Highly wear-resistant antiskid road marking paint and preparation method thereof

Abstract

The invention discloses a high-wear-resistance antiskid road marking coating and a preparation method thereof, and belongs to the technical field of road marking coatings. The coating comprises the following components in parts by weight: 15-25 parts of petroleum resin, 2-5 parts of a plasticizer, 30-40 parts of a composite wear-resistant aggregate, 15-25 parts of a composite antiskid aggregate, 5-10 parts of titanium dioxide, 0.5-2 parts of a silane coupling agent, 0.5-1.5 parts of polyethylene wax, 5-10 parts of glass beads, 0.1-0.3 part of an antioxidant 1010 and 10-20 parts of a filler. Through the synergistic effect of two types of specific aggregates, a hard-supporting and elastic-buffering wear-resistant matrix and a lasting multi-stage anti-skid surface are constructed in the coating, and the technical problems that a traditional marking coating is poor in wear resistance, insufficient in anti-skid performance and short in reflective life are solved; the obtained coating has the characteristics of ultrahigh wear resistance, lasting high skid resistance, strong adhesive force and slow reflection performance attenuation.

Description

Technical Field

[0001] This invention relates to a high wear-resistant and anti-skid road marking paint and its preparation method, belonging to the technical field of road marking paint. Background Technology

[0002] Road markings, as an important component of road traffic safety facilities, play a crucial role in guiding vehicle movement, regulating traffic order, and ensuring driving safety. Under various complex weather conditions, road markings need to remain clear, visible, and in good working order to ensure drivers can accurately identify them and make correct driving decisions. Road marking paints are classified into room-temperature solvent-based paints, heated solvent-based paints, and hot-melt road marking paints. Traditional hot-melt reflective road marking paints are widely used due to their fast drying and low cost. However, they have the following significant drawbacks: Insufficient wear resistance: Under the frequent crushing of heavy vehicles and the washing of rain and snow, the road markings wear out too quickly, resulting in a sharp decline in reflectivity, shortened service life, and the need for frequent repainting, which is costly in the long run and affects traffic.

[0003] Poor anti-slip properties: The surface is smooth, especially in wet conditions, and its anti-slip value (BPN) is low, which poses a safety hazard to two-wheeled vehicles and can easily lead to skidding accidents.

[0004] Early reflectivity depends on surface-sprinkled glass beads: The initial reflectivity is highly dependent on the surface premixing and surface-sprinkled glass beads. Once the surface wears down, the reflectivity is quickly lost.

[0005] Some improved technologies have been developed, such as adding quartz sand to increase hardness or using special fillers to improve slip resistance. However, it is often difficult to achieve a balance between wear resistance, slip resistance, workability, and cost. For example, excessively increasing hardness may lead to increased brittleness and reduced adhesion to the road surface; while simply increasing coarse aggregate may improve slip resistance, it will severely wear down vehicle tires and affect the leveling and reflectivity of the coating.

[0006] Therefore, developing a road marking paint that combines ultra-high wear resistance, long-lasting high anti-slip properties, excellent adhesion, and good construction performance is of great practical significance and economic value. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing road marking paints, such as poor wear resistance, insufficient anti-skid performance, and short service life, and to provide a high wear-resistant and anti-skid road marking paint with high cohesive strength, optimized aggregate structure, and excellent comprehensive performance, as well as its preparation method.

[0008] To achieve the above-mentioned technical objectives, the present invention adopts the following technical solution: A high wear-resistant and anti-slip road marking coating, by weight, comprises the following components: 15-25 parts petroleum resin, 2-5 parts plasticizer, 30-40 parts composite wear-resistant aggregate, 15-25 parts composite anti-slip aggregate, 5-10 parts titanium dioxide, 0.5-2 parts silane coupling agent, 0.5-1.5 parts polyethylene wax, 5-10 parts glass microspheres, 0.1-0.3 parts antioxidant 1010, and 10-20 parts filler; wherein the composite wear-resistant aggregate is composed of modified nano-silica and modified polyimide-polyurethane block copolymer in a mass ratio of (6-7):(1-3).

[0009] Furthermore, the composite anti-slip aggregate is chromium-titanium doped ceramic particles, wherein the coarse particles are 20-40 mesh and the fine particles are 80-120 mesh, with a weight ratio of (2-3):1; the filler is heavy calcium carbonate or quartz powder.

[0010] Furthermore, the modified polyimide-polyurethane block copolymer is prepared using the following method: (1) Using N-methylpyrrolidone as solvent, under nitrogen protection, add 4,4'-diaminodiphenyl ether and stir magnetically until completely dissolved. After heating to 30°C, add pyromellitic anhydride in 4 portions and continue to stir magnetically to keep the reaction warm until the reaction system changes from a colorless liquid to a light green transparent liquid. Add deionized water to the reaction product solution under high-speed stirring to obtain a milky white suspension. Filter the filter cake and wash it 3 times with acetone and deionized water before drying to obtain the product polyamic acid. (2) Dissolve isophorone diisocyanate in DMF, purge with nitrogen for protection, stir magnetically and heat to 80°C, then slowly add polytetrahydrofuran PTMG-1000 dissolved in a small amount of DMF, add the catalyst dibutyltin dilaurate after the addition is complete, and then keep the reaction at 80°C for 110-120 min, then add the chain extender 1,4-butanediol and continue to keep the reaction at 80°C for 50-60 min, then slowly add the polyamic acid obtained in step (1) dissolved in a small amount of DMF, and after the addition is complete, continue to keep the reaction at 80°C for 30-40 min, and the reaction is completed to obtain a composite resin solution with a solid content of 30%; (3) The obtained composite resin solution was placed in a polytetrafluoroethylene mold and vulcanized in a flat vulcanizing machine at 150°C and 5MPa pressure for 2 hours. Then the temperature was raised to 180°C and kept for 1.5 hours. Heating was stopped, the pressure was released and the mold was demolded. The mixture was allowed to cool naturally to room temperature and then transferred to liquid nitrogen for embrittlement. Finally, it was pulverized in a high-energy ball mill to obtain polyimide-polyurethane block copolymer powder. (4) Dissolve octadecyltrimethoxysilane in an ethanol-water mixture, add acetic acid to adjust the pH to 4-5, hydrolyze for 30-40 min, then add polyimide-polyurethane block copolymer powder, and reflux at 60-80℃ for 2-3 h with magnetic stirring. After filtration, wash with ethanol and vacuum dry to constant weight to obtain modified polyimide-polyurethane block copolymer.

[0011] Furthermore, in step (1), the molar ratio of pyromellitic anhydride and 4,4'-diaminodiphenyl ether is 4:3, and the ratio of N-methylpyrrolidone to pyromellitic anhydride is 1 mmol: 10 mL.

[0012] Furthermore, in step (2), the molar ratio of isophorone diisocyanate, polytetrahydrofuran PTMG-1000, 1,4-butanediol, and polyamic acid is 4:1:1.4:0.9, and the amount of the catalyst dibutyltin dilaurate is 0.07-0.08% of the total mass of the reactants.

[0013] Furthermore, in step (4), the ethanol-water mixture is composed of ethanol and water in a volume ratio of 9:1; the solid-liquid ratio of the polyimide-polyurethane block copolymer powder to the ethanol-water mixture is 1g:10-15mL.

[0014] Furthermore, the modified nano-silica is obtained by modification treatment with silane coupling agent KH560 or KH570.

[0015] Furthermore, the chromium-titanium doped ceramic particles are prepared by the following method: using cordierite powder as raw material, adding 1-3% titanium dioxide and 2-4% chromium trioxide, placing the raw material powders in a ball mill, using zirconia balls as grinding balls, using deionized water as the medium, with a material:ball:water ratio of 1:2:0.8, wet ball milling is performed at a speed of 300-400 rpm for 8-10 hours. After ball milling, the mixture is dried, placed in a crucible, and then calcined at high temperature in a sintering furnace. The temperature is raised to 600℃ at a rate of 2℃ / min, and then raised to 1300℃ at a rate of 5℃ / min. After holding at this temperature for 2 hours, the mixture is cooled and crushed and sieved to obtain coarse particles of 20-40 mesh and fine particles of 80-120 mesh.

[0016] Furthermore, the silane coupling agent is KH550 or KH560.

[0017] The plasticizer is a phthalate or trimellitate plasticizer.

[0018] This invention also provides a method for preparing the above-mentioned high wear-resistant and anti-skid road marking paint, which includes the following steps: (1) Weigh each component according to the proportion; (2) Add petroleum resin, plasticizer, polyethylene wax and antioxidant 1010 into the reactor, heat to 160-180℃, and stir until completely melted and mixed evenly; (3) While stirring, add titanium dioxide, filler, composite wear-resistant aggregate and composite anti-slip aggregate in sequence, keep the temperature at 150-170℃, stir at high speed for 20-40 minutes to make the components evenly dispersed; (4) Add silane coupling agent and continue stirring for 10-20 minutes; (5) Cool down to 120-130℃, add glass microspheres, stir at low speed for 5-10 minutes to avoid breaking the glass microspheres; discharge, cool, and you will get the product.

[0019] This invention overcomes the technical contradiction of simultaneously achieving both wear resistance and anti-skid properties in road marking paints through the synergistic combination of composite wear-resistant aggregate and composite anti-skid aggregate. The composite wear-resistant aggregate forms a strong and tough supporting matrix within the coating, providing a firm anchor for the composite anti-skid aggregate and preventing it from detaching due to premature wear of the matrix. Simultaneously, the multi-level rough structure formed on the surface of the composite anti-skid aggregate is preferentially consumed during wear, protecting the underlying wear-resistant matrix and reflective elements. Both components mutually protect and complement each other during dynamic wear, jointly ensuring that the coating possesses both excellent initial performance and long-term durability, achieving a simultaneous and significant improvement in wear resistance, anti-skid properties, and reflective durability.

[0020] The beneficial effects of this invention are: 1. The composite wear-resistant aggregate used in this invention is composed of modified nano-silica and modified polyimide-polyurethane block copolymer powder in a specific ratio. The nano-silica has high hardness and strong wear resistance, providing basic wear-resistant support. The polyimide-polyurethane block copolymer has the characteristics of high strength, high toughness and wear resistance. After surface modification with octadecyltrimethoxysilane, hydrophobic long chains are introduced on its surface, which improves the compatibility and interfacial bonding with the petroleum resin matrix. The nano-silica is treated with KH560 / KH570 coupling agent to enhance its dispersibility and interfacial adhesion in the resin, avoiding local stress concentration caused by agglomeration. The two work synergistically to form a composite wear-resistant phase of "hard support + elastic buffer" in the coating. It can resist vehicle rolling and abrasive wear, and absorb impact stress through elastic deformation to avoid brittle cracking, significantly improving the overall wear resistance and fatigue resistance of the coating.

[0021] 2. The composite anti-skid aggregate used in this invention employs chromium-titanium doped ceramic particles, designed as a blend of 20-40 mesh coarse particles and 80-120 mesh fine particles in a specific ratio to form a multi-level rough surface. The coarse particles provide macroscopic protrusions that directly contact the tire, creating significant mechanical interlocking and drainage channels, thus improving wet-state anti-skid performance. The fine particles fill the gaps between the coarse particles, forming a microscopic rough texture, further increasing the surface friction coefficient and avoiding problems such as poor leveling during pavement marking and uneven glass bead distribution caused by excessively large particles. Furthermore, TiO2 and Cr2O3 are incorporated into the ceramic particles, and after sintering at 1300℃, a high-hardness, high-chemical-stability chromium-titanium solid solution is formed. Its wear resistance is far superior to ordinary quartz sand, ensuring that the anti-skid aggregate is not easily worn during long-term use and maintains its anti-skid function for a long time.

[0022] 3. The synergistic effect of silane system and modified aggregate results in excellent coating adhesion and flexural toughness with no peeling; glass microspheres are not easily detached under the protection of dense wear-resistant layer, and reflective performance decays slowly; the synergistic effect of composite wear-resistant aggregate and ceramic aggregate gives the coating good acid resistance, salt resistance, and water resistance, significantly extending its service life. This technical solution achieves comprehensive optimization in terms of wear resistance, adhesion, anti-slip properties, and construction performance, providing an innovative solution for the field of road marking paint. Detailed Implementation

[0023] The technical solution of the present invention will be further described below with reference to specific embodiments, but it is not limited thereto.

[0024] Example 1 A high wear-resistant and anti-slip road marking coating, by weight, comprises the following components: 25 parts petroleum resin, 5 parts trioctyl trimellitate, 40 parts composite wear-resistant aggregate, 25 parts composite anti-slip aggregate, 10 parts titanium dioxide, 2 parts silane coupling agent KH550, 1.5 parts polyethylene wax, 10 parts glass microspheres, 0.3 parts antioxidant 1010, and 20 parts quartz powder.

[0025] The composite wear-resistant aggregate is composed of modified nano-silica and modified polyimide-polyurethane block copolymer in a mass ratio of 7:3.

[0026] The composite anti-slip aggregate is chromium-titanium doped ceramic particles, wherein the coarse particles are 20-40 mesh and the fine particles are 80-120 mesh, with a weight ratio of 3:1.

[0027] The modified polyimide-polyurethane block copolymer is prepared by the following method: (1) Using 100 mL of N-methylpyrrolidone as solvent, under nitrogen protection, add 0.03 mol of 4,4'-diaminodiphenyl ether and stir magnetically until completely dissolved. After heating to 30 °C, add 0.04 mol of pyromellitic anhydride in 4 portions and continue to stir magnetically to keep the reaction warm until the reaction system changes from a colorless liquid to a light green transparent liquid. Add deionized water to the reaction product solution under high-speed stirring to obtain a milky white suspension. Filter the filter cake and wash it 3 times with acetone and deionized water before drying to obtain the product polyamic acid. (2) Dissolve 17.8g of isophorone diisocyanate in 50mL of DMF, purge with nitrogen for protection, stir magnetically and heat to 80℃, then slowly add 20.5g of polytetrahydrofuran PTMG-1000 dissolved in 50mL of DMF, add 2.5mL of catalyst dibutyltin dilaurate, then keep the reaction at 80℃ for 110-120min, then add 2.5g of 1,4-butanediol and keep the reaction at 80℃ for 50-60min, then slowly add 27.1g of polyamic acid obtained in step (1) dissolved in 50mL of DMF, keep the reaction at 80℃ for 30-40min, and then the reaction ends to obtain a composite resin solution with a solid content of 30%; (3) The obtained composite resin solution was placed in a polytetrafluoroethylene mold and vulcanized in a flat vulcanizing machine at 150°C and 5MPa pressure for 2 hours. Then the temperature was raised to 180°C and kept for 1.5 hours. Heating was stopped, the pressure was released and the mold was demolded. The mixture was allowed to cool naturally to room temperature and then transferred to liquid nitrogen for embrittlement. Finally, it was pulverized in a high-energy ball mill to obtain polyimide-polyurethane block copolymer powder. (4) Dissolve octadecyltrimethoxysilane in an ethanol-water mixture, add acetic acid to adjust the pH to 4-5, hydrolyze for 30-40 min, then add polyimide-polyurethane block copolymer powder, and reflux the reaction at 60-80℃ for 2-3 h with magnetic stirring. After filtration, wash with ethanol and vacuum dry to constant weight to obtain modified polyimide-polyurethane block copolymer; wherein the ethanol-water mixture is composed of ethanol and water in a volume ratio of 9:1; the solid-liquid ratio of polyimide-polyurethane block copolymer powder to ethanol-water mixture is 1 g: 15 mL.

[0028] The modified nano-silica is obtained by modification treatment with silane coupling agent KH560 or KH570.

[0029] The chromium-titanium doped ceramic particles are prepared by the following method: Cordierite powder is used as raw material, with 3% TiO2 and 4% Cr2O3 added. The raw material powders are placed in a ball mill, with zirconia balls as grinding balls and deionized water as the medium. The ratio of material:ball:water = 1:2:0.8 is used for wet ball milling and mixing at a speed of 300-400 rpm for 8-10 hours. After ball milling, the particles are dried, placed in a crucible, and then calcined at high temperature in a sintering furnace. The temperature is increased to 600℃ at a rate of 2℃ / min, and then increased to 1300℃ at a rate of 5℃ / min. After holding at this temperature for 2 hours, the particles are cooled and crushed and sieved to obtain coarse particles of 20-40 mesh and fine particles of 80-120 mesh.

[0030] The preparation method of the above-mentioned high wear-resistant and anti-skid road marking paint includes the following steps: (1) Weigh each component according to the proportion; (2) Add petroleum resin, plasticizer, polyethylene wax and antioxidant 1010 into the reactor, heat to 160-180℃, and stir until completely melted and mixed evenly; (3) While stirring, add titanium dioxide, filler, composite wear-resistant aggregate and composite anti-slip aggregate in sequence, keep the temperature at 150-170℃, stir at high speed for 20-40 minutes to make the components evenly dispersed; (4) Add silane coupling agent and continue stirring for 10-20 minutes; (5) Cool down to 120-130℃, add glass microspheres, stir at low speed for 5-10 minutes to avoid breaking the glass microspheres; discharge, cool, and you will get the product.

[0031] Example 2 A high wear-resistant and anti-slip road marking coating, by weight, comprises the following components: 15 parts petroleum resin, 2 parts dioctyl phthalate, 30 parts composite wear-resistant aggregate, 15 parts composite anti-slip aggregate, 5 parts titanium dioxide, 0.5 parts silane coupling agent KH560, 0.5 parts polyethylene wax, 5 parts glass microspheres, 0.1 parts antioxidant 1010, and 10 parts heavy calcium carbonate.

[0032] The composite wear-resistant aggregate is composed of modified nano-silica and modified polyimide-polyurethane block copolymer in a mass ratio of 6:1.

[0033] The composite anti-slip aggregate is chromium-titanium doped ceramic particles, wherein the coarse particles are 20-40 mesh and the fine particles are 80-120 mesh, with a weight ratio of 2:1.

[0034] The modified polyimide-polyurethane block copolymer is prepared by the following method: (1) Using 100 mL of N-methylpyrrolidone as solvent, under nitrogen protection, add 0.03 mol of 4,4'-diaminodiphenyl ether and stir magnetically until completely dissolved. After heating to 30 °C, add 0.04 mol of pyromellitic anhydride in 4 portions and continue to stir magnetically to keep the reaction warm until the reaction system changes from a colorless liquid to a light green transparent liquid. Add deionized water to the reaction product solution under high-speed stirring to obtain a milky white suspension. Filter the filter cake and wash it 3 times with acetone and deionized water before drying to obtain the product polyamic acid. (2) Dissolve 17.8g of isophorone diisocyanate in 50mL of DMF, purge with nitrogen for protection, stir magnetically and heat to 80℃, then slowly add 20.5g of polytetrahydrofuran PTMG-1000 dissolved in 50mL of DMF, add 2.5mL of catalyst dibutyltin dilaurate after the addition is complete, then keep the reaction at 80℃ for 110min, then add 2.5g of 1,4-butanediol and keep the reaction at 80℃ for 50min, then slowly add 27.1g of polyamic acid obtained in step (1) dissolved in 50mL of DMF, keep the reaction at 80℃ for 30min after the addition is complete, and then the reaction is completed to obtain a composite resin solution with a solid content of 30%; (3) The obtained composite resin solution was placed in a polytetrafluoroethylene mold and vulcanized in a flat vulcanizing machine at 150°C and 5MPa pressure for 2 hours. Then the temperature was raised to 180°C and kept for 1.5 hours. Heating was stopped, the pressure was released and the mold was demolded. The mixture was allowed to cool naturally to room temperature and then transferred to liquid nitrogen for embrittlement. Finally, it was pulverized in a high-energy ball mill to obtain polyimide-polyurethane block copolymer powder. (4) Dissolve octadecyltrimethoxysilane in an ethanol-water mixture, add acetic acid to adjust the pH to 4-5, hydrolyze for 30-40 min, then add polyimide-polyurethane block copolymer powder, and reflux the reaction at 60-80℃ for 2-3 h with magnetic stirring. After filtration, wash with ethanol and vacuum dry to constant weight to obtain modified polyimide-polyurethane block copolymer; wherein the ethanol-water mixture is composed of ethanol and water in a volume ratio of 9:1; the solid-liquid ratio of polyimide-polyurethane block copolymer powder to ethanol-water mixture is 1 g: 10 mL.

[0035] The modified nano-silica is obtained by modification treatment with silane coupling agent KH560 or KH570.

[0036] The chromium-titanium doped ceramic particles are prepared by the following method: Cordierite powder is used as raw material, with 1% TiO2 and 2% Cr2O3 added. The raw material powders are placed in a ball mill, with zirconia balls as grinding balls and deionized water as the medium. The ratio of material:ball:water = 1:2:0.8 is used for wet ball milling and mixing at a speed of 300-400 rpm for 8-10 hours. After ball milling, the particles are dried, placed in a crucible, and then calcined at high temperature in a sintering furnace. The temperature is increased to 600℃ at a rate of 2℃ / min, and then increased to 1300℃ at a rate of 5℃ / min. After holding at this temperature for 2 hours, the particles are cooled and crushed and sieved to obtain coarse particles of 20-40 mesh and fine particles of 80-120 mesh.

[0037] The preparation method of the above-mentioned high wear-resistant and anti-skid road marking paint includes the following steps: (1) Weigh each component according to the proportion; (2) Add petroleum resin, plasticizer, polyethylene wax and antioxidant 1010 into the reactor, heat to 160-180℃, and stir until completely melted and mixed evenly; (3) While stirring, add titanium dioxide, filler, composite wear-resistant aggregate and composite anti-slip aggregate in sequence, keep the temperature at 150-170℃, stir at high speed for 20-40 minutes to make the components evenly dispersed; (4) Add silane coupling agent and continue stirring for 10-20 minutes; (5) Cool down to 120-130℃, add glass microspheres, stir at low speed for 5-10 minutes to avoid breaking the glass microspheres; discharge, cool, and you will get the product.

[0038] Example 3 A high wear-resistant and anti-slip road marking coating, by weight, comprises the following components: 20 parts petroleum resin, 4 parts diisononyl phthalate, 35 parts composite wear-resistant aggregate, 20 parts composite anti-slip aggregate, 8 parts titanium dioxide, 1.5 parts silane coupling agent KH560, 1 part polyethylene wax, 8 parts glass microspheres, 0.2 parts antioxidant 1010, and 15 parts heavy calcium carbonate.

[0039] The composite wear-resistant aggregate is composed of modified nano-silica and modified polyimide-polyurethane block copolymer in a mass ratio of 7:2.

[0040] The composite anti-slip aggregate is chromium-titanium doped ceramic particles, wherein the coarse particles are 20-40 mesh and the fine particles are 80-120 mesh, with a weight ratio of 2:1.

[0041] The modified polyimide-polyurethane block copolymer is prepared by the following method: (1) Using 100 mL of N-methylpyrrolidone as solvent, under nitrogen protection, add 0.03 mol of 4,4'-diaminodiphenyl ether and stir magnetically until completely dissolved. After heating to 30 °C, add 0.04 mol of pyromellitic anhydride in 4 portions and continue to stir magnetically to keep the reaction warm until the reaction system changes from a colorless liquid to a light green transparent liquid. Add deionized water to the reaction product solution under high-speed stirring to obtain a milky white suspension. Filter the filter cake and wash it 3 times with acetone and deionized water before drying to obtain the product polyamic acid. (2) Dissolve 17.8g of isophorone diisocyanate in 50mL of DMF, purge with nitrogen for protection, stir magnetically and heat to 80℃, then slowly add 20.5g of polytetrahydrofuran PTMG-1000 dissolved in 50mL of DMF, add 2.5mL of catalyst dibutyltin dilaurate, then keep the reaction at 80℃ for 110-120min, then add 2.5g of 1,4-butanediol and keep the reaction at 80℃ for 50-60min, then slowly add 27.1g of polyamic acid obtained in step (1) dissolved in 50mL of DMF, keep the reaction at 80℃ for 30-40min, and then the reaction ends to obtain a composite resin solution with a solid content of 30%; (3) The obtained composite resin solution was placed in a polytetrafluoroethylene mold and vulcanized in a flat vulcanizing machine at 150°C and 5MPa pressure for 2 hours. Then the temperature was raised to 180°C and kept for 1.5 hours. Heating was stopped, the pressure was released and the mold was demolded. The mixture was allowed to cool naturally to room temperature and then transferred to liquid nitrogen for embrittlement. Finally, it was pulverized in a high-energy ball mill to obtain polyimide-polyurethane block copolymer powder. (4) Dissolve octadecyltrimethoxysilane in an ethanol-water mixture, add acetic acid to adjust the pH to 4-5, hydrolyze for 30-40 min, then add polyimide-polyurethane block copolymer powder, and reflux the reaction at 60-80℃ for 2-3 h with magnetic stirring. After filtration, wash with ethanol and vacuum dry to constant weight to obtain modified polyimide-polyurethane block copolymer; wherein the ethanol-water mixture is composed of ethanol and water in a volume ratio of 9:1; the solid-liquid ratio of polyimide-polyurethane block copolymer powder to ethanol-water mixture is 1 g: 15 mL.

[0042] The modified nano-silica is obtained by modification treatment with silane coupling agent KH560 or KH570.

[0043] The chromium-titanium doped ceramic particles are prepared by the following method: Cordierite powder is used as raw material, with 2% TiO2 and 3% Cr2O3 added. The raw material powders are placed in a ball mill, with zirconia balls as grinding balls and deionized water as the medium. The ratio of material:ball:water = 1:2:0.8 is used for wet ball milling and mixing at a speed of 300-400 rpm for 8-10 hours. After ball milling, the particles are dried, placed in a crucible, and then calcined at high temperature in a sintering furnace. The temperature is increased to 600℃ at a rate of 2℃ / min, and then increased to 1300℃ at a rate of 5℃ / min. After holding at this temperature for 2 hours, the particles are cooled and crushed and sieved to obtain coarse particles of 20-40 mesh and fine particles of 80-120 mesh.

[0044] The preparation method of the above-mentioned high wear-resistant and anti-skid road marking paint includes the following steps: (1) Weigh each component according to the proportion; (2) Add petroleum resin, plasticizer, polyethylene wax and antioxidant 1010 into the reactor, heat to 160-180℃, and stir until completely melted and mixed evenly; (3) While stirring, add titanium dioxide, filler, composite wear-resistant aggregate and composite anti-slip aggregate in sequence, keep the temperature at 150-170℃, stir at high speed for 20-40 minutes to make the components evenly dispersed; (4) Add silane coupling agent and continue stirring for 10-20 minutes; (5) Cool down to 120-130℃, add glass microspheres, stir at low speed for 5-10 minutes to avoid breaking the glass microspheres; discharge, cool, and you will get the product.

[0045] Comparative Example 1 A traditional road marking paint, whose raw material composition and preparation method are basically the same as in Example 1, except that it does not contain composite wear-resistant aggregate and composite anti-skid aggregate. It is a traditional hot-melt marking paint formulation, prepared according to conventional hot-melt paint preparation methods.

[0046] Comparative Example 2 Similar to the formulation of Example 1, but the composite wear-resistant aggregate is only KH560 modified nano silica, while the other components and preparation methods are the same as in Example 1.

[0047] Comparative Example 3 Similar to the formulation in Example 1, but the composite wear-resistant aggregate is only a modified polyimide-polyurethane block copolymer, while the other components and preparation methods are the same as in Example 1.

[0048] Comparative Example 4 Similar to the formulation in Example 1, but the modified polyimide-polyurethane block copolymer was not modified with octadecyltrimethoxysilane. The remaining components and preparation methods are the same as in Example 1.

[0049] Comparative Example 5 The formulation is similar to that of Example 1, but does not contain composite anti-slip aggregate. The remaining components and preparation methods are the same as those of Example 1.

[0050] Comparative Example 6 The formulation is similar to that of Example 1, but does not contain composite wear-resistant aggregate. The remaining components and preparation methods are the same as those of Example 1.

[0051] Comparative Example 7 Similar to the formulation of Example 1, but the composite anti-slip aggregate is replaced with an equal amount of ordinary corundum sand in the same proportion of coarse (20-40 mesh) and fine (80-120 mesh), while the other components and preparation methods are the same as in Example 1.

[0052] In accordance with the "Road Marking Paint" (JT / T 280-2022) and related industry standards, the following performance tests were conducted on the paint samples of Examples 1-3 and Comparative Examples 1-7.

[0053] Abrasion resistance: The abrasion amount (mg) was tested using a Taber abrasion tester with a load of 1kg and a rotation speed of 500 rpm. Anti-slip properties: The anti-slip value (BPN) under dry and wet conditions was tested using a pendulum friction coefficient tester. Adhesion: The cross-cut test was used with a 1mm spacing between the cuts. The coating peeling was observed and the adhesion level was rated (1-5, with 1 being the best). Reflective properties: The retroreflective coefficient (mcd·m) was tested using a retroreflective marking measuring instrument, both initially and after abrasion resistance testing. -2 ・lx -1 ); Aging resistance: After aging in a UV aging chamber for 1000 hours, the changes in appearance and the retention rate of wear resistance were tested. Corrosion resistance: The coating was immersed in 5% hydrochloric acid solution, 5% sodium hydroxide solution, and 3% sodium chloride solution for 72 hours respectively. The coating was observed to see if it blistered or peeled off, and the adhesion was tested. Application performance: Observe the melt flowability, coating uniformity, and distribution of glass microspheres. Specific test results are shown in Tables 1 and 2 below.

[0054] Table 1 Performance test results of different embodiments and comparative examples Table 2 Performance test results of different embodiments and comparative examples As can be seen from the data in Tables 1 and 2 above, the wear amount of Examples 1-3 of the present invention is significantly lower than that of Comparative Examples 1-7, with Comparative Example 1 showing the highest wear amount (68.4 mg). This indicates that the introduction of composite wear-resistant aggregate greatly improves the wear resistance of the coating. Comparative Examples 2 and 3 use only a single wear-resistant component, and although their wear resistance is better than that of the traditional formulation, it is still inferior to the composite system of the examples, verifying the synergistic effect of hard support + elastic buffer. Furthermore, the applicant also studied the change in the ratio of the two components in the composite wear-resistant aggregate. When the weight ratio of modified nano-silica to modified polyimide-polyurethane block copolymer is higher or lower than (6-7):(1-3), the wear amount of the coating increases significantly, indicating that a specific ratio in the composite wear-resistant aggregate is crucial to the present invention. The decrease in wear resistance in Comparative Example 4 proves that surface modification treatment is crucial for improving interfacial bonding and final wear resistance. Examples 1-3 exhibit significantly better anti-slip properties than Comparative Example 5, which lacks anti-slip aggregate. Comparative Example 7 initially shows similar anti-slip properties to the examples, but its post-wear reflectivity and wear resistance retention are significantly lower than Example 1. This indicates that the chromium-titanium doped ceramic particles of the present invention, due to their higher hardness and better adhesion to the matrix, can better maintain surface texture and overall coating structure after long-term wear, thus providing more durable anti-slip and reflective properties. Comparative Examples 6 and 1 are severely deficient in wear resistance, reflectivity retention, and aging resistance, highlighting the core contribution of the composite wear-resistant aggregate of the present invention to the long-term durability of the coating. All examples maintain Grade 1 adhesion, and the wear resistance retention rate after UV aging exceeds 90%, demonstrating excellent corrosion resistance. In contrast, traditional formulations and single-component modified comparative examples perform poorly in these aspects.

[0055] The experimental data above demonstrate that this invention, through the synergistic combination of composite wear-resistant aggregate and composite anti-skid aggregate, resolves the technical contradiction of simultaneously achieving wear resistance, anti-skid properties, and durability in road marking paint. Comparing Example 1 with Comparative Example 5, the addition of anti-skid aggregate not only provides excellent anti-skid properties but also further increases the coating's wear resistance from 22.1 mg to 18.5 mg. Comparing Example 1 with Comparative Example 6, the addition of wear-resistant aggregate not only provides superior wear resistance but also increases the dry anti-skid value from 79 BPN to 82 BPN and the wet anti-skid value from 70 BPN to 76 BPN. This indicates a mutually beneficial effect between the two types of aggregates in the system. Furthermore, comparing Example 1 with Comparative Example 7, with similar initial anti-skid properties, Example 1 exhibits significant advantages in post-wear reflectivity retention and wear resistance retention, proving that the specific composite anti-skid aggregate (chromium-titanium doped ceramic) and the specific composite wear-resistant aggregate of this invention form a unique synergistic mechanism that significantly improves coating durability. This synergistic mechanism ensures that the coating maintains its wear resistance, anti-slip properties, and reflective properties simultaneously under long-term harsh operating conditions.

[0056] It should be noted that the above embodiments are merely some preferred embodiments of the present invention, and not all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

Claims

1. A high abrasion resistant, skid resistant pavement marking paint characterized by, By weight parts, including the following components: petroleum resin 15-25 parts, plasticizer 2-5 parts, composite wear-resistant aggregate 30-40 parts, composite anti-skid aggregate 15-25 parts, titanium dioxide 5-10 parts, silane coupling agent 0.5-2 parts, polyethylene wax 0.5-1.5 parts, glass beads 5-10 parts, antioxidant 1010 0.1-0.3 parts, filler 10-20 parts;The composite wear-resistant aggregate is composed of modified nano silicon dioxide and modified polyimide-polyurethane block copolymer according to the mass ratio of (6-7): (1-3).

2. The high abrasion resistant, skid resistant pavement marking paint of claim 1, wherein, The composite anti-skid aggregate is chromium-titanium doped ceramic particles, wherein the coarse particles are 20-40 mesh, the fine particles are 80-120 mesh, and the weight ratio of the two is (2-3):1;The filler is heavy calcium carbonate or quartz powder.

3. The high abrasion resistant, skid resistant pavement marking paint of claim 1, wherein, The modified polyimide-polyurethane block copolymer is prepared by the following method: (1) N-methyl pyrrolidone as solvent, under nitrogen protection, 4.4´-diamino diphenyl ether was added, magnetic stirring until completely dissolved, heated to 30℃, then 4 times into the reaction system, continue to magnetic stirring, until the reaction system from colorless liquid to light green transparent liquid, high speed stirring into the reaction product solution, deionized water was obtained, the filter cake was obtained by suction filtration and washed with acetone and deionized water for 3 times, then dried to obtain the product polyamide acid; (2) Isophorone diisocyanate was dissolved in DMF, protected by nitrogen, magnetic stirring and heating to 80℃, then slowly dropwise adding polytetrahydrofuran PTMG-1000 dissolved in a small amount of DMF, after dropwise addition, adding catalyst dibutyltin dilaurate, then keeping at 80℃ for 110-120min, then adding chain extender 1,4-butanediol, continuing to keep at 80℃ for 50-60min, then slowly dropwise adding polyamide acid obtained in step (1) dissolved in a small amount of DMF, after dropwise addition, continuing to keep at 80℃ for 30-40min, the reaction was completed to obtain a composite resin solution with a solid content of 30%; (3) The obtained composite resin solution was placed in a polytetrafluoroethylene mold, and vulcanized in a flat vulcanizing machine at 150℃ and 5MPa pressure for 2h, then continued to heat to 180℃ for 1.5h, stopped heating, decompressed demolding, natural cooling to room temperature, then transferred into liquid nitrogen for embrittlement, then pulverized with high-energy ball mill to obtain polyimide-polyurethane block copolymer powder; (4) Octadecyl trimethoxysilane was dissolved in an ethanol-water mixed solution, acetic acid was added to adjust the pH to 4-5, hydrolyzed for 30-40min, then the polyimide-polyurethane block copolymer powder was added, magnetic stirring under reflux at 60-80℃ for 2-3h, filtered, washed with ethanol, then vacuum dried to constant weight to obtain the modified polyimide-polyurethane block copolymer.

4. The high abrasion resistant, skid resistant pavement marking paint of claim 3, wherein, The molar ratio of phthalic anhydride, 4.4´-diaminodiphenyl ether in the step (1) is 4:3, and the N - The use amount ratio of methylpyrrolidone and phthalic anhydride is 1 mmol: 10 mL.

5. The high abrasion resistant, skid resistant pavement marking paint of claim 3, wherein, The molar ratio of isophorone diisocyanate, polytetramethylene glycol PTMG-1000, 1,4-butanediol and polyamic acid in step (2) is 4:1:1.4:0.9, and the amount of the catalyst dibutyltin dilaurate is 0.07-0.08% of the total mass of the reactants.

6. The high wear resistant, skid resistant pavement marking paint of claim 3, wherein, The ethanol and water mixed solution in step (4) is composed of ethanol and water in a volume ratio of 9:1; and the solid-liquid ratio of the polyimide-polyurethane block copolymer powder to the ethanol and water mixed solution is 1g:10-15mL.

7. The high wear resistant, skid resistant pavement marking paint of claim 2, wherein, The modified nano-silicon dioxide is obtained by modification treatment with silane coupling agent KH560 or KH570.

8. The high wear resistant, skid resistant pavement marking paint of claim 2, wherein, The chromium-titanium doped ceramic particles are prepared by the following method: taking cordierite powder as raw material, adding 1-3% titanium dioxide and 2-4% chromium sesquioxide, placing the raw material powder in a ball mill, using zirconium oxide balls as grinding balls and deionized water as medium, material:ball:water=1:2:0.8, wet ball milling, rotation speed 300-400 rpm, time 8-10h, drying after ball milling, loading into a crucible and then high-temperature calcining in a sintering furnace, increasing the temperature to 600℃ at a rate of 2℃ / min and then increasing the temperature to 1300℃ at a rate of 5℃ / min, keeping the temperature for 2h, cooling and crushing with a crusher, and sieving to obtain 20-40 mesh coarse particles and 80-120 mesh fine particles.

9. The high wear resistant, skid resistant pavement marking paint of claim 1, wherein, The silane coupling agent is KH550 or KH560.

10. A process for the preparation of the high abrasion resistant, skid- resistant pavement marking coating as claimed in any one of claims 1 to 9, characterized in that, It comprises the following steps: (1) weighing each component according to the proportion; (2) adding petroleum resin, plasticizer, polyethylene wax and antioxidant 1010 into a reaction kettle, heating to 160-180℃, and stirring until completely melted and mixed uniformly; (3) under stirring, adding titanium dioxide, filler, composite wear-resistant aggregate and composite anti-slip aggregate in sequence, keeping the temperature at 150-170℃, and high-speed stirring for 20-40 minutes to uniformly disperse each component; (4) adding silane coupling agent and continuing to stir for 10-20 minutes; (5) cooling to 120-130℃, adding glass beads, low-speed stirring for 5-10 minutes to avoid glass bead breaking, discharging, and cooling to obtain the product.

Images