Self-cleaning coating for waterproofing membrane, waterproofing membrane and preparation method thereof

Abstract

The present application relates to a kind of self-cleaning coating for waterproofing membrane, waterproofing membrane and its preparation method, self-cleaning coating includes water-based acrylate emulsion and water-based fluorocarbon resin emulsion;Water-based fluorocarbon resin emulsion is by first polymeric monomer in the presence of solvent and the action of initiator first solution polymerization, obtain prepolymer, then join unsaturated isocyanate monomer and obtain photo-crosslinkable prepolymer, then join photo-initiator mixture, remove solvent, emulsification preparation is obtained by adding water.The self-cleaning coating prepared by redesigning fluorocarbon resin emulsion and using water-based acrylate emulsion can be used on waterproofing membrane, realize long-lasting stain resistance, while it can greatly slow down the aging of the membrane caused by environmental factors during outdoor use, improve the long-term durability of the membrane.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of waterproofing membranes, and particularly relates to a self-cleaning coating for waterproofing membranes, a waterproofing membrane and a preparation method thereof. BACKGROUND

[0002] Fluorocarbon coating is a new type of coating with fluororesin as the main film-forming material. Due to the strong electronegativity of fluorine and the high energy of C-F bond, it has a very stable physical and chemical structure, and performs outstandingly in terms of weather resistance, durability, heat resistance, low-temperature resistance, corrosion resistance and other aspects, especially in terms of ultraviolet resistance, which has excellent performance that other resin coatings cannot match. At present, fluorocarbon coatings have been widely used in many fields, such as building materials, electronic industry, machinery industry, aerospace, etc., and have become a high-comprehensive-performance coating after acrylic coating, polyurethane coating and silicone coating. Fluorocarbon coatings have very excellent stain resistance due to their low surface energy, and are often used to build easy-to-clean surfaces. However, conventional fluorocarbon coatings are mostly solvent-based coatings, which produce a large amount of organic gas during production and use, causing harm to the environment and workers, so water-based fluorocarbon coatings have become a trend. However, due to the unique low surface energy properties of fluorocarbon resins, it is challenging to disperse them in water. At present, the market uses vinyl ether and ionic acrylate to modify fluorocarbon resins by emulsion polymerization to obtain water-dispersible fluorocarbon resin emulsion, but the presence of a large amount of hydrophilic surfactants leads to a decrease in stain resistance.

[0003] Polyvinyl chloride (PVC) membrane is a high-molecular waterproof material with excellent performance, which is mainly made of polyvinyl chloride resin as raw material, adding various special additives and anti-aging agents, and is produced by advanced equipment and process. It has the characteristics of high tensile strength, high elongation, low shrinkage, good low-temperature flexibility, convenient construction, etc., and can be used for exposed use in roofing engineering. It has a long service life and good aging resistance, and can be used for 30 years. However, PVC membrane is easily adhered to dust on its surface in long-term outdoor exposure, affecting its appearance, and the attachment of pollutants for a long time accelerates the aging and corrosion of PVC material, reducing its service life. Therefore, it is of great significance to endow PVC membrane with stain resistance.

[0004] There are also patents that use fluorocarbon resins on the membrane, such as Chinese patent CN115960521A, which discloses a kind of membrane self-cleaning coating and its preparation method and application. The self-cleaning coating prepared by using high molecular weight polyurethane resin, fluorocarbon resin, self-extinction resin, amino resin, solvent, anti-fouling additive and other additives is used on the membrane, which has the effects of anti-fouling and anti-graffiti, and has high light transmittance without affecting the appearance of decorative coating. However, the self-cleaning coating is a solvent-based coating, which produces a large amount of organic gas during production and use, and is not environmentally friendly.

[0005] At present, there are few fluorocarbon emulsions used on the coiled material to meet the self-cleaning property of the exposed coiled material of the roof. SUMMARY

[0006] The present application actually solves the technical problem of the prior art, and provides a self-cleaning coating for exposed coiled material of the roof, which endows the waterproof coiled material with long-lasting stain resistance.

[0007] To achieve the above-mentioned purposes, the technical solution adopted by the present application is as follows:

[0008] A self-cleaning coating for waterproof coiled material, comprising a water-based acrylate emulsion and a water-based fluorocarbon resin emulsion.

[0009] In the present application, the water-based fluorocarbon resin emulsion is prepared by self-emulsification of a photo-crosslinkable fluorine-containing acrylate resin. The use of hydrophilic surfactants is avoided to prevent the problem of decreased stain resistance of the fluorocarbon resin emulsion.

[0010] In some embodiments, the water-based fluorocarbon resin emulsion is prepared by first solution polymerization of the polymerization monomers in the presence of a solvent and under the action of an initiator to obtain a prepolymer, then adding an unsaturated isocyanate monomer to obtain a photo-crosslinkable prepolymer, then adding a photoinitiator, removing the solvent, and emulsifying with water.

[0011] The polymerization monomers include fluorine-containing acrylate monomers, fluorine-containing olefin vinyl ether monomers, fluorine-containing olefin monomers, acrylate monomers, and acrylic acid.

[0012] According to some embodiments of the present application, the molar ratio of the fluorine-containing acrylate monomers, fluorine-containing olefin vinyl ether monomers, fluorine-containing olefin monomers, acrylate monomers, and acrylic acid is 1:1-2:1-2:1-2:0.5-1; and the molar ratio of the unsaturated isocyanate monomer to the fluorine-containing olefin monomer is 0.8-1.2:1.

[0013] In some embodiments, the fluorine-containing propenoate monomer is one or a combination of 3,3,4,4,4-pentafluorobutene, perfluorobut-l-ene, 1H,1H,2H-heptafluoro-l-pentene, perfluoro-l-hexene, (perfluorohexyl) ethylene, perfluorohept-l-ene, perfluoronon-l-ene, perfluoro-l-decene, 1H,1H,2H-perfluoro-l-dodecene, perfluorotetradecyl-l-ene, 4-vinylbenzyl perfluorooctanoate, hexafluorobutyl acrylate, heptafluorobutyl acrylate, allyl perfluoropentanoate, dodecafluoroheptyl acrylate, perfluoro-n-octyl acrylate, vinyl perfluorononanoate, allyl perfluoro-n-nonanoate, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, perfluoro-undecyl acrylate, perfluoroalkylethyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, dodecafluoroheptyl methacrylate, trifluoroethyl methacrylate, perfluoro-octyl methacrylate, perfluoro-octyl methacrylate, perfluoro-undecyl methacrylate, hexafluorobutyl methacrylate.

[0014] In some embodiments, the fluorine-containing olefin vinyl ether monomer is one or a combination of perfluoro-n-propyl vinyl ether, perfluoro 3,6-dioxa-4-methyl-7- octenesulfonyl fluoride, methyl perfluoro (5-methyl-4,7-dioxan-8-ene acid ethyl ester), 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether, allyl 1H,1H-perfluorooctyl ether.

[0015] In some embodiments, the fluorine-containing olefin vinyl ether monomer is one or a combination of perfluoro-n-propyl vinyl ether, perfluoro 3,6-dioxa-4-methyl-7- octenesulfonyl fluoride, methyl perfluoro (5-methyl-4,7-dioxan-8-ene acid ethyl ester), 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether, allyl 1H,1H-perfluorooctyl ether.

[0016] In some embodiments, the acrylate monomer is one or a combination of ethyl acrylate, hydroxyethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, lauryl methacrylate, isotridecyl acrylate, cetyl acrylate, ethoxyethoxyethyl acrylate, isodecyl methacrylate, methoxy polyethylene glycol methacrylate.

[0017] In some embodiments, the unsaturated isocyanate monomer is an unsaturated aliphatic isocyanate.

[0018] Preferably, the unsaturated aliphatic isocyanate is one or a combination of isocyanate ethyl acrylate, isocyanatoethyl methacrylate, 3-isopropyl-dimethylbenzyl isocyanate.

[0019] In some embodiments, the polymerizable monomers further comprise an unsaturated silane, the unsaturated silane being present in a feed mole amount of 5-15% of the total mole amount of the polymerizable monomers.

[0020] In some embodiments, the unsaturated silane is one or a combination of vinyltriethoxysilane, 3-(isobutyryloxy)propyltrimethoxysilane, methacryloxypropyltris(trimethylsiloxy)silane, allyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, (3-acryloxypropyl)tris(trimethylsiloxy)silane.

[0021] In some embodiments, the mass of the initiator is 1-5% of the total mass of the polymerized monomers.

[0022] In some embodiments, the initiator is one or a combination of azobisisobutyronitrile, azobisisoheptanitrile, dimethyl azobisisobutyrate.

[0023] In some embodiments, the mass of the photoinitiator is 3-4% of the total mass of the polymerized monomers.

[0024] In some embodiments, the photoinitiator is one or a combination of benzophenone ammonium chloride, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, polymerized [2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propanone].

[0025] According to some embodiments of the present application, the method for preparing the aqueous fluorocarbon resin emulsion comprises mixing the polymerized monomers, initiator and solvent, reacting at 70-85°C under an inert gas atmosphere, then cooling to 55-65°C, adding the unsaturated isocyanate monomer dropwise, then adding the catalyst and stabilizer, reacting in the dark, adding the photoinitiator and mixing in the dark, then adjusting the pH to 7-8, removing the solvent by reduced pressure distillation, adding water to emulsify, and obtaining the aqueous fluorocarbon resin emulsion.

[0026] In some embodiments, the method for preparing the aqueous fluorocarbon resin emulsion comprises dissolving the polymerized monomers in the solvent and mixing uniformly, then adding to the reaction kettle, adding the initiator under a nitrogen atmosphere, reacting at 75-80°C for 20-30h; cooling to 60-80°C, adding the unsaturated isocyanate monomer dropwise to the reaction kettle, adding the catalyst and stabilizer after the dropwise addition is complete, reacting in the dark for 8-10h; cooling to 50-60°C, adding the photoinitiator and mixing uniformly in the dark, then adjusting the pH of the system to 7-8, then removing the solvent and low-boiling-point residues by reduced pressure distillation at 50±5°C and 130±10mmHg, adding water and emulsifying at high speed with stirring, and obtaining the aqueous fluorocarbon resin emulsion.

[0027] The solid content of the aqueous fluorocarbon resin emulsion is 40-50%. The solid content of the aqueous acrylate emulsion is 40-50%.

[0028] In some embodiments, the solvent is one or a combination of 1,4-dioxane, tetrahydrofuran, N,N-dimethylformamide.

[0029] In some embodiments, the catalyst is one or a combination of dibutyltin dilaurate, dibutyltin dodecanethiolate, stannous octoate, and the mass of the catalyst is 0.05-0.15% of the total mass of the polymerized monomers.

[0030] In some embodiments, the stabilizer is 2,6-di-tert-butyl-p-cresol, and the mass of the stabilizer is 0.05-0.15% of the total mass of the polymerized monomers.

[0031] In some embodiments, the pH adjustment is performed using one or a combination of dimethylethanolamine and ethylenediamine.

[0032] According to some embodiments of the present application, the aqueous acrylate emulsion is a self-crosslinking type acrylate copolymer emulsion.

[0033] In some embodiments, the aqueous acrylate emulsion is one or a combination of BLJ-968M, HXL-2000, and Neocryl A-1127.

[0034] According to some embodiments of the present application, the mass ratio of the aqueous fluorocarbon resin emulsion and the aqueous acrylate emulsion is 1:1-3.

[0035] According to some embodiments of the present application, the self-cleaning coating further comprises one or a combination of film-forming aids, defoamers, and leveling agents.

[0036] According to some embodiments of the present application, the self-cleaning coating comprises, by weight parts:

[0037]

[0038] In some embodiments, the film-forming aid is an aqueous polyurethane resin having an adhesion promoting effect. Specifically, the film-forming aid is one or a combination of RL-8302, PU406, and P-613.

[0039] The second technical solution adopted by the present application is a waterproofing membrane comprising a substrate and a coating layer formed on the surface of the substrate, wherein the coating layer is prepared using the self-cleaning coating for waterproofing membranes described above.

[0040] In some embodiments, the substrate is a polyvinyl chloride substrate. The polyvinyl chloride substrate is a polymer substrate extruded once with polyvinyl chloride resin as the base material, with plasticizers, anti-aging agents, stabilizers, ultraviolet absorbers, lubricants, and fillers, such as CL-PVC polyvinyl chloride substrate, which can also be a common waterproofing membrane.

[0041] In some embodiments, the coating is obtained by coating the waterproofing membrane with a self-cleaning coating on the surface of the substrate, drying, and then curing by ultraviolet light irradiation.

[0042] The third technical solution adopted by the present application is: the preparation method of the waterproofing membrane described above includes the steps of coating the waterproofing membrane with a self-cleaning coating on the surface of the substrate, drying, and then curing by ultraviolet light irradiation to obtain a coating.

[0043] Further, the drying temperature used is 60-70℃. The drying is performed using an oven, and the length of the oven is 30-40m and the speed is 10-30m / min.

[0044] Further, the wavelength used for ultraviolet light irradiation curing is 310-420nm, the irradiation time is 60±10s, and the maximum light intensity of the irradiation center position is 100±10mW / cm 2 .

[0045] Further, the coating is performed using an anilox roller, and the specification of the anilox roller is 50-200 mesh.

[0046] Due to the use of the above technical solutions, the present application has the following advantages compared with the prior art:

[0047] The self-cleaning coating prepared by redesigning the fluorocarbon resin emulsion and using water-based acrylate emulsion can be used on waterproofing membranes to achieve long-lasting stain resistance, while greatly slowing down the aging of the membrane caused by environmental factors during outdoor use, and improving the long-term durability of the membrane. DETAILED DESCRIPTION

[0048] Currently, few fluorocarbon emulsions are used on the coil to meet the self-cleaning property of the exposed coil of the roof. The present application prepares a self-cleaning coating by redesigning the formula of the water-based fluorocarbon resin emulsion and using the acrylate emulsion. In the first aspect, the water-based fluorocarbon resin emulsion is designed to be prepared from a self-emulsifying light-crosslinking fluorine-containing acrylate resin, which has the advantages of low energy consumption, simple operation, high efficiency, environmental protection and wide adaptability compared with the traditional two-component heat-curing solvent-based fluorocarbon resin, and can be applied to the waterproof coil without cracking. In the second aspect, the crosslinked network structure formed by the curing of the water-based fluorocarbon resin emulsion can increase the compactness of the coating, and the use of the water-based acrylate resin emulsion can improve the adhesion of the coating to the substrate. The interpenetrating structure between the fluorocarbon resin molecules and the acrylate molecules can further increase the compactness of the coating, improve the physical and chemical resistance of the coating, and improve the adhesion of the coating through the bite effect of the crosslinked structure, thereby improving the poor mechanical stability and poor durability of the traditional structure of the super-hydrophobic surface. In the third aspect, the coating prepared from the water-based fluorocarbon resin emulsion and the water-based acrylate resin emulsion has low surface energy, high chemical inertness and high thermal stability, and can achieve long-lasting stain resistance. The gradual self-crosslinking of the coating can further strengthen the stability of the double-crosslinked network structure, thereby greatly slowing down the aging of the coil caused by environmental factors during the exposed use, and improving the long-term durability of the coil.

[0049] The technical solutions of the present application will be described in detail below in conjunction with specific examples, so that those skilled in the art can better understand and implement the technical solutions of the present application, but the present application is not limited to the examples described.

[0050] Example 1

[0051] The waterproof coil provided in the present embodiment comprises a substrate and a coating layer formed on the surface of the substrate, wherein the coating layer is prepared from the self-cleaning coating.

[0052] The self-cleaning coating is composed of the following components: 20 parts of water-based fluorocarbon resin emulsion, 40 parts of water-based acrylate emulsion, 1 part of film-forming aid, 0.2 parts of defoaming agent, 0.3 parts of leveling agent and 5 parts of water; wherein the water-based acrylate emulsion is BLJ-968M, the film-forming aid is RL-8302, the defoaming agent is BYK-022, and the leveling agent is BYK-346. All components of the self-cleaning coating are mixed in a mixing kettle to obtain the self-cleaning coating.

[0053] In this example, the substrate is a polyvinyl chloride substrate.

[0054] In this example, the water-based fluorocarbon resin emulsion is prepared by the following method:

[0055] (1) Preparation of polymerization monomer solution

[0056] 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, allyl 1H, 1H-perfluorooctyl ether, 3-(perfluoro-n-hexyl)prop-2-en-1-ol, lauryl methacrylate, and acrylic acid were weighed according to a molar ratio of 1:1:1:1:0.5, and then the polymerization monomers were dissolved in 1,4-dioxane to a molar concentration of 0.5 mol / L calculated on the basis of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate.

[0057] (2) Synthesis of fluorocarbon resin

[0058] The monomer mixture was added to a reaction kettle equipped with a mechanical stirrer, a thermometer, and a condenser reflux tube, and 1% of azobis isobutyronitrile based on the total mass of the polymerization monomers was added under a nitrogen atmosphere, and the reaction was carried out at 75°C for 24 h.

[0059] (3) Synthesis of photo-crosslinkable fluorocarbon resin

[0060] The system of step (2) was cooled to 60°C, and the same molar amount of isocyanate ethyl acrylate as 3-(perfluoro-n-hexyl)prop-2-en-1-ol was slowly added dropwise to the system, and after the dropwise addition was completed, 0.1% of dibutyl tin dilaurate based on the total mass of the polymerization monomers and 0.1% of 2,6-di-tert-butyl-p-cresol based on the total mass of the polymerization monomers were added, and the reaction was carried out in the dark for 10 h; then the temperature was lowered to 50°C, 3% of benzophenone ammonium chloride based on the total mass of the polymerization monomers was added thereto, and mixed uniformly in the dark, and then dimethyl ethanolamine was added dropwise to adjust the pH to 7-8, and then the solvent and low-boiling-point residues were removed by distillation under reduced pressure at 50°C / 130 mmHg, and then deionized water was added and emulsified at high speed to obtain a water-based fluorocarbon resin emulsion with a solid content of 45%.

[0061] The waterproofing membrane of this example was prepared by the following method:

[0062] The self-cleaning coating was applied to the surface of the polyvinyl chloride substrate using an 80-mesh textured roller, and after drying with hot air at 60°C, a coating layer with a thickness of 20 μm was obtained by ultraviolet irradiation curing, the curing conditions being a wavelength of 310-420 nm, a maximum light intensity of 100±10 mW / cm2 at the irradiation center position, and an irradiation time of 60 s; and then the product was slit and wound. 2

[0063] Example 2

[0064] ​The waterproofing membrane provided in the embodiment differs from that of Embodiment 1 in that the molar ratio of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, allyl 1H, 1H-perfluorooctyl ether, 3-(perfluoro-n-hexyl)prop-2-en-1-ol, lauryl methacrylate, and acrylic acid in step (1) in the preparation of the water-based fluorocarbon resin emulsion is 1:2:2:2:1.

[0065] Embodiment 3

[0066] The waterproofing membrane provided in the embodiment differs from that of Embodiment 1 in that the amounts of the components of the self-cleaning coating are as follows: 40 parts of the water-based fluorocarbon resin emulsion, 40 parts of the water-based acrylate emulsion, 8 parts of the film-forming aid, 0.4 parts of the defoaming agent, 1 part of the leveling agent, and 12 parts of water.

[0067] Embodiment 4

[0068] The waterproofing membrane provided in the embodiment differs from that of Embodiment 1 in that 1H, 1H, 2H-perfluoro-1-dodecene, perfluoro-n-propyl vinyl ether, 3-perfluoro-hexyl-2-hydroxypropyl acrylate, butyl acrylate, and acrylic acid are used as the polymerization monomers in step (1) in the preparation of the water-based fluorocarbon resin emulsion, and the molar ratio is 1:1.5:1.5:1.5:0.7.

[0069] In step (3), 3-isopropyl-dimethylbenzyl isocyanate is used instead of isocyanate ethyl acrylate.

[0070] Embodiment 5

[0071] The waterproofing membrane provided in the embodiment differs from that of Embodiment 1 in that vinyl triethoxysilane is additionally added to the polymerization monomers in step (1) in the preparation of the water-based fluorocarbon resin emulsion, and the amount is 2% of the total mass of the polymerization monomers.

[0072] Comparative Example 1

[0073] The waterproofing membrane provided in the comparative example differs from that of Embodiment 1 in that allyl 1H, 1H-perfluorooctyl ether is not added in step (1) in the preparation of the water-based fluorocarbon resin emulsion.

[0074] Comparative Example 2

[0075] The waterproofing membrane provided in the comparative example differs from that of Embodiment 1 in that isocyanate ethyl acrylate is not added in the self-cleaning coating.

[0076] Comparative Example 3

[0077] The waterproofing membrane provided in the comparative example differs from that of Embodiment 1 in that the waterproofing membrane is not cured by ultraviolet light irradiation in the preparation process.

[0078] Comparative Example 4

[0079] The waterproofing membrane provided by the present comparative example is different from Example 1 in that no water-based acrylic emulsion is added to the self-cleaning coating.

[0080] Comparative Example 5

[0081] The waterproofing membrane provided by the present comparative example is different from Example 1 in that the water-based acrylic emulsion in the self-cleaning coating is replaced by Bardufu FS-230.

[0082] The waterproofing membranes of Examples 1-5 and Comparative Examples 1-5 were tested for stain resistance by the Immersion A method according to GB / T 9780-2013, and for adhesion by the Cross-cut method according to GBT9286-2021. The results are shown in Tables 1 and 2.

[0083] Table 1 Performance test results of the waterproofing membranes of Examples 1-5

[0084] Example 1 Example 2 Example 3 Example 4 Example 5 stain resistance 3％ 3％ 2％ 5％ 4％ stain resistance rating 0 0 0 0 0 adhesion 0 0 0 0 0

[0085] Table 2 Performance test results of the waterproofing membranes of Comparative Examples 1-5

[0086] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 stain resistance 8％ 18％ 19％ 16％ 5％ stain resistance rating 0 2 2 2 0 adhesion 1 5 5 2 2

[0087] As can be seen from Table 1, the waterproofing membranes of Examples 1-5 have good stain resistance, high stain resistance grade, and excellent adhesion, and can achieve long-lasting stain resistance. Although Comparative Examples 1 and 2 have relatively high stain resistance and stain resistance grade, they have poor adhesion. The waterproofing membranes of Comparative Examples 3-4 not only have poor stain resistance, but also have poor adhesion.

[0088] The above examples are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the content of the present application and to implement it, and it cannot limit the protection scope of the present application. Any equivalent changes or modifications made in accordance with the spirit and essence of the present application should be covered within the protection scope of the present application.

[0089] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited. The ranges or values should be interpreted as being approximate, and include values near the recited values. For numeric values, the endpoints between the various ranges, the endpoints between the various ranges and the individual point values, and the individual point values can be combined with each other to generate one or more new numeric ranges, which should be considered as specifically disclosed herein.

Claims

1. A self-cleaning coating for waterproofing membranes, characterized by: The self-cleaning coating comprises a water-based acrylate emulsion and a water-based fluorocarbon resin emulsion; The water-based fluorocarbon resin emulsion is prepared by first solution polymerization of polymerization monomers in the presence of a solvent and under the action of an initiator to obtain a prepolymer, then adding an unsaturated isocyanate monomer to react to obtain a light-crosslinkable prepolymer, then adding a photoinitiator, removing the solvent, and emulsifying with water; The polymerization monomers comprise a fluorine-containing acrylate monomer, allyl 1H, 1H-perfluorooctyl ether, a fluorine-containing enol monomer, an acrylate monomer, and acrylic acid; The acrylate monomer is a combination of one or more of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, lauryl methacrylate, isotridecyl acrylate, cetyl acrylate, ethoxyethoxyethyl acrylate, isodecyl methacrylate, and methoxypolyethylene glycol methacrylate; The unsaturated isocyanate monomer is a combination of one or more of isocyanate ethyl acrylate, isocyanethyl methacrylate, and 3-isopropyl-dimethylbenzyl isocyanate; The water-based acrylate emulsion is a self-crosslinking acrylate copolymer emulsion; The mass ratio of the water-based fluorocarbon resin emulsion to the water-based acrylate emulsion is 1:1-3.

2. The self-cleaning coating for waterproofing membranes according to claim 1, characterized in that: The molar ratio of the fluorine-containing acrylate monomer, allyl 1H, 1H-perfluorooctyl ether, fluorine-containing enol monomer, acrylate monomer, and acrylic acid is 1:1-2:1-2:1-2:0.5-1; and the molar ratio of the unsaturated isocyanate monomer to the fluorine-containing enol monomer is 0.8-1.2:

1.

3. The self-cleaning coating for waterproofing membranes according to claim 1 or 2, characterized in that: The fluorine-containing acrylate monomer is a combination of one or more of hexafluorobutyl acrylate, heptafluorobutyl acrylate, dodecafluoroheptyl acrylate, perfluoro-n-octyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, perfluoro-undecyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, dodecafluoroheptyl methacrylate, trifluoroethyl methacrylate, perfluoro-octyl methacrylate, perfluoro-undecyl methacrylate, and hexafluorobutyl methacrylate.

4. The self-cleaning coating for waterproofing membranes according to claim 1, characterized in that: The fluorine-containing enol monomer is a combination of one or more of 3-(perfluoro-n-hexyl)prop-2-en-1-ol and perfluorohept-2-en-1-ol.

5. The self-cleaning coating for waterproofing membranes according to claim 1, characterized in that: The polymerization monomers further comprise an unsaturated silane, and the feeding molar amount of the unsaturated silane is 5-15% of the total molar amount of the polymerization monomers.

6. The self-cleaning coating for waterproofing membranes according to claim 5, characterized in that: The unsaturated silane is a combination of one or more of vinyltriethoxysilane, 3-(isobutenoyloxy)propyltrimethoxysilane, methacryloyloxypropyltris(trimethylsiloxy)silane, allyltrimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, and (3-acryloyloxypropyl)tris(trimethylsiloxy)silane.

7. The self-cleaning coating for waterproofing membranes according to claim 1, characterized in that: The mass of the initiator is 1-5% of the total mass of the polymerization monomers; and / or, The mass of the photoinitiator is 3-4% of the total mass of the polymerization monomers; and / or, The initiator is a combination of one or more of azobisisobutyronitrile, azobisisoheptyl nitrile, and dimethyl azobisisobutyrate; and / or, The photoinitiator is a combination of one or more of 2,2-dimethoxy-1,2-diphenyl-1-hydrazyl, 2,2-dimethyl-4-methoxy-2-phenyl-1-phenylhydrazyl, and 2,2-dimethyl-4-morpholinobutyrophenone. The photoinitiator is one or a combination of benzophenone ammonium chloride, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, and polymeric [2-hydroxy-2-methyl-1-[4-(1-methylethenyl)phenyl]propanone].

8. The self-cleaning coating for waterproofing membranes according to any one of claims 1 to 2, 5 to 7, characterized in that: The preparation method of the aqueous fluorocarbon resin emulsion comprises mixing polymerization monomers, initiators and solvents, reacting at 70-85°C under an inert gas atmosphere, then cooling to 55-65°C, adding unsaturated isocyanate monomers dropwise, then adding catalysts and stabilizers, avoiding light reaction, then adding photoinitiators and mixing in the dark, adjusting the pH to 7-8, removing the solvent by pressure distillation, and emulsifying with water to obtain the aqueous fluorocarbon resin emulsion.

9. The self-cleaning coating for waterproofing membranes according to claim 8, characterized in that: The solvent is one or a combination of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide; and / or, The catalyst is one or a combination of dibutyltin dilaurate, bis(dodecylthio) dibutyltin, and stannous octoate, and the mass of the catalyst is 0.05-0.15% of the total mass of the polymerization monomers.

10. The self-cleaning coating for waterproofing membranes as claimed in claim 8, wherein: The stabilizer is 2,6-di-tert-butyl-p-cresol, and the mass of the stabilizer is 0.05-0.15% of the total mass of the polymerization monomers.

11. The self-cleaning coating for waterproofing membranes as claimed in claim 8, wherein: The pH adjustment is performed using one or a combination of dimethyl ethanolamine and ethylenediamine.

12. The self-cleaning coating for waterproofing membranes according to any one of claims 1 to 2, 5 to 7, characterized in that: The self-cleaning coating further comprises one or a combination of film-forming aids, defoaming agents, and leveling agents.

13. The self-cleaning coating for waterproofing membranes according to claim 12, characterized in that, The self-cleaning coating comprises, by weight parts: aqueous fluorocarbon resin emulsion 20-40 parts; aqueous acrylate emulsion 40-50 parts; film-forming aid 1-8 parts; defoaming agent 0.1-0.4 parts; leveling agent 0.3-1 part.

14. The self-cleaning coating for waterproofing membranes according to claim 12, characterized in that: The film-forming aid is an aqueous polyurethane resin.

15. A waterproofing membrane comprising a substrate and a coating formed on a surface of the substrate, characterized in that: The coating is prepared using the self-cleaning coating for waterproofing membranes according to any one of claims 1-14.

16. The waterproofing membrane of claim 15, wherein: The substrate is a polyvinyl chloride substrate or a thermoplastic polyolefin substrate; and / or, The coating is obtained by coating the self-cleaning coating for waterproofing membranes on the surface of the substrate, drying, and then curing by ultraviolet light irradiation.

17. The method of producing a waterproofing membrane according to claim 15 or 16, characterized in that: The preparation method of the waterproofing membrane comprises the steps of coating the self-cleaning coating for waterproofing membranes on the surface of the substrate, drying, and then curing by ultraviolet light irradiation to obtain a coating.

18. The method of producing a waterproofing membrane according to claim 17, characterized in that: The drying is performed at a temperature of 60-70°C; and / or, the ultraviolet light irradiation curing is performed at a wavelength of 310-420 nm for an irradiation time of 60±10 s.

Images