A kind of stain-resistant long-lasting anti-skid agent and preparation method thereof

Abstract

The present invention discloses a stain-resistant, long-lasting anti-slip agent and a preparation method thereof. The anti-slip agent comprises, by weight, 10-15 parts of an organic acid, 5-10 parts of a fluoride salt, 0.5-2 parts of a surfactant, 0.5-1 parts of zirconium phosphate, 5-10 parts of a silane coupling agent, 0.2-0.5 parts of a defoaming agent, and 30-60 parts of water. The surfactant is a mixture of sodium dodecylbenzenesulfonate and dodecylethoxysulfobetaine in a mass ratio of 1:2-3. The formula of the present invention is gentle and can form uniform micro-nanoscale pores on the surface of floor tiles without compromising the glossiness of the tiles. Zirconium phosphate, as a filling material, can be distributed in the micro-nanoscale pores formed by the floor tiles where the anti-slip agent is applied, forming new friction points to increase friction. At the same time, zirconium phosphate and dodecylethoxysulfobetaine can also impart certain antibacterial properties to the floor tiles, enhancing their stain resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-skid agents, and in particular to a stain-resistant long-lasting anti-skid agent and a preparation method thereof. Background Art

[0002] As living standards improve, floor tiles are becoming an increasingly popular choice for decoration. However, their application has presented some challenges, such as slippage when exposed to water. Therefore, anti-slip treatment of floor tiles has become a hot topic of research. Compared to mechanical polishing of floor tiles, anti-slip agents have a wider range of applications and a relatively low impact on the tiles. Anti-slip agents effectively penetrate the pores of tiles and dissolve small amounts of silicon, coarsening the pores and forming numerous tiny, invisible micro- and nano-scale grooves on the surface. When the floor surface comes into contact with water, the pores fill with water. When the soles of feet or shoes pass over the surface, the water is squeezed out of the pores under pressure, creating a vacuum inside the pores. This creates a physical suction cup effect on the soles of the feet, significantly increasing the friction coefficient of the floor surface and reducing the risk of slips and falls when the tiles are wet. The anti-slip agent has a "wet-on-wet" effect, making the floor surface more slip-resistant than dry.

[0003] However, the anti-slip agents currently available on the market still have the disadvantage of weak penetration, resulting in a matte surface on the floor tiles after application. Some anti-slip agents with good stain resistance and brightness have also been reported. For example, CN109705811A discloses a safe, environmentally friendly, stain-resistant anti-slip agent and its preparation method. The anti-slip agent comprises, by weight, 0.1 to 15 parts of an organic acid; 10 to 40 parts of an inorganic acid; 10 to 30 parts of a fluoride salt; 5 to 20 parts of an additive; and 30 to 60 parts of water. The system formed by the organic acid, inorganic acid, additive, and fluoride salt cooperates with each other to form nanoscale pores of uniform size and depth on the floor tiles, thereby improving the anti-slip coefficient of the floor tiles without causing a matte finish. However, the fluoride salt in this anti-slip agent accounts for a relatively high proportion, and it easily forms hydrofluoric acid when reacting with strongly acidic inorganic acids. The vaporization of hydrofluoric acid may pose a threat to the health of workers. CN113388367A discloses an environmentally friendly, long-lasting anti-slip agent and its preparation method. The anti-slip agent comprises, by weight, 1-10 parts of rare earth oxide, 25-40 parts of diatomaceous earth, 1-5 parts of a nano-silver ion antibacterial agent, 15-35 parts of humic acid, 7-15 parts of a surfactant, 20-30 parts of a fluoride salt, 5-18 parts of silicone oil, 20-40 parts of a binder, and 30-45 parts of water. The synergistic effect of these ingredients forms an anti-slip film on the surface of floor tiles, improving the tiles' anti-slip properties. However, the film formed by this anti-slip agent on the tile surface is easily degraded, resulting in a short lifespan.

[0004] Therefore, it is still necessary to provide long-lasting, safe and environmentally friendly anti-slip agents. Summary of the Invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a long-lasting anti-fouling anti-slip agent, which comprises, by weight,

[0006] 10-15 parts of organic acid, 5-10 parts of fluoride salt, 0.5-2 parts of surfactant, 0.5-1 part of zirconium phosphate, 5-10 parts of silane coupling agent, 0.2-0.5 parts of defoaming agent, 30-60 parts of water;

[0007] The surfactant is prepared by mixing sodium dodecylbenzenesulfonate and dodecylethoxysulfobetaine in a mass ratio of 1:1.5-3.

[0008] The formula of the anti-slip agent is generally acidic and supplemented with fluorine salts to react with silicates in the pores of the tiles, thereby forming micro-nanoscale pores. The formula of the present invention adds a surfactant and a silane coupling agent, and optimizes the ratio of the anionic surfactant sodium dodecylbenzenesulfonate and the amphoteric surfactant dodecylethoxysulfobetaine to reduce the tension of the anti-slip agent and make it easier to react with the tile surface. Zirconium phosphate has a unique layered structure and excellent adsorption capacity. It is insoluble in water and common organic solvents, has strong chemical stability, and can withstand strong acids and alkalis. Therefore, zirconium phosphate is very suitable as a filling material that can be distributed in the micro-nanoscale pores formed by the tiles on which the anti-slip agent is applied, forming new friction points to increase friction.

[0009] In addition, zirconium phosphate can also exert an antibacterial effect through ion dissolution. The zirconium phosphate filled in the pores can not only exert its own effect, but the dodecylethoxysulfobetaine in the surfactant of the present invention also has good bactericidal properties. The zirconium phosphate can also absorb the dodecylethoxysulfobetaine and slowly release it, thereby enhancing and prolonging the antibacterial effect. This makes the anti-slip agent not only have good anti-slip properties but also have long-lasting antibacterial properties.

[0010] Furthermore, the zirconium phosphate is in the form of flakes with an average particle size of 0.8 to 1.5 μm.

[0011] The present invention adopts the relatively mature fluorine coordination method to prepare zirconium phosphate, using hydrofluoric acid to react with soluble zirconium salt to form a zirconium complex [ZrF6 2- The complex decomposes into zirconium ions, which then react with phosphoric acid to form zirconium phosphate precipitates. The present invention further wet-ball-mills the zirconium phosphate precipitates and calcines them to increase their crystallinity.

[0012] Furthermore, the preparation method of the zirconium phosphate comprises:

[0013] Dissolve a soluble zirconium salt in water, then add 37 wt % concentrated hydrochloric acid, 40 wt % hydrofluoric acid, and 85 wt % phosphoric acid, stirring and reacting to obtain an intermediate;

[0014] The intermediate is wet ball-milled to collect insoluble matter, and the insoluble matter is calcined to obtain zirconium phosphate;

[0015] The ratio of soluble zirconium salt, water, concentrated hydrochloric acid, hydrofluoric acid and phosphoric acid is 5~10g:80~100mL:5~10mL:5~10mL:30~50mL.

[0016] Furthermore, the wet ball milling process involves mixing the intermediate with an ethanol aqueous solution at a mass ratio of 2-5:50-100, followed by ball milling at a speed of 200-500 rpm for 1-3 hours. The present invention does not limit the choice of soluble zirconium salt; for example, it can be at least one of zirconyl sulfate tetrahydrate, zirconyl oxychloride octahydrate, and the like.

[0017] Conventional ball milling still cannot effectively separate the lamellar zirconium phosphate, and a large amount of agglomeration and lamination still exist. Therefore, tetraethylammonium hydroxide is added during ball milling, which has a certain intercalation effect and can reduce agglomeration and increase the specific surface area without affecting the lamellar structure of zirconium phosphate.

[0018] Furthermore, tetraethylammonium hydroxide in an amount of 0.1 to 0.3 times the mass of the intermediate is added during wet ball milling.

[0019] The concentration of the ethanol aqueous solution used in the wet ball milling in the present invention does not need to be strictly limited, and can be 5 wt % to 95 wt % by way of example.

[0020] Furthermore, the organic acid includes at least one of oxalic acid, citric acid, tartaric acid, and malic acid.

[0021] Furthermore, the fluoride salt includes at least one of sodium fluoride, potassium fluoride, ammonium fluoride, sodium bifluoride, potassium bifluoride, and ammonium bifluoride.

[0022] Furthermore, the silane coupling agent includes at least one of KH550, KH560, KH570, KH580, KH602, and KH792.

[0023] Furthermore, the defoaming agent is at least one of a higher alcohol defoaming agent and a silicone defoaming agent.

[0024] Further preferably, the anti-fouling and long-lasting anti-slip agent further comprises 1 to 5 parts by weight of 1,4-bis(2',3'-epoxypropyl)perfluorobutane.

[0025] The present invention also provides a method for preparing the above-mentioned stain-resistant and long-lasting anti-slip agent, comprising:

[0026] The fluoride salt, surfactant, zirconium phosphate and water are stirred and mixed, and then organic acid, silane coupling agent and defoaming agent are added, and stirring is continued to obtain a stain-resistant and long-lasting anti-slip agent.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The formula of the present invention is gentle and can form uniform micro-nano pores on the surface of the floor tiles without compromising the glossiness of the floor tiles. Zirconium phosphate, as a filling material, can be distributed in the micro-nano pores formed by the floor tiles coated with the anti-slip agent, forming new friction points to increase friction. At the same time, zirconium phosphate and dodecylethoxysulfobetaine can also impart certain antibacterial properties to the floor tiles, thereby enhancing the anti-fouling properties of the floor tiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 The microstructure of the zirconium phosphate prepared in Example 1 is shown;

[0031] Figure 2 The microstructure of the zirconium phosphate prepared in Example 2 is shown. DETAILED DESCRIPTION

[0032] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to form one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed in the present invention.

[0033] Some of the raw materials used in the examples and comparative examples of the present invention are described as follows:

[0034] Dodecylethoxysulfobetaine, model BS-12, was purchased from Jining Huipeng Chemical Co., Ltd.

[0035] Tetraethylammonium hydroxide (TEAH) was purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0036] Higher alcohol defoamer, model LC-WQ403, was purchased from Tianjin Lichuang Environmental Protection Technology Co., Ltd.

[0037] All other raw materials not mentioned are commonly used in the art. The above description is merely provided to illustrate the present invention and is not to be construed as a strict limitation of the present invention. Those skilled in the art can purchase or prepare the same or similar raw materials commercially. These details will not be further detailed in the examples.

[0038] The following will be combined with specific embodiments of the present invention to clearly and completely describe the technical solutions in 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 ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0039] Example 1

[0040] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0041] S1, weighed 100g of oxalic acid, 80g of ammonium fluoride, 2.5g of sodium dodecylbenzenesulfonate, 7.5g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0042] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0043] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0044] Wherein, the preparation method of zirconium phosphate is:

[0045] T1. Dissolve 100 g of zirconium oxychloride octahydrate in 1000 mL of water at 300 rpm, then add 80 mL of 37 wt % concentrated hydrochloric acid, 75 mL of 40 wt % hydrofluoric acid, and 400 mL of 85 wt % phosphoric acid, maintain the reaction speed at 300 rpm for 100 h, then filter, wash three times with water and ethanol, and transfer to a constant temperature oven at 120 ° C. and dry for 8 h to obtain an intermediate;

[0046] T2. 50 g of the intermediate was mixed with 1000 g of a 50 wt% ethanol aqueous solution and wet ball milled at a ball speed of 350 rpm for 2 h. The mixture was then filtered, washed three times with water and ethanol, and dried in a constant temperature oven at 120 ° C for 8 h. The mixture was then calcined in a nitrogen atmosphere muffle furnace at 450 ° C for 2 h to obtain zirconium phosphate.

[0047] Example 2

[0048] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0049] S1, weighed 100g of oxalic acid, 80g of ammonium fluoride, 4g of sodium dodecylbenzenesulfonate, 6g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0050] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0051] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0052] Wherein, the preparation method of zirconium phosphate is:

[0053] T1. Dissolve 100 g of zirconium oxychloride octahydrate in 1000 mL of water at 300 rpm, then add 80 mL of 37 wt % concentrated hydrochloric acid, 75 mL of 40 wt % hydrofluoric acid, and 400 mL of 85 wt % phosphoric acid, maintain the reaction speed at 300 rpm for 100 h, then filter, wash three times with water and ethanol, and transfer to a constant temperature oven at 120 ° C. and dry for 8 h to obtain an intermediate;

[0054] T2. 50 g of the intermediate, 10 g of tetraethylammonium hydroxide and 1000 g of a 50 wt% ethanol aqueous solution were mixed and wet ball milled at a ball speed of 350 rpm for 2 h. The mixture was then filtered, washed three times with water and ethanol, and transferred to a constant temperature oven at 120 ° C. and dried for 8 h. It was then placed in a nitrogen atmosphere muffle furnace at 450 ° C. and calcined for 2 h to obtain zirconium phosphate.

[0055] Example 3

[0056] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0057] S1, weighed 100g of oxalic acid, 80g of ammonium fluoride, 3.34g of sodium dodecylbenzenesulfonate, 6.64g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0058] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0059] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0060] The preparation method of zirconium phosphate is the same as that in Example 2.

[0061] Example 4

[0062] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0063] S1, weighed 100g of oxalic acid, 80g of ammonium fluoride, 2.5g of sodium dodecylbenzenesulfonate, 7.5g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0064] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0065] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0066] The preparation method of zirconium phosphate is the same as that in Example 2.

[0067] Example 5

[0068] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0069] S1. Weigh 100 g of oxalic acid, 80 g of ammonium fluoride, 2.5 g of sodium dodecylbenzenesulfonate, 7.5 g of dodecylethoxysulfobetaine, 8 g of zirconium phosphate, 70 g of KH580, 3 g of a higher alcohol defoamer, 2 g of 1,4-bis(2',3'-epoxypropyl)perfluorobutane, and 498 g of water;

[0070] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0071] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0072] The preparation method of zirconium phosphate is the same as that in Example 2.

[0073] Comparative Example 1

[0074] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0075] S1, weighed 100g of oxalic acid, 80g of ammonium fluoride, 2g of sodium dodecylbenzenesulfonate, 8g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0076] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0077] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0078] The preparation method of zirconium phosphate is the same as that in Example 2.

[0079] Comparative Example 2

[0080] A method for preparing an anti-slip agent comprises the following steps:

[0081] S1, weighed 100g of oxalic acid, 80g of ammonium fluoride, 2.5g of sodium dodecylbenzenesulfonate, 7.5g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0082] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0083] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0084] Wherein, the preparation method of zirconium phosphate is:

[0085] T1. Dissolve 100 g of zirconium oxychloride octahydrate in 1000 mL of water at 300 rpm, then add 80 mL of 37 wt % concentrated hydrochloric acid, 75 mL of 40 wt % hydrofluoric acid, and 400 mL of 85 wt % phosphoric acid, maintain the reaction speed at 300 rpm for 100 h, then filter, wash three times with water and ethanol, and transfer to a constant temperature oven at 120 ° C. and dry for 8 h to obtain an intermediate;

[0086] T2. Calcine 50 g of the intermediate in a muffle furnace at 450° C. for 2 h in a nitrogen atmosphere to obtain zirconium phosphate.

[0087] Comparative Example 3

[0088] A method for preparing a stain-resistant and long-lasting anti-slip agent comprises the following steps:

[0089] S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 10g of sodium dodecylbenzenesulfonate, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0090] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0091] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0092] The preparation method of zirconium phosphate is the same as that in Example 2.

[0093] Comparative Example 4

[0094] A method for preparing a stain-resistant and long-lasting anti-slip agent, comprising the following steps:

[0095] S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 10g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of higher alcohol defoamer, and 500g of water;

[0096] S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture;

[0097] S3. Add oxalic acid, KH580, and higher alcohol defoamer to the mixture, and stir at 500 rpm for 15 minutes to obtain a stain-resistant and long-lasting anti-slip agent.

[0098] The preparation method of zirconium phosphate is the same as that in Example 2.

[0099] Test Case

[0100] The microstructures of the zirconium phosphates prepared in Example 1 and Example 2 were observed using a scanning electron microscope. The results were as follows: Figure 1 and Figure 2 As shown, the zirconium phosphates prepared in Example 1 and Example 2 both exhibited obvious lamellar structures with an average particle size of 0.8 to 1.5 μm. It can also be seen that Example 1, which was not ball-milled with tetraethylammonium hydroxide, had more obvious agglomeration, while Example 2 had a more obvious lamellar structure, which may have better dispersion performance.

[0101] The specific surface area and average pore size of the zirconium phosphate prepared in Example 1 and Example 2 were also tested using nitrogen adsorption and desorption. The results are shown in Table 1:

[0102]

[0103] Combine Figure 1 and Figure 2 As can be seen from the data in Table 1, the addition of tetraethylammonium hydroxide during wet ball milling is beneficial to the preparation of thin, uniform zirconium phosphate with obvious lamellar structure, larger specific surface area and pore size.

[0104] The anti-slip agent prepared in the examples and comparative examples was used to treat floor tiles with a size of 150 mm × 150 mm × 5 mm. The amount of the anti-slip agent used was 40 g / m 2 After drying at 25°C for 1 hour, the tiles were tested in both dry and wet conditions according to the friction coefficient determination in Annex M of the national standard GB / T 4100-2015, "Ceramic Tiles." During the wet test, the water level on the tile surface was set at 0.1 mm. A higher friction coefficient indicates better anti-slip properties. A gloss meter was used to measure the gloss of the tiles after anti-slip treatment. The results are shown in Table 2.

[0105]

[0106] The test results in Table 2 show that treatment with an anti-slip agent does not significantly affect the gloss of the tiles. It can be seen that, while maintaining the same formula, Example 4, in which tetraethylammonium hydroxide was added during wet ball milling to prepare zirconium phosphate, exhibited a significantly higher friction coefficient than Example 1, which did not. This is because, based on the optimization of other formulas, the less agglomerated zirconium phosphate can be better dispersed within the resulting micro- and nano-scale pores, creating more contact points and micro-suction cups. Compared to Example 4, Examples 2, 3, Comparative Example 1, 3, and 4 differ in the ratios of sodium dodecylbenzenesulfonate to dodecylethoxysulfobetaine added: 1:1.5, 1:2, 1:3, 1:4, 4:0, and 0:4, respectively. This demonstrates that, while maintaining the same formula composition, optimizing the surfactant composition can further promote the dispersion of zirconium phosphate within the micro- and nano-scale pores, thereby improving the friction coefficient. Furthermore, optimizing the surfactant composition can inhibit corrosion of the anti-slip agent on the tile surface, preventing a decrease in gloss. The wet friction coefficients of both the Examples and the Comparative Examples were higher than the dry friction coefficients. This demonstrates the rationality of the basic formulation of the present invention, which effectively forms micro- and nano-scale pores on the tile surface. When the floor encounters water, the pores are filled with water, which is then squeezed out of the pores under pressure, creating a vacuum inside the pores and thereby increasing the floor friction coefficient. Compared to Example 4, Example 5 further improves the dry (wet) friction coefficient by adding 1,4-bis(2',3'-epoxypropyl)perfluorobutane. This is likely because the addition of 1,4-bis(2',3'-epoxypropyl)perfluorobutane further reduces the surface tension of the zirconium phosphate, allowing water to more easily accumulate on the surface and enhancing the micro-suction cup effect.

[0107] The anti-slip agent prepared in the examples and comparative examples was used to treat floor tiles with a size of 150 mm × 150 mm × 5 mm. The amount of the anti-slip agent used was 40 g / m 2 After obtaining the treated floor tiles, the antibacterial properties and antibacterial durability were tested according to JC / T 897-2014 "Antibacterial Properties of Antibacterial Ceramic Products". The results are shown in Table 3:

[0108]

[0109] The antibacterial standard requires an antibacterial rate ≥ 90% and an antibacterial durability ≥ 85%. It can be seen that only the anti-slip agent-treated floor tiles of Examples 4 and 5 can meet the antibacterial durability standards. This is because the zirconium phosphate treated with tetraethylammonium hydroxide has a larger specific surface area and better dispersion properties, can adsorb more dodecylethoxysulfobetaine, and can prevent dodecylethoxysulfobetaine from being eluted during washing. The zirconium phosphate with more binding sites and the adsorbed dodecylethoxysulfobetaine are evenly dispersed in the micro-nano pores, thereby enhancing and prolonging the antibacterial effect. The addition of 1,4-bis(2',3'-epoxypropyl)perfluorobutane further promotes this effect.

[0110] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A long-lasting anti-slip agent, characterized in that: In parts by weight, 10-15 parts of organic acid, 5-10 parts of fluoride salt, 0.5-2 parts of surfactant, 0.5-1 part of zirconium phosphate, 5-10 parts of silane coupling agent, 0.2-0.5 parts of defoaming agent, 30-60 parts of water; and 1-5 parts by weight of 1,4-bis(2',3'-epoxypropyl)perfluorobutane; The surfactant is prepared by mixing sodium dodecylbenzenesulfonate and dodecylethoxysulfobetaine in a mass ratio of 1:1.5-3. The preparation method of the zirconium phosphate comprises: Dissolve a soluble zirconium salt in water, then add 37 wt % concentrated hydrochloric acid, 40 wt % hydrofluoric acid, and 85 wt % phosphoric acid, stirring and reacting to obtain an intermediate; The intermediate and tetraethylammonium hydroxide (0.1 to 0.3 times the mass of the intermediate) are wet ball-milled to collect insoluble matter, and the insoluble matter is calcined to obtain zirconium phosphate.

2. The stain-resistant and long-lasting anti-slip agent according to claim 1, characterized in that: The zirconium phosphate is in the form of flakes with an average particle size of 0.8 to 1.5 μm.

3. The stain-resistant and long-lasting anti-slip agent according to claim 1, characterized in that: The ratio of soluble zirconium salt, water, concentrated hydrochloric acid, hydrofluoric acid, and phosphoric acid is 5~10g:80~100mL:5~10mL:5~10mL:30~50mL.

4. The stain-resistant and long-lasting anti-slip agent according to claim 3, characterized in that: In the wet ball milling, the intermediate and the ethanol aqueous solution are mixed at a mass ratio of 2-5:50-100, and then ball milled at a ball speed of 200-500 rpm for 1-3 hours.

5. The stain-resistant and long-lasting anti-slip agent according to claim 1, characterized in that: The organic acid includes at least one of oxalic acid, citric acid, tartaric acid and malic acid.

6. The stain-resistant and long-lasting anti-slip agent according to claim 1, characterized in that: The fluoride salt includes at least one of sodium fluoride, potassium fluoride, ammonium fluoride, sodium bifluoride, potassium bifluoride, and ammonium bifluoride.

7. The stain-resistant and long-lasting anti-slip agent according to claim 1, characterized in that: The silane coupling agent includes at least one of KH550, KH560, KH570, KH580, KH602, and KH792.

8. The stain-resistant and long-lasting anti-slip agent according to claim 1, characterized in that: The defoaming agent is at least one of a higher alcohol defoaming agent and an organosilicon defoaming agent.

9. A method for preparing the stain-resistant and long-lasting anti-slip agent according to any one of claims 1 to 8, characterized in that: include, The fluoride salt, surfactant, zirconium phosphate and water are stirred and mixed, and then organic acid, silane coupling agent and defoaming agent are added, and stirring is continued to obtain a stain-resistant and long-lasting anti-slip agent.

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