface of traditional glazed tiles can easily adsorb pollutants, resulting in an increase of more than 30% in cleaning cost.

[0003] The existing technology mainly improves the antiskid and antifouling properties through two schemes: the first one is mold imprinting method, that is, to press concave-convex texture on the surface of tile blank, to increase the static friction coefficient in wet state, however, the texture groove becomes the area where dirt accumulates, so the stain retention rate is even higher, and the continuity of glaze layer is damaged, which causes the gloss to decrease seriously. The second one is surface coating method, that is, to coat protective layer on the surface of tile blank, in the existing technology, ordinary fluorosilicone resin is coated to enhance the antiskid and antifouling properties, but the wear-resistant life is insufficient, which cannot be used for a long time; in addition, nano-TiO2 is sprayed on the surface to realize self-cleaning under UV, but the catalytic efficiency is low in indoor environment, which results in unsatisfactory effect.

[0004] Therefore, how to prepare a kind of glazed tile with coexisting antiskid and antifouling properties is a problem urgently to be solved in the field. SUMMARY

[0005] In view of the problems existing in the prior art, the purpose of the present application is to provide a kind of antiskid and antifouling glazed tile and preparation method thereof.

[0006] The purpose of the present application is realized by adopting the following technical scheme:

[0007] In the first aspect, the present application provides a kind of antiskid and antifouling glazed tile, which comprises, from top to bottom, antiskid and antifouling layer, glaze layer and ceramic tile blank.

[0008] Preferably, the antiskid and antifouling layer comprises, calculated by weight fraction:

[0009] 100 parts of fluorosilicone resin, 5-10 parts of coated nanowire material, 0.3-0.8 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 30-50 parts of solvent.

[0010] Preferably, the fluorosilicone resin is fluorosilicone resin HLR-Si, and the fluorine content is ≥26%.

[0011] Preferably, the defoaming agent is BYK-077 or BYK-141; the leveling agent is BYK-331 or BYK-378.

[0012] Preferably, the solvent is at least one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, toluene, xylene.

[0013] Preferably, the glaze layer comprises, by weight fraction:

[0014] 40-50 parts of quartz sand, 6-12 parts of calcined magnesium oxide, 10-15 parts of magnesium aluminate spinel, 7-15 parts of calcium carbonate, 10-20 parts of strontium borate glass powder, 2-5 parts of yttrium stabilized zirconia, and 1-3 parts of hydroxyapatite nanorods.

[0015] Preferably, the quartz sand has a particle size of 40-50 μm and a SiO2 content of ≥ 99.5%.

[0016] Preferably, the calcined magnesium oxide is magnesium oxide sintered at 800-1000°C, with an active MgO content of ≥ 95% and a particle size of 10-20 μm.

[0017] Preferably, the magnesium aluminate spinel has a composition of Al2O3: 70-75 wt%, MgO: 25-30 wt%, and a particle size of 5-10 μm.

[0018] Preferably, the calcium carbonate is calcite-type calcium carbonate with a particle size of 1-2 μm.

[0019] Preferably, the strontium borate glass powder has a composition of SrO: 15-20%, B2O3: 20-25%, SiO2: 50-55%, and a particle size of 10-15 μm.

[0020] Preferably, the yttrium stabilized zirconia is tetragonal phase ZrO2 doped with Y2O3, with a doping molar amount of Y2O3 of 3%.

[0021] Preferably, the hydroxyapatite nanorods have a particle size of 20-50 nm and an aspect ratio of 5-10:1.

[0022] Preferably, the preparation method of the coated nanowire material comprises:

[0023] S1. Weigh eugenol and dissolve it in tetrahydrofuran, introduce nitrogen as a protective gas, add coupling agent KH-901, stir thoroughly, then add a catalyst, heat to 50-60°C, and maintain the temperature and stir for 4-8 hours. After the reaction is complete, remove the solvent under reduced pressure to obtain eugenol-modified silane;

[0024] S2. Weigh coupling agent KH-580 and dissolve it in an ethanol solution, add tungsten-doped vanadium dioxide nanowires, disperse thoroughly, and then reflux and stir at 60-70°C for 4-10 hours. After filtration, washing, and drying, we obtain mercapto-functionalized W-VO2 nanowires.

[0025] S3, eugenol-modified silane and thiolated W-VO2 nanowires are weighed and added into tetrahydrofuran, and are uniformly dispersed at room temperature, a photoinitiator is added, and ultraviolet irradiation and stirring reaction is performed for 1-3 h, and the solid is collected by centrifugation, washed with ethanol for 3 times, and dried to obtain a coated nanowire material.

[0026] Preferably, the preparation method of the tungsten-doped vanadium dioxide nanowire comprises:

[0027] Vanadium pentoxide and oxalic acid are weighed and added into deionized water, and after stirring and mixing, a mixed solution A is obtained; tungstic acid is weighed and added into hydrogen peroxide to obtain a mixed solution B; the mixed solution B is added dropwise into the mixed solution A, and is poured into a reaction kettle, and is kept at 200-240℃ for 18-36 h under stirring, after the reaction is completed, filtration, washing and drying are performed to obtain tungsten-doped vanadium dioxide nanowires W-VO2 nanowires.

[0028] Preferably, the ratio of vanadium pentoxide, oxalic acid, tungstic acid, hydrogen peroxide and deionized water is 1.8 g:(2.2-2.5) g:(0.06-0.1) g:(0.7-1) g:(100-200) mL.

[0029] Preferably, in S1, the coupling agent KH-901 is 3-isocyanate propyl trimethoxysilane, and the ratio of eugenol, coupling agent KH-901 and tetrahydrofuran is 1.6 g:(2.1-2.3) g:(15-25) mL.

[0030] Preferably, in S1, the catalyst is dibutyltin dilaurate, and the addition amount is 3%-8% of the mass of eugenol.

[0031] Preferably, in S2, the coupling agent KH-580 is γ-mercapto propyl triethoxysilane, the mass fraction of the ethanol solution is 70%-80%, and the particle size of the W-VO2 nanowires is 150-200 nm.

[0032] Preferably, in S2, the ratio of tungsten-doped vanadium dioxide nanowires, coupling agent KH-580 and ethanol solution is 1 g:(0.1-0.3) g:(15-25) mL.

[0033] Preferably, in S3, the ratio of eugenol-modified silane, thiolated W-VO2 nanowires and tetrahydrofuran is 1 g:(2-3) g:(15-25) mL.

[0034] Preferably, in S3, the initiator is a photoinitiator 1173, that is, 2-hydroxy-2-methyl-1-phenyl-1-propanone; and the addition amount of the initiator is 5%-10% of the mass of the eugenol-modified silane.

[0035] In a second aspect, the application provides a preparation method of a slip-resistant and stain-resistant glazed tile, comprising the following steps:

[0036] (1) Take quartz sand, calcined magnesium oxide, calcium carbonate, strontium boron glass powder into a ball mill, add deionized water and corundum grinding balls, the mass ratio of material, water and balls is 1:0.3-0.6:2-3, after ball milling for 3-5h, a mixture is obtained;

[0037] (2) Add magnesium aluminate spinel, yttrium stabilized zirconium oxide and hydroxyapatite nanorods to the mixture, stir and mix at a speed of 200-300r / min for 20-40min, then adjust the viscosity to 3000-4000cP (25℃) using carboxymethyl cellulose to obtain a glaze;

[0038] (3) Take the ceramic tile blank and polish the surface to a roughness Ra≤50μm, then place it in a 100℃ oven to dry until the water content is less than 0.8%;

[0039] (4) Apply the glaze evenly on the surface of the ceramic tile blank, first heat to 250℃, heat treatment for 1-3h, then heat to 1100-1150℃, heat treatment for 2-3h, and cool to room temperature in the furnace to obtain a ceramic tile with a glaze layer;

[0040] (5) Take the components of the slip-resistant and stain-resistant layer and mix them, and shear them at a speed of 5000-8000r / min for 10-20min to obtain a uniform slip-resistant and stain-resistant mixture;

[0041] (6) Spray the slip-resistant and stain-resistant mixture onto the surface of the ceramic tile with the glaze layer, let it dry at room temperature, then place it in an oven for stepwise solidification treatment: first heat to 80℃ for 10-20min, then heat to 100℃ for 20-30min, and cool to room temperature to complete the preparation.

[0042] The application has the following advantages:

[0043] 1. The application prepares a slip-resistant and stain-resistant glazed tile, which has a glaze layer and a slip-resistant and stain-resistant layer on the surface of the tile blank. The glaze layer is made of multiple high-strength and wear-resistant components, which ensures high hardness, wear resistance and thermal shock resistance of the glaze. The slip-resistant and stain-resistant layer uses fluorosilicone resin as the base material and adds multiple additives, achieving the intelligent balance of "slip-resistant when stepped on and easy to clean when stationary", and is especially suitable for high-humidity and high-oil-stain scenes such as bathrooms and kitchens.

[0044] 2. The slip-resistant and stain-resistant layer of the application adds coated nanowire materials as modified additives, which not only enhances the slip resistance and stain resistance of fluorosilicone resin, but also further enhances its self-cleaning property and durability, prolonging the service life of the glazed tile.

[0045] 3. The coated nanowire material prepared by this invention is a coated structural material with a core of tungsten-doped vanadium dioxide nanowires and an outer shell consisting of a mercapto-alkene click chemical reaction product of eugenol-modified silane and mercapto groups on the nanowire surface. The eugenol-modified silane is obtained by reacting the phenolic hydroxyl groups of eugenol with the isocyanate groups of the silane.

[0046] 4. The anti-slip and stain-removing mechanism of coated nanowire materials for fluorosilicone resin is as follows: After vanadium dioxide nanowires are doped with tungsten, the thermally induced phase transition temperature drops to 20-30℃. Within this temperature range, the nanowires undergo an insulator-metal phase transition (IMT), converting light energy into heat energy to rapidly evaporate the surface water layer, thereby playing an anti-slip role. The coating layer of the nanowires contains silane compounds with eugenol and thioether groups, which not only have better compatibility with the resin, but also enhance the stain resistance and durability of the resin material. Detailed Implementation

[0047] The technical solution of the present invention is illustrated below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or defining the scope of the present invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the present invention.

[0048] To better understand the above technical solutions, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the invention to those skilled in the art.

[0049] The present invention will be further described below with reference to the following embodiments.

[0050] Example 1

[0051] A type of anti-slip and stain-resistant glazed tile, comprising, from top to bottom, an anti-slip and stain-resistant layer, a glaze layer, and a ceramic tile body;

[0052] The glaze layer, calculated by weight, comprises:

[0053] 45 parts quartz sand, 9 parts calcined magnesium oxide, 12 parts magnesium aluminum spinel, 11 parts calcium carbonate, 15 parts strontium boron glass powder, 3 parts yttrium stabilized zirconium oxide and 2 parts hydroxyapatite nanorods.

[0054] The quartz sand has a particle size of 40-50 mu m and a SiO2 content of 99.5% or more; the calcined magnesium oxide is magnesium oxide sintered at 900 DEG C, has an active MgO of 95% or more, and has a particle size of 10-20 mu m; the magnesium-aluminum spinel has a composition of Al2O3: 70-75 wt%, MgO: 25-30 wt%, and a particle size of 5-10 mu m; the calcium carbonate is calcite-type calcium carbonate and has a particle size of 1-2 mu m; the strontium borate glass powder has a composition of SrO: 15-20%, B2O3: 20-25%, SiO2: 50-55%, and a particle size of 10-15 mu m; the yttrium-stabilized zirconium oxide is tetragonal phase ZrO2 doped with Y2O3, and the doping amount of Y2O3 is 3% by mole; and the hydroxyapatite nanorod has a particle size of 20-50 nm and a length-diameter ratio of 5-10:1.

[0055] The anti-skid and anti-fouling layer comprises, by weight fraction:

[0056] 100 parts of fluorosilicon resin, 8 parts of coated nanowire material, 0.5 parts of defoaming agent, 0.4 parts of leveling agent, and 40 parts of solvent.

[0057] The fluorosilicon resin is fluorosilicon resin HLR-Si, and the fluorine content is 26% or more; the defoaming agent is BYK-077; the leveling agent is BYK-331; and the solvent is ethyl acetate.

[0058] The preparation method of the coated nanowire material comprises:

[0059] S1, 1.8g of vanadium pentoxide and 2.3g of oxalic acid are weighed and added to 150mL of deionized water, stirred at 45 DEG C for 2.5h, and a mixed solution A is obtained; 0.08g of tungstic acid is weighed and added to 0.8g of hydrogen peroxide, stirred thoroughly, and a mixed solution B is obtained; the mixed solution B is added dropwise to the mixed solution A, poured into a reaction kettle, and stirred at 220 DEG C for 24h, and after the reaction is completed, filtration, washing, and drying are performed, and tungsten-doped vanadium dioxide nanowires W-VO2 nanowires are obtained;

[0060] S2, 1.6g of eugenol is dissolved in 20mL of tetrahydrofuran, nitrogen gas is introduced as a protective gas, 2.2g of coupling agent KH-901 (3-isocyanate propyl trimethoxysilane) is added, stirred thoroughly, a catalyst dibutyltin dilaurate is added in an amount of 5% of the mass of eugenol, the temperature is raised to 55 DEG C, and stirring is performed for 6h, and after the reaction is completed, the solvent is removed under reduced pressure, and eugenol-modified silane is obtained.

[0061] S3, 0.2 g of coupling agent KH-580 (γ-mercaptopropyl triethoxysilane) was weighed into 20 mL of 75 wt% ethanol solution, 1 g of W-VO2 nanowires with a particle size of 150-200 nm was added, after sufficient dispersion, reflux stirring was carried out at 65°C for 8 h, and then filtration, washing and drying were carried out to obtain mercapto-functionalized W-VO2 nanowires;

[0062] S4, 1 g of eugenol-modified silane and 2.5 g of mercapto-functionalized W-VO2 nanowires were weighed into 20 mL of tetrahydrofuran, and were uniformly dispersed at room temperature, a photoinitiator 1173 was added in an amount of 8% of the mass of the eugenol-modified silane, and under the protection of nitrogen, 365 nm ultraviolet light was used for irradiation and stirring reaction for 2 h, and then the solid was collected by centrifugation, washed with ethanol for three times, and dried to obtain a coated nanowire material.

[0063] The preparation method of the above-mentioned anti-skid and anti-fouling glazed tile comprises the following steps:

[0064] (1) quartz sand, calcined magnesium oxide, calcium carbonate, strontium boron glass powder were weighed into a ball mill, deionized water and corundum grinding balls were added, and the mass ratio of material, water and balls was 1:0.4:2.5, after ball milling for 4 h, a mixture was obtained;

[0065] (2) magnesium aluminate spinel, yttrium stabilized zirconia and hydroxyapatite nanorods were added to the mixture, and stirring and mixing were carried out at a speed of 250 r / min for 30 min, then carboxymethyl cellulose was used to adjust the viscosity to 3000-4000 cP (25°C) to obtain a glaze;

[0066] (3) the surface of the ceramic tile blank was polished to a roughness Ra≤50 μm, and then placed in an oven at 100°C to dry to a water content of less than 0.8%;

[0067] (4) the glaze was uniformly applied to the surface of the ceramic tile blank, first heated to 250°C, and then heat treated for 2 h, then heated to 1100°C, and then heat treated for 2.5 h, and then cooled to room temperature in the furnace to obtain a ceramic tile with a glaze layer;

[0068] (5) the components of the anti-skid and anti-fouling layer were weighed and mixed, and sheared at 6000 r / min for 15 min to obtain a uniform anti-skid and anti-fouling mixed solution;

[0069] (6) the anti-skid and anti-fouling mixed solution was sprayed onto the surface of the ceramic tile with the glaze layer, and after air drying at room temperature, it was placed in an oven for stepwise solidification treatment: first heated to 80°C for 15 min, then heated to 100°C for 25 min, and then cooled to room temperature to complete the preparation.

[0070] Example 2

[0071] An anti-skid and anti-fouling glazed tile, which is different from that of Example 1 only in that the composition of the glaze layer is slightly different.

[0072] The glaze layer comprises, in terms of weight fraction:

[0073] 40 parts of quartz sand, 6 parts of calcined magnesia, 10 parts of magnesium aluminate spinel, 7 parts of calcium carbonate, 10 parts of strontium borate glass powder, 2 parts of yttrium stabilized zirconia and 1 part of hydroxyapatite nanorod.

[0074] The particle size of the quartz sand is 40-50 μm, and the SiO2 content is ≥99.5%; the calcined magnesia is magnesia sintered at 900 ℃, the active MgO is ≥95%, and the particle size is 10-20 μm; the composition of the magnesium aluminate spinel is Al2O3: 70-75 wt%, MgO: 25-30 wt%, and the particle size is 5-10 μm; the calcium carbonate is calcite-type calcium carbonate, and the particle size is 1-2 μm; the composition of the strontium borate glass powder is SrO: 15-20%, B2O3: 20-25%, SiO2: 50-55%, and the particle size is 10-15 μm; the yttrium stabilized zirconia is tetragonal phase ZrO2 doped with Y2O3, and the doping molar amount of Y2O3 is 3%; the particle size of the hydroxyapatite nanorod is 20-50 nm, and the aspect ratio is 5-10:1.

[0075] Example 3

[0076] An anti-skid and anti-fouling glazed tile, which is different from that of Example 1 only in that the composition of the glaze layer is slightly different.

[0077] The glaze layer comprises, in terms of weight fraction:

[0078] 50 parts of quartz sand, 12 parts of calcined magnesia, 15 parts of magnesium aluminate spinel, 15 parts of calcium carbonate, 20 parts of strontium borate glass powder, 5 parts of yttrium stabilized zirconia and 3 parts of hydroxyapatite nanorod.

[0079] The particle size of the quartz sand is 40-50 μm, and the SiO2 content is ≥99.5%; the calcined magnesia is magnesia sintered at 900 ℃, the active MgO is ≥95%, and the particle size is 10-20 μm; the composition of the magnesium aluminate spinel is Al2O3: 70-75 wt%, MgO: 25-30 wt%, and the particle size is 5-10 μm; the calcium carbonate is calcite-type calcium carbonate, and the particle size is 1-2 μm; the composition of the strontium borate glass powder is SrO: 15-20%, B2O3: 20-25%, SiO2: 50-55%, and the particle size is 10-15 μm; the yttrium stabilized zirconia is tetragonal phase ZrO2 doped with Y2O3, and the doping molar amount of Y2O3 is 3%; the particle size of the hydroxyapatite nanorod is 20-50 nm, and the aspect ratio is 5-10:1.

[0080] Example 4

[0081] A slip-resistant and stain-resistant glazed tile, which is different from example 1 only in that the composition of the slip-resistant and stain-resistant layer is slightly different.

[0082] The slip-resistant and stain-resistant layer comprises, by weight fraction:

[0083] 100 parts of fluorosilicon resin, 5 parts of coated nanowire material, 0.3 parts of defoaming agent, 0.2 parts of leveling agent and 30 parts of solvent.

[0084] The fluorosilicon resin is fluorosilicon resin HLR-Si, the fluorine content is ≥26%; the defoaming agent is BYK-077; the leveling agent is BYK-331; and the solvent is butyl acetate.

[0085] The preparation method of the coated nanowire material comprises:

[0086] S1, weigh 1.8g vanadium pentoxide and 2.2g oxalic acid into 100mL deionized water, stir at 40℃ for 2-3h, and obtain a mixed solution A; weigh 0.06g tungstic acid into 0.7g hydrogen peroxide, stir thoroughly, and obtain a mixed solution B; drop the mixed solution B into the mixed solution A, pour into a reaction kettle, and heat and stir at 200℃ for 18h, then filter, wash and dry after the reaction is completed, and obtain tungsten-doped vanadium dioxide nanowires W-VO2 nanowires;

[0087] S2, dissolve 1.6g eugenol into 15mL tetrahydrofuran, introduce nitrogen as a protective gas, add 2.1g coupling agent KH-901 (3-isocyanate propyl trimethoxysilane), stir thoroughly, then add a catalyst dibutyltin dilaurate, the amount of which is 3% of the mass of eugenol, heat to 50℃, and heat and stir for 4h, then remove the solvent under reduced pressure after the reaction is completed, and obtain eugenol-modified silane;

[0088] S3, dissolve 0.1g coupling agent KH-580 (γ-mercapto propyl triethoxysilane) into 15mL 70wt% ethanol solution, add 1g W-VO2 nanowires with a particle size of 150-200nm, disperse thoroughly, and reflux and stir at 60℃ for 4h, then filter, wash and dry, and obtain mercapto W-VO2 nanowires;

[0089] S4, weigh 1g eugenol-modified silane and 2g mercapto W-VO2 nanowires into 15mL tetrahydrofuran, disperse uniformly at room temperature, add a photoinitiator 1173, the amount of which is 5% of the mass of eugenol-modified silane, irradiate with 365nm ultraviolet light under the protection of nitrogen and stir for 1h, centrifugally collect the solid, wash with ethanol for three times, and dry, and obtain coated nanowire material.

[0090] Example 5

[0091] A slip-resistant and stain-resistant glazed tile, which is different from that of Example 1 only in that the composition of the slip-resistant and stain-resistant layer is slightly different.

[0092] The slip-resistant and stain-resistant layer comprises, by weight fraction:

[0093] 100 parts of fluorosilicon resin, 5 parts of coated nanowire material, 0.3 parts of defoaming agent, 0.2 parts of leveling agent and 30 parts of solvent.

[0094] The fluorosilicon resin is fluorosilicon resin HLR-Si, the fluorine content is ≥26%; the defoaming agent is BYK-141; the leveling agent is BYK-378; and the solvent is propylene glycol methyl ether acetate.

[0095] The preparation method of the coated nanowire material comprises:

[0096] S1, weigh 1.8g of vanadium pentoxide and 2.5g of oxalic acid into 200mL of deionized water, stir at 50℃ for 3h, and obtain a mixed solution A; weigh 0.1g of tungstic acid into 1g of hydrogen peroxide, stir thoroughly, and obtain a mixed solution B; add the mixed solution B dropwise into the mixed solution A, pour into a reaction kettle, and heat at 240℃ for 36h, then filter, wash and dry after the reaction is completed, and obtain tungsten-doped vanadium dioxide nanowires W-VO2 nanowires;

[0097] S2, weigh 1.6g of eugenol into 25mL of tetrahydrofuran, introduce nitrogen as a protective gas, add 2.3g of coupling agent KH-901 (3-isocyanate propyl trimethoxysilane), stir thoroughly, then add a catalyst dibutyltin dilaurate, the amount is 8% of the mass of eugenol, heat to 60℃, and heat and stir for 8h, then remove the solvent under reduced pressure after the reaction is completed, and obtain eugenol-modified silane;

[0098] S3, weigh 0.3g of coupling agent KH-580 (γ-mercapto propyl triethoxysilane) into 25mL of 80wt% ethanol solution, add 1g of W-VO2 nanowires with a particle size of 150-200nm, disperse thoroughly, then reflux and stir at 70℃ for 10h, and filter, wash and dry to obtain mercapto W-VO2 nanowires;

[0099] S4, 1 g of eugenol-modified silane and 3 g of thiolated W-VO2 nanowires were weighed into 25 mL of tetrahydrofuran, and were uniformly dispersed at room temperature. A photoinitiator 1173 was added in an amount of 10% of the mass of the eugenol-modified silane, and the reaction was carried out under the irradiation of ultraviolet light of 365 nm and stirring for 3 h under the protection of nitrogen. The solid was collected by centrifugation, washed with ethanol three times, and dried to obtain a coated nanowire material.

[0100] Comparative Example 1

[0101] A slip-resistant and stain-resistant glazed tile, which is different from Example 1 only in that the components of the slip-resistant and stain-resistant layer are slightly different. In the comparative example, the coated nanowire material of the slip-resistant and stain-resistant layer is replaced by thiolated W-VO2 nanowires (prepared in the same way as in Example 1), and the other components and preparation methods remain unchanged.

[0102] The slip-resistant and stain-resistant layer comprises, by weight fraction:

[0103] 100 parts of fluorosilicon resin, 8 parts of thiolated W-VO2 nanowires, 0.5 parts of defoaming agent, 0.4 parts of leveling agent, and 40 parts of solvent.

[0104] Comparative Example 2

[0105] A slip-resistant and stain-resistant glazed tile, which is different from Example 1 only in that the components of the slip-resistant and stain-resistant layer are slightly different. In the comparative example, the preparation method of the coated nanowire material is different from that of Example 1, and the other components and preparation methods remain unchanged.

[0106] The slip-resistant and stain-resistant layer comprises, by weight fraction:

[0107] 100 parts of fluorosilicon resin, 8 parts of thiolated W-VO2 nanowires, 0.5 parts of defoaming agent, 0.4 parts of leveling agent, and 40 parts of solvent.

[0108] The preparation method of the coated nanowire material comprises:

[0109] S1, thiolated W-VO2 nanowires were prepared (the same as in Example 1);

[0110] S2, 1 g of eugenol and 2.5 g of thiolated W-VO2 nanowires were weighed into 20 mL of tetrahydrofuran, and were uniformly dispersed at room temperature. A photoinitiator 1173 was added in an amount of 8% of the mass of the eugenol, and the reaction was carried out under the irradiation of ultraviolet light of 365 nm and stirring for 2 h under the protection of nitrogen. The solid was collected by centrifugation, washed with ethanol three times, and dried to obtain a coated nanowire material.

[0111] In order to more clearly illustrate the content of the present application, the performance of the anti-slip and anti-fouling layer prepared for Example 1, Comparative Example 1 and Comparative Example 2 was detected, the detection method of wet-state static friction coefficient referred to GB / T 9263-2020 (block method), the detection method of water contact angle referred to ISO 27448 (sessile drop method), the detection method of breaking strength referred to GB / T5210-2006 (adhesion breaking strength with glaze layer), the detection method of stain resistance grade referred to GB / T 9780-2013 (treated with three types of pollutants of soy sauce, coffee and red wine for 24 h), and the detection method of self-cleaning efficiency referred to ISO 27448 (UV light irradiation for 2 h, methylene blue degradation rate).

[0112] The results are shown in the following table:

[0113] Table 1 Performance of different anti-slip and anti-fouling layers

[0114] Example 1 Comparative Example 1 Comparative Example 2 Wet-state friction coefficient 0.83 0.61 0.70 Contact angle with water (°) 159 104 133 Breaking strength (MPa) 12.7 8.1 10.2 Stain resistance grade (grade) 5 3 4 Wear resistance (turns) 2200 890 1310 Self-cleaning efficiency 98.7 44.8 73.2

[0115] As can be seen from Table 1, the anti-slip and anti-fouling layer prepared in Example 1 has higher anti-slip and anti-fouling properties, in addition, has higher bonding strength with the glaze layer, more excellent wear resistance, and also has excellent self-cleaning property. Compared with Example 1, the performance of Comparative Example 1 is insufficient, which indicates the necessity of surface coating of W-VO2 nanowires, and the performance after coating has a more obvious improvement; the performance of Comparative Example 2 is obviously better than that of Comparative Example 1, but slightly weaker than that of Example 1, which indicates that eugenol-based modified silane is better than pure eugenol in improving various aspects of the system.

[0116] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms should not be understood as necessarily referring to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in the present specification.

[0117] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present application.

Claims

1. A non-slip and stain-resistant glazed tile, characterized in that, From top to bottom, it includes an anti-slip and anti-fouling layer, a glaze layer, and a ceramic tile body; wherein, the glaze layer, calculated by weight, comprises: 40-50 parts quartz sand, 6-12 parts calcined magnesium oxide, 10-15 parts magnesium aluminum spinel, 7-15 parts calcium carbonate, 10-20 parts strontium boron glass powder, 2-5 parts yttrium stabilized zirconium oxide and 1-3 parts hydroxyapatite nanorods; The anti-slip and anti-fouling layer, calculated by weight, comprises: 100 parts fluorosilicone resin, 5-10 parts coated nanowire material, 0.3-0.8 parts defoamer, 0.2-0.6 parts leveling agent and 30-50 parts solvent.

2. The anti-slip and stain-resistant glazed tile according to claim 1, characterized in that, The defoamer is BYK-077 or BYK-141; the leveling agent is BYK-331 or BYK-378.

3. The anti-slip and stain-resistant glazed tile according to claim 1, characterized in that, The solvent is at least one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, toluene, and xylene.

4. The anti-slip and stain-resistant glazed tile according to claim 1, characterized in that, The preparation method of the coated nanowire material includes: S1. Weigh eugenol and dissolve it in tetrahydrofuran. Purge with nitrogen as a protective gas, add coupling agent KH-901, stir thoroughly, then add catalyst, heat to 50-60℃, keep warm and stir for 4-8 hours. After the reaction is complete, remove the solvent under reduced pressure to obtain eugenol-modified silane. S2. Weigh out coupling agent KH-580 and dissolve it in ethanol solution. Add tungsten-doped vanadium dioxide nanowires and disperse them thoroughly. Then, reflux and stir at 60-70℃ for 4-10 hours. Filter, wash and dry to obtain mercapto-modified W-VO2 nanowires. S3. Weigh eugenol-modified silane and mercapto-modified W-VO2 nanowires and add them to tetrahydrofuran. Disperse them thoroughly and evenly at room temperature. Add a photoinitiator, irradiate with ultraviolet light and stir for 1-3 hours. Collect the solid by centrifugation, wash it three times with ethanol, and dry it to obtain the coated nanowire material.

5. The anti-slip and stain-resistant glazed tile according to claim 4, characterized in that, In S1, the coupling agent KH-901 is 3-isocyanate-propyltrimethoxysilane, and the ratio of eugenol, coupling agent KH-901 and tetrahydrofuran is 1.6g:(2.1-2.3)g:(15-25)mL; the catalyst is dibutyltin dilaurate, and the amount added is 3%-8% of the mass of eugenol.

6. The anti-slip and stain-resistant glazed tile according to claim 4, characterized in that, In S2, the ratio of tungsten-doped vanadium dioxide nanowires, coupling agent KH-580, and ethanol solution is 1g:(0.1-0.3)g:(15-25)mL.

7. The anti-slip and stain-resistant glazed tile according to claim 4, characterized in that, In S3, the ratio of eugenol-modified silane, mercapto-modified W-VO2 nanowires and tetrahydrofuran is 1g:(2-3)g:(15-25)mL; the initiator is photoinitiator 1173, and the amount of initiator added is 5%-10% of the mass of eugenol-modified silane.

8. The anti-slip and stain-resistant glazed tile according to claim 1, characterized in that, The method for preparing the tungsten-doped vanadium dioxide nanowires includes: Vanadium pentoxide and oxalic acid were weighed and added to deionized water. After stirring and mixing, a mixture A was obtained. Tungstic acid was weighed and added to hydrogen peroxide to obtain a mixture B. Mixture B was added dropwise to mixture A and poured into a reaction vessel. The mixture was kept at 200-240℃ and stirred for 18-36 hours. After the reaction was completed, the mixture was filtered, washed and dried to obtain tungsten-doped vanadium dioxide nanowires (W-VO2 nanowires).

9. The anti-slip and stain-resistant glazed tile according to claim 8, characterized in that, The ratio of vanadium pentoxide, oxalic acid, tungstic acid, hydrogen peroxide and deionized water is 1.8g:(2.2-2.5)g:(0.06-0.1)g:(0.7-1)g:(100-200)mL.

10. A method for preparing the anti-slip and stain-resistant glazed tile according to claim 1, comprising the following steps: (1) Weigh out quartz sand, calcined magnesium oxide, calcium carbonate and strontium boron glass powder and add them to a ball mill for ball milling to obtain a mixture; (2) Add magnesium aluminum spinel, yttrium stabilized zirconium oxide and hydroxyapatite nanorods to the mixture and stir evenly to obtain glaze; (3) Grind the surface of the ceramic tile blank and bake it until the moisture content is below 0.8%; (4) Apply the glaze evenly to the surface of the ceramic tile blank, first heat it to 250℃, keep it warm for 1-3 hours, then heat it to 1100-1150℃, keep it warm for 2-3 hours, and then cool it to room temperature in the furnace to obtain a ceramic tile with a glaze layer. (5) Weigh the components of the anti-slip and anti-fouling layer, mix them, and shear at high speed to obtain a uniform anti-slip and anti-fouling mixture; (6) Spray the anti-slip and anti-fouling mixture onto the surface of the ceramic tile with the glaze layer. After it is surface dry at room temperature, place it in an oven for step curing treatment: first heat it to 80℃ for 10-20 minutes, then heat it to 100℃ for 20-30 minutes, and then cool it to room temperature to complete the preparation.