Stain-resistant long-acting anti-slip agent and preparation method thereof

Abstract

The invention discloses a stain-resistant long-acting anti-slip agent and a preparation method thereof. The anti-slip agent comprises the following components in parts by weight: 10-15 parts of organic acid, 5-10 parts of villiaumite, 0.5-2 parts of a surfactant, 0.5-1 part of zirconium phosphate, 5-10 parts of a silane coupling agent, 0.2-0.5 part of a defoaming agent and 30-60 parts of water. Wherein the surface active agent is prepared by mixing sodium dodecyl benzene sulfonate and dodecyl ethyoxyl sulphobetaine according to a mass ratio of 1: (2-3). The formula is soft, uniform micro-nano-scale pores can be formed in the surface of the floor tile on the premise that the glossiness of the floor tile is not discounted, zirconium phosphate serving as a filling material can be distributed in the micro-nano-scale pores formed in the floor tile coated with the anti-slip agent to form new friction points so as to increase friction force, and meanwhile, the anti-slip agent has a good anti-slip effect. Zirconium phosphate and dodecyl ethyoxyl sulphobetaine can also endow the floor tile with certain antibacterial performance, and the stain resistance of the floor tile is enhanced.

Description

Technical Field

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

[0002] With the improvement of people's living standards, the use of floor tiles for decoration has become the choice of more and more people, but some problems have arisen in the process of application, such as the surface is easy to slip after contacting water, so the anti-slip treatment of the floor tile surface has become a hot topic of research. Compared with the mechanical grinding treatment of the floor tile surface, the application scenarios of the use of anti-slip agents are richer and the impact on the floor tiles is relatively low. Anti-slip agents can effectively penetrate into the pores of floor tiles to dissolve a small amount of silicon, making the pores coarser, and forming many tiny micro-nano grooves invisible to the naked eye on the surface. When the ground is wet, the pores will be filled with water. When the soles of the feet or shoes pass through the ground, the water will be squeezed out of the pores under pressure and the pores will be in a vacuum state, so that the contact with the soles of the feet can form a physical suction cup effect, greatly enhancing the friction coefficient of the ground, reducing the risk of slipping and falling after the floor tiles are wet, and having a "water-sensitive" effect, making the ground more anti-slip than when it is dry.

[0003] However, the anti-skid agents currently available on the market still have the disadvantage of weak penetration, which leads to a matte surface of the floor tiles after construction. Some anti-skid agents with good stain resistance and brightness have also been reported. For example, CN109705811A discloses a safe, environmentally friendly, stain-resistant anti-skid agent and a preparation method thereof. The anti-skid agent includes 0.1 to 15 parts of organic acid, 10 to 40 parts of inorganic acid, 10 to 30 parts of fluoride salt, 5 to 20 parts of auxiliary agent, and 30 to 60 parts of water by weight. The system formed by organic acid, inorganic acid, auxiliary agent and fluoride salt cooperates with each other to form nano-scale pores of uniform size and depth on the floor tiles, thereby improving the anti-skid coefficient of the floor tiles without causing matte. However, the proportion of fluoride salt in this anti-skid agent is relatively high, and it is easy to form hydrofluoric acid when it reacts with strongly acidic inorganic acids, and gasification may pose a threat to the health of operators. CN113388367A discloses an environmentally friendly long-lasting anti-skid agent and a preparation method thereof, wherein the anti-skid agent comprises, by weight, 1-10 parts of rare earth oxide, 25-40 parts of diatomite, 1-5 parts of nano silver ion antibacterial agent, 15-35 parts of humic acid, 7-15 parts of surfactant, 20-30 parts of fluoride salt, 5-18 parts of silicone oil, 20-40 parts of adhesive and 30-45 parts of water, and forms an anti-skid film on the surface of floor tiles under the synergistic effect of various raw materials, thereby improving the anti-skid property of floor tiles. The film layer formed by the anti-skid agent on the surface of floor tiles is easily degraded, and the life of the anti-skid film is not long.

[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 stain-resistant and long-lasting anti-slip agent, which comprises, by weight, 10-15 parts of organic acid, 5-10 parts of fluoride salt, 0.5-2 parts of surfactant, 0.5-1 parts of zirconium phosphate, 5-10 parts of silane coupling agent, 0.2-0.5 parts of defoaming agent, 30-60 parts of water; The surfactant is prepared by mixing sodium dodecylbenzene sulfonate and dodecylethoxysulfobetaine in a mass ratio of 1:1.5-3.

[0006] The formula of anti-skid agent is generally acidic, and fluoride salt is added to react with silicate in the pores of floor tiles to form micro-nano pores. Surfactant and silane coupling agent are added to the formula of the present invention, and the ratio of anionic surfactant sodium dodecylbenzene sulfonate and amphoteric surfactant dodecylethoxy sulfobetaine is optimized to reduce the tension of anti-skid agent and make it easier to react with the surface of floor tiles. Zirconium phosphate has a unique layered structure and excellent adsorption capacity, is insoluble in water and general 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-nano pores formed by floor tiles on which anti-skid agent is applied, forming new friction points to increase friction.

[0007] In addition, zirconium phosphate can also exert antibacterial effects through ion dissolution. The zirconium phosphate filled in the pores can not only exert antibacterial effects through its own effects, but also the dodecyl ethoxy sulfobetaine in the surfactant of the present invention has good bactericidal properties. Zirconium phosphate can also absorb dodecyl ethoxy sulfobetaine 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.

[0008] Furthermore, the zirconium phosphate is in the form of flakes with an average particle size of 0.8 to 1.5 μm.

[0009] 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 [ZrF 6 2- ], the complex decomposes into zirconium ions, and then the zirconium ions react with phosphoric acid to form zirconium phosphate precipitates. The present invention also wet-ball-mills the zirconium phosphate precipitates and calcines them to increase crystallinity.

[0010] Furthermore, the method for preparing 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, and stir to react to obtain an intermediate; The intermediate is wet-milled, the insoluble matter is collected, and the insoluble matter is calcined to obtain zirconium phosphate; Among them, 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.

[0011] Furthermore, the wet ball milling is to mix the intermediate with an ethanol aqueous solution at a mass ratio of 2-5:50-100 and then ball mill at a ball speed of 200-500 rpm for 1-3 hours. In the present invention, the selection of the soluble zirconium salt is not limited, and illustratively, it can be at least one of tetrahydrate zirconyl sulfate, octahydrate zirconium oxychloride, and the like.

[0012] Conventional ball milling still cannot effectively separate the lamellar zirconium phosphate, and there are still a large number of agglomerates and stacking. For this reason, 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.

[0013] Furthermore, during the wet ball milling, tetraethylammonium hydroxide in an amount of 0.1 to 0.3 times the mass of the intermediate is added.

[0014] 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.

[0015] Furthermore, the organic acid includes at least one of oxalic acid, citric acid, tartaric acid and malic acid.

[0016] Furthermore, the fluoride salt includes at least one of sodium fluoride, potassium fluoride, ammonium fluoride, sodium bifluoride, potassium bifluoride, and ammonium bifluoride.

[0017] Furthermore, the silane coupling agent includes at least one of KH550, KH560, KH570, KH580, KH602, and KH792.

[0018] Furthermore, the defoaming agent is at least one of a high-carbon alcohol defoaming agent and a silicone defoaming agent.

[0019] Further preferably, the anti-fouling and long-lasting anti-slip agent further comprises 1 to 5 parts by weight of 1,4-di(2',3'-epoxypropyl)perfluorobutane.

[0020] The present invention also provides a method for preparing the above-mentioned stain-resistant long-lasting anti-slip agent, comprising: 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-skid agent.

[0021] Compared with the prior art, the present invention has the following beneficial effects: 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 applied with anti-slip agents to form new friction points to increase friction. At the same time, zirconium phosphate and dodecylethoxysulfobetaine can also give the floor tiles certain antibacterial properties, thereby enhancing the anti-fouling properties of the floor tiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. 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 creative work.

[0023] Figure 1 The microscopic morphology of zirconium phosphate prepared in Example 1 is shown; Figure 2 The microstructure of the zirconium phosphate prepared in Example 2 is shown. DETAILED DESCRIPTION

[0024] The endpoints and any values ​​of the ranges disclosed in the present invention 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 endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in the present invention.

[0025] Some of the raw materials used in the examples and comparative examples of the present invention are described as follows: Dodecylethoxysulfobetaine, model BS-12, purchased from Jining Huipeng Chemical Co., Ltd.; Tetraethylammonium hydroxide, model TEAH, was purchased from Wuhan Jiyesheng Chemical Co., Ltd.; Higher carbon alcohol defoamer, model LC-WQ403, purchased from Tianjin Lichuang Environmental Protection Technology Co., Ltd.; Other raw materials not mentioned are common raw materials in the art. The above content is only to help illustrate the present invention and shall not be construed as a strict limitation of the present invention. Those skilled in the art can directly purchase the same / similar raw materials from the market or prepare them by themselves. These contents will not be repeated in the examples.

[0026] The following will be combined with the specific embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 2.5g of sodium dodecylbenzene sulfonate, 7.5g of dodecylethoxy sulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0029] Wherein, the preparation method of zirconium phosphate is: 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, keep the reaction at 300 rpm for 100 h, then filter, wash with water and ethanol three times each, and transfer to a 120° C. constant temperature oven for drying for 8 h to obtain an intermediate; T2. Mix 50 g of the intermediate with 1000 g of a 50 wt% ethanol aqueous solution and perform wet ball milling at a ball speed of 350 rpm for 2 h. Then filter, wash with water and ethanol three times each, transfer to a constant temperature oven at 120°C and dry for 8 h. Then, place in a muffle furnace at 450°C in a nitrogen atmosphere and calcine for 2 h to obtain zirconium phosphate.

[0030] Example 2

[0031] A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 4g of sodium dodecylbenzenesulfonate, 6g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0032] Wherein, the preparation method of zirconium phosphate is: 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, keep the reaction at 300 rpm for 100 h, then filter, wash with water and ethanol three times each, and transfer to a 120° C. constant temperature oven for drying for 8 h to obtain an intermediate; T2. Mix 50 g of the intermediate, 10 g of tetraethylammonium hydroxide and 1000 g of a 50 wt% ethanol aqueous solution and perform wet ball milling at a ball speed of 350 rpm for 2 h. Then filter, wash three times with water and ethanol respectively, transfer to a constant temperature oven at 120°C and dry for 8 h, then place in a muffle furnace at 450°C in a nitrogen atmosphere and calcine for 2 h to obtain zirconium phosphate.

[0033] Example 3

[0034] A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 3.34g of sodium dodecylbenzene sulfonate, 6.64g of dodecylethoxy sulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0035] Wherein, the preparation method of zirconium phosphate is the same as that in Example 2.

[0036] Example 4

[0037] A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 2.5g of sodium dodecylbenzene sulfonate, 7.5g of dodecylethoxy sulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0038] Wherein, the preparation method of zirconium phosphate is the same as that in Example 2.

[0039] Example 5

[0040] A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1. Weigh 100 g of oxalic acid, 80 g of ammonium fluoride, 2.5 g of sodium dodecylbenzene sulfonate, 7.5 g of dodecylethoxysulfobetaine, 8 g of zirconium phosphate, 70 g of KH580, 3 g of high-carbon alcohol defoamer, 2 g of 1,4-di(2',3'-epoxypropyl)perfluorobutane, and 498 g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine and water at a rotation speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0041] Wherein, the preparation method of zirconium phosphate is the same as that in Example 2.

[0042] Comparative Example 1 A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 2g of sodium dodecylbenzenesulfonate, 8g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0043] Wherein, the preparation method of zirconium phosphate is the same as that in Example 2.

[0044] Comparative Example 2 A method for preparing an anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 2.5g of sodium dodecylbenzene sulfonate, 7.5g of dodecylethoxy sulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine and water at a rotation speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0045] Wherein, the preparation method of zirconium phosphate is: 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, keep the reaction at 300 rpm for 100 h, then filter, wash with water and ethanol three times each, and transfer to a 120° C. constant temperature oven for drying for 8 h to obtain an intermediate; 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.

[0046] Comparative Example 3 A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 10g of sodium dodecylbenzene sulfonate, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0047] Wherein, the preparation method of zirconium phosphate is the same as that in Example 2.

[0048] Comparative Example 4 A method for preparing a stain-resistant long-lasting anti-slip agent, comprising the following steps: S1, weigh 100g of oxalic acid, 80g of ammonium fluoride, 10g of dodecylethoxysulfobetaine, 8g of zirconium phosphate, 70g of KH580, 3g of high carbon alcohol defoamer, and 500g of water; S2, stirring ammonium fluoride, sodium dodecylbenzenesulfonate, dodecylethoxysulfobetaine, zirconium phosphate and water at a speed of 300 rpm for 20 min to obtain a mixture; S3. Add oxalic acid, KH580 and high carbon alcohol defoamer into the mixture and stir at 500 rpm for 15 min to obtain a stain-resistant and long-lasting anti-slip agent.

[0049] Wherein, the preparation method of zirconium phosphate is the same as that in Example 2.

[0050] Test Case 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 Examples 1 and 2 both exhibited obvious lamellar structures with an average particle size of 0.8-1.5 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 and may have better dispersion properties.

[0051] 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:

[0052] Combination Figure 1 and Figure 2 As can be seen from the data in Table 1, adding 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.

[0053] 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 for 1 hour at 25℃, the test was carried out according to the determination of friction coefficient in Annex M of the national standard GB / T 4100-2015 "Ceramic Tiles". The dry and wet friction coefficient tests were carried out respectively. The water storage height on the tile surface during the wet friction coefficient test was 0.1mm. Among them, the higher the friction coefficient, the better the anti-slip property. A gloss meter was used to test the gloss of the floor tiles treated with anti-slip agents. These results are shown in Table 2:

[0054] From the test results in Table 2, it can be seen that the treatment with the anti-slip agent will not have a significant impact on the glossiness of the floor tiles. It can be seen that on the basis of the same other formulas, the friction coefficient of Example 4 in which tetraethylammonium hydroxide is added during wet ball milling to prepare zirconium phosphate is significantly improved compared with Example 1 in which it is not added. This is because on the basis of the optimization of other formulas, the less agglomerated zirconium phosphate can be better dispersed in the formed micro-nano pores, creating more contact points and more micro-suckers. Compared with Example 4, the addition ratios of sodium dodecylbenzene sulfonate and dodecylethoxysulfobetaine in Example 2, Example 3, Comparative Example 1, Comparative Example 3 and Comparative Example 4 are different, namely 1:1.5, 1:2, 1:3, 1:4, 4:0 and 0:4, respectively. This shows that when the other ingredients of the formula are the same, optimizing the composition of the surfactant can further promote the dispersion of zirconium phosphate in the micro-nano pores, thereby improving the friction coefficient; at the same time, optimizing the composition of the surfactant can also inhibit the corrosion of the anti-slip agent on the surface of the floor tiles and avoid the decline of glossiness. The wet friction coefficients of the examples and the comparative examples are higher than the dry friction coefficients, which shows that the basic formula of the present invention is reasonable and can effectively form micro-nano pores on the surface of the floor tiles. When the ground meets water, the pores will be filled with water, and the water will be squeezed out of the pores under pressure, and the pores will be in a vacuum state, thereby enhancing the ground friction coefficient. Compared with Example 4, Example 5 further adds 1,4-bis(2',3'-epoxypropyl)perfluorobutane to the formula, and the dry (wet) friction coefficient is further improved. This may be because the addition of 1,4-bis(2',3'-epoxypropyl)perfluorobutane further reduces the surface tension of zirconium phosphate, making it easier for water to gather on the surface of zirconium phosphate, thereby improving the micro-suction cup effect.

[0055] 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 the treated floor tiles were obtained, the antibacterial properties and antibacterial durability were tested according to JC / T 897-2014 "Antibacterial Performance of Antibacterial Ceramic Products". The results are shown in Table 3:

[0056] The antibacterial standard requires an antibacterial rate of ≥90% and an antibacterial durability of ≥85%. It can be seen that only the anti-slip agent treated floor tiles of Example 4 and Example 5 can meet the antibacterial durability standard. This is because the zirconium phosphate treated with tetraethylammonium hydroxide has a larger specific surface area and better dispersion performance, and can adsorb more dodecylethoxysulfobetaine. At the same time, it 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-di(2',3'-epoxypropyl)perfluorobutane further promotes this effect.

[0057] 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, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to 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 protection scope of the present invention.

Claims

1. A stain-resistant and 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 parts of zirconium phosphate, 5-10 parts of silane coupling agent, 0.2-0.5 parts of defoaming agent, 30-60 parts of water; The surfactant is prepared by mixing sodium dodecylbenzene sulfonate and dodecylethoxysulfobetaine in a mass ratio of 1:1.5-3.

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-skid agent according to claim 1, characterized in that: The preparation method of 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, and stir to react to obtain an intermediate; The intermediate is wet-milled, the insoluble matter is collected, and the insoluble matter is calcined to obtain zirconium phosphate; Among them, 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-skid agent according to claim 3, characterized in that: In the wet ball milling, the intermediate is mixed with an ethanol aqueous solution 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-skid agent according to claim 4, characterized in that: During wet ball milling, 0.1 to 0.3 times the mass of the intermediate is added with tetraethylammonium hydroxide.

6. The stain-resistant and long-lasting anti-skid 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.

7. 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.

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

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

10. A method for preparing the stain-resistant long-lasting anti-slip agent according to any one of claims 1 to 9, 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-skid agent.

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