Long-acting self-luminous coating with self-cleaning function

Abstract

The invention discloses a long-acting self-luminous paint with a self-cleaning function, and relates to the technical field of road paints.The long-acting self-luminous paint is prepared through the following steps that S1, a hot-melting fluorescent base material is prepared, specifically, 40-45% by weight of C5 petroleum resin, 20-30% by weight of a long-afterglow luminescent material SrAl2O4: Eu < 2 + >, Dy < 3 + >, 25-35% by weight of glass beads and 2-5% by weight of auxiliaries are weighed; heating and melting the C5 petroleum resin and the auxiliary agent at 220-240 DEG C; according to the long-acting self-luminous coating with the self-cleaning function, the technical bottleneck that a traditional hot-melting fluorescent marking function is single is effectively broken through, through the synergistic effect of an energy storage-luminous mechanism and the self-cleaning effect, the maintenance and energy consumption cost of roads in high-altitude unmanned areas of Sichuan and Tibet is remarkably reduced, and the long-acting self-luminous coating with the self-cleaning function is suitable for popularization and application. The visibility of a traditional road traffic sign at night is improved, the problem of road safety at night is solved to a great extent, and important engineering application value is shown in the fields of green traffic infrastructure construction and future intelligent roads.

Description

Technical Field

[0001] This invention relates to the field of road coating technology, specifically to a long-lasting self-luminous coating with self-cleaning function. Background Technology

[0002] With the large-scale construction of urban and rural roads, especially expressways, in my country, the total mileage of highways in China reached 5.35 million kilometers by the end of 2022. In special sections of the high-altitude areas of Sichuan and Tibet, road markings not only have to face extreme climates, but also the real challenge of maintenance difficulties in uninhabited areas. As a key traffic safety facility, the visibility of road marking materials is crucial to road traffic safety [2]. Road marking paints are generally classified into three categories: hot melt, solvent, and water-based [3][4]. In order to minimize traffic interference during construction, marking materials need to have rapid curing characteristics, but traditional solvent and water-based paints cannot meet the actual needs due to their long drying time. Hot melt marking paints have excellent properties such as fast drying, long service life, and good nighttime reflectivity, and have become the marking paint with the longest usage time and the largest usage in my country.

[0003] Traditional road marking materials generally have the limitation of insufficient visibility under rain or low light conditions. In particular, the poor guidance effect of road markings is a key factor in the frequent occurrence of traffic accidents. Therefore, it is crucial to improve the visibility of traffic markings, especially the visibility of markings in wet conditions at night. At present, the methods used to improve the visibility of road markings are mainly divided into passive and active types [8]. Passive luminous markings mainly rely on the retroreflective effect of glass microspheres, but the visibility of the markings is significantly reduced at night and in rainy weather conditions. Existing technologies are difficult to meet the guidance needs of roads in rainy night environments. Active luminous markings can be divided into LED type and energy storage self-luminous type. Among them, LED type active luminous markings can emit light on their own, but they have the defects of high energy consumption and high maintenance costs. In contrast, energy storage type long afterglow markings can achieve continuous light emission at night by absorbing sunlight, showing significant advantages. Therefore, we propose a long-lasting self-luminous coating with self-cleaning function. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a long-lasting self-luminous coating with self-cleaning function, solving the problems mentioned in the background section.

[0005] To achieve the above objectives, the present invention provides a long-lasting self-luminous coating with self-cleaning function, comprising the following steps: S1. Preparation of hot-melt fluorescent substrate: Weigh 40-45% C5 petroleum resin and 20-30% long afterglow luminescent material SrAl2O4:Eu according to weight percentage. 2+ Dy 3+25-35% glass microspheres and 2-5% additives; C5 petroleum resin and additives are heated and melted at 220-240℃, then long afterglow luminescent material and glass microspheres are added, stirred evenly, coated on a substrate and cooled and cured to obtain a hot-melt fluorescent substrate. S2. Constructing a gradient hydrophobic coating: Preparing the bottom slurry: Dispersing micron-sized silica particles in an ethanol solution of an organosilane coupling agent to obtain the bottom slurry; then preparing the top slurry: Dispersing fumed nano-silica, fluorinated silicone oil microcapsules and a hydrophobic modifier in ethyl acetate to obtain the top slurry; S3. Stepwise coating of hydrophobic layer: First, the hot-melt fluorescent substrate is immersed in the bottom slurry, pulled up and dried to form a micron-level rough bottom layer; then it is immersed in the top slurry, pulled up and dried to form a nano-level hydrophobic surface layer, and finally a long-lasting self-luminous coating with a gradient hydrophobic structure is obtained.

[0006] Furthermore, the micron-sized silica particles in step (2) have a particle size of 1-10 μm and a solid content of 5-15 wt% in the bottom slurry.

[0007] Furthermore, the capsule wall material of the fluorinated silicone oil microcapsules is urea-formaldehyde resin or polyurethane, the core is perfluoropolyether oil, the average particle size of the microcapsules is 1-5 μm, and the amount added to the surface slurry is 0.5-2 wt%.

[0008] Furthermore, the hydrophobic modifier is heptadecafluorodecyltrimethoxysilane or tridecafluorooctyltriethoxysilane.

[0009] Furthermore, the total thickness of the gradient hydrophobic coating is 10-50 μm, wherein the thickness of the bottom layer is 5-20 μm and the thickness of the top layer is 5-30 μm.

[0010] Furthermore, the coating has a water contact angle ≥150° and a roll-off angle ≤10°; after being excited by sunlight for 2 hours, the afterglow time can last for more than 8 hours; when the hydrophobicity of the coating surface decreases to a contact angle <130° due to wear, under simulated sunlight irradiation or rain rinsing conditions, its hydrophobicity can be partially restored to a contact angle ≥140° within 24 hours.

[0011] Furthermore, the long-lasting self-luminous coating is used in road markings, tunnel signs, or building exterior decoration.

[0012] This invention provides a long-lasting self-luminous coating with self-cleaning function, which has the following beneficial effects: This long-lasting self-luminous coating with self-cleaning function, through testing of the coating's phase composition, cross-sectional microstructure and elemental distribution, excitation spectrum, emission spectrum, afterglow spectrum, afterglow decay curve, pure water contact angle, and anti-fouling performance, explored the optimal formulation of the hot-melt fluorescent coating. Combining actual production cost conditions and the coating's luminescent performance, the optimal formulation of the hot-melt fluorescent coating was determined: 42wt% C5 petroleum resin, 25wt% phosphor, 30wt% glass microspheres, and 3wt% additives. The self-luminous coating prepared with this formulation can maintain an afterglow time of 8 hours after 2 hours of sunlight excitation, and its luminescent performance is stable under different meteorological conditions, sufficient to meet the lighting needs at night and in severe weather conditions. After comprehensively evaluating the synergistic effects of various factors, it was determined that the coating achieved its optimal luminescence and hydrophobic properties after 2 minutes of hydrophobic modification in a nano-silica solution, with a pure water contact angle reaching 153.279°. This demonstrates excellent anti-fouling and self-cleaning properties, providing a foundation for reducing the daily cleaning and maintenance costs of road markings. The hot-melt hydrophobic self-luminescent coating prepared in this application effectively overcomes the technical bottleneck of the single function of traditional hot-melt fluorescent markings. Through the synergistic effect of its energy storage-luminescence mechanism and self-cleaning effect, it significantly reduces the maintenance and energy consumption costs of highways in the high-altitude uninhabited areas of Sichuan and Tibet, improves the visibility of traditional road traffic signs at night, and largely solves the problem of nighttime road safety. It demonstrates significant engineering application value in the construction of green transportation infrastructure and the future of smart highways. Detailed Implementation

[0013] A long-lasting self-luminous coating with self-cleaning function includes the following steps: Raw material preparation: C5 petroleum resin: industrial grade; long afterglow luminescent powder SrAl2O4:Eu²⁺,Dy³⁺: average particle size 30μm; glass microspheres: S-2000 type, particle size 200-300μm; micron-sized SiO2: particle size 5μm; fumed nano-SiO2: specific surface area 200m² / g; organosilane coupling agent: KH-550; hydrophobic modifier: heptadecafluorodecyltrimethoxysilane; fluorinated silicone oil microcapsules: core is perfluoropolyether oil, capsule wall is urea-formaldehyde resin, average particle size 3μm; solvent: anhydrous ethanol, ethyl acetate. S1. Preparation of hot-melt fluorescent substrate: Weigh out 42 parts of C5 petroleum resin, 25 parts of long-afterglow luminescent powder, 30 parts of glass microspheres, and 3 parts of antioxidant 1010 (additive). Add the C5 petroleum resin and antioxidant to a reactor and heat to 230°C to melt. Stir until completely dissolved. Then, slowly add the long-afterglow luminescent powder and glass microspheres while stirring, and continue stirring for 30 minutes until uniformly mixed. Pour the molten mixture onto a clean steel plate with dimensions of 10cm × 10cm and allow it to cool and solidify at room temperature to obtain a fluorescent substrate board with a thickness of approximately 1.5mm.

[0014] S2. Prepare gradient hydrophobic coating slurry: Bottom slurry: 10g of micron-sized SiO2 was added to 90g of anhydrous ethanol solution containing 2wt% KH-550 and ultrasonically dispersed for 30 minutes to obtain a uniform bottom slurry. Then, 8g of fumed nano-SiO2, 1g of heptadecafluorodecyltrimethoxysilane, and 0.8g of fluorinated silicone oil microcapsules were added to 90.2g of ethyl acetate and high-speed sheared dispersed for 60 minutes to obtain a uniform and stable surface slurry.

[0015] S3. Step-by-step dip coating: The fluorescent substrate board is vertically immersed in the bottom layer slurry and pulled up at a uniform speed of 5 mm / s. Then it is dried in an oven at 80°C for 30 minutes. After the bottom layer is cured, it is vertically immersed in the surface layer slurry and pulled up at the same speed of 5 mm / s. It is then dried at 60°C for 1 hour to finally obtain the gradient hydrophobic self-healing long-lasting self-luminous coating sample of the present invention.

[0016] Performance Tests and Results Luminous performance: After irradiating the sample under a 1000 lux fluorescent lamp for 2 hours, it was moved to a dark room, and the afterglow brightness was measured using a luminance meter. The results showed that after 8 hours, the afterglow brightness was still higher than 0.32 mcd / m² (the threshold that can be discerned by the human eye), meeting the requirements for road safety at night.

[0017] Hydrophobic properties: Tested using a contact angle meter, the initial water contact angle was 158° and the roll-off angle was 5°, demonstrating excellent superhydrophobicity.

[0018] Self-healing performance: The sample surface was lightly sanded with 600-grit sandpaper to simulate actual wear. After sanding, the water contact angle decreased to 125°. The worn sample was placed outdoors in a natural environment (experiencing one round of sun exposure and rain), and tested again after 24 hours. The water contact angle recovered to 145°, proving its effective self-healing ability.

[0019] Self-cleaning effect: Dust was sprinkled on the sample surface and rinsed with water. The water droplets quickly rolled off the surface, carrying away most of the dust, while the untreated control sample had a large amount of residue left.

[0020] In summary, the application of this long-lasting self-luminous coating with self-cleaning function involves the following specific steps: S1. Preparation of hot-melt fluorescent substrate: Weigh 40-45% C5 petroleum resin and 20-30% long afterglow luminescent material SrAl2O4:Eu according to weight percentage. 2+ Dy³⁺, 25-35% glass microspheres and 2-5% additives; C5 petroleum resin and additives are heated and melted at 220-240℃, then long afterglow luminescent material and glass microspheres are added, stirred evenly, coated on the substrate and cooled and cured to obtain hot-melt fluorescent substrate. S2. Constructing a gradient hydrophobic coating: Preparing the bottom slurry: Dispersing micron-sized silica particles in an ethanol solution of an organosilane coupling agent to obtain the bottom slurry; then preparing the top slurry: Dispersing fumed nano-silica, fluorinated silicone oil microcapsules and a hydrophobic modifier in ethyl acetate to obtain the top slurry; S3. Stepwise coating of hydrophobic layer: First, the hot-melt fluorescent substrate is immersed in the bottom slurry, pulled up and dried to form a micron-level rough bottom layer; then it is immersed in the top slurry, pulled up and dried to form a nano-level hydrophobic surface layer, and finally a long-lasting self-luminous coating with a gradient hydrophobic structure is obtained.

[0021] Furthermore, the micron-sized silica particles in step (2) have a particle size of 1-10 μm and a solid content of 5-15 wt% in the bottom slurry.

[0022] Furthermore, the capsule wall material of the fluorinated silicone oil microcapsules is urea-formaldehyde resin or polyurethane, the core is perfluoropolyether oil, the average particle size of the microcapsules is 1-5 μm, and the amount added to the surface slurry is 0.5-2 wt%.

[0023] Furthermore, the hydrophobic modifier is heptadecafluorodecyltrimethoxysilane or tridecafluorooctyltriethoxysilane.

[0024] Furthermore, the total thickness of the gradient hydrophobic coating is 10-50 μm, wherein the thickness of the bottom layer is 5-20 μm and the thickness of the top layer is 5-30 μm.

[0025] Furthermore, the coating has a water contact angle ≥150° and a roll-off angle ≤10°; after being excited by sunlight for 2 hours, the afterglow time can last for more than 8 hours; when the hydrophobicity of the coating surface decreases to a contact angle <130° due to wear, under simulated sunlight irradiation or rain rinsing conditions, its hydrophobicity can be partially restored to a contact angle ≥140° within 24 hours.

[0026] Furthermore, the long-lasting self-luminous coating is used in road markings, tunnel signs, or building exterior decoration.

Claims

1. A long-lasting self-luminous coating with self-cleaning function, characterized in that, Includes the following steps: S1. Preparation of hot-melt fluorescent substrate: Weigh 40-45% C5 petroleum resin and 20-30% long afterglow luminescent material SrAl2O4:Eu according to weight percentage. 2+ Dy 3+ 25-35% glass microspheres and 2-5% additives; C5 petroleum resin and additives are heated and melted at 220-240℃, then long afterglow luminescent material and glass microspheres are added, stirred evenly, coated on a substrate and cooled and cured to obtain a hot-melt fluorescent substrate. S2. Constructing a gradient hydrophobic coating: Preparing the bottom slurry: Dispersing micron-sized silica particles in an ethanol solution of an organosilane coupling agent to obtain the bottom slurry; then preparing the top slurry: Dispersing fumed nano-silica, fluorinated silicone oil microcapsules and a hydrophobic modifier in ethyl acetate to obtain the top slurry; S3. Stepwise coating of hydrophobic layer: First, the hot-melt fluorescent substrate is immersed in the bottom slurry, then pulled up and dried to form a micron-level rough bottom layer; It is then immersed in a surface slurry, pulled up and dried to form a nano-scale hydrophobic surface layer, ultimately yielding a long-lasting self-luminous coating with a gradient hydrophobic structure.

2. The long-lasting self-luminous coating with self-cleaning function according to claim 1, characterized in that, The micron-sized silica particles in step (2) have a particle size of 1-10 μm and a solid content of 5-15 wt% in the bottom slurry.

3. The long-lasting self-luminous coating with self-cleaning function according to claim 1, characterized in that: The wall material of the fluorinated silicone oil microcapsules is urea-formaldehyde resin or polyurethane, the core is perfluoropolyether oil, the average particle size of the microcapsules is 1-5 μm, and the amount added to the surface slurry is 0.5-2 wt%.

4. The long-lasting self-luminous coating with self-cleaning function according to claim 1, characterized in that: The hydrophobic modifier is heptadecafluorodecyltrimethoxysilane or tridecafluorooctyltriethoxysilane.

5. A long-lasting self-luminous coating with self-cleaning function according to claim 1, characterized in that: The total thickness of the gradient hydrophobic coating is 10-50 μm, of which the thickness of the bottom layer is 5-20 μm and the thickness of the top layer is 5-30 μm.

6. A long-lasting self-luminous coating with self-cleaning function according to any one of claims 1-5, characterized in that: The coating has a water contact angle ≥150° and a roll-off angle ≤10°; after being excited by sunlight for 2 hours, the afterglow time can last for more than 8 hours; when the hydrophobicity of the coating surface decreases to a contact angle <130° due to wear, under simulated sunlight exposure or rain washing conditions, its hydrophobicity can be partially restored to a contact angle ≥140° within 24 hours.

7. A long-lasting self-luminous coating with self-cleaning function according to claim 6, characterized in that: The application of the long-lasting self-luminous coating in road markings, tunnel signs, or building exterior decoration.