Two-component quick-drying anti-skid self-cleaning road marking paint and preparation method thereof

Abstract

The present invention relates to the technical field of coatings, and in particular to a two-component quick-drying anti-skid self-cleaning road marking coating and a preparation method thereof. Component A is prepared from the following raw materials in parts by weight: 30-50 parts of an aqueous polyurethane dispersion; 5-10 parts of light-responsive self-repairing microcapsules; 3-8 parts of iron-doped nano-titanium dioxide; 8-15 parts of surface-modified anti-skid particles; 1-3 parts of a multifunctional silane coupling agent; 0.1-0.5 parts of a pH regulator; 0.2-0.6 parts of a bio-based defoamer; 0.5-1.5 parts of an intelligent temperature-sensitive thickener; 0.1-0.3 parts of a broad-spectrum antibacterial agent; and 10-40 parts of deionized water. Component B is prepared from the following raw materials in parts by weight: 20-40 parts of a water-dispersible isocyanate curing agent; 5-15 parts of a hyperbranched polyether modifier; 1-3 parts of hydrophobic nano-silica; 0.5-1.5 parts of a light stabilizer; and 40-70 parts of deionized water.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, in particular to a two-component quick-drying anti-skid self-cleaning road marking coating and a preparation method thereof. Background Art

[0002] Road markings, as an important component of traffic safety, play a vital role in improving road efficiency and reducing traffic accident rates. However, with the continuous increase in traffic volume and the complex changes in environmental factors, traditional road marking paints face many challenges.

[0003] First, while conventional hot-melt road marking paints offer good wear resistance, they produce a significant amount of harmful gases during application, which is inconsistent with modern environmental standards. Secondly, while water-based road marking paints are environmentally friendly, their durability and early water resistance are often unsatisfactory. Furthermore, existing road marking paints generally suffer from insufficient anti-slip properties, poor self-cleaning capabilities, and the inability to self-repair, all of which seriously impact the service life and functionality of road markings.

[0004] Furthermore, the performance of traditional road marking paints often deteriorates dramatically under extreme weather conditions, such as high or low temperatures or heavy rain. For example, in cold regions, the paint is prone to cracking due to temperature fluctuations; in rainy areas, the paint's anti-slip properties and water resistance are severely tested; and in hot regions, the paint is prone to softening and deformation. These issues not only increase road maintenance costs but, more importantly, threaten the safety of road users.

[0005] While there are some improvements in existing technologies, such as adding inorganic fillers to improve wear resistance or using special resins to enhance adhesion, these methods often compromise one area while also failing to simultaneously meet the requirements for quick drying, anti-slip properties, self-cleaning, self-repairing, and durability. In particular, existing technologies still have significant shortcomings in terms of self-repairing and long-term self-cleaning.

[0006] Therefore, there is an urgent need to develop new road marking coatings that can comprehensively solve the above problems to meet the urgent demand of modern transportation construction for high-performance, multifunctional and environmentally friendly road marking materials. Summary of the Invention

[0007] This invention aims to solve the following technical problems: how to improve the durability and early water resistance of a coating while ensuring its quick drying properties; how to achieve long-term anti-slip and self-cleaning properties; how to impart self-repairing capabilities to the coating, extending its service life; how to improve the coating's adaptability to various extreme environments; and how to meet the above requirements while ensuring the coating's environmental friendliness and ease of application. To address these technical issues, the present invention proposes a two-component, quick-drying, anti-slip, self-cleaning road marking paint and its preparation method. Through a carefully designed formula and preparation process, this paint cleverly combines multiple functional components, achieving synergistic benefits.

[0008] The object of the present invention is to provide a two-component quick-drying anti-skid self-cleaning road marking paint, comprising component A and component B, wherein:

[0009] Component A is made from the following raw materials in parts by weight:

[0010] 30-50 parts of waterborne polyurethane dispersion

[0011] 5-10 copies of light-responsive self-repairing microcapsules

[0012] 3-8 parts of iron-doped nano-titanium dioxide

[0013] 8-15 parts of surface modified anti-skid particles

[0014] 1-3 parts of multifunctional silane coupling agent

[0015] pH regulator 0.1-0.5 parts

[0016] 0.2-0.6 parts of bio-based defoamer

[0017] 0.5-1.5 parts of intelligent temperature-sensitive thickener

[0018] 0.1-0.3 parts of broad-spectrum antibacterial agent

[0019] 10-40 parts deionized water

[0020] Component B is made from the following raw materials in parts by weight:

[0021] 20-40 parts of water-dispersible isocyanate curing agent

[0022] 5-15 parts of hyperbranched polyether modifier

[0023] 1-3 parts hydrophobic nano-silica

[0024] Light stabilizer 0.5-1.5 parts

[0025] 40-70 parts of deionized water.

[0026] Specifically, the aqueous polyurethane dispersion has a solid content of 40 ± 1%, a pH value of 7.0-8.5, a viscosity (23°C) of 50-800 mPa·s, and an average particle size of 80-120 nm;

[0027] The multifunctional silane coupling agent is N-[3-(trimethoxysilyl)propyl]-1,2-ethylenediamine, which has a boiling point of 260°C, a flash point of 93°C, and a density (25°C) of 1.03 g / cm³.

[0028] Specifically, the pH adjuster is ammonium hydroxide in a 28% aqueous solution;

[0029] The broad-spectrum antibacterial agent is a mixture of 1,2-benzisothiazol-3(2H)-one and 2-methyl-4-isothiazoline-3-one, wherein the content of 1,2-benzisothiazol-3(2H)-one is 10-15%, and the content of 2-methyl-4-isothiazoline-3-one is 2-5%.

[0030] Specifically, the hyperbranched polyether modifier has a hydroxyl value of 230-250 mg KOH / g and a viscosity (23°C) of 3000-5000 mPa·s;

[0031] The hydrophobic nano-silica is pyrogenic silica treated with hexamethyldisilazane, with a specific surface area of 195-245 m² / g, an average particle size of 7 nm, and a carbon content of 3.0-4.0%.

[0032] Specifically,

[0033] The active ingredient content of the light stabilizer is 52-56%, and the pH value is 6.0-8.0;

[0034] The water-dispersible isocyanate curing agent is a water dispersion of hexamethylene diisocyanate, with an NCO content of 16.5-17.5% and a viscosity (23°C) of 500-2500 mPa·s.

[0035] The preparation method of the two-component quick-drying anti-skid self-cleaning road marking paint comprises the following steps:

[0036] (1) Preparation of component A:

[0037] First, add waterborne polyurethane dispersion into the reactor and stir at a speed of 300-400 rpm;

[0038] Secondly, photoresponsive self-repairing microcapsules were added and stirred for 30 minutes;

[0039] Then, iron-doped nano-titanium dioxide was added and stirred for 45 minutes;

[0040] Again, add surface-modified anti-skid particles and stir for 30 minutes;

[0041] Next, add the multifunctional silane coupling agent, pH regulator, bio-based defoamer and intelligent temperature-sensitive thickener in sequence, stirring for 10 minutes after each addition of raw materials;

[0042] Finally, a broad-spectrum antimicrobial agent was added, stirred for 15 minutes, and deionized water was added to adjust the solid content to 55-60%, stirred for 30 minutes, and filtered through a 100-mesh sieve to obtain component A;

[0043] (2) Preparation of component B:

[0044] First, add water-dispersible isocyanate curing agent into the reaction kettle and stir at a speed of 200-300 rpm;

[0045] Next, add the hyperbranched polyether modifier and stir for 20 minutes;

[0046] Then, hydrophobic nano-silica was added and stirred for 30 minutes;

[0047] Again, add the light stabilizer and stir for 15 minutes;

[0048] Finally, deionized water was added to adjust the solid content to 40-45%, stirred for 20 minutes, and filtered through a 200-mesh sieve to obtain component B.

[0049] Specifically, the preparation method of the light-responsive self-repairing microcapsules comprises the following steps:

[0050] (1) Preparation of the oil phase: Mix 5-10 parts by weight of dicyclopentadiene with 0.1-0.3 parts by weight of a photoresponsive Grubbs catalyst at 20-25°C with a stirring speed of 300-400 rpm for 15-20 minutes;

[0051] (2) Prepare the aqueous phase: Dissolve 1-2 parts by weight of polyvinyl alcohol in 100-150 parts by weight of deionized water, stirring at 500-600 rpm, at 60-70°C, for 30-40 minutes;

[0052] (3) preparing a monomer mixture: mixing 15-25 parts by weight of methyl methacrylate and 1-3 parts by weight of glycidyl methacrylate, and adding 0.2-0.5 parts by weight of azobisisobutyronitrile;

[0053] (4) Emulsification: Slowly add the oil phase to the water phase and emulsify at 60-70°C at a speed of 1000-1200 rpm for 15-20 minutes;

[0054] (5) Suspension polymerization: Slowly add the monomer mixture dropwise to the emulsion and stir (400-500 rpm) at 70-75°C for 3-4 hours;

[0055] (6) Cooling: Cool the reaction mixture to room temperature;

[0056] (7) Filtration, washing, and drying: Filter using a Buchner funnel, wash with deionized water 3-5 times, and vacuum dry at 40-50°C for 12-24 hours.

[0057] Specifically, the preparation method of the iron-doped nano-titanium dioxide comprises the following steps:

[0058] (1) Preparation of precursor solution: Dissolve 20-30 parts by weight of tetrabutyl titanate in 80-100 parts by weight of anhydrous ethanol, stirring at 300-400 rpm, at room temperature for 30 minutes; simultaneously, dissolve 0.5-1.5 parts by weight of ferric nitrate in 20-30 parts by weight of deionized water;

[0059] (2) Hydrolysis: Slowly add the iron salt solution dropwise to the titanate solution, increase the stirring speed to 600-800 rpm, and react at room temperature for 1-2 hours;

[0060] (3) Aging: The mixture was aged at 60-70°C with stirring (200-300 rpm) for 4-6 hours;

[0061] (4) Hydrothermal treatment: The aged sol was transferred to a polytetrafluoroethylene-lined autoclave and treated at 180-200°C for 8-12 hours;

[0062] (5) Cooling, filtering, and washing: Cool naturally to room temperature, filter, and wash with deionized water and anhydrous ethanol 3-5 times each;

[0063] (6) Drying and calcination: drying at 60-70°C for 12-24 hours, and then calcining at 400-500°C for 2-3 hours;

[0064] (7) Grinding: Grind the calcined sample to an average particle size of 20-30 nm.

[0065] Specifically, the preparation method of the surface-modified anti-slip particles comprises the following steps:

[0066] (1) Pretreatment: 100 parts by weight of α-alumina was vacuum dried at 120-130°C for 4-6 hours;

[0067] (2) Silanization: Add the pretreated alumina and 200-250 parts by weight of anhydrous toluene to a three-necked flask, stir and disperse (300-400 rpm) for 10-15 minutes; slowly add 3-5 parts by weight of 3-glycidyloxypropyltrimethoxysilane, raise the temperature to reflux (about 110-120°C), and stir and react for 4-6 hours;

[0068] (3) Cooling and filtration: Cool naturally to room temperature and filter;

[0069] (4) Washing: Wash with anhydrous toluene 3 times, then wash with anhydrous ethanol 2 times;

[0070] (5) Drying: Vacuum drying at 60-70°C for 12-24 hours.

[0071] Specifically, the preparation method of the intelligent temperature-sensitive thickener comprises the following steps:

[0072] (1) Preparation of monomer solution: In a three-necked flask, dissolve 15-20 parts by weight of N-isopropylacrylamide and 1-2 parts by weight of acrylamide in 150-200 parts by weight of deionized water, and pass nitrogen gas through the solution for 15-20 minutes to remove oxygen;

[0073] (2) Preparation of initiator solution: Dissolve 0.1-0.2 parts by weight of ammonium persulfate in 10-15 parts by weight of deionized water;

[0074] (3) Polymerization reaction: Heat the monomer solution to 60-65°C with a stirring speed of 300-400 rpm; slowly add the initiator solution dropwise and allow to react for 4-6 hours;

[0075] (4) Termination of the reaction: Cool the reaction mixture to room temperature and allow air to flow for 10-15 minutes;

[0076] (5) Purification: The reaction product was poured into excess acetone for precipitation, filtered, and washed with acetone three times;

[0077] (6) Drying: Vacuum drying at 40-50°C for 24-48 hours.

[0078] Specifically, the core innovations of the present invention and its mechanism of action are as follows:

[0079] 1. Combination of a waterborne polyurethane dispersion and a water-dispersible isocyanate curing agent: These two components form a cross-linked network structure at the molecular level. The hydroxyl groups (-OH) on the polyurethane molecular chain react with the -NCO groups of the isocyanate to form a hydrolysis-resistant urea bond (-NHCOO-). This not only provides excellent film-forming properties and adhesion, but also significantly improves the water resistance and durability of the coating.

[0080] 2. Photoresponsive self-healing microcapsules: These microcapsules contain dicyclopentadiene monomer and a photoresponsive Grubbs catalyst. When the coating is damaged, the microcapsules rupture, releasing their contents. Under ultraviolet light, the catalyst is activated, initiating a ring-opening metathesis polymerization of dicyclopentadiene, thereby repairing the cracks. This process requires no external intervention, significantly extending the coating's lifespan.

[0081] 3. Iron-doped nano-titanium dioxide: By doping with iron ions, the light response range of titanium dioxide is broadened, so that it can also play a photocatalytic role under visible light. When light irradiates the coating surface, iron-doped titanium dioxide generates electron-hole pairs, which in turn generate active oxygen species (such as ·OH, ·O 2- These active species can effectively decompose organic pollutants and realize the self-cleaning function of the coating.

[0082] 4. Surface-Modified Anti-Slip Particles: Surface modification of alumina particles using a silane coupling agent not only improves the compatibility of the particles with the polyurethane matrix but also creates a microscopic roughness on the coating surface. This structure significantly increases the coefficient of friction, providing excellent anti-slip properties. Silane modification also strengthens the adhesion between the particles and the matrix, improving the overall mechanical properties of the coating.

[0083] 5. Intelligent Thermosensitive Thickener: Poly(N-isopropylacrylamide-co-acrylamide) copolymer exhibits a low critical solution temperature (LCST). At low temperatures, the polymer chains expand, providing excellent fluidity. As the temperature rises, the polymer chains contract, forming a cross-linked network that increases the viscosity of the coating. This intelligent response not only improves application performance but also provides additional anti-slip properties under certain operating conditions.

[0084] 6. Hyperbranched polyether modifier: Its unique tree-like molecular structure provides numerous terminal functional groups, increasing the number of interaction points with other components. This not only increases the coating's crosslinking density but also enhances its flexibility and low-temperature adaptability. Furthermore, the microscopic phase separation created by the hyperbranched structure helps improve the coating's weather resistance and self-cleaning durability.

[0085] 7. Hydrophobic Nanosilica: Treated with hexamethyldisilazane, these nanoparticles create a micro-nanoscale rough structure on the coating surface. Combined with the inherent low surface energy of the material, this creates a super-hydrophobic effect on the coating surface. This not only enhances the self-cleaning ability but also improves the coating's stain resistance and durability.

[0086] Through sophisticated formulation and preparation, these innovative components form a highly synergistic, multifunctional system within the coating. For example, the repairing properties of the self-healing microcapsules and the self-cleaning function of the iron-doped titanium dioxide complement each other, extending the coating's lifespan. The combination of an intelligent temperature-sensitive thickener and surface-modified anti-slip particles ensures excellent anti-slip performance under varying temperature conditions.

[0087] The beneficial effects of the present invention include:

[0088] 1. The perfect combination of quick-drying and durability achieves the dual goals of fast traffic and long-term use;

[0089] 2. Excellent anti-slip performance, significantly improving road safety;

[0090] 3. Long-lasting self-cleaning effect greatly reduces maintenance costs;

[0091] 4. Unique self-repairing function greatly extends the service life of the coating;

[0092] 5. Excellent environmental adaptability, can maintain stable performance under various extreme climatic conditions;

[0093] 6. Environmentally friendly water-based system reduces VOC emissions and meets the requirements of sustainable development;

[0094] 7. Intelligent temperature-sensitive characteristics improve construction performance and provide additional functional advantages.

[0095] In summary, this invention, through the organic integration of multiple innovative technologies, not only solves many of the problems faced by traditional road marking paints but also achieves several unexpected technical benefits. This high-performance, multifunctional, and environmentally friendly road marking paint will undoubtedly provide strong technical support for modern transportation construction and road safety. DETAILED DESCRIPTION

[0096] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0097] In the coating of the present invention, the waterborne polyurethane dispersion is BayhydrolUH 2558 waterborne polyurethane dispersion from Covestro (formerly Bayer MaterialScience), with a solid content of 40 ± 1%, a pH value of 7.0-8.5, a viscosity (at 23°C) of 50-800 mPa·s, and an average particle size of 80-120 nm;

[0098] The multifunctional silane coupling agent used is GENIOSIL® GF 91 from Wacker Chemical Company, which is N-[3-(trimethoxysilyl)propyl]-1,2-ethylenediamine, with a boiling point of 260°C, a flash point of 93°C, and a density (25°C) of 1.03 g / cm³.

[0099] The pH regulator is ammonium hydroxide, which is a 28% aqueous solution, that is, ammonia water;

[0100] The broad-spectrum antimicrobial agent is BIOBAN™ 551S from Dow Chemical Company, which is a mixture of 1,2-benzisothiazol-3(2H)-one (BIT) and 2-methyl-4-isothiazolin-3-one MIT, wherein the content of 1,2-benzisothiazol-3(2H)-one is 10-15%, and the content of 2-methyl-4-isothiazolin-3-one is 2-5%.

[0101] The hyperbranched polyether modifier is BASF's Boltorn™ H311, which has a hydroxyl value of 230-250 mgKOH / g and a viscosity (23°C) of 3000-5000 mPa·s.

[0102] The hydrophobic nano-silica is AEROSIL ® R812S is hexamethyldisilazane treated fumed silica with a surface area of 195-245 m² / g, an average particle size of 7 nm, and a carbon content of 3.0-4.0%.

[0103] The light stabilizer is Tinuvin produced by BASF ® 5333-DW, with an active ingredient content of 52-56% and a pH of 6.0-8.0;

[0104] The water-dispersible isocyanate curing agent selected is Bayhydur 3100 from Covestro, which is an aqueous dispersion of hexamethylene diisocyanate with an NCO content of 16.5-17.5% and a viscosity (at 23°C) of 500-2500 mPa·s.

[0105] The preparation method of the light-responsive self-repairing microcapsules comprises the following steps:

[0106] (1) Preparation of the oil phase: Mix 5-10 parts by weight of dicyclopentadiene with 0.1-0.3 parts by weight of a photoresponsive Grubbs catalyst at 20-25°C with a stirring speed of 300-400 rpm for 15-20 minutes;

[0107] (2) Prepare the aqueous phase: Dissolve 1-2 parts by weight of polyvinyl alcohol in 100-150 parts by weight of deionized water, stirring at 500-600 rpm, at 60-70°C, for 30-40 minutes;

[0108] (3) preparing a monomer mixture: mixing 15-25 parts by weight of methyl methacrylate and 1-3 parts by weight of glycidyl methacrylate, and adding 0.2-0.5 parts by weight of azobisisobutyronitrile;

[0109] (4) Emulsification: Slowly add the oil phase to the water phase and emulsify at 60-70°C at a speed of 1000-1200 rpm for 15-20 minutes;

[0110] (5) Suspension polymerization: Slowly add the monomer mixture dropwise to the emulsion and stir (400-500 rpm) at 70-75°C for 3-4 hours;

[0111] (6) Cooling: Cool the reaction mixture to room temperature;

[0112] (7) Filtration, washing, and drying: Filter using a Buchner funnel, wash with deionized water 3-5 times, and vacuum dry at 40-50°C for 12-24 hours.

[0113] The preparation method of the iron-doped nano-titanium dioxide comprises the following steps:

[0114] (1) Preparation of precursor solution: Dissolve 20-30 parts by weight of tetrabutyl titanate in 80-100 parts by weight of anhydrous ethanol, stirring at 300-400 rpm, at room temperature for 30 minutes; simultaneously, dissolve 0.5-1.5 parts by weight of ferric nitrate in 20-30 parts by weight of deionized water;

[0115] (2) Hydrolysis: Slowly add the iron salt solution dropwise to the titanate solution, increase the stirring speed to 600-800 rpm, and react at room temperature for 1-2 hours;

[0116] (3) Aging: The mixture was aged at 60-70°C with stirring (200-300 rpm) for 4-6 hours;

[0117] (4) Hydrothermal treatment: The aged sol was transferred to a polytetrafluoroethylene-lined autoclave and treated at 180-200°C for 8-12 hours;

[0118] (5) Cooling, filtering, and washing: Cool naturally to room temperature, filter, and wash with deionized water and anhydrous ethanol 3-5 times each;

[0119] (6) Drying and calcination: drying at 60-70°C for 12-24 hours, and then calcining at 400-500°C for 2-3 hours;

[0120] (7) Grinding: Grind the calcined sample to an average particle size of 20-30 nm.

[0121] The preparation method of the surface-modified anti-skid particles comprises the following steps:

[0122] (1) Pretreatment: 100 parts by weight of α-alumina was vacuum dried at 120-130°C for 4-6 hours;

[0123] (2) Silanization: Add the pretreated alumina and 200-250 parts by weight of anhydrous toluene to a three-necked flask, stir and disperse (300-400 rpm) for 10-15 minutes; slowly add 3-5 parts by weight of 3-glycidyloxypropyltrimethoxysilane, raise the temperature to reflux (about 110-120°C), and stir and react for 4-6 hours;

[0124] (3) Cooling and filtration: Cool naturally to room temperature and filter;

[0125] (4) Washing: Wash with anhydrous toluene 3 times, then wash with anhydrous ethanol 2 times;

[0126] (5) Drying: Vacuum drying at 60-70°C for 12-24 hours. Example

[0127] The two-component quick-drying anti-skid self-cleaning road marking paint of this embodiment includes component A and component B.

[0128] Component A is made from the following raw materials in parts by weight:

[0129] 30 parts of waterborne polyurethane dispersion

[0130] 5 copies of light-responsive self-repairing microcapsules

[0131] 3 parts of iron-doped nano-titanium dioxide

[0132] 8 parts of surface modified anti-slip particles

[0133] 1 part multifunctional silane coupling agent

[0134] 0.1 part pH adjuster

[0135] 0.2 parts of bio-based defoamer

[0136] 0.5 parts of intelligent temperature-sensitive thickener

[0137] 0.1 part of broad-spectrum antibacterial agent

[0138] 40 parts deionized water

[0139] Component B is made from the following raw materials in parts by weight:

[0140] 20 parts of water-dispersible isocyanate curing agent

[0141] 5 parts of hyperbranched polyether modifier

[0142] 1 part hydrophobic nano-silica

[0143] 0.5 parts of light stabilizer

[0144] 70 parts of deionized water.

[0145] The preparation method of this embodiment comprises the following steps:

[0146] (1) Preparation of component A:

[0147] First, 30 parts of aqueous polyurethane dispersion (solid content 40%, pH 7.0, viscosity 75mPa·s, average particle size 100nm) were added to the reactor with stirring at 300rpm. Secondly, 5 parts of light-responsive self-healing microcapsules were added and stirred for 30 minutes. Then, 3 parts of iron-doped nano-titanium dioxide (iron doping amount 0.5wt%, specific surface area 80m² / g) were added and stirred for 45 minutes. Finally, 8 parts of surface-modified anti-slip particles (surface silanization degree 1.5 μmol / m²) were added and stirred for 30 minutes. Then, 1 part of multifunctional silane coupling agent, 0.1 part of pH regulator, 0.2 part of bio-based defoamer and 0.5 part of intelligent temperature-sensitive thickener (weight-average molecular weight 100,000) were added in sequence. g / mol, LCST is 32°C), stirring for 10 minutes after each addition of raw materials; finally, 0.1 parts of a broad-spectrum antibacterial agent was added, stirred for 15 minutes, and 40 parts of deionized water were added to adjust the solid content to 55%, stirred for 30 minutes, and filtered through a 100-mesh sieve to obtain component A.

[0148] (2) Preparation of component B:

[0149] First, 20 parts of a water-dispersible isocyanate curing agent (NCO content 16.5%, viscosity 500 mPa·s) were added to the reactor with a stirring speed of 200 rpm; secondly, 5 parts of a hyperbranched polyether modifier (hydroxyl value 230 mg KOH / g, viscosity 3000 mPa·s) were added and stirred for 20 minutes; then, 1 part of hydrophobic nano-silica (specific surface area 195 m² / g, carbon content 3.0%) was added and stirred for 30 minutes; then, 0.5 parts of a light stabilizer (active ingredient content 52%, pH 6.0) was added and stirred for 15 minutes; finally, 70 parts of deionized water were added to adjust the solid content to 40%, stirred for 20 minutes, and filtered through a 200-mesh sieve to obtain component B.

[0150] Preferably, in an embodiment of the present invention, an aqueous polyurethane dispersion is used as the main film-forming substance, providing excellent film-forming properties and adhesion. Light-responsive self-repairing microcapsules can trigger a self-repairing process under ultraviolet light irradiation, and work in conjunction with iron-doped nano-titanium dioxide to achieve a perfect combination of self-cleaning and self-repairing functions, significantly extending the service life of the coating. The surface-modified anti-slip particles and the multifunctional silane coupling agent work together to not only improve the anti-slip properties of the coating, but also enhance the overall mechanical properties. The intelligent temperature-sensitive thickener maintains good fluidity during construction and increases viscosity during use, further enhancing the anti-slip effect and durability of the coating. Example

[0151] The two-component quick-drying anti-skid self-cleaning road marking paint of this embodiment includes component A and component B.

[0152] Component A is made from the following raw materials in parts by weight:

[0153] 40 parts of waterborne polyurethane dispersion

[0154] 7.5 parts of photoresponsive self-repairing microcapsules

[0155] 5.5 parts of iron-doped nano-titanium dioxide

[0156] 11.5 parts of surface-modified anti-skid particles

[0157] 2 parts of multifunctional silane coupling agent

[0158] 0.3 parts pH adjuster

[0159] 0.4 parts of bio-based defoamer

[0160] 1 part intelligent temperature-sensitive thickener

[0161] 0.2 parts of broad-spectrum antibacterial agent

[0162] 25 parts deionized water

[0163] Component B is made from the following raw materials in parts by weight:

[0164] 30 parts of water-dispersible isocyanate curing agent

[0165] 10 parts of hyperbranched polyether modifier

[0166] 2 parts of hydrophobic nano-silica

[0167] 1 part of light stabilizer

[0168] 55 parts of deionized water.

[0169] The preparation method of this embodiment comprises the following steps:

[0170] (1) Preparation of component A:

[0171] First, 40 parts of aqueous polyurethane dispersion (solid content 40.5%, pH value 7.5, viscosity 425mPa·s, average particle size 100nm) were added to the reactor with stirring at 350rpm. Secondly, 7.5 parts of light-responsive self-healing microcapsules were added and stirred for 30 minutes. Then, 5.5 parts of iron-doped nano-titanium dioxide (iron doping amount 1wt%, specific surface area 100m² / g) were added and stirred for 45 minutes. Finally, 11.5 parts of surface-modified anti-slip particles (surface silanization degree 2μmol / m²) were added and stirred for 30 minutes. Then, 2 parts of multifunctional silane coupling agent, 0.3 parts of pH regulator, 0.4 parts of bio-based defoamer and 1 part of intelligent temperature-sensitive thickener (weight-average molecular weight 125,000) were added in sequence. g / mol, LCST is 33°C), stirring for 10 minutes after each addition of raw materials; finally, 0.2 parts of a broad-spectrum antibacterial agent was added, stirred for 15 minutes, and 25 parts of deionized water were added to adjust the solid content to 57.5%, stirred for 30 minutes, and filtered through a 100-mesh sieve to obtain component A.

[0172] (2) Preparation of component B:

[0173] First, 30 parts of a water-dispersible isocyanate curing agent (NCO content 17%, viscosity 1500 mPa·s) were added to the reactor with stirring at 250 rpm; secondly, 10 parts of a hyperbranched polyether modifier (hydroxyl value 240 mg KOH / g, viscosity 4000 mPa·s) were added and stirred for 20 minutes; then, 2 parts of hydrophobic nano-silica (specific surface area 220 m² / g, carbon content 3.5%) were added and stirred for 30 minutes; thirdly, 1 part of a light stabilizer (active ingredient content 54%, pH 7.0) was added and stirred for 15 minutes; finally, 55 parts of deionized water were added to adjust the solid content to 42.5%, stirred for 20 minutes, and filtered through a 200-mesh sieve to obtain component B.

[0174] In this example, increasing the amount of aqueous polyurethane dispersion and adjusting its physical parameters further improved the film-forming properties and durability of the coating. Increasing the content of iron-doped nano-titanium dioxide enhanced the coating's photocatalytic self-cleaning properties. Furthermore, increasing the amount of surface-modified anti-skid particles significantly improved the coating's anti-skid properties.

[0175] Example 3: Two-component quick-drying anti-slip self-cleaning road marking paint

[0176] The two-component quick-drying anti-skid self-cleaning road marking paint of this embodiment includes component A and component B.

[0177] Component A is made from the following raw materials in parts by weight:

[0178] 50 parts of waterborne polyurethane dispersion

[0179] 10 copies of light-responsive self-repairing microcapsules

[0180] 8 parts of iron-doped nano-titanium dioxide

[0181] 15 parts of surface modified anti-skid particles

[0182] 3 parts of multifunctional silane coupling agent

[0183] 0.5 parts pH regulator

[0184] 0.6 parts of bio-based defoamer

[0185] 1.5 parts of intelligent temperature-sensitive thickener

[0186] 0.3 parts of broad-spectrum antibacterial agent

[0187] 10 parts deionized water;

[0188] Component B is made from the following raw materials in parts by weight:

[0189] 40 parts of water-dispersible isocyanate curing agent

[0190] 15 parts of hyperbranched polyether modifier

[0191] 3 parts of hydrophobic nanosilica

[0192] 1.5 parts of light stabilizer

[0193] 40 parts of deionized water.

[0194] The preparation method of this embodiment comprises the following steps:

[0195] (1) Preparation of component A:

[0196] First, 50 parts of aqueous polyurethane dispersion (solid content 41%, pH value 8.5, viscosity 775mPa·s, average particle size 120nm) were added to the reactor with stirring at 400rpm. Then, 10 parts of light-responsive self-healing microcapsules were added and stirred for 30 minutes. Then, 8 parts of iron-doped nano-titanium dioxide (iron doping amount 1.5wt%, specific surface area 120m² / g) were added and stirred for 45 minutes. Finally, 15 parts of surface-modified anti-slip particles (surface silanization degree 2.5μmol / m²) were added and stirred for 30 minutes. Then, 3 parts of multifunctional silane coupling agent, 0.5 parts of pH regulator, 0.6 parts of bio-based defoamer and 1.5 parts of intelligent temperature-sensitive thickener (weight-average molecular weight 150,000) were added in sequence. g / mol, LCST is 34°C), stirring for 10 minutes after each addition of raw materials; finally, 0.3 parts of a broad-spectrum antibacterial agent was added, stirred for 15 minutes, and 10 parts of deionized water were added to adjust the solid content to 60%, stirred for 30 minutes, and filtered through a 100-mesh sieve to obtain component A.

[0197] (2) Preparation of component B:

[0198] First, 40 parts of a water-dispersible isocyanate curing agent (NCO content 17.5%, viscosity 2500 mPa·s) were added to the reactor with a stirring speed of 300 rpm; secondly, 15 parts of a hyperbranched polyether modifier (hydroxyl value 250 mg KOH / g, viscosity 5000 mPa·s) were added and stirred for 20 minutes; then, 3 parts of hydrophobic nano-silica (specific surface area 245 m² / g, carbon content 4.0%) were added and stirred for 30 minutes; thirdly, 1.5 parts of a light stabilizer (active ingredient content 56%, pH value 8.0) were added and stirred for 15 minutes; finally, 40 parts of deionized water were added to adjust the solid content to 45%, stirred for 20 minutes, and filtered through a 200-mesh sieve to obtain component B.

[0199] In this example, by maximizing the dosage of the aqueous polyurethane dispersion and light-responsive self-healing microcapsules, the coating's self-healing ability and durability were significantly enhanced. Simultaneously, the dosage of iron-doped nano-titanium dioxide and surface-modified anti-skid particles was also maximized, further enhancing the coating's self-cleaning and anti-skid properties. Increasing the dosage of the multifunctional silane coupling agent helped improve the coating's adhesion to various road surface materials. Example

[0200] The two-component quick-drying anti-skid self-cleaning road marking paint of this embodiment includes component A and component B.

[0201] Component A is made from the following raw materials in parts by weight:

[0202] 45 parts of waterborne polyurethane dispersion

[0203] 8 copies of light-responsive self-repairing microcapsules

[0204] 6 parts of iron-doped nano-titanium dioxide

[0205] 12 parts of surface modified anti-slip particles

[0206] 2.5 parts of multifunctional silane coupling agent

[0207] 0.4 parts pH regulator

[0208] 0.5 parts of bio-based defoamer

[0209] 1.2 parts of intelligent temperature-sensitive thickener

[0210] 0.25 parts of broad-spectrum antibacterial agent

[0211] 20 parts of deionized water;

[0212] Component B is made from the following raw materials in parts by weight:

[0213] 35 parts of water-dispersible isocyanate curing agent

[0214] 12 parts of hyperbranched polyether modifier

[0215] 2.5 parts of hydrophobic nano-silica

[0216] 1.2 parts of light stabilizer

[0217] 50 parts of deionized water.

[0218] The preparation method of this embodiment comprises the following steps:

[0219] (1) Preparation of component A:

[0220] First, 45 parts of an aqueous polyurethane dispersion (solid content 40.8%, pH 8.0, viscosity 600 mPa·s, average particle size 110 nm) was added to the reactor with stirring at 375 rpm. Next, 8 parts of photoresponsive self-healing microcapsules were added and stirred for 30 minutes. Then, 6 parts of iron-doped nano-titanium dioxide (iron doping amount 1.2 wt%, specific surface area 110 m² / g) were added and stirred for 45 minutes. Finally, 12 parts of surface-modified anti-slip particles (surface silanization degree 2.2 μmol / m²) were added and stirred for 30 minutes. Subsequently, 2.5 parts of a multifunctional silane coupling agent, 0.4 parts of a pH regulator, 0.5 parts of a bio-based defoamer, and 1.2 parts of an intelligent temperature-sensitive thickener (weight-average molecular weight 135,000 g / mol, LCST is 33.5°C), stirring for 10 minutes after each addition of raw materials; finally, 0.25 parts of a broad-spectrum antibacterial agent was added, stirred for 15 minutes, and 20 parts of deionized water were added to adjust the solid content to 58.5%, stirred for 30 minutes, and filtered through a 100-mesh sieve to obtain component A.

[0221] (2) Preparation of component B:

[0222] First, 35 parts of a water-dispersible isocyanate curing agent (NCO content 17.2%, viscosity 2000 mPa·s) were added to the reactor with a stirring speed of 275 rpm; secondly, 12 parts of a hyperbranched polyether modifier (hydroxyl value 245 mg KOH / g, viscosity 4500 mPa·s) were added and stirred for 20 minutes; then, 2.5 parts of hydrophobic nano-silica (specific surface area 230 m² / g, carbon content 3.7%) were added and stirred for 30 minutes; thirdly, 1.2 parts of a light stabilizer (active ingredient content 55%, pH value 7.5) were added and stirred for 15 minutes; finally, 50 parts of deionized water were added to adjust the solid content to 43.5%, stirred for 20 minutes, and filtered through a 200-mesh sieve to obtain component B.

[0223] In this example, an overall balance of performance was achieved by optimizing the dosage and physical parameters of each component. The moderate dosages of the aqueous polyurethane dispersion and the photoresponsive self-healing microcapsules ensured the coating possessed good film-forming properties and self-healing capabilities. The iron-doped nano-titanium dioxide content was slightly above the median, providing excellent photocatalytic self-cleaning effects. The moderate dosage of the surface-modified anti-slip particles also ensured anti-slip performance without compromising other properties of the coating.

[0224] Notably, the intelligent temperature-sensitive thickener in this example has a weight-average molecular weight of 135,000 g / mol and a liquid-cooled standstill (LCST) of 33.5°C. This ensures the coating possesses suitable fluidity during application and rapid thickening at the application temperature, providing excellent anti-slip properties. Furthermore, the increased amount of hyperbranched polyether modifier further enhances the coating's crosslinking density and flexibility, making it more adaptable to the temperature fluctuations and mechanical stresses of road environments.

[0225] Through the above four embodiments, the two-component quick-drying anti-skid self-cleaning road marking paint of the present invention fully demonstrates its excellent performance and wide applicability.

[0226] For example, Example 1 represents a basic formula, which is suitable for general road conditions; Example 2 improves the durability and anti-skid performance of the coating by increasing the content of functional components, and is suitable for roads with heavy traffic; Example 3 represents a high-performance formula, which is suitable for extreme climates or heavy traffic conditions; and Example 4 is a balanced formula that balances various performance properties and can be widely used in various road environments.

[0227] This flexibility allows the coating to be customized to suit different regions' climate conditions, traffic volumes, and road types, providing a comprehensive solution for road marking. Furthermore, by adjusting process parameters such as stirring speed, reaction temperature, and reaction time, the coating's performance can be further optimized to meet even more stringent application requirements.

[0228] In general, these four embodiments fully demonstrate the technical characteristics and advantages of the two-component quick-drying anti-skid self-cleaning road marking paint of the present invention, and fully demonstrate its innovation and practicality in the field of road marking.

[0229] Comparative Example 1: Two-component road marking paint lacking light-responsive self-repairing microcapsules

[0230] The coating formulation of this comparative example is based on Example 1, but the photoresponsive self-repairing microcapsules are removed to verify the effect of this component on the self-repairing properties of the coating.

[0231] Component A is made from the following raw materials in parts by weight:

[0232] 30 parts of aqueous polyurethane dispersion, 3 parts of iron-doped nano-titanium dioxide, 8 parts of surface-modified anti-slip particles, 1 part of multifunctional silane coupling agent, 0.1 part of pH regulator, 0.2 part of bio-based defoamer, 0.5 part of intelligent temperature-sensitive thickener, 0.1 part of broad-spectrum antibacterial agent, and 45 parts of deionized water.

[0233] The formula of component B is the same as that of Example 1.

[0234] The preparation method is basically the same as that of Example 1, except that the step of adding light-responsive self-repairing microcapsules is omitted when preparing component A.

[0235] Comparative testing revealed that while the coating still exhibited certain anti-slip and self-cleaning properties, tiny scratches and cracks on the surface could not be repaired over time, leading to a gradual decline in coating performance. This result fully demonstrates the key role of light-responsive self-healing microcapsules in extending the coating's service life.

[0236] Comparative Example 2: Two-component road marking paint using ordinary titanium dioxide instead of iron-doped nano-titanium dioxide

[0237] This comparative example is based on Example 2, except that the iron-doped nano-titanium dioxide is replaced with ordinary titanium dioxide to verify the effect of iron doping on the photocatalytic self-cleaning effect.

[0238] In the formulation of component A, 5.5 parts of iron-doped nano-titanium dioxide was replaced with 5.5 parts of ordinary nano-titanium dioxide (average particle size 25 nm, specific surface area 50 m² / g). The formulations of the other components and component B were the same as in Example 2.

[0239] The preparation method is basically the same as that of Example 2, except that ordinary nano-titanium dioxide is used instead of iron-doped nano-titanium dioxide when adding titanium dioxide.

[0240] Test results show that while the coating still has some self-cleaning capabilities, its photocatalytic efficiency under visible light is significantly reduced. This suggests that iron doping not only expands the photoresponse range of titanium dioxide but also enhances its catalytic activity under visible light, thereby enhancing the coating's self-cleaning properties. Furthermore, the iron-doped nano-titanium dioxide creates a synergistic effect with the self-healing microcapsules, further improving the coating's durability.

[0241] Comparative Example 3: Two-component road marking paint without surface-modified anti-skid particles

[0242] This comparative example is based on Example 3, but removes the surface-modified anti-skid particles to verify the contribution of this component to the anti-skid performance of the coating.

[0243] In the formulation of component A, 15 parts of the surface-modified anti-slip particles were removed and the amount of the aqueous polyurethane dispersion was increased to 65 parts. The formulation of the other components and component B was the same as in Example 3.

[0244] The preparation method is basically the same as that of Example 3, except that the step of adding the surface-modified anti-skid particles is omitted.

[0245] Test results showed that while the coating's other properties remained largely unchanged, its anti-slip performance significantly decreased. In particular, the coefficient of friction decreased by approximately 40% under wet conditions. This clearly demonstrates the important role of surface-modified anti-slip particles in improving the coating's anti-slip properties. Furthermore, the coating's overall mechanical properties were also reduced due to the lack of synergistic effects between the anti-slip particles and the multifunctional silane coupling agent.

[0246] Comparative Example 4: Two-component road marking paint using conventional thickener instead of intelligent temperature-sensitive thickener

[0247] This comparative example is based on Example 4, except that the intelligent temperature-sensitive thickener is replaced with a conventional polyacrylic acid thickener to verify the unique effect of the intelligent temperature-sensitive thickener.

[0248] In the formula of component A, 1.2 parts of the intelligent temperature-sensitive thickener was replaced with 1.2 parts of a polyacrylic acid thickener (molecular weight of approximately 200,000). The formula of the other components and component B was the same as in Example 4.

[0249] The preparation method is basically the same as that of Example 4, except that polyacrylic acid thickener is used instead of the intelligent temperature-sensitive thickener when adding the thickener.

[0250] Test results show that coatings using conventional thickeners exhibit poor fluidity during application, making uniform coating difficult. Furthermore, in high-temperature environments, the coating's viscosity decreases significantly, resulting in reduced anti-slip performance. This demonstrates the unique advantages of intelligent temperature-sensitive thickeners in regulating coating rheological properties, ensuring ease of application while providing stable anti-slip performance under operational conditions.

[0251] Comparative Example 5: Two-component road marking paint without hyperbranched polyether modifier

[0252] This comparative example is based on Example 1, except that the hyperbranched polyether modifier in component B is removed to verify the effect of this component on the crosslinking density and flexibility of the coating.

[0253] In the formulation of component B, 5 parts of the hyperbranched polyether modifier was removed and the amount of the water-dispersible isocyanate curing agent was increased to 25 parts. The formulation of component A was the same as that of Example 1.

[0254] The preparation method is basically the same as that of Example 1, except that the step of adding the hyperbranched polyether modifier is omitted when preparing component B.

[0255] Test results showed that while the coating had good initial performance, it exhibited significant cracking and shedding after multiple temperature cycling tests. This suggests that the hyperbranched polyether modifier played a key role in increasing the coating's crosslinking density and flexibility, enabling it to better adapt to the temperature fluctuations and mechanical stresses of the road environment.

[0256] Comparative Example 6: Two-component road marking paint without hydrophobic nano-silica

[0257] This comparative example is based on Example 2, but removes the hydrophobic nano-silica in component B to verify the effect of this component on the self-cleaning durability of the coating.

[0258] In the formulation of component B, 2 parts of hydrophobic nano-silica were removed and deionized water was increased to 57 parts. The formulation of component A was the same as that of Example 2.

[0259] The preparation method is basically the same as that of Example 2, except that the step of adding hydrophobic nano-silica is omitted when preparing component B.

[0260] Long-term exposure test results show that while the coating initially exhibits good self-cleaning properties, this ability decreases significantly over time. This is because the lack of hydrophobic nano-silica prevents the coating from maintaining its long-term hydrophobicity, making it more susceptible to contaminants. This result fully demonstrates the important role of hydrophobic nano-silica in maintaining the coating's long-term self-cleaning properties.

[0261] These six comparative examples clearly demonstrate the unique roles and synergistic effects of the key components of the present invention. The introduction of innovative components such as photoresponsive self-repairing microcapsules, iron-doped nano-titanium dioxide, surface-modified anti-skid particles, intelligent temperature-sensitive thickeners, hyperbranched polyether modifiers, and hydrophobic nano-silica enables the present two-component, quick-drying, anti-skid, self-cleaning road marking coating to demonstrate significant advantages in self-repairing ability, photocatalytic self-cleaning effect, anti-skid performance, ease of construction, environmental adaptability, and long-term durability. These results strongly demonstrate the innovative and practical value of the present invention, providing a comprehensive and effective solution to the technical challenges faced by traditional road marking coatings.

[0262] Test experimental design:

[0263] 1. Quick-drying performance test

[0264] Experimental conditions: temperature 25±2°C, relative humidity 50±5%

[0265] Experimental methods:

[0266] (1) Apply the mixed coating on a standard glass plate with a wet film thickness of 400 μm.

[0267] (2) Use a BYK drying time recorder to measure the surface drying time and through drying time.

[0268] (3) Each sample was tested 3 times and the average value was taken.

[0269] 2. Anti-slip performance test

[0270] Experimental conditions: temperature 25±2°C, relative humidity 50±5%

[0271] Experimental methods:

[0272] (1) Apply the coating on the asphalt board with a dry film thickness of 300 μm and cure it naturally for 7 days.

[0273] (2) Determination of the slip resistance value (BPN) under dry and wet conditions using a British pendulum tester.

[0274] (3) Each sample was tested at 5 points under dry and wet conditions, and the average value was taken.

[0275] 3. Self-cleaning effect test

[0276] Experimental conditions: outdoor natural environment, lasting 30 days

[0277] Experimental methods:

[0278] (1) Apply the coating to the concrete slab with a dry film thickness of 300 μm and allow to cure naturally for 7 days.

[0279] (2) Apply methyl orange solution (10 mg / L) evenly on the coating surface as a simulated pollutant.

[0280] (3) Place the sample outdoors under natural light conditions and measure the reflectance of the sample surface using a spectrophotometer every 5 days.

[0281] (4) Calculate the self-cleaning efficiency: η = (R - R0) / (R1 - R0) × 100%

[0282] Where R is the reflectivity during testing, R0 is the reflectivity at initial contamination, and R1 is the reflectivity of the clean surface.

[0283] 4. Self-repair performance test

[0284] Experimental conditions: temperature 25±2°C, relative humidity 50±5%, UV intensity 10mW / cm²

[0285] Experimental methods:

[0286] (1) The coating was applied on an aluminum plate with a dry film thickness of 400 μm and cured naturally for 7 days.

[0287] (2) Use a sharp blade to scratch the coating surface with a length of 50 mm and a width of 0.5 mm.

[0288] (3) Place the sample under ultraviolet light and observe and record the degree of scratch healing using an optical microscope every 2 hours.

[0289] (4) Calculate the self-repair efficiency: η = (W0 - Wt) / W0 × 100%

[0290] Where W0 is the initial scratch width and Wt is the scratch width after t time.

[0291] 5. Durability test

[0292] Experimental conditions: QUV accelerated weathering test, cycle of 8 hours of UVA-340 lamp exposure (60±2°C) and 4 hours of condensation (50±2°C)

[0293] Experimental methods:

[0294] (1) The coating was applied on an aluminum plate with a dry film thickness of 400 μm and cured naturally for 7 days.

[0295] (2) The samples were placed in a QUV aging test chamber for testing, with a total testing time of 1000 hours.

[0296] (3) Take out samples every 200 hours and test the gloss retention, adhesion and abrasion resistance.

[0297] 6. Low temperature flexibility test

[0298] Experimental conditions: Temperature -25±2°C

[0299] Experimental methods:

[0300] (1) The coating was applied to galvanized steel sheets with a dry film thickness of 400 μm and cured naturally for 7 days.

[0301] (2) Cool the sample at -25°C for 2 hours.

[0302] (3) Perform a bending test using a flexibility tester and record the minimum bending diameter at which the coating cracks.

[0303] The test results are shown in the following table:

[0304] Table 1. Quick-drying performance and anti-slip performance test results

[0305] sample Surface drying time (min) Drying time (min) Dry BPN Wet BPN Example 1 15 45 65 55 Example 2 12 40 70 60 Example 3 10 35 75 65 Example 4 13 42 72 62 Comparative Example 1 16 48 64 54 Comparative Example 2 14 44 68 58 Comparative Example 3 11 38 50 40 Comparative Example 4 20 55 65 50 Comparative Example 5 14 43 66 56 Comparative Example 6 13 41 69 59

[0306] Table 2. Self-cleaning effect test results (self-cleaning efficiency %)

[0307] sample 5 days 10 days 15 days 20 days 25 days 30 days Example 1 35 55 70 80 85 88 Example 2 40 60 75 85 90 92 Example 3 45 65 80 88 93 95 Example 4 42 62 77 86 91 93 Comparative Example 1 33 52 68 78 83 86 Comparative Example 2 25 40 55 65 70 72 Comparative Example 3 38 58 73 83 88 90 Comparative Example 4 39 59 74 84 89 91 Comparative Example 5 37 57 72 82 87 89 Comparative Example 6 30 45 58 65 70 72

[0308] Table 3. Self-repair performance test results (self-repair efficiency%)

[0309] sample 2 hours 4 hours 6 hours 8 hours 10 hours 12 hours Example 1 20 45 65 80 90 95 Example 2 25 50 70 85 93 97 Example 3 30 55 75 88 95 98 Example 4 28 52 72 86 94 97 Comparative Example 1 0 0 0 0 0 0 Comparative Example 2 18 40 60 75 85 90 Comparative Example 3 22 47 67 82 91 96 Comparative Example 4 23 48 68 83 92 96 Comparative Example 5 15 35 55 70 80 85 Comparative Example 6 24 49 69 84 92 96

[0310] Table 4. Durability test results

[0311] sample Gloss retention rate (%) Adhesion (grade) Wear resistance (mg / 1000 times) Example 1 92 1 35 Example 2 94 0 30 Example 3 96 0 25 Example 4 95 0 28 Comparative Example 1 88 1 40 Comparative Example 2 85 1 38 Comparative Example 3 90 1 45 Comparative Example 4 91 1 37 Comparative Example 5 80 2 50 Comparative Example 6 86 1 42

[0312] Table 5. Low temperature flexibility test results

[0313] sample Minimum bending diameter (mm) Example 1 6 Example 2 5 Example 3 4 Example 4 5 Comparative Example 1 7 Comparative Example 2 6 Comparative Example 3 6 Comparative Example 4 8 Comparative Example 5 10 Comparative Example 6 6

[0314] According to the above test results, Example 3 performs the best and can be regarded as the best embodiment of the present invention.

[0315] The analysis and discussion are as follows:

[0316] 1. Fast-Drying Performance: Examples 1-4 all exhibited excellent fast-drying performance, particularly Example 3, which achieved a tack-free time of only 10 minutes and a through-drying time of 35 minutes. This is attributed to the rapid crosslinking reaction between the aqueous polyurethane dispersion and the water-dispersible isocyanate curing agent, as well as the synergistic effect of the intelligent temperature-sensitive thickener. In contrast, Comparative Example 4, lacking the intelligent temperature-sensitive thickener, exhibited significantly longer drying times.

[0317] 2. Anti-slip Performance: Examples 1-4 exhibit significantly better anti-slip performance than the comparative example, particularly Example 3, whose BPN values reached 75 and 65 under dry and wet conditions, respectively. This is primarily attributed to the addition of surface-modified anti-slip particles and their synergistic effect with the multifunctional silane coupling agent. Comparative Example 3 exhibits significantly reduced anti-slip performance due to the lack of anti-slip particles.

[0318] 3. Self-cleaning effect: Examples 1-4 demonstrated excellent and long-lasting self-cleaning effects, with self-cleaning efficiencies exceeding 88% after 30 days. Among them, Example 3 performed the best, reaching 95%. This is attributed to the efficient photocatalytic effect of iron-doped nano-titanium dioxide and the long-lasting hydrophobicity provided by hydrophobic nano-silica. Comparative Examples 2 and 6 showed significantly reduced self-cleaning effects due to the lack of these two key components.

[0319] 4. Self-repair Performance: Examples 1-4 all exhibited excellent self-repair capabilities, with self-repair efficiencies exceeding 95% after 12 hours. This is primarily attributed to the photoresponsive self-repairing microcapsules. Comparative Example 1, lacking this component, exhibited no self-repair capability.

[0320] 5. Durability: After 1000 hours of accelerated aging testing, Examples 1-4 maintained high gloss retention (>92%), excellent adhesion (grade 0-1), and good abrasion resistance (<35 mg / 1000 times). This is attributed to the synergistic effect of the waterborne polyurethane dispersion, hyperbranched polyether modifier, and light stabilizer. Comparative Example 5, due to the lack of a hyperbranched polyether modifier, exhibited significantly reduced durability.

[0321] 6. Low-Temperature Flexibility: Examples 1-4 exhibit excellent low-temperature flexibility, with minimum bending diameters exceeding 6 mm. This is primarily due to the synergistic effect of the aqueous polyurethane dispersion and the hyperbranched polyether modifier, which enables the coating to maintain good flexibility even at low temperatures. Comparative Example 5, due to the lack of a hyperbranched polyether modifier, exhibits significantly reduced low-temperature flexibility.

[0322] Unexpected technical effects:

[0323] 1. Synergistic Self-Repair and Self-Cleaning: The combination of light-responsive self-repairing microcapsules and iron-doped nano-titanium dioxide in this invention not only enables the coating's self-repair and self-cleaning functions but also produces an unexpected synergistic effect. The fresh surface exposed during the self-repair process is more conducive to the photocatalytic self-cleaning reaction, while the self-cleaning process maintains the cleanliness of the coating surface, improving the self-repair efficiency. This dual effect significantly enhances the overall performance and service life of the coating.

[0324] 2. Intelligent Thermosensitive Rheology Control: The introduction of an intelligent thermosensitive thickener not only improves the coating's application performance but also unexpectedly enhances the coating's anti-slip properties. This is because the thermosensitive thickener maintains good fluidity during low-temperature application, but rapidly thickens as road temperatures rise, forming microscopic raised structures that further enhance the coating's anti-slip properties.

[0325] 3. Multiple effects of hyperbranched polyether modifiers: Hyperbranched polyether modifiers not only increase the crosslinking density and flexibility of the coating, but also unexpectedly enhance the self-cleaning durability of the coating. This may be because the hyperbranched structure provides more functional end groups, which facilitates interaction with other components and forms a more stable network structure.

[0326] 4. Environmental adaptability: The coating of the present invention exhibits excellent performance under various extreme environmental conditions (such as high temperature, low temperature, humidity, etc.).

[0327] The foregoing is merely an embodiment of the present invention and is not intended to limit the present invention. It will be apparent to those skilled in the art that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention are intended to be included within the scope of the claims of the present invention.

Claims

1. Two-component quick-drying anti-skid self-cleaning road marking paint, characterized by: The invention comprises component A and component B, wherein component A is prepared from the following raw materials in parts by weight: 30-50 parts of aqueous polyurethane dispersion, 5-10 parts of light-responsive self-repairing microcapsules, 3-8 parts of iron-doped nano-titanium dioxide, 8-15 parts of surface-modified anti-slip particles, 1-3 parts of multifunctional silane coupling agent, 0.1-0.5 parts of pH regulator, 0.2-0.6 parts of bio-based defoamer, 0.5-1.5 parts of intelligent temperature-sensitive thickener, 0.1-0.3 parts of broad-spectrum antibacterial agent, and 10-40 parts of deionized water; and component B is prepared from the following raw materials in parts by weight: 20-40 parts of water-dispersible isocyanate curing agent, 5-15 parts of hyperbranched polyether modifier, 1-3 parts of hydrophobic nano-silica, 0.5-1.5 parts of light stabilizer, and 40-70 parts of deionized water. The aqueous polyurethane dispersion has a solid content of 40 ± 1%, a pH value of 7.0-8.5, a viscosity of 50-800 mPa·s at 23°C, and an average particle size of 80-120 nm; the multifunctional silane coupling agent is N-[3-(trimethoxysilyl)propyl]-1,2-ethylenediamine, which has a boiling point of 260°C, a flash point of 93°C, and a density of 1.03 g / cm³ at 25°C; The hyperbranched polyether modifier has a hydroxyl value of 230-250 mg KOH / g and a viscosity of 3000-5000 mPa·s at 23°C; the hydrophobic nano-silica is pyrogenic silica treated with hexamethyldisilazane, has a specific surface area of 195-245 m² / g, an average particle size of 7 nm, and a carbon content of 3.0-4.0%; The preparation method of the two-component quick-drying anti-skid self-cleaning road marking paint is characterized in that it comprises the following steps: (1) preparing component A: first, adding an aqueous polyurethane dispersion into a reactor with a stirring speed of 300-400 rpm; secondly, adding light-responsive self-repairing microcapsules and stirring for 30 minutes; then, adding iron-doped nano-titanium dioxide and stirring for 45 minutes; thirdly, adding surface-modified anti-skid particles and stirring for 30 minutes; then, adding a multifunctional silane coupling agent, a pH regulator, a bio-based defoamer and an intelligent temperature-sensitive thickener in sequence, stirring for 10 minutes after each addition of the raw materials; finally, adding a broad-spectrum antibacterial agent and stirring for 15 minutes, and adding deionized water to adjust the pH. The solid content was adjusted to 55-60%, stirred for 30 minutes, and filtered through a 100-mesh sieve to obtain component A; (2) preparation of component B: first, a water-dispersible isocyanate curing agent was added to the reactor at a stirring speed of 200-300 rpm; secondly, a hyperbranched polyether modifier was added and stirred for 20 minutes; then, hydrophobic nano-silica was added and stirred for 30 minutes; thirdly, a light stabilizer was added and stirred for 15 minutes; finally, deionized water was added to adjust the solid content to 40-45%, stirred for 20 minutes, and filtered through a 200-mesh sieve to obtain component B.

2. The two-component quick-drying anti-skid self-cleaning road marking paint according to claim 1, characterized in that: The pH regulator is ammonium hydroxide, which is a 28% aqueous solution. The broad-spectrum antibacterial agent is a mixture of 1,2-benzisothiazol-3(2H)-one and 2-methyl-4-isothiazoline-3-one, wherein the content of 1,2-benzisothiazol-3(2H)-one is 10-15%, and the content of 2-methyl-4-isothiazoline-3-one is 2-5%.

3. The two-component quick-drying anti-skid self-cleaning road marking paint according to claim 1, characterized in that: The active ingredient content of the light stabilizer is 52-56%, and the pH value is 6.0-8.0; the water-dispersible isocyanate curing agent is an aqueous dispersion of hexamethylene diisocyanate, with an NCO content of 16.5-17.5% and a viscosity of 500-2500 mPa·s at 23°C.

4. The two-component quick-drying anti-skid self-cleaning road marking paint according to claim 3, characterized in that: The preparation method of the photoresponsive self-repairing microcapsules comprises the following steps: (1) preparing an oil phase: mixing 5-10 parts by weight of dicyclopentadiene with 0.1-0.3 parts by weight of a photoresponsive Grubbs catalyst at 20-25°C, stirring at a speed of 300-400 rpm, and for 15-20 minutes; (2) preparing an aqueous phase: dissolving 1-2 parts by weight of polyvinyl alcohol in 100-150 parts by weight of deionized water, stirring at a speed of 500-600 rpm, at a temperature of 60-70°C, and for 30-40 minutes; (3) preparing a monomer mixture: mixing 15-25 parts by weight of methyl methacrylate with 1-3 parts by weight of glycidyl methacrylate, and adding 0.2-0.5 parts by weight of azobisisobutyronitrile; (4) emulsifying: slowly adding the oil phase to the aqueous phase, and shearing and emulsifying at a speed of 1000-1200 rpm at 60-70°C for 15-20 minutes; (5) Suspension polymerization: slowly add the monomer mixture dropwise to the emulsion, stir at 70-75°C, 400-500 rpm and react for 3-4 hours; (6) Cooling: cool the reaction mixture to room temperature; (7) Filtration, washing and drying: filter using a Buchner funnel, wash with deionized water 3-5 times, and vacuum dry at 40-50°C for 12-24 hours.

5. The two-component quick-drying anti-skid self-cleaning road marking paint according to claim 1, characterized in that: The preparation method of the iron-doped nano-titanium dioxide comprises the following steps: (1) preparing a precursor solution: dissolving 20-30 parts by weight of tetrabutyl titanate in 80-100 parts by weight of anhydrous ethanol, stirring at a speed of 300-400 rpm, and stirring at room temperature for 30 minutes; at the same time, dissolving 0.5-1.5 parts by weight of ferric nitrate in 20-30 parts by weight of deionized water; (2) hydrolysis: slowly adding the iron salt solution dropwise to the titanate solution, stirring at a speed of 600-800 rpm, and reacting at room temperature for 1-2 hours; (3) aging: stirring the mixture at 60-70°C and 200-300 rpm, and aging for 4-6 hours; (4) hydrothermal treatment: transferring the aged sol to a polytetrafluoroethylene-lined autoclave and treating it at 180-200°C for 8-12 hours; (5) Cooling, filtering, and washing: Cool naturally to room temperature, filter, and wash with deionized water and anhydrous ethanol 3-5 times each; (6) Drying and calcining: Dry at 60-70°C for 12-24 hours, and then calcine at 400-500°C for 2-3 hours; (7) Grinding: Grind the calcined sample to an average particle size of 20-30 nm.

6. The two-component quick-drying anti-skid self-cleaning road marking paint according to claim 1, characterized in that: The preparation method of the surface-modified anti-skid particles comprises the following steps: (1) pretreatment: vacuum drying 100 parts by weight of α-alumina at 120-130°C for 4-6 hours; (2) silanization: adding the pretreated alumina and 200-250 parts by weight of anhydrous toluene into a three-necked flask, stirring and dispersing, and stirring at 300-400 rpm for 10-15 minutes; slowly adding 3-5 parts by weight of 3-glycidyloxypropyltrimethoxysilane, heating to reflux, 110-120°C, stirring and reacting for 4-6 hours; (3) cooling and filtering: naturally cooling to room temperature and filtering; (4) washing: washing with anhydrous toluene three times, and then washing with anhydrous ethanol twice; (5) drying: vacuum drying at 60-70°C for 12-24 hours.

7. The two-component quick-drying anti-skid self-cleaning road marking paint according to claim 1, characterized in that: The preparation method of the intelligent temperature-sensitive thickener comprises the following steps: (1) preparing a monomer solution: dissolving 15-20 parts by weight of N-isopropylacrylamide and 1-2 parts by weight of acrylamide in 150-200 parts by weight of deionized water in a three-necked flask, and passing nitrogen for 15-20 minutes to deoxygenate; (2) preparing an initiator solution: dissolving 0.1-0.2 parts by weight of ammonium persulfate in 10-15 parts by weight of deionized water; (3) polymerizing the monomer solution: heating the monomer solution to 60-65°C, controlling the stirring speed to 300-400 rpm; slowly adding the initiator solution dropwise, and reacting for 4-6 hours; (4) terminating the reaction: cooling the reaction mixture to room temperature, and passing air for 10-15 minutes; (5) purifying: pouring the reaction product into excess acetone for precipitation, filtering, and washing with acetone three times; and (6) drying: vacuum drying at 40-50°C for 24-48 hours.