A highway marking material suitable for coastal areas and a method for preparing the same

Abstract

This invention discloses a road marking material suitable for coastal areas and its preparation method, belonging to the field of road marking materials. The material is a two-component system, including component A and component B. Component A comprises: an unsaturated acid-modified waterborne epoxy resin emulsion, an organosilicon-modified chlorinated polyethylene coating, and a composite anti-slip and anti-mildew filler dispersed in the two-phase composite matrix formed by the unsaturated acid-modified waterborne epoxy resin emulsion and the organosilicon-modified chlorinated polyethylene coating. The composite anti-slip and anti-mildew filler includes nano-hydroxyapatite-modified sepiolite. Component B contains a curing agent capable of undergoing a curing reaction with component A to form a coating film. This invention constructs a two-phase composite matrix of epoxy resin and organosilicon-modified chlorinated polyethylene, and introduces functional components such as nano-hydroxyapatite-modified sepiolite. The marking material achieves multiple properties suitable for the specific needs of road markings in coastal areas, including salt spray resistance, strong anti-slip properties, mildew inhibition, and low-temperature crack resistance.

Description

Technical Field

[0001] This invention relates to the field of road engineering materials technology, specifically to a road marking material suitable for coastal areas and its preparation method. Background Technology

[0002] Road markings are crucial for guiding traffic flow and ensuring driving safety. Exposed to the natural environment for extended periods, they must withstand sun, rain, and vehicle impacts and abrasion, thus requiring strict control over drying time, reflectivity, skid resistance, and wear resistance. Coastal areas, in particular, present unique challenges due to their unique geographical environment, characterized by the coexistence and interaction of heat, humidity, salt spray, and mold, which impose extremely stringent requirements on the corrosion resistance, durability, and stability of road marking materials.

[0003] Currently, commonly used base materials for road marking paints include epoxy resin, polyurethane, and chlorinated rubber. Among them, epoxy resin coatings are widely used due to their excellent adhesion, impermeability, and mechanical strength. However, traditional epoxy resins are brittle and lack flexibility, making them prone to cracking and peeling in coastal areas due to temperature differences and substrate deformation. Furthermore, their resistance to salt spray and mold is insufficient, making it difficult to maintain stable performance in the harsh coastal environment over long periods. Although existing technologies have attempted modification by adding elastomers or fillers, such as introducing graphene or chlorosulfonated polyethylene into the epoxy system to improve certain properties, they have not yet systematically solved the problem of synergistically improving the six key properties: salt spray corrosion resistance, high reflectivity, strong anti-slip properties, rapid curing, mold inhibition, and low-temperature crack resistance, thus failing to meet the special service requirements of coastal areas. Summary of the Invention

[0004] This invention aims to solve the above-mentioned problems in the prior art and provide a road marking material and its preparation method that can achieve multiple advantages such as salt spray corrosion resistance, high reflectivity, strong anti-skid performance, rapid curing, mold inhibition, and low temperature crack resistance, and is particularly suitable for coastal areas.

[0005] To achieve the above objectives, the present invention provides a road marking material suitable for coastal areas, comprising component A and component B; component A comprises: an unsaturated acid-modified waterborne epoxy resin emulsion, an organosilicon-modified chlorinated polyethylene coating, and a composite anti-slip and anti-mildew filler dispersed in a biphase composite matrix formed by the unsaturated acid-modified waterborne epoxy resin emulsion and the organosilicon-modified chlorinated polyethylene coating, wherein the composite anti-slip and anti-mildew filler comprises nano-hydroxyapatite-modified sepiolite; component B comprises a curing agent capable of undergoing a curing reaction with component A to form a coating film.

[0006] Furthermore, the composite anti-slip and mildew-resistant filler also contains one or more of the following: nano-alumina modified diatomaceous earth, titanium dioxide, mica powder, quartz sand, and calcium carbonate.

[0007] Furthermore, component A also contains double-bond nano-zirconia composite modified graphene.

[0008] Furthermore, component A also includes gradient-modified glass reflective microspheres, which are a mixture of two or more glass microspheres of different particle sizes that have been surface-treated with a silane coupling agent.

[0009] Furthermore, component A further comprises coloring pigment and auxiliary agent one, and component B further comprises auxiliary agent two; the composition of each component by weight is as follows: Component A: 15-25 parts of unsaturated acid-modified waterborne epoxy resin emulsion; 5-10 parts of organosilicon-modified chlorinated polyethylene coating; 0.5-0.8 parts of double bond-nanozirconia composite modified graphene; 40-50 parts of composite anti-slip and mildew-resistant filler; 2-10 parts of coloring pigment; 8-12 parts of gradient-modified glass reflective microspheres; 1-5 parts of additives. Component B: 5-10 parts curing agent; 1-2 parts additive II.

[0010] Furthermore, the first additive includes a dispersant, an anti-settling agent, a thickener, an adhesion promoter, and an anti-salt spray agent; the second additive includes a film-forming agent, an anti-foaming agent, and an anti-sagging agent.

[0011] Furthermore, the organosilicon-modified chlorinated polyethylene coating is prepared by a method comprising the following steps: dissolving chlorinated polyethylene in a solvent, adding γ-aminopropyltriethoxysilane and an initiator, and carrying out a grafting reaction under an inert gas atmosphere to obtain organosilicon-modified chlorinated polyethylene; emulsifying the organosilicon-modified chlorinated polyethylene to obtain the organosilicon-modified chlorinated polyethylene coating.

[0012] Furthermore, the nano-hydroxyapatite-modified sepiolite is prepared by a method comprising the following steps: acid activation treatment of sepiolite to obtain activated sepiolite; preparation of a nano-hydroxyapatite precursor solution; addition of the activated sepiolite to the nano-hydroxyapatite precursor solution, so that the nano-hydroxyapatite is deposited in situ in the pores and / or surface of the sepiolite; and drying and calcination to obtain nano-hydroxyapatite-modified sepiolite.

[0013] Furthermore, the double-bond-nanozirconia composite modified graphene is prepared by a method comprising the following steps: refluxing graphene with maleic anhydride solution to obtain double-bond modified graphene; mixing the double-bond modified graphene with nanozirconia, followed by ultrasonic dispersion and drying to obtain double-bond-nanozirconia composite modified graphene.

[0014] This invention also provides a method for preparing road marking materials suitable for coastal areas, characterized by the following steps: Preparing component A: A waterborne epoxy resin emulsion modified with unsaturated acid is mixed evenly with an organosilicon-modified chlorinated polyethylene coating to form a biphase composite matrix; then, composite anti-slip and anti-mildew fillers and other components are added sequentially to the biphase composite matrix, stirred evenly, and then ground to obtain component A; Preparing component B: A curing agent and additives are mixed evenly to obtain component B; When using, component A and component B are mixed.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: I. The road marking material prepared by this invention is designed for the harsh environment of coastal areas where humidity, heat, salt spray, and mold coexist. By constructing a two-phase composite matrix of epoxy resin and organosilicon-modified chlorinated polyethylene, and introducing multifunctional fillers such as nano-hydroxyapatite-modified sepiolite, the salt spray resistance of the marking material is improved to more than 190 hours, and the anti-mold performance reaches level 0 (the highest level), which significantly extends the service life of road markings in coastal areas.

[0016] II. This invention achieves a retroreflective coefficient of 230 mcd·lx at night through the synergistic optical effects of double-bond-nanozirconia composite modified graphene, gradient-modified reflective glass microspheres, and high-refractive-index pigments. -1 ·m -2 In addition, the multi-level anti-skid structure constructed by modifying diatomaceous earth, quartz sand and mica powder with nano-alumina achieves an anti-skid coefficient (BPN) of over 62, which steadily improves the safety of driving at night and in rainy weather.

[0017] Third, the technical solution of this invention achieves rapid curing in 10-12 minutes through a two-component design, reducing traffic interference. The introduction of organosilicon-modified chlorinated polyethylene endows the coating with excellent flexibility (Grade 1), and combined with the composite curing system, ensures that the coating does not crack at low temperatures, has strong adhesion (Grade 1-2), and excellent comprehensive mechanical properties. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below with reference to specific embodiments. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0019] In the following examples, all raw materials used are commercially available (unless otherwise stated) or can be prepared by known methods.

[0020] "Unsaturated acid-modified waterborne epoxy resin emulsion" is selected from waterborne epoxy resin emulsions grafted with acrylic acid or methacrylic acid.

[0021] The "coloring pigments" can be selected as needed, such as titanium dioxide (white) or iron oxide red (red).

[0022] In "Additive 1", the dispersant is a nonionic polymer, the anti-settling agent is fumed silica, the thickener is acrylic, the adhesion promoter is silane, and the anti-salt spray additive is a polyacid-amine complex type anti-salt spray additive.

[0023] In “Auxiliary Agent 2”, the film-forming aid is propylene glycol, the anti-sagging aid is fumed silica, and the defoamer is organosilicon.

[0024] The "curing agent" is selected from at least one of polyamide-amine copolymer and propylene oxide butyl ether.

[0025] Preparation Example 1 (1) Preparation of organosilicon-modified chlorinated polyethylene coating S1: Raw material dissolution: Add chlorinated polyethylene with a chlorine content of 30%~35% and a molecular weight of 20000~30000 to toluene solvent at a solid-liquid ratio of 1:5, and stir at a constant temperature of 80℃ for 3 hours until completely dissolved.

[0026] S2: Grafting modification: Add 3%~5% by weight of γ-aminopropyltriethoxysilane to the solution of chlorinated polyethylene, add 0.5% benzoyl peroxide (initiator), purge with nitrogen for protection, and heat to 100℃ for 4 h.

[0027] S3: After product purification, the toluene solvent is removed by vacuum distillation (80℃, -0.09MPa) to obtain solid organosilicon-modified chlorinated polyethylene.

[0028] S4: In the emulsification process, silicone-modified chlorinated polyethylene is added to deionized water, the solid content is controlled at 40%, 0.3% emulsifier OP-10 is added, and emulsification is carried out for 30 minutes using a high-speed shear emulsifier (10000 r / min) to obtain a stable emulsion.

[0029] (2) Preparation of nano-hydroxyapatite-modified sepiolite S1: Raw material pretreatment: Take natural sepiolite mineral powder with a particle size ≤10 μm, add 10% hydrochloric acid solution (solid-liquid ratio 1:10), stir at 80℃ for 2 h, filter and wash until neutral, and dry at 110℃ for 4 h to obtain activated sepiolite.

[0030] S2: Precursor preparation: Calcium nitrate and diammonium hydrogen phosphate were dissolved in deionized water at a Ca / P molar ratio of 1.67 to prepare a 0.1 mol / L mixed solution, and the pH was adjusted to 9.0 with ammonia.

[0031] S3 loading modification involves adding activated sepiolite to a precursor solution (solid-liquid ratio 1:20), stirring at 60°C for 4 h, filtering, vacuum drying at 80°C for 6 h, and then calcining at 300°C for 2 h to obtain nano-hydroxyapatite modified sepiolite.

[0032] (3) Preparation of double bond-nanozirconia composite modified graphene S1: Double bond modification, increasing the specific surface area to 150~250 m² 2 / g of nanosheet graphene with ≤10 layers was added to a 5%~8% maleic anhydride ethanol solution and refluxed at 80~90℃ for 3~4 h. After filtration and drying, double bond modified graphene was obtained.

[0033] S2: Nano-zirconia doping: Add 1~2% by weight of nano-zirconia (particle size 1~5 μm) to graphene, disperse by ultrasonication at 300~500 W for 15~20 min, and vacuum dry (80℃, 2 h) to obtain composite modified graphene.

[0034] (4) Preparation of gradient-modified glass reflective microspheres Mix two or more glass microspheres of different sizes, immerse them in an ethanol solution of 2%~3% silane coupling agent KH-560, stir at 60~70℃ for 1.5~2 h, dry at 120℃ for 30 min, and set aside for later use.

[0035] (5) Pretreatment of composite anti-slip and mildew-proof filler Titanium dioxide, mica powder, quartz sand, nano-alumina modified diatomaceous earth, nano-hydroxyapatite modified sepiolite and calcium carbonate are mixed according to the formula ratio, and passed through an 80-100 mesh sieve to remove impurities and large particles, and then set aside.

[0036] Example 1 Component A: 15 parts acrylic modified waterborne epoxy resin emulsion, 5 parts organosilicon modified chlorinated polyethylene coating, 0.5 parts composite modified graphene, 40 parts composite anti-slip and mildew-resistant filler (mixed from 11.2 parts titanium dioxide, 7.2 parts mica powder, 4 parts quartz sand, 3.2 parts nano alumina modified diatomaceous earth, 2.4 parts nano hydroxyapatite modified sepiolite, and 12 parts calcium carbonate), 4 parts titanium dioxide (coloring pigment), 8 parts gradient reflective microspheres, 1.8 parts additive one (0.5 parts dispersant, 0.3 parts anti-settling agent, 0.2 parts thickener, 0.5 parts adhesion promoter, and 0.3 parts anti-salt spray additive).

[0037] Prepared using the following process: Add acrylic-modified waterborne epoxy resin emulsion to a mixing tank, and slowly add organosilicon-modified chlorinated polyethylene coating while stirring at 600 r / min. Stir for 30 min to obtain a composite emulsion.

[0038] Reduce the rotation speed to 300-500 r / min, slowly add the composite modified graphene, and stir for 15-20 min.

[0039] Add the pretreated composite filler and pigment in 3 to 4 batches, stirring for 10 to 15 minutes after each batch.

[0040] Add each component of Additive 1 in sequence, stirring for 8-12 minutes after each addition, and adjust the system viscosity to 5000-8000 mPa·s.

[0041] The mixture is fed into a three-roll mill and ground 2-3 times to control the particle size ≤30 μm, thus obtaining component A.

[0042] Component B: 5 parts composite curing agent (4 parts polyamide-amine copolymer, 1 part propylene oxide butyl ether), 1 part auxiliary agent II (0.5 parts film-forming aid, 0.3 parts anti-sagging aid, 0.2 parts defoamer). Mix thoroughly in a stirred tank at 200~300 r / min, and adjust the viscosity to 3000~5000 mPa·s.

[0043] Mixed application: Mix components A and B evenly at a mass ratio of 10:1, and apply to the road surface using an external spray gun.

[0044] Example 2 Component A: 20 parts methacrylic acid modified waterborne epoxy resin emulsion, 8 parts organosilicon modified chlorinated polyethylene coating, 0.6 parts composite modified graphene, 45 parts composite anti-slip and mildew-resistant filler (12.6 parts titanium dioxide, 8.1 parts mica powder, 4.5 parts quartz sand, 3.6 parts nano-alumina modified diatomaceous earth, 2.7 parts nano-hydroxyapatite modified sepiolite, 13.5 parts calcium carbonate), 6 parts titanium dioxide, 10 parts gradient reflective microspheres, 3.3 parts additive one (1.0 part dispersant, 0.5 part anti-settling agent, 0.5 part thickener, 0.8 part adhesion promoter, 0.5 part anti-salt spray additive). The preparation process is the same as in Example 1.

[0045] Component B: 8 parts composite curing agent (6.4 parts polyamide-amine copolymer, 1.6 parts propylene oxide butyl ether), 1.5 parts auxiliary agent II (0.8 parts film-forming aid, 0.5 parts anti-sagging aid, 0.3 parts defoamer). The preparation process is the same as in Example 1.

[0046] Mixed application: Mix components A and B evenly at a mass ratio of 11:1 and spray onto the road surface.

[0047] Example 3 Component A: 25 parts acrylic-modified waterborne epoxy resin emulsion, 10 parts silicone-modified chlorinated polyethylene coating, 0.8 parts composite modified graphene, 50 parts composite anti-slip and mildew-resistant filler (14 parts titanium dioxide, 9 parts mica powder, 5 parts quartz sand, 4 parts nano-alumina-modified diatomaceous earth, 3 parts nano-hydroxyapatite-modified sepiolite, 15 parts calcium carbonate), 10 parts titanium dioxide, 12 parts gradient reflective microspheres, 5 parts additive one (1.5 parts dispersant, 0.8 parts anti-settling agent, 0.7 parts thickener, 1.2 parts adhesion promoter, 0.8 parts anti-salt spray additive). The preparation process is the same as in Example 1.

[0048] Component B: 10 parts composite curing agent (8 parts polyamide-amine copolymer, 2 parts propylene oxide butyl ether), 2 parts auxiliary agent II (1.0 part film-forming aid, 0.6 parts anti-sagging aid, 0.4 parts defoamer). The preparation process is the same as in Example 1.

[0049] Mixed application: Mix components A and B evenly at a mass ratio of 12:1 and spray onto the road surface.

[0050] Comparative Example The comparative example uses a conventional epoxy marking system, without introducing the core modifying component of this invention, as detailed below: Component A: 25 parts ordinary waterborne epoxy resin emulsion, 5 parts unmodified chlorinated polyethylene coating (commercially available), 0.5 parts ordinary graphene (unmodified), 45 parts ordinary filler (titanium dioxide + heavy calcium carbonate + quartz sand), 10 parts ordinary glass microspheres (single particle size, untreated), 2 parts additives (dispersant, defoamer, etc.). The preparation process is the same as in Example 1.

[0051] Component B: 8 parts ordinary polyamide curing agent, 1 part additive. The preparation process is the same as in Example 1.

[0052] Mixed application: Mix components A and B evenly at a mass ratio of 10:1 and spray onto the road surface.

[0053] Performance test results and analysis: Table 1 Comparison of performance test results between the examples and the comparative examples

[0054] (1) Salt spray resistance analysis Salt spray resistance is a key indicator for evaluating the corrosion resistance of materials in coastal salt spray environments. Table 1 shows that the salt spray resistance times of Examples 1-3 reached 190 h, 195 h, and 192 h, respectively, while the comparative example only reached 96 h. The salt spray resistance performance of the embodiments of this invention is nearly 100% improved. This significant improvement in performance is mainly attributed to the construction of the dual-phase composite matrix and the synergistic effect of the multifunctional filler. Organosilicon-modified chlorinated polyethylene coatings form a continuous elastic dispersed phase in the epoxy resin matrix. Its low surface energy and hydrophobic properties effectively block the penetration path of chloride ions, inhibiting the intrusion of corrosive media at the source. The introduction of nano-hydroxyapatite-modified sepiolite and composite modified graphene further strengthens the anti-corrosion barrier of the coating. The unique microporous structure of sepiolite can physically adsorb salt spray ions, while hydroxyapatite can chemically fix corrosive ions, forming a dual barrier combining physical adsorption and chemical fixation. Sheet graphene forms a "maze effect" in the coating, greatly extending the diffusion path of corrosive media. The synergistic effect of these three elements results in excellent salt spray resistance of the coating material.

[0055] (2) Analysis of retroreflection coefficient Retroreflection coefficient directly determines the visibility of road markings at night and is a core indicator for ensuring nighttime driving safety. Test results show that the retroreflection coefficients of Examples 1-3 reach 235, 245, and 242 mcd·lx, respectively. -1 ·m -2 It is significantly higher than the comparative example of 180 mcd·lx -1 ·m -2 The optimized design of gradient-modified glass reflective microspheres plays an effective role: two or more microspheres with different particle sizes form a tightly packed structure in the coating. After surface treatment with silane coupling agent, the interfacial bonding force between the microspheres and the substrate is greatly enhanced, effectively avoiding the problem of microspheres falling off during use and ensuring the long-term stability of reflective performance.

[0056] Meanwhile, optical synergy and matrix transparency jointly contribute to the high retroreflection performance. The nano-zirconia in the double-bond-nano-zirconia composite modified graphene has high refractive index characteristics, forming an optical coupling system with titanium dioxide and glass microspheres, which significantly improves the incident efficiency and reflection intensity of light. The epoxy-chlorinated polyethylene composite matrix itself has high light transmittance, effectively reducing the scattering loss of light during propagation, allowing more light to reach the reflective microspheres and be reflected back to the light source, thus achieving a retroreflection coefficient far exceeding the standard.

[0057] (3) Analysis of anti-skid coefficient The coefficient of friction (BPN) is an important indicator for ensuring driving safety in rainy weather, directly reflecting the anti-skid ability of the pavement surface. Test results show that the BPN values ​​of Examples 1-3 are 62, 65, and 64 respectively, exceeding the 45 BPN requirement specified in GB / T 16311.

[0058] Quartz sand provides macroscopic roughness, nano-alumina-modified diatomaceous earth provides microscopic roughness, and the flake-like structure of mica powder forms layered protrusions. These three elements work synergistically to construct a multi-scale anti-skid surface ranging from millimeters to nanometers, effectively increasing the coefficient of friction between the tire and the road marking surface. Furthermore, the nano-zirconia in the double-bond-nano-zirconia composite-modified graphene possesses high hardness and excellent wear resistance. When uniformly dispersed in the coating, it significantly improves the coating's wear resistance, allowing the surface's microscopic roughness structure to be maintained under long-term vehicle pressure. This optimized design of "multi-level anti-skid structure + high wear resistance enhancement" ensures that the road markings maintain stable anti-skid performance throughout their service life, providing a guarantee for driving safety in rainy and snowy weather.

[0059] (4) Flexibility and Adhesion Analysis Flexibility and adhesion are important indicators for evaluating the mechanical properties and crack resistance of coatings, directly affecting the integrity of markings under substrate deformation and temperature changes. Examples 1-3 all achieved a flexibility level of 1 (optimal level) and adhesion level of 1-2 (excellent level), while the comparative example only achieved a level of 3 (poor level). Chlorinated polyethylene itself possesses excellent flexibility. After organosilicon grafting modification, it forms a semi-interpenetrating network structure with epoxy resin. While maintaining the high bonding strength of epoxy resin, it effectively alleviates its inherent brittleness and cracking tendency. The introduction of organosilicon-modified chlorinated polyethylene achieves a good balance between strength and toughness.

[0060] Meanwhile, the toughening effect of nanofillers and the synergistic effect of adhesion promoters further enhance the mechanical properties of the coating. The fibrous structure of sepiolite can act as a bridge during crack propagation, effectively preventing further crack development; the needle-like crystals of nano-hydroxyapatite also have a toughening effect, forming a multi-scale toughening network with sepiolite. In addition, silane-based adhesion promoters form chemical bonds between the coating and the inorganic substrate (concrete, asphalt), significantly improving the interfacial bonding strength, making the coating less prone to peeling when subjected to impact or substrate deformation, ensuring the long-term service capability of the road markings in the complex coastal environment.

[0061] (5) Curing time analysis Curing speed directly affects construction efficiency and the degree of traffic disruption, and is an important indicator for evaluating the practicality of road marking materials. Test results show that the surface drying time of Examples 1-3 at room temperature is only 10-12 minutes, and the surface drying time at low temperature (5℃) is only 18-20 minutes, while the comparative examples take as long as 25 minutes at room temperature and even more than 45 minutes at low temperature. The curing speed of the embodiments of the present invention is more than doubled.

[0062] The combined use of polyamide-amine copolymer and propylene oxide butyl ether ensures the curing crosslinking density while accelerating the ring-opening reaction of epoxy groups through catalysis, enabling the coating to reach surface dryness in a shorter time. Unsaturated acid-modified waterborne epoxy resin has better hydrophilicity and reactivity. The unsaturated acid groups introduced into its molecular structure can promote the rapid evaporation of water molecules and undergo a more efficient crosslinking reaction with the curing agent. This allows the material of this invention to achieve rapid curing in 10-12 minutes at room temperature and maintain a relatively fast curing speed of 18-20 minutes even at low temperatures. This significantly reduces road closure time, minimizes the impact on traffic on busy road sections, and has a significant advantage in construction efficiency.

[0063] (6) Anti-mildew performance analysis Anti-mold performance is a key indicator for road marking materials in coastal areas, as the humid and hot environment easily breeds mold, leading to fading and peeling of the markings, severely affecting their functionality and aesthetics. Examples 1-3 all achieved the highest anti-mold performance level of 0 (no mold growth after 28 days of incubation), while the comparative example only reached level 2 (slight mold growth). The innovative introduction of nano-hydroxyapatite-modified sepiolite played a crucial role. Hydroxyapatite possesses natural antibacterial activity; its calcium ions can interact with the cell walls of bacteria and mold, disrupting the structural integrity of microorganisms, thereby achieving antibacterial and anti-mold effects. Sepiolite, with its excellent adsorption properties, can fix mold spores in its microporous structure, inhibiting their reproduction and growth.

[0064] Building upon this, the hydrophobic properties of silicone-modified chlorinated polyethylene further enhance the coating's anti-mold capability. The silicone segments possess low surface energy and hydrophobic / oleophobic properties, effectively reducing the likelihood of mold adhesion and growth on the coating surface, forming a physical anti-mold barrier. This dual mechanism of chemical antibacterial action and physical anti-mold treatment allows the material of this invention to maintain surface cleanliness for extended periods in humid coastal environments, preventing fading and peeling of markings due to mold erosion, thus providing a reliable guarantee for the long-term service life of the markings.

[0065] In summary, this invention, through innovative integration of a two-phase composite matrix, multifunctional synergistic filler, and dedicated curing control technology, has successfully achieved significant superiority over the comparative examples in key indicators such as salt spray resistance, retroreflective coefficient, anti-slip coefficient, flexibility, adhesion, curing speed, and anti-mildew performance in Examples 1-3. In particular, the salt spray resistance is improved by nearly 100%, the anti-mildew performance is improved from level 2 to level 0, and the anti-slip coefficient is improved from unqualified (45) to excellent (62+), demonstrating the excellent adaptability of the technical solution of this invention to the complex coastal environment and the significant technological advancement.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A highway marking material suitable for use in coastal areas, characterized in that, Includes component A and component B; Component A comprises: an unsaturated acid-modified waterborne epoxy resin emulsion, an organosilicon-modified chlorinated polyethylene coating, and a composite anti-slip and anti-mildew filler dispersed in the biphase composite matrix formed by the unsaturated acid-modified waterborne epoxy resin emulsion and the organosilicon-modified chlorinated polyethylene coating, wherein the composite anti-slip and anti-mildew filler comprises nano-hydroxyapatite-modified sepiolite. Component B contains a curing agent that can react with component A to form a coating film.

2. The highway marking material suitable for use in coastal areas according to claim 1, wherein, The composite anti-slip and mildew-resistant filler also contains one or more of the following: nano-alumina modified diatomaceous earth, titanium dioxide, mica powder, quartz sand, and calcium carbonate.

3. The highway marking material suitable for use in coastal areas according to claim 1, wherein, Component A also contains double-bond nano-zirconia composite modified graphene.

4. The highway marking material suitable for use in coastal areas according to claim 3, wherein, Component A further includes gradient-modified glass reflective microspheres, which are a mixture of two or more glass microspheres of different particle sizes that have been surface-treated with a silane coupling agent.

5. The road marking material suitable for coastal areas according to claim 4, characterized in that, Component A further includes coloring pigment and additive one, and component B further includes additive two; The composition of each component, by weight, is as follows: Component A: 15-25 parts of unsaturated acid-modified waterborne epoxy resin emulsion; 5-10 parts of silicone-modified chlorinated polyethylene coating; 0.5~0.8 parts of double bond-nanozirconia composite modified graphene; 40-50 parts of composite anti-slip and mildew-resistant filler; 2-10 parts of coloring pigment; Gradient-modified glass reflective microspheres, 8-12 parts; Additive 1-5 parts; Component B: 5-10 parts of curing agent; Additive 2, 1-2 parts.

6. The road marking material suitable for coastal areas according to claim 5, characterized in that, The first auxiliary agent includes a dispersant, an anti-settling agent, a thickener, an adhesion promoter, and an anti-salt spray agent; the second auxiliary agent includes a film-forming agent, an anti-foaming agent, and an anti-sagging agent.

7. The road marking material suitable for coastal areas according to claim 1, characterized in that, The organosilicon-modified chlorinated polyethylene coating is prepared by a method comprising the following steps: Chlorinated polyethylene is dissolved in a solvent, and γ-aminopropyltriethoxysilane and an initiator are added. A grafting reaction is carried out under inert gas protection to obtain organosilicon-modified chlorinated polyethylene. The organosilicon-modified chlorinated polyethylene is emulsified to obtain an organosilicon-modified chlorinated polyethylene coating.

8. The road marking material suitable for coastal areas according to claim 1, characterized in that, The nano-hydroxyapatite-modified sepiolite is prepared by a method comprising the following steps: Sepiolite was acid-activated to obtain activated sepiolite; a nano-hydroxyapatite precursor solution was prepared; the activated sepiolite was added to the nano-hydroxyapatite precursor solution, so that the nano-hydroxyapatite was deposited in situ in the pores and / or surface of the sepiolite; after drying and calcination, nano-hydroxyapatite-modified sepiolite was obtained.

9. The road marking material suitable for coastal areas according to claim 3, characterized in that, The double-bond-nanozirconia composite modified graphene is prepared by a method comprising the following steps: Graphene was refluxed with maleic anhydride solution to obtain double-bond modified graphene; the double-bond modified graphene was mixed with nano-zirconia, and then ultrasonically dispersed and dried to obtain double-bond-nano-zirconia composite modified graphene.

10. A method for preparing a road marking material suitable for coastal areas as described in any one of claims 1-9, characterized in that, Includes the following steps: Preparation of Component A: Unsaturated acid-modified waterborne epoxy resin emulsion and organosilicon-modified chlorinated polyethylene coating are mixed evenly to form a two-phase composite matrix; then composite anti-slip and mildew-resistant filler and other components are added to the two-phase composite matrix in sequence, stirred evenly and then ground to obtain Component A. Preparation of component B: The curing agent and the additives are mixed evenly to obtain component B; When using, mix component A with component B.

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