High-performance hot-melt marking coating as well as preparation method and use method thereof

Abstract

The invention relates to a high-performance hot-melt marking coating. The environment-friendly plastic comprises the following components in parts by mass: 30-40 parts of maleic anhydride modified rosin resin, 10-15 parts of low-density polyethylene, 3-8 parts of a plasticizer, 15-25 parts of glass beads, 2-5 parts of nano silicon dioxide, 0.25-0.5 part of graphene, 0.25-0.5 part of carbon nanotubes, 3-5 parts of a castor oil-based biological lubricant, 1-2 parts of an amino silane coupling agent, 0.5-1 part of a hindered phenol antioxidant and 5-8 parts of titanium dioxide. Compared with the traditional petroleum resin system marking paint, the high-performance hot-melt marking paint provided by the invention has the advantages that the prepared marking has remarkable advantages in key performances such as adhesive force, wear resistance, compressive strength, low-temperature crack resistance and retroreflection brightness; the inherent defects of the traditional marking paint in the aspects of durability, environmental adaptability and reflective function durability are systematically solved. The invention also provides a preparation method and a use method of the high-performance hot-melt marking paint.

Description

Technical Field

[0001] This invention belongs to the field of road construction materials technology, specifically relating to a high-performance hot-melt road marking paint. This invention also provides a method for preparing the paint. Background Technology

[0002] In recent years, among the paint technologies used for road markings, hot-melt marking paint technology has formed a mature system based on thermoplastic resins and using glass microspheres as the reflective medium. Industry applications typically improve adhesion and flexibility through resin modification, such as using petroleum resins or rosin resins. Premixing or surface-spreading glass beads technology is also introduced to enhance retroreflective properties. Some products integrate temperature-sensitive color-changing and self-healing materials to adapt to complex traffic environments. In terms of road marking construction processes, high-temperature melting (180℃-210℃) and mechanical spraying technologies are widely used, combined with water-based primers to reduce volatile organic compound (VOC) emissions. However, traditional technologies still face core problems such as insufficient durability, high construction energy consumption, and rapid decay of reflective performance, limiting their application in high-end scenarios.

[0003] Existing hot-melt road marking paint technology suffers from three major drawbacks. Firstly, its durability is a significant bottleneck. Long-term UV exposure causes resin aging and yellowing, weakening the bond between glass beads and resin, leading to easy detachment after vehicle traffic. The reflective lifespan is only 1-2 years, and markings are prone to cracking under heavy traffic, especially on cement surfaces where adhesion is insufficient, resulting in high maintenance costs. Secondly, its environmental performance is poor. The high-temperature melting process is energy-intensive, and solvent-based primers release large amounts of VOCs. Some products contain lead and cadmium, posing a risk of ecological pollution. Thirdly, its functionality is limited. Conventional markings exhibit a sharp drop in anti-skid properties on wet surfaces, and the surface easily attracts dust and oil, significantly reducing visibility over time. Furthermore, construction is greatly affected by ambient temperature and humidity; poor film formation at low temperatures limits its application range. Summary of the Invention

[0004] The technical problem to be solved by this invention is to provide a high-performance hot-melt road marking paint to reduce or avoid the aforementioned problems. This invention also provides its preparation method and application method.

[0005] This invention provides a high-performance hot-melt road marking paint, comprising the following components by weight: 30-40 parts maleic anhydride modified rosin resin, 10-15 parts low-density polyethylene, 3-8 parts plasticizer, 15-25 parts glass microspheres, 2-5 parts nano-silica, 0.25-0.5 parts graphene, 0.25-0.5 parts carbon nanotubes, 3-5 parts castor oil-based bio-lubricant, 1-2 parts aminosilane coupling agent, 0.5-1 part hindered phenolic antioxidant, and 5-8 parts titanium dioxide.

[0006] Preferably, the glass microspheres have a particle size of 100-600 μm.

[0007] This invention also provides a method for preparing the above-mentioned high-performance hot-melt road marking paint, which includes the following steps: S1: Preparation of matrix particles: Maleic anhydride-modified rosin resin, low-density polyethylene, and plasticizer are fed into a mixer or twin-screw extruder. Simultaneously, dicumyl peroxide is added at 0.1%–0.8% of the total mass of the maleic anhydride-modified rosin resin and low-density polyethylene as a dynamic crosslinking agent. The mixture undergoes a melt blending reaction at 160–190°C under nitrogen protection or screw shearing. After the reaction, the product is extruded, water-cooled, and pelletized to obtain dynamically crosslinked modified resin matrix particles. S2: Glass microsphere treatment: Immerse glass microspheres in a 5% concentration of vinyl silane coupling agent ethanol solution, ultrasonically disperse for no less than 30 minutes, filter and dry, and then surface composite the pretreated glass microspheres with 5%-10% of nano silica (equivalent to the mass of glass microspheres) in a high-speed mixer in a dry state for no less than 5 minutes to obtain surface composite glass microspheres. S3: Composite filler treatment: Graphene and carbon nanotubes are dispersed in ethanol at a ratio of 1:1, and sodium dodecylbenzenesulfonate (SDBS) at 0.1% of the mass of ethanol is added as a dispersant. After ultrasonic treatment, the mixture is spray-dried to obtain a uniformly dispersed graphene-carbon nanotube composite filler. S4: The resin matrix particles obtained in S1, the surface composite glass microspheres obtained in S2, the graphene-carbon nanotube composite filler obtained in S3, titanium dioxide, the remaining nano silica, castor oil-based bio-lubricant, aminosilane coupling agent and antioxidant are put into a high-speed mixer and mixed at room temperature for 10-15 minutes until all components are uniformly dispersed to obtain the finished high-performance hot-melt road marking paint.

[0008] Preferably, in step S2, glass microspheres are immersed in a 5% concentration of vinyl silane coupling agent ethanol solution and ultrasonically dispersed at 50°C for 30 minutes. They are then filtered, dried at 85°C for 1 hour, and subsequently compounded with nano-silica in a high-speed mixer at a linear velocity of 25 m / s for 5 minutes.

[0009] Preferably, in S2, glass microspheres are immersed in a 5% concentration of vinyl silane coupling agent ethanol solution, sonicated at 55°C for 35 minutes, dried at 90°C for 1.5 hours, and then compounded with nano-silica in a high-speed mixer at a linear velocity of 28 m / s for 6 minutes.

[0010] Preferably, in step S3, the glass microspheres are immersed in a 5% concentration of vinyl silane coupling agent ethanol solution, ultrasonically treated at 800W power for 60 minutes, and then spray-dried at an inlet temperature of 200°C and an outlet temperature of 90°C.

[0011] This invention also provides a method for using the above-mentioned high-performance hot-melt road marking paint. In use, the finished product produced by S4 is heated to 180-220℃ to melt, stirred evenly, and then applied to the road surface. The coating thickness is controlled at 1.5-2.5 mm. Immediately after application, glass microspheres treated with perfluorosiloxane are sprinkled, with the amount sprinkled controlled at 500-600 g / m². 2 Once it cools and solidifies naturally, it will form a marking.

[0012] Compared with traditional petroleum resin-based road marking paints, the high-performance hot-melt road marking paint provided by this invention exhibits significant advantages in key properties such as adhesion, abrasion resistance, compressive strength, low-temperature crack resistance, and retroreflective brightness. It systematically solves the inherent defects of traditional road marking paints in terms of durability, environmental adaptability, and the persistence of reflective function. This invention also provides a method for preparing and using the aforementioned high-performance hot-melt road marking paint. Detailed Implementation

[0013] To provide a clearer understanding of the technical features, objectives, and effects of the present invention, the present invention will now be further described through specific embodiments.

[0014] This invention provides a high-performance hot-melt road marking paint, comprising the following components by weight: 30-40 parts of maleic anhydride modified rosin resin, 10-15 parts of low-density polyethylene (LDPE), 3-8 parts of plasticizer (e.g., DOP, naphthenic oil, chlorinated paraffin, trimellitate, polyester plasticizer, etc.), 15-25 parts of glass microspheres (particle size 100-600μm), 2-5 parts of nano-silica, 0.25-0.5 parts of graphene, 0.25-0.5 parts of carbon nanotubes, 3-5 parts of castor oil-based bio-lubricant, 1-2 parts of aminosilane coupling agent, 0.5-1 part of hindered phenolic antioxidant, and 5-8 parts of titanium dioxide.

[0015] The maleic anhydride-modified rosin resin provides high-temperature adhesion and film-forming properties. Its carboxyl groups enhance the chemical bonding with inorganic fillers, thus facilitating good wetting and coating of the fillers. The graphene and carbon nanotubes, after ultrasonic dispersion and spray drying, form a three-dimensional network structure of graphene-carbon nanotube composite filler, which improves the heat resistance, anti-aging properties, and inhibits crack propagation of the marking paint. The nano-silica, on the one hand, enhances the interfacial bonding between the glass microspheres and the resin matrix by constructing a micro-rough structure on the surface; on the other hand, it acts as a filler dispersed in the paint matrix, playing a role in reinforcement, toughening, and improving thixotropy. The hindered phenolic antioxidant extends the heat resistance life of the coating based on the maleic anhydride-modified rosin resin and inhibits high-temperature oxidative degradation. The synergistic effect of the maleic anhydride-modified rosin resin and the graphene-carbon nanotube composite filler effectively transfers and disperses stress, thereby significantly improving the low-temperature crack resistance of the coating. The aminosilane coupling agent can enhance the interfacial bonding force by bridging the organic resin and inorganic filler, thereby improving the crack resistance of the coating.

[0016] The preparation method of the above-mentioned high-performance hot-melt road marking paint includes the following steps: S1: Preparation of matrix particles: Maleic anhydride-modified rosin resin, low-density polyethylene, and plasticizer are fed into a mixer or twin-screw extruder. Simultaneously, dicumyl peroxide is added at 0.1%–0.8% of the total mass of the maleic anhydride-modified rosin resin and low-density polyethylene as a dynamic crosslinking agent. The mixture is melt-blended at 160–190°C under nitrogen protection (for the mixer) or under screw shearing. After the reaction, the product is extruded, water-cooled, and pelletized to obtain dynamically crosslinked modified resin matrix particles. S2: Glass microsphere treatment: Immerse glass microspheres in a 5% concentration of vinyl silane coupling agent ethanol solution, ultrasonically disperse for no less than 30 minutes, and dry to form a siloxane coating layer. Then, surface composite the pretreated glass microspheres with 5%-10% of nano silica (equivalent to the mass of the glass microspheres) in a high-speed mixer in a dry state for no less than 5 minutes. This allows the nano silica to adhere to the surface of the silane coating layer through physical action, forming a micro-rough structure, thus obtaining surface composite glass microspheres. S3: Composite filler treatment: Graphene and carbon nanotubes are dispersed in ethanol at a ratio of 1:1, and sodium dodecylbenzenesulfonate (SDBS) at 0.1% of the mass of ethanol is added as a dispersant. After ultrasonic treatment, the mixture is spray-dried to obtain a uniformly dispersed graphene-carbon nanotube composite filler. S4: The resin matrix particles obtained in S1, the surface-composite glass microspheres obtained in S2, the graphene-carbon nanotube composite filler obtained in S3, titanium dioxide, the remaining nano-silica, castor oil-based bio-lubricant, aminosilane coupling agent, and antioxidant are all added to a high-speed mixer and mixed at room temperature for 10-15 minutes until all components are uniformly dispersed to obtain the high-performance hot-melt road marking paint product. This product is a homogeneous mixture of granules and powder that can be directly packaged and transported.

[0017] The high-performance hot-melt road marking paint prepared by the above method can be used by heating the finished product produced by S4 to 180-220℃ to melt it, stirring it evenly, and then applying it to the road surface. The coating thickness can be controlled at 1.5-2.5 mm. Immediately after coating, glass microspheres treated with perfluorosiloxane are sprinkled on, with the amount sprinkled controlled at 500-600 g / m². 2 This creates a low surface energy region on the marking surface, which reduces the adhesion of pollutants through its hydrophobic effect, thus maintaining the long-term reflective performance of the marking. Example 1

[0018] Experimental materials: 30 parts maleic anhydride modified rosin resin, 10 parts low-density polyethylene, 3 parts plasticizer, 15 parts glass microspheres, 2 parts nano silica, 0.25 parts graphene, 0.25 parts carbon nanotubes, 3 parts castor oil-based bio-lubricant, 1 part aminosilane coupling agent, 0.5 parts antioxidant (hindered phenols), 5 parts titanium dioxide (rutile type), 0.2 parts dicumyl peroxide, appropriate amount of 5% concentration vinylsilane coupling agent ethanol solution, and 0.05 parts sodium dodecylbenzenesulfonate.

[0019] Experimental steps: S1: 30 parts of maleic anhydride-modified rosin resin, 10 parts of low-density polyethylene, and 3 parts of plasticizer were added to an internal mixer, along with 0.2 parts of dicumyl peroxide. Under nitrogen protection, the mixture was melt-blended at 185°C using a rotor shearing method for 15 minutes. After the reaction was complete, the melt product was extruded, water-cooled, and pelletized to obtain dynamically cross-linked modified resin matrix particles. S2: Immerse 15 parts of glass microspheres in a sufficient amount of 5% vinyl silane coupling agent ethanol solution and ultrasonically disperse at 50°C for 30 minutes. Then filter and dry at 85°C for 1 hour to form a siloxane coating layer. Subsequently, add the dried glass microspheres and 1 part of nano-silica to a high-speed mixer and dry disperse at a linear velocity of 25 m / s for 5 minutes to ensure firm adhesion of the nano-silica, forming a surface composite glass microsphere with a microscopic rough structure. S3: 0.25 parts graphene and 0.25 parts carbon nanotubes were dispersed in an appropriate amount of ethanol (e.g., approximately 50 parts by weight of ethanol derived from 0.05 parts sodium dodecylbenzenesulfonate), with 0.05 parts sodium dodecylbenzenesulfonate added as a dispersant. The mixture was ultrasonically treated at 800W for 60 minutes, followed by spray drying at an inlet temperature of 200℃ and an outlet temperature of 90℃ to obtain a uniformly dispersed graphene-carbon nanotube composite filler. S4: The resin matrix particles obtained in S1, the surface-composite glass microspheres obtained in S2, 5 parts of titanium dioxide, 1 part of nano-silica, the graphene-carbon nanotube composite filler obtained in S3, 3 parts of castor oil-based bio-lubricant, 1 part of aminosilane coupling agent, and 0.5 parts of hindered phenolic antioxidant are all added to a high-speed mixer. The mixture is stirred at 1000 rpm for 10 minutes at room temperature until all components are uniformly dispersed, yielding the high-performance hot-melt road marking paint product.

[0020] In use, the finished coating obtained from S4 is placed into a melting kettle, heated to 190°C, and stirred until completely melted. It is then applied to a clean and dry road surface, with the wet film thickness controlled at 2.0 mm. Immediately afterward, glass microspheres treated with perfluorosiloxane are evenly spread at a spreading rate of 500 g / m². After natural cooling and curing, the markings are formed. Example 2

[0021] Experimental materials: 35 parts maleic anhydride modified rosin resin, 12 parts low-density polyethylene, 5 parts plasticizer, 20 parts glass microspheres, 3 parts nano silica, 0.35 parts graphene, 0.35 parts carbon nanotubes, 4 parts castor oil-based bio-lubricant, 1.5 parts aminosilane coupling agent, 0.8 parts antioxidant (hindered phenols), 6 parts titanium dioxide (rutile type), 0.3 parts dicumyl peroxide, appropriate amount of 5% concentration vinylsilane coupling agent ethanol solution, and 0.05 parts sodium dodecylbenzenesulfonate.

[0022] Experimental steps: S1: 35 parts of maleic anhydride-modified rosin resin, 12 parts of low-density polyethylene, and 5 parts of plasticizer were added to an internal mixer, along with 0.3 parts of dicumyl peroxide. Under nitrogen protection, the mixture was melt-blended at 185°C using a rotor shear in the internal mixer for 15 minutes to complete the dynamic crosslinking reaction. The melt product was then extruded, water-cooled, and pelletized to obtain modified resin matrix particles. S2: 20 parts of glass microspheres were immersed in a sufficient amount of 5% vinyl silane coupling agent ethanol solution, ultrasonically dispersed at 50℃ for 30 minutes, filtered, and dried at 85℃ for 1 hour to form a siloxane coating layer. The treated glass microspheres were then added to 1.5 parts of nano-silica in a high-speed mixer and dry-dispersed at a linear velocity of 25 m / s for 5 minutes to obtain surface-composite glass microspheres. S3: 0.35 parts graphene and 0.35 parts carbon nanotubes were dispersed in ethanol, and 0.05 parts sodium dodecylbenzenesulfonate were added. After ultrasonic treatment at 800W for 60 minutes, the mixture was spray-dried at an inlet temperature of 200℃ and an outlet temperature of 90℃ to obtain a graphene-carbon nanotube composite filler. S4: The resin matrix particles obtained in S1, the surface composite glass microspheres obtained in S2, 6 parts of titanium dioxide, 1.5 parts of nano silica, the graphene-carbon nanotube composite filler obtained in S3, 4 parts of castor oil-based bio-lubricant, 1.5 parts of aminosilane coupling agent and 0.8 parts of antioxidant are put into a high-speed mixer and mixed at 1000 rpm for 10 minutes at room temperature to obtain the high-performance hot melt marking paint product.

[0023] When using: heat the finished paint to 190℃ to melt it and then apply it to the road surface, controlling the wet film thickness to 2.0 mm. Immediately spread glass microspheres treated with perfluorosiloxane at a spreading rate of 550 g / m². After cooling and solidification, functional traffic markings are obtained. Example 3

[0024] Experimental materials: 40 parts maleic anhydride modified rosin resin, 15 parts low-density polyethylene, 8 parts plasticizer, 25 parts glass microspheres, 5 parts nano silica, 0.5 parts graphene, 0.5 parts carbon nanotubes, 5 parts castor oil-based biological lubricant, 2 parts aminosilane coupling agent, 1 part antioxidant (hindered phenol), 8 parts titanium dioxide (rutile type), 0.4 parts dicumyl peroxide, appropriate amount of 5% vinylsilane coupling agent ethanol solution, and 0.08 parts sodium dodecylbenzenesulfonate.

[0025] Experimental steps: S1: 40 parts of maleic anhydride modified rosin resin, 15 parts of low-density polyethylene and 8 parts of plasticizer were put into a mixer, and 0.4 parts of dicumyl peroxide were added. The mixture was melt-blended at 188°C under nitrogen protection for 18 minutes. After the reaction was completed, the mixture was extruded, water-cooled and pelletized to obtain highly cross-linked resin matrix particles. S2: 25 parts of glass microspheres were immersed in a 5% vinyl silane ethanol solution, sonicated at 55°C for 35 minutes, and dried at 90°C for 1.5 hours. Subsequently, they were compounded with 2.5 parts of nano-silica in a high-speed mixer at a linear velocity of 28 m / s for 6 minutes to form composite glass microspheres with a high-density rough structure. S3: 0.5 parts graphene and 0.5 parts carbon nanotubes were dispersed in ethanol containing 0.08 parts sodium dodecylbenzenesulfonate, sonicated at 850W for 70 minutes, and spray-dried at an inlet temperature of 205℃ and an outlet temperature of 95℃ to obtain a three-dimensional network structure composite filler; S4: The resin matrix particles obtained in S1, the surface composite glass microspheres obtained in S2, 8 parts of titanium dioxide, 2.5 parts of nano silica, the graphene-carbon nanotube composite filler obtained in S3, 5 parts of castor oil-based lubricant, 2 parts of aminosilane coupling agent and 1 part of antioxidant are put into a high-speed mixer and mixed at 1100 rpm for 12 minutes at room temperature to obtain the finished coating.

[0026] When using it, the coating is melted at 200℃ and then applied, with the wet film thickness controlled at 2.2 mm. Perfluorosiloxane-treated glass microspheres are then sprinkled at a dosage of 600 g / m² to form a superhydrophobic reflective interface marking line.

[0027] Comparative Example 1: A method for preparing and using a conventional petroleum resin system-based hot-melt road marking paint.

[0028] Experimental materials: 35 parts C5 petroleum resin, 28 parts heavy calcium carbonate (800 mesh), 6 parts titanium dioxide (rutile type), 16 parts glass microspheres (refractive index 1.5, unmodified), 2 parts polyethylene wax, and 3 parts dioctyl phthalate.

[0029] Experimental steps: S1: Add 35 parts of C5 petroleum resin granules, 28 parts of heavy calcium carbonate, and 6 parts of titanium dioxide to a high-speed mixer and mix at 800 r / min for 15 minutes at room temperature. S2: Add 16 parts of glass microspheres, reduce the rotation speed to 400 r / min, and mix for 10 minutes; S3: Add 2 parts polyethylene wax and 3 parts DOP, increase the rotation speed to 800 r / min, mix for 10 minutes and then discharge to obtain the finished product of conventional hot melt road marking paint.

[0030] During construction, the finished coating obtained from S3 is heated to 200-220℃ to melt, applied to the road surface, and the wet film thickness is controlled to be 2.0 mm. Glass microspheres are then immediately spread at a rate of 300 g / m².

[0031] Comparative Example 2: A method for preparing and using a hot-melt marking paint based on an EVA / C5 petroleum resin composite system.

[0032] Experimental materials: 8 parts EVA resin (VA content 28%), 32 parts C5 petroleum resin, 25 parts heavy calcium carbonate (800 mesh), 6 parts titanium dioxide (rutile type), 15 parts glass microspheres (refractive index 1.5, untreated), 3 parts dioctyl phthalate, and 2 parts polyethylene wax.

[0033] Experimental steps: S1: Add 8 parts of EVA resin particles, 32 parts of C5 petroleum resin particles, 25 parts of heavy calcium carbonate, and 6 parts of titanium dioxide to a high-speed mixer and mix at 750 r / min for 15 minutes at room temperature. S2: Add 15 parts of glass microspheres, reduce the rotation speed to 350 r / min, and mix for 10 minutes; S3: Add 3 parts DOP and 2 parts polyethylene wax, increase the rotation speed to 750 r / min, mix for 10 minutes and then discharge to obtain the finished EVA / C5 composite hot melt marking paint.

[0034] During construction, the finished coating obtained from S3 is heated to 195-215℃ to melt, applied to the road surface, and the wet film thickness is controlled at 1.8 mm. Glass microspheres are then immediately spread at a rate of 350 g / m².

[0035] Comparative Example 3: A method for preparing and using a hot-melt marking paint with the same components as in Example 2 but without dynamic crosslinking and filler composite treatment.

[0036] Experimental materials: 35 parts maleic anhydride modified rosin resin, 12 parts low-density polyethylene, 5 parts plasticizer, 20 parts glass microspheres (refractive index 1.5, unmodified), 3 parts nano silica, 0.35 parts graphene, 0.35 parts carbon nanotubes, 4 parts castor oil-based bio-lubricant, 1.5 parts aminosilane coupling agent, 0.8 parts antioxidant (hindered phenols), and 6 parts titanium dioxide (rutile type).

[0037] Experimental steps: S1: 35 parts of maleic anhydride-modified rosin resin and 12 parts of low-density polyethylene were fed into an internal mixer and simply melt-blended at 185°C for 15 minutes. After the reaction was completed, the melt product was extruded, water-cooled, and pelletized to obtain uncrosslinked resin matrix particles.

[0038] S2: Add 0.35 parts graphene and 0.35 parts carbon nanotubes into a high-speed mixer and premix in a dry state for 5 minutes to obtain a physical mixture of nano-carbon materials without dispersion treatment.

[0039] S3: Add 20 parts of glass microspheres, 3 parts of nano-silica, and the mixture of graphene and carbon nanotubes obtained in S2 into a high-speed mixer and dry mix for 10 minutes to allow the components to mix initially.

[0040] S4: The uncrosslinked resin matrix particles obtained in S1, 6 parts of titanium dioxide, 4 parts of castor oil-based bio-lubricant, 1.5 parts of aminosilane coupling agent, and 0.8 parts of hindered phenolic antioxidant are all added to the high-speed mixer described in S3. The mixture is stirred at 1000 rpm for 15 minutes at room temperature to obtain the comparative hot-melt road marking paint product.

[0041] During construction, the finished coating obtained from S4 is placed into a melting kettle, heated to 190°C, and stirred until completely melted. It is then applied to a clean and dry road surface, with the wet film thickness controlled at 2.0 mm. Immediately afterward, glass microspheres are evenly spread at a rate of 500 g / m². After natural cooling and curing, the markings are formed.

[0042] The samples of hot-melt road marking paints prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to tests on adhesion, abrasion resistance, compressive strength, low-temperature crack resistance, retroreflective brightness coefficient, and other related properties.

[0043] Adhesion test: The test was conducted according to GB / T 5210-2007 "Paints and Varnishes - Pull-off Method for Adhesion Test". This method quantitatively determines the adhesion strength of the coating by pulling it off the substrate, and the result is expressed in megapascals (MPa).

[0044] Abrasion resistance test: The abrasion resistance was tested using a paint film abrasion tester according to the method specified in JT / T 280-2022 "Road Marking Paint". The abrasion resistance was evaluated by measuring the mass loss of the coating at a specified number of revolutions, and the results were expressed in milligrams (mg).

[0045] Compressive strength test: The test was conducted according to the method specified in the JT / T 280-2022 standard "Road Marking Paint". The paint was made into standard test blocks, and the maximum stress it could withstand when compressed to failure was determined using a universal testing machine. The result was expressed in megapascals (MPa).

[0046] Low-temperature crack resistance test: The low-temperature crack resistance of the coating was tested according to method 6.2.7 of the standard JT / T 280-2022 "Road Marking Paint". In order to simulate the actual environment of low-temperature areas, the temperature inside the low-temperature chamber was adjusted to -20℃±2℃.

[0047] Retroreflective brightness coefficient: measured in accordance with the national standard GB / T18833-2002 "Road Traffic Sign Reflective Film".

[0048] The test results of the hot-melt road marking paints prepared in Examples 1-3 and Comparative Examples 1-3 are shown in the table below:

[0049] As can be observed from the data in the table above, compared with the traditional petroleum resin systems represented by Comparative Examples 1 to 3, the high-performance hot-melt marking paint provided by this invention exhibits significant advantages in key properties such as adhesion, wear resistance, compressive strength, low-temperature crack resistance, and retroreflective brightness. The main reasons are as follows: In the specific embodiments of this invention, the interpenetrating network structure formed by maleic anhydride-modified rosin resin and low-density polyethylene under dynamic cross-linking is used as the matrix, which gives the coating better flexibility and cohesion; the glass microspheres treated by aminosilane coupling agent bridging and surface composite technology enhance the interfacial bonding force between the glass microspheres and the organic resin, thereby improving wear resistance and adhesion; the introduction of a three-dimensional graphene-carbon nanotube thermally conductive network constructed by ultrasonic dispersion and spray drying can effectively transfer and disperse stress, enhancing low-temperature crack resistance; the internally mixed surface composite glass microspheres provide stable reflective base points, and the surface-sprinkled perfluorosiloxane-treated microspheres construct a hydrophobic self-cleaning surface, ensuring high and durable retroreflective performance of the marking. In contrast, although Comparative Example 3 used similar basic raw materials, its overall performance was significantly reduced due to the lack of dynamic crosslinking, filler surface composite and three-dimensional thermally conductive network construction steps, especially low-temperature crack resistance. This proves that the present invention is not a simple accumulation of components, but a systematic solution to the inherent defects of traditional road marking paint in terms of durability, environmental adaptability and reflective function durability through a synergistic material system and preparation technology.

[0050] Those skilled in the art should understand that although the present invention has been described with reference to multiple embodiments, not every embodiment contains only one independent technical solution. This description is provided merely for clarity; those skilled in the art should understand the specification as a whole and consider the technical solutions involved in each embodiment as being able to be combined with each other to form different embodiments to understand the scope of protection of the present invention.

[0051] The above description is merely an illustrative embodiment of the present invention and is not intended to limit the scope of the invention. Any equivalent changes, modifications, and combinations made by those skilled in the art without departing from the concept and principles of the present invention should fall within the scope of protection of the present invention.

Claims

1. A high-performance hot-melt road marking paint, characterized in that, It comprises the following components by weight: 30-40 parts maleic anhydride modified rosin resin, 10-15 parts low-density polyethylene, 3-8 parts plasticizer, 15-25 parts glass microspheres, 2-5 parts nano silica, 0.25-0.5 parts graphene, 0.25-0.5 parts carbon nanotubes, 3-5 parts castor oil-based bio-lubricant, 1-2 parts aminosilane coupling agent, 0.5-1 part hindered phenolic antioxidant, and 5-8 parts titanium dioxide.

2. The high-performance hot-melt road marking paint according to claim 1, characterized in that, The glass microspheres have a particle size of 100-600 μm.

3. A method for preparing a high-performance hot-melt road marking paint according to claim 1 or 2, comprising the following steps, S1: Preparation of matrix particles: Maleic anhydride modified rosin resin, low-density polyethylene and plasticizer are put into a mixer or twin-screw extruder. At the same time, dicumyl peroxide is added as a dynamic crosslinking agent at a mass of 0.1% to 0.8% of the total mass of maleic anhydride modified rosin resin and low-density polyethylene. The mixture is melt-blended at a temperature of 160 to 190°C under nitrogen protection or screw shearing. After the reaction is completed, the product is extruded, water-cooled and pelletized to obtain dynamically crosslinked modified resin matrix particles. S2: Glass microsphere treatment: Immerse glass microspheres in a 5% concentration of vinyl silane coupling agent ethanol solution, ultrasonically disperse for no less than 30 minutes, filter and dry, and then surface composite the pretreated glass microspheres with 5%-10% of nano silica (equivalent to the mass of glass microspheres) in a high-speed mixer in a dry state for no less than 5 minutes to obtain surface composite glass microspheres. S3: Composite filler treatment: Graphene and carbon nanotubes are dispersed in ethanol at a ratio of 1:1, and sodium dodecylbenzenesulfonate (SDBS) at 0.1% of the mass of ethanol is added as a dispersant. After ultrasonic treatment, the mixture is spray-dried to obtain a uniformly dispersed graphene-carbon nanotube composite filler. S4: The resin matrix particles obtained in S1, the surface composite glass microspheres obtained in S2, the graphene-carbon nanotube composite filler obtained in S3, titanium dioxide, the remaining nano silica, castor oil-based bio-lubricant, aminosilane coupling agent and antioxidant are put into a high-speed mixer and mixed at room temperature for 10-15 minutes until all components are uniformly dispersed to obtain the finished high-performance hot-melt road marking paint.

4. The method according to claim 3, characterized in that, In S2, glass microspheres were immersed in a 5% concentration of vinyl silane coupling agent ethanol solution, ultrasonically dispersed at 50°C for 30 minutes, then filtered, dried at 85°C for 1 hour, and then compounded with nano-silica in a high-speed mixer at a linear velocity of 25 m / s for 5 minutes.

5. The method according to claim 3, characterized in that, In S2, glass microspheres were immersed in a 5% concentration of vinyl silane coupling agent ethanol solution, sonicated at 55°C for 35 minutes, dried at 90°C for 1.5 hours, and then compounded with nano-silica at a linear velocity of 28 m / s for 6 minutes in a high-speed mixer.

6. The method according to claim 3, characterized in that, In S3, glass microspheres are immersed in a 5% concentration of vinyl silane coupling agent ethanol solution, ultrasonically treated at 800W power for 60 minutes, and then spray-dried at an inlet temperature of 200℃ and an outlet temperature of 90℃.

7. The method of using the high-performance hot-melt road marking paint prepared according to any one of claims 3 to 6, characterized in that, When using, heat the finished product produced by S4 to 180-220℃ to melt it, stir it evenly, and then apply it to the road surface. The coating thickness should be controlled at 1.5-2.5 mm. Immediately after coating, spread glass microspheres treated with perfluorosiloxane at a rate of 500-600 g / m². 2 Once it cools and solidifies naturally, it forms a marking.

Images