High-efficiency anti-slip agent for ceramic tiles and preparation method thereof

Abstract

This invention relates to the field of ceramic tile surface treatment technology, specifically to a high-efficiency anti-slip agent for ceramic tiles and its preparation method. The invention provides a high-efficiency anti-slip agent for ceramic tiles, comprising component A and component B, which are individually packaged in a weight ratio of 1:(3~5). Component A consists of citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, dispersant, and deionized water; component B consists of dialdehyde chitosan, modified nano-silica, and deionized water. Applying the anti-slip agent prepared by this invention to the surface of ceramic tiles forms a hydrophobic anti-slip layer, significantly improving the surface roughness of the tile and substantially increasing the coefficient of friction. The hydrophobic anti-slip layer exhibits good wear resistance and effectively prolongs the anti-slip effect.

Description

Technical Field

[0001] This invention relates to the field of ceramic tile surface treatment technology, specifically to a high-efficiency anti-slip agent for ceramic tiles and its preparation method. Background Technology

[0002] Tiles are a common building material, made from clay, quartz sand, and other raw materials through processes such as ball milling, pressing, and high-temperature sintering, resulting in a high degree of hardness. With the continuous improvement of living standards, the use of tiles is increasing, especially in public places such as hospitals, schools, bathrooms, and shopping malls. However, smooth and hard surfaces pose inconvenience for vulnerable groups such as the elderly, children, the sick, the disabled, and pregnant women, leading to frequent falls and injuries, and even posing risks of disability and death. Floor slip resistance has become an issue that cannot be ignored in the field of public safety.

[0003] Therefore, anti-slip agents specifically developed for ceramic tile materials have emerged. Anti-slip agents are liquids that act on the surface of stone or hard ceramic tiles. Through a chemical reaction with the silicates in the tile, they form microporous structures invisible to the naked eye on the surface, thereby increasing the coefficient of friction between the shoe sole and the ground, achieving an anti-slip effect. Chinese patent CN201610442790.8 discloses an anti-slip agent for ceramic tiles, its preparation method, and its application. The anti-slip agent consists of component A and component B. Component A includes an organic or inorganic acid, a dispersant, and water; component B includes silicone oil, a silane coupling agent, a dispersant, an emulsifier, and water. This patent combines components A and B to enhance the friction of the ceramic tile surface and prevent slipping. However, the anti-slip and anti-fouling effects of this method are generally limited, and the anti-slip effect is not long-lasting, requiring further improvement. Summary of the Invention

[0004] The purpose of this invention is to provide a high-efficiency anti-slip agent for ceramic tiles and its preparation method, so as to solve the problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A high-efficiency anti-slip agent for ceramic tiles, comprising component A and component B.

[0007] Furthermore, component A comprises the following ingredients by weight percentage: 15-20% citric acid, 7-10% fluoride salt, 6-9% amino-modified silicone oil, 3-4% methyl silicone oil, 5-7% surfactant, 0.5-0.8% dispersant, and the balance being deionized water.

[0008] Furthermore, the fluoride salt is ammonium bifluoride or ammonium fluoride; the dispersant is one or more of diethylene glycol dimethyl ether, ethyl acetate, ethylene glycol ethyl ether, and triethylhexyl phosphoric acid; and the surfactant is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, stearic acid, sodium hexadecyl sulfate, and sodium octadecyl sulfate.

[0009] Furthermore, the preparation method of amino-modified silicone oil is as follows: hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 90~95℃ for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at the temperature for 30~40 minutes. Then, n-propanol is added to end-cap the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain amino-modified silicone oil.

[0010] Furthermore, the molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:1.

[0011] Furthermore, the hydrogen content of the hydrogen-containing silicone oil is 1.2~1.6% by mass.

[0012] Furthermore, component B comprises the following ingredients: by weight percentage, 3-5% dialdehyde chitosan, 1-2% modified nano-silica, and the balance being deionized water.

[0013] Further, the preparation method of dialdehyde chitosan is as follows: chitosan is dissolved in an acetic acid solution with a mass concentration of 2-3%, and stirred at a speed of 1200-1500 r / min for 1-2 h. 0.3-0.5 mol / L sodium hydroxide solution is added to neutralize the acetic acid to obtain a chitosan solution. Sodium periodate solution is added to the chitosan solution, the temperature is raised to 40-60℃ and stirred in the dark for 10-15 min. Anhydrous ethanol is added to the reaction solution to produce a precipitate. The precipitate is separated by filtration, freeze-dried under vacuum, and then ground to obtain dialdehyde chitosan.

[0014] Furthermore, the weight ratio of sodium periodate to chitosan is 1:(3.5~4).

[0015] Furthermore, the modified silica is prepared by dispersing silica and KH-550 in ethanol, heating to 65-75℃ and stirring for 2-3 hours, washing until neutral and vacuum drying to obtain modified silica.

[0016] Furthermore, the weight ratio of silicon dioxide to KH-550 is 1:1.

[0017] Furthermore, the preparation method of the high-efficiency anti-slip agent is as follows:

[0018] Citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant were added to deionized water in sequence and stirred to obtain component A; dialdehyde chitosan and modified nano silica were added to deionized water in sequence and stirred to obtain component B; component A and component B were packaged separately, and the weight ratio of component A to component B was 1:(3~5).

[0019] Furthermore, in the application of the high-efficiency anti-slip agent to the anti-slip surface of ceramic tiles, the ceramic tile surface is first treated with component A, and then treated with component B.

[0020] Compared with existing technologies, the beneficial effects achieved by this invention are as follows: This invention provides a high-efficiency anti-slip agent for ceramic tiles and its preparation method. When using the high-efficiency anti-slip agent, components A and B are applied sequentially to the ceramic tile surface in a specific ratio to produce an anti-slip effect. Component A contains a fluoride salt and citric acid. The fluoride salt is one or more of ammonium fluoride and ammonium bifluoride. The fluoride salt can chemically react with the silicate components in the ceramic tile to generate silicon fluoride gas, forming a nanoscale microporous structure on the ceramic tile surface. Citric acid, as a corrosion inhibitor, can effectively control the corrosion rate of the fluoride salt on the ceramic tile surface, ensuring that the micropores on the ceramic tile surface have a uniform shape and size. Silicone oil is also added to component A, increasing the viscosity of the anti-slip agent solution, improving the adhesion performance of the anti-slip agent on the ceramic tile surface, and forming a hydrophobic film layer on the ceramic tile surface, achieving anti-fouling and anti-slip effects.

[0021] Component B of this invention incorporates dialdehyde chitosan and modified nano-silica. The dialdehyde chitosan is obtained by modifying chitosan with sodium periodate, resulting in better water solubility. The nano-silica, after modification with KH550, exhibits better dispersibility in water. When the dialdehyde chitosan and modified nano-silica are dispersed in water, the aldehyde groups in the dialdehyde chitosan react with the amino groups on the surface of the modified nano-silica, resulting in a grafting reaction on the nano-silica surface and further improving its dispersibility. When component B is coated onto the ceramic surface treated with component A, the unreacted aldehyde groups in the dialdehyde chitosan, grafted onto the nano-silica surface, react with the amino groups on the amino-modified silicone oil, further cross-linking with the hydrophobic film layer on the tile surface to form a stronger nano-silica layer. The nano-silica, along with the nanopores formed by the corrosion of the tile surface by fluoride salts and citric acid, synergistically increases the surface roughness of the tile, improving its anti-slip effect. In addition, because the nano-silica layer has higher wear resistance, the anti-slip coating will not wear out or fail due to friction between the sole and the ground or cleaning in a short period of time, so the anti-slip effect is more durable than existing technologies. Attached Figure Description

[0022] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0023] Figure 1 This is the reaction equation for the amino-modified silicone oil of the present invention. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] The materials used in this invention and their sources are as follows: the fluoride salt is ammonium fluoride, the surfactant is sodium dodecylbenzenesulfonate, and the dispersant is ethylene glycol ethyl ether, all of which are from Sinopharm Chemical Reagent Co., Ltd.; the hydrogen-containing silicone oil is from Jiashan Jiangnan Textile Materials Co., Ltd., model JF-M22-26; the chitosan (degree of deacetylation ≥85%, industrial grade) is from Qingdao Bozhi Huili Biotechnology Co., Ltd.; the nano silica is from Xi'an Bona Materials Technology Co., Ltd., with an average particle size of 50nm; and other materials, unless otherwise specified, are from commercially available products.

[0026] Example 1: A method for preparing a high-efficiency anti-slip agent for ceramic tiles, comprising the following steps:

[0027] Step 1:

[0028] Citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant were added to deionized water in sequence and stirred to obtain component A. By weight percentage, the components were 15% citric acid, 7% fluoride salt, 6% amino-modified silicone oil, 3% methyl silicone oil, 5% surfactant, 0.5% dispersant, and the remainder was deionized water.

[0029] The preparation method of the amino-modified silicone oil is as follows: Hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 90°C for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at this temperature for 30 minutes. Then, n-propanol is added to seal the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain the amino-modified silicone oil. The molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:1, and the hydrogen content of the hydrogen-containing silicone oil is 1.2%.

[0030] Step 2: Add the dialdehyde chitosan and modified nano silica to deionized water in sequence and stir to obtain component B; by weight percentage, 3% dialdehyde chitosan, 1% modified nano silica, and the remainder is deionized water.

[0031] The preparation method of the dialdehyde chitosan is as follows: chitosan is dissolved in a 2% (w / w) acetic acid solution, stirred at 1200 r / min for 1 h, and then 0.3 mol / L sodium hydroxide solution is added to neutralize the acetic acid to obtain a chitosan solution; sodium periodate solution is added to the chitosan solution, the temperature is raised to 40℃ and stirred in the dark for 10 min, then anhydrous ethanol is added to the reaction solution to produce a precipitate, the precipitate is separated by filtration, and then freeze-dried under vacuum and ground to obtain dialdehyde chitosan; wherein the weight ratio of sodium periodate to chitosan is 1:3.5;

[0032] The modified nano-silica is prepared as follows: silica and KH-550 are dispersed in ethanol, heated to 65°C and stirred for 2 hours, washed until neutral and dried under vacuum to obtain modified silica; wherein the weight ratio of silica to KH-550 is 1:1.

[0033] Step 3: Package component A and component B separately, and mix component A and component B in a weight ratio of 1:3 to obtain a high-efficiency anti-slip agent for ceramic tiles.

[0034] Example 2: A method for preparing a high-efficiency anti-slip agent for ceramic tiles, comprising the following steps:

[0035] Step 1:

[0036] Citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant were added to deionized water in sequence and stirred to obtain component A. By weight percentage, the components were 17% citric acid, 8% fluoride salt, 7% amino-modified silicone oil, 3.5% methyl silicone oil, 6% surfactant, 0.7% dispersant, and the remainder was deionized water.

[0037] The preparation method of the amino-modified silicone oil is as follows: Hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 93°C for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at this temperature for 35 minutes. Then, n-propanol is added to seal the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain the amino-modified silicone oil. The molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:1, and the hydrogen content of the hydrogen-containing silicone oil is 1.3%.

[0038] Step 2: Add the dialdehyde chitosan and modified nano silica to deionized water in sequence and stir to obtain component B; by weight percentage, 4% dialdehyde chitosan, 1.5% modified nano silica, and the remainder is deionized water.

[0039] The preparation method of the dialdehyde chitosan is as follows: chitosan is dissolved in a 2.5% acetic acid solution and stirred at 1400 r / min for 1.5 h. A 0.4 mol / L sodium hydroxide solution is added to neutralize the acetic acid, resulting in a chitosan solution. Sodium periodate solution is added to the chitosan solution, and the mixture is heated to 50℃ and stirred in the dark for 12 min. Anhydrous ethanol is then added to the reaction solution to produce a precipitate. The precipitate is separated by filtration, freeze-dried under vacuum, and then ground to obtain dialdehyde chitosan. The weight ratio of sodium periodate to chitosan is 1:3.8.

[0040] The modified nano-silica is prepared as follows: silica and KH-550 are dispersed in ethanol, heated to 70°C and stirred for 2.5 h, washed until neutral and vacuum dried to obtain modified silica; wherein the weight ratio of silica to KH-550 is 1:1.

[0041] Step 3: Package component A and component B separately, and mix component A and component B in a weight ratio of 1:4 to obtain a high-efficiency anti-slip agent for ceramic tiles.

[0042] Example 3: A method for preparing a high-efficiency anti-slip agent for ceramic tiles, comprising the following steps:

[0043] Step 1:

[0044] Citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant were added to deionized water in sequence and stirred to obtain component A; by weight percentage, 20% citric acid, 10% fluoride salt, 9% amino-modified silicone oil, 4% methyl silicone oil, 7% surfactant, 0.8% dispersant, and the balance being deionized water;

[0045] The preparation method of the amino-modified silicone oil is as follows: Hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 95°C for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at this temperature for 40 minutes. Then, n-propanol is added to seal the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain the amino-modified silicone oil. The molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:1, and the hydrogen content of the hydrogen-containing silicone oil is 1.58%.

[0046] Step 2: Add the dialdehyde chitosan and modified nano silica to deionized water in sequence and stir to obtain component B; by weight percentage, 5% dialdehyde chitosan, 2% modified nano silica, and the remainder is deionized water.

[0047] The preparation method of the dialdehyde chitosan is as follows: chitosan is dissolved in a 3% acetic acid solution, stirred at 1500 r / min for 2 h, and then 0.5 mol / L sodium hydroxide solution is added to neutralize the acetic acid to obtain a chitosan solution; sodium periodate solution is added to the chitosan solution, the temperature is raised to 60℃ and stirred in the dark for 15 min, then anhydrous ethanol is added to the reaction solution to produce a precipitate, the precipitate is separated by filtration, and then freeze-dried under vacuum and ground to obtain dialdehyde chitosan; wherein the weight ratio of sodium periodate to chitosan is 1:4;

[0048] The modified nano-silica is prepared as follows: silica and KH-550 are dispersed in ethanol, heated to 75°C and stirred for 3 hours, washed until neutral and dried under vacuum to obtain modified silica; wherein the weight ratio of silica to KH-550 is 1:1.

[0049] Step 3: Package component A and component B separately, and mix component A and component B in a weight ratio of 1:5 to obtain a high-efficiency anti-slip agent for ceramic tiles.

[0050] Comparative Example 1: No modification was made to the hydrogen-containing silicone oil, and the other parameters were the same as in Example 1.

[0051] Step 1:

[0052] Citric acid, fluoride salt, hydrogen-containing silicone oil, methyl silicone oil, surfactant, and dispersant were added sequentially to deionized water and stirred to obtain component A. By weight percentage, component A consisted of 15% citric acid, 7% fluoride salt, 6% hydrogen-containing silicone oil, 3% methyl silicone oil, 5% surfactant, 0.5% dispersant, with the remainder being deionized water. The hydrogen content of the hydrogen-containing silicone oil was 1.2%.

[0053] Step 2: Add the dialdehyde chitosan and modified nano silica to deionized water in sequence and stir to obtain component B; by weight percentage, 3% dialdehyde chitosan, 1% modified nano silica, and the remainder is deionized water.

[0054] The preparation method of the dialdehyde chitosan is as follows: chitosan is dissolved in a 2% (w / w) acetic acid solution, stirred at 1200 r / min for 1 h, and then 0.3 mol / L sodium hydroxide solution is added to neutralize the acetic acid to obtain a chitosan solution; sodium periodate solution is added to the chitosan solution, the temperature is raised to 40℃ and stirred in the dark for 10 min, then anhydrous ethanol is added to the reaction solution to produce a precipitate, the precipitate is separated by filtration, and then freeze-dried under vacuum and ground to obtain dialdehyde chitosan; wherein the weight ratio of sodium periodate to chitosan is 1:3.5;

[0055] The modified nano-silica is prepared as follows: silica and KH-550 are dispersed in ethanol, heated to 65°C and stirred for 2 hours, washed until neutral and dried under vacuum to obtain modified silica; wherein the weight ratio of silica to KH-550 is 1:1.

[0056] Step 3: Package component A and component B separately, and mix component A and component B in a weight ratio of 1:3 to obtain a high-efficiency anti-slip agent for ceramic tiles.

[0057] Comparative Example 2: Carboxymethyl chitosan (Beijing Biolab Technology Co., Ltd., carboxylation degree ≥80%) was used instead of dialdehyde chitosan, and the other parameters were the same as in Example 2.

[0058] Step 1:

[0059] Citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant were added to deionized water in sequence and stirred to obtain component A. By weight percentage, the components were 17% citric acid, 8% fluoride salt, 7% amino-modified silicone oil, 3.5% methyl silicone oil, 6% surfactant, 0.7% dispersant, and the remainder was deionized water.

[0060] The preparation method of the amino-modified silicone oil is as follows: Hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 93°C for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at this temperature for 35 minutes. Then, n-propanol is added to seal the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain the amino-modified silicone oil. The molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:1, and the hydrogen content of the hydrogen-containing silicone oil is 1.3%.

[0061] Step 2: Add carboxymethyl chitosan and modified nano-silica to deionized water in sequence and stir to obtain component B; by weight percentage, 4% carboxymethyl chitosan, 1.5% modified nano-silica, and the remainder is deionized water;

[0062] The modified nano-silica is prepared as follows: silica and KH-550 are dispersed in ethanol, heated to 70°C and stirred for 2.5 h, washed until neutral and vacuum dried to obtain modified silica; wherein the weight ratio of silica to KH-550 is 1:1.

[0063] Step 3: Package component A and component B separately, and mix component A and component B in a weight ratio of 1:4 to obtain a high-efficiency anti-slip agent for ceramic tiles.

[0064] Comparative Example 3: No modification was made to the nano-silica, and the other parameters were the same as in Example 3.

[0065] Step 1:

[0066] Citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant were added to deionized water in sequence and stirred to obtain component A; by weight percentage, 20% citric acid, 10% fluoride salt, 9% amino-modified silicone oil, 4% methyl silicone oil, 7% surfactant, 0.8% dispersant, and the balance being deionized water;

[0067] The preparation method of the amino-modified silicone oil is as follows: Hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 95°C for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at this temperature for 40 minutes. Then, n-propanol is added to seal the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain the amino-modified silicone oil. The molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:1, and the hydrogen content of the hydrogen-containing silicone oil is 1.58%.

[0068] Step 2: Add dialdehyde chitosan and nano silica to deionized water in sequence and stir to obtain component B; by weight percentage, 5% dialdehyde chitosan, 2% nano silica, and the remainder is deionized water.

[0069] The preparation method of the dialdehyde chitosan is as follows: chitosan is dissolved in a 3% acetic acid solution, stirred at 1500 r / min for 2 h, and then 0.5 mol / L sodium hydroxide solution is added to neutralize the acetic acid to obtain a chitosan solution; sodium periodate solution is added to the chitosan solution, the temperature is raised to 60℃ and stirred in the dark for 15 min, then anhydrous ethanol is added to the reaction solution to produce a precipitate, the precipitate is separated by filtration, and then freeze-dried under vacuum and ground to obtain dialdehyde chitosan; wherein the weight ratio of sodium periodate to chitosan is 1:4;

[0070] Step 3: Package component A and component B separately, and mix component A and component B in a weight ratio of 1:5 to obtain a high-efficiency anti-slip agent for ceramic tiles.

[0071] Experiment: Tile samples (with the same surface friction coefficient) from the same batch were selected. These samples were Bib-type tiles as specified in standard GB / T4100-2015, with a size of 50cm × 50cm. The samples were divided into six groups, with three samples in each group, and were treated as follows:

[0072] Drying the sample: Wipe the surface of the tile sample treated with anti-slip agent dry and dry it to constant weight.

[0073] Wet sample: The tile sample treated with anti-slip agent was soaked in deionized water for 24 hours.

[0074] Apply soapy water sample: Weigh 2g of soap and dissolve it in 500g of deionized water to obtain soapy water. Apply the soapy water evenly to the surface of the tile sample after it has been treated with anti-slip agent.

[0075] Anti-slip performance test: Referring to standard JC / T 1050-2007, place the sample horizontally on the workbench. Place the slider assembly on the sample surface treated with anti-slip agent, and place a 200g weight on the slider assembly. Hook the tensile tester onto the ring head screw of the slider assembly, keeping the pull rod of the tensile tester parallel to the sample surface. Slowly pull the tensile tester until the slider assembly just moves, and record the reading of the tensile tester at this point. After the test, wash the sample surface with clean water, dry it, and then repeatedly wipe the tile surface with a canvas 50 times. Then, repeat the test using the method described above and record the corresponding data. Calculate the coefficient of friction according to the formula: μ=f max / N, where f max The reading of the force gauge is given when the slider assembly just begins to move, and N is the pressure exerted on the sample surface by the weight and the slider assembly. To ensure the accuracy of the test results, each group of samples was tested 5 times, and a random area on the tile surface was selected for each test. The maximum and minimum values ​​were removed, and the average value was taken as the final result. The experimental results are shown in Table 1.

[0076] Table 1. Test results of friction coefficient for each group of samples

[0077]

[0078] Conclusion: Data from Examples 1-3 show that the high-efficiency anti-slip agent prepared in this invention can effectively increase the coefficient of friction of ceramic tiles and improve the anti-slip effect. Even when the tiles are wet or have soapy water on the surface, the anti-slip agent maintains its good performance. In Comparative Examples 1-3, in Comparative Example 1, the hydrogen-containing silicone oil was not modified, and the nano-silica failed to react with the silicone oil to form a wear-resistant layer. In Comparative Example 2, the carboxymethyl chitosan used could not react with the amino-modified silicone oil and nano-silica, and therefore could not form a hydrophobic wear-resistant layer. In Comparative Example 3, the nano-silica was not modified; on the one hand, the nano-silica had poor dispersibility, and on the other hand, it could not react with the amino-modified silicone oil to form a wear-resistant hydrophobic layer. In Examples 1-3, however, because the amino-modified silicone oil, dialdehyde chitosan, and nano-silica reacted chemically to form an anti-slip layer, the canvas maintained a high coefficient of friction even after repeated wiping, indicating that the anti-slip layer had strong adhesion and good wear resistance on the ceramic tile surface.

[0079] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0080] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-efficiency anti-slip agent for ceramic tiles, comprising component A and component B, wherein the weight ratio of component A to component B is 1:(3~5), characterized in that: Component A It includes the following components by weight percentage: 15-20% citric acid, 7-10% fluoride salt, 6-9% amino-modified silicone oil, 3-4% methyl silicone oil, 5-7% surfactant, 0.5-0.8% dispersant, and the balance being deionized water; Component B includes the following ingredients: by weight percentage, 3-5% dialdehyde chitosan, 1-2% modified nano silica, and the balance being deionized water; The preparation method of the high-efficiency anti-slip agent includes the following steps: Step 1: Add citric acid, fluoride salt, amino-modified silicone oil, methyl silicone oil, surfactant, and dispersant to deionized water in sequence, and stir to obtain component A; Step 2: Add dialdehyde chitosan and modified nano-silica to deionized water in sequence and stir to obtain component B; Step 3: Package component A and component B separately, with a weight ratio of component A to component B of 1:(3~5). In component B, the modified nano-silica is prepared by dispersing silica and KH-550 in ethanol, heating to 65~75℃ and stirring for 2~3 hours, washing until neutral and vacuum drying to obtain modified silica. The application of the high-efficiency anti-slip agent is as follows: the surface of the tile is first treated with component A, and then treated with component B.

2. The high-efficiency anti-slip agent for ceramic tiles according to claim 1, characterized in that: In component A, the fluoride salt is ammonium bifluoride or ammonium fluoride; the dispersant is one or more of diethylene glycol dimethyl ether, ethyl acetate, ethylene glycol ethyl ether, and triethylhexyl phosphoric acid; and the surfactant is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, stearic acid, sodium hexadecyl sulfate, and sodium octadecyl sulfate.

3. The high-efficiency anti-slip agent for ceramic tiles according to claim 1, characterized in that: In component A, the preparation method of amino-modified silicone oil is as follows: hydrogen-containing silicone oil is dispersed in toluene, and 1-amino-10-undecene is added while stirring at 90~95℃ for 2 hours. After the 1-amino-10-undecene is completely added, the reaction is maintained at the temperature for 30~40 minutes. Then, n-propanol is added to end-cap the unreacted silane-hydrogen bonds. Impurities are removed by vacuum distillation to obtain amino-modified silicone oil. The hydrogen content of the hydrogen-containing silicone oil is 1.2~1.6%.

4. The high-efficiency anti-slip agent for ceramic tiles according to claim 3, characterized in that: The molar ratio of 1-amino-10-undecene to hydrogen in the hydrogen-containing silicone oil is 1:

1.

5. The high-efficiency anti-slip agent for ceramic tiles according to claim 1, characterized in that: In component B, the preparation method of dialdehyde chitosan is as follows: chitosan is dissolved in an acetic acid solution with a mass concentration of 2-3%, stirred at a speed of 1200-1500 r / min for 1-2 h, and then acetic acid is neutralized by adding 0.3-0.5 mol / L sodium hydroxide solution to obtain chitosan solution; Sodium periodate solution was added to the chitosan solution, the temperature was raised to 40-60℃ and stirred in the dark for 10-15 minutes. Then anhydrous ethanol was added to the reaction solution to produce a precipitate. The precipitate was separated by filtration, freeze-dried under vacuum and then ground to obtain dialdehyde chitosan.

6. The high-efficiency anti-slip agent for ceramic tiles according to claim 5, characterized in that: The weight ratio of sodium periodate to chitosan is 1:(3.5~4).

7. The high-efficiency anti-slip agent for ceramic tiles according to claim 1, characterized in that: In the preparation of modified nano-silica, the weight ratio of silica to KH-550 is 1:1.

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