A road marking composite coating, preparation method and application

Abstract

The present invention relates to the field of coating technology, and more specifically to a road marking composite coating, preparation method, and application. The road marking composite coating comprises: 35-45 parts of petroleum resin, 18-25 parts of a toughening modifier, 3-6 parts of a compatibilizer, 25-28 parts of a filler, 15-25 parts of glass microspheres, 0.3-0.8 parts of an antioxidant, 4-8 parts of nano-titanium dioxide, and 0.2-0.5 parts of a dispersant; the toughening modifier is a mixture of toughening modifier A and toughening modifier B. The road marking composite coating tightly adheres to the road surface, has strong adhesion, and exhibits excellent toughness, wear resistance, weather resistance, and temperature resistance. It is not prone to cracking or falling off, and is also effectively resistant to ultraviolet rays, thereby improving the overall performance of the coating. The preparation method optimizes the overall coating performance and has high production efficiency. The resulting coating has stable performance and is suitable for road marking applications on various roads and in complex environments.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a road marking composite coating, a preparation method and applications thereof. Background Art

[0002] In recent years, with the rapid development of the road transport industry (such as the express delivery industry), my country's highway construction has also rapidly followed suit. The rapidly growing demand for transportation volume and capacity has placed higher demands on road infrastructure. Consequently, traffic safety issues have become increasingly prominent. The government has also given this issue greater attention, issuing a large number of relevant policies and national standards.

[0003] Traffic markings, as crucial traffic safety features, play an irreplaceable role in ensuring safe driving and efficient travel. The Ministry of Transport has established strict requirements for the quality and performance of road marking coatings. Hot-melt road marking coatings are currently the most widely used type of road marking coating in my country, accounting for nearly 90% of total usage, due to their low cost, fast drying, thick film thickness, and simple application equipment. Existing hot-melt road marking coating preparation processes are mostly based on traditional single petroleum resin or synthetic resin systems. However, current processes suffer from several deficiencies: raw material selection does not meet performance requirements; precise temperature control is lacking during the heating and melting process; uniformity is insufficient during mixing and stirring; volume concentrations of fillers and pigments are not systematically optimized; the type and amount of additives added are inappropriate; temperature control during application is insufficiently rigorous; curing time is not optimized; and final finishing and quality inspection procedures are insufficiently meticulous. These factors collectively lead to defects such as cracking in the coating during actual use, impacting its performance and lifespan.

[0004] Chinese Patent Publication No. CN116948516A discloses a low-odor, self-cleaning two-component road marking paint and its preparation method. While this paint uses polyurethane-modified acrylates to improve toughness and strength, its toughness, mechanical strength, and safety are still relatively poor. Chinese Patent Application Publication No. CN106675224A discloses a hot-melt road marking paint modified with a solid epoxy resin to achieve high- and low-temperature crack resistance. However, the addition of vegetable oil to the formula makes the marking sticky when heated, making it susceptible to contaminants and soiling, thus affecting its visual effectiveness.

[0005] Therefore, it is very necessary to obtain a road marking with good comprehensive properties such as strength, toughness, temperature resistance, weather resistance and adhesion. Summary of the Invention

[0006] To address the aforementioned issues, the present invention provides a composite road marking coating, preparation method, and application. This composite road marking coating adheres tightly to the road surface, exhibits strong adhesion, and resists shedding, maintaining excellent adhesion even in adverse weather and traffic conditions. It also exhibits excellent toughness, wear resistance, and weatherability, withstanding prolonged vehicle impact and friction. It is also resistant to cracking or shedding, resists breakage even at low temperatures and softens at high temperatures. It also effectively resists UV rays, ensuring no signs of aging during use, thereby enhancing the overall performance of the coating. This preparation method achieves overall optimized coating performance and high production efficiency through precise control of process parameters (temperature, speed, pressure), optimized component addition sequence, and spraying technology. The resulting coating exhibits stable performance and is suitable for road marking applications on a variety of roads and in complex environments.

[0007] The technical solutions adopted by the present invention to achieve the above-mentioned purpose are:

[0008] A road marking composite coating comprises the following components by weight: 35-45 parts of petroleum resin, 18-25 parts of toughening modifier, 3-6 parts of compatibilizer, 25-28 parts of filler, 15-25 parts of glass microspheres, 0.3-0.8 parts of antioxidant, 4-8 parts of nano-titanium dioxide, and 0.2-0.5 parts of dispersant;

[0009] The toughening modifier is a mixture of toughening modifier A and toughening modifier B. The preparation method of the toughening modifier A comprises the following steps:

[0010] Step 1, dissolve SBS in toluene, add acrylic acid and potassium persulfate under nitrogen protection, react at 78-82°C for 5.8-6.2 hours, and purify to obtain product 1;

[0011] Step 2, dynamically vulcanizing the product 1 with sulfur and zinc stearate at 175-185° C. and a screw speed of 300-350 rpm for 4.5-5.5 minutes to purify the product 2;

[0012] Step 3: Mix product 2 with methyl methacrylate, then add sodium lauryl sulfate and ammonium persulfate, react at a temperature of 78-82° C. for 5-5.5 hours, and purify to obtain toughening modifier A.

[0013] Preferably, in step 1, the weight ratio of SBS, toluene, acrylic acid and potassium persulfate is 100:350-380:2.5-3.2:0.8-1.0.

[0014] Preferably, in step 2, the weight ratio of the product 1, sulfur, and zinc stearate is 100:0.35-0.45:0.15-0.25.

[0015] Preferably, in step 3, the weight ratio of the product 2, methyl methacrylate, sodium lauryl sulfate, and ammonium persulfate is 100:18-22:1.0-1.3:0.3-0.4.

[0016] Toughening modifier A constructs a multi-stage toughening system through a three-step chemical reaction, significantly improving the coating's impact resistance, wear resistance, and environmental adaptability through molecular structural design. Acrylic acid introduces carboxyl groups into the SBS chain, forming a graft copolymer. The introduction of carboxyl groups significantly improves the compatibility of SBS with polar components (such as fillers and nano-titanium dioxide), reduces phase separation, and enhances interfacial bonding. Furthermore, the grafted SBS exhibits improved weathering and chemical resistance, making it more adaptable to the diverse environmental requirements of road marking coatings. During dynamic vulcanization, SBS forms a thermosetting elastomer with a three-dimensional network structure under high temperature and shear forces. This significantly enhances the heat resistance and mechanical strength of SBS, thereby enhancing the wear resistance and impact resistance of the road marking coating. Furthermore, the polar groups introduced by acrylic acid grafting create additional active sites on the SBS molecular chain. These active sites can cross-link with sulfur during dynamic vulcanization, forming a more uniform and stable vulcanized network structure. This structure further improves the material's toughness and impact resistance. The introduction of methyl methacrylate in step 3 further increases the glass transition temperature of SBS, enhancing its stability and mechanical strength under high temperature conditions. Furthermore, the grafted SBS has a higher surface energy, which enhances its interfacial bonding with other polar components in the road marking coating, enabling better interaction with other components in the road marking coating and improving the overall performance of the coating. Furthermore, the vulcanized network structure of step 2 provides excellent physical support for the third step. The methyl methacrylate monomer introduced in step 3 can form new crosslinking points on the basis of the vulcanized network, further enhancing the thermal stability and mechanical strength of the material. Through the above three-step reaction, toughening modifier A not only possesses high toughness, impact resistance, and thermal stability, but also exhibits good processing properties and interfacial bonding. Through the organic combination of the three-step reaction, toughening modifier A constructs a ternary synergistic structure of "flexible main chain-crosslinked network-rigid side chains" at the molecular level. This synergistic effect enables the material to meet the requirements of various complex working conditions in practical applications, achieving improvements in comprehensive properties such as toughness, wear resistance, and temperature resistance.

[0017] Preferably, the preparation method of the toughening modifier B comprises the following steps:

[0018] Step A, dispersing nanocellulose in a mixed solution of ethanol and water, adding a silane coupling agent, and stirring the mixture at 55-65° C. for 1.8-2.2 hours to obtain surface-modified nanocellulose;

[0019] Step B: mixing SBS and polybutadiene at 155-165° C. for 4.5-5.5 minutes; adding the surface-modified nanocellulose and nanosilica of step A, raising the temperature to 175-185° C., and mixing for 7.5-8.5 minutes to obtain toughening modifier B.

[0020] Preferably, in step A, the ratio of the nanocellulose to the silane coupling agent is 3-4:1.0-1.5, and in step B, the weight ratio of the SBS, polybutadiene, surface-modified nanocellulose, and nano-silica is 85-90:2-3:4-5:2-3.

[0021] Preferably, the weight ratio of the toughening modifier A to the toughening modifier B is 50-65:35-45.

[0022] In toughening modifier B, the nanocellulose is treated with a silane coupling agent, improving its surface properties and enhancing its compatibility with SBS and polybutadiene. This surface-modified nanocellulose forms a reinforcing phase in the composite, significantly enhancing the material's tensile strength and impact resistance. The addition of nanosilica further strengthens the interfacial bonding between the filler and the matrix (e.g., SBS and polybutadiene), forming a stable network structure. Nanosilica acts as a rigid particle, bearing loads, inhibiting molecular chain slip and limiting high-temperature segment motion, thereby raising the glass transition temperature, mechanical strength, and toughness, enhancing the material's overall properties, including mechanical strength, heat resistance, and wear resistance. The silane coupling agent improves the surface properties of the nanocellulose, enabling it to disperse evenly in a mixture of ethanol and water. This uniform dispersion of nanocellulose allows for better bonding with SBS and polybutadiene during the subsequent mixing process, forming a homogeneous composite material. The addition of nanocellulose and nanosilica improves the material's heat and weather resistance. These nanomaterials maintain stable performance under high temperatures and harsh environments, extending the material's service life.

[0023] Toughening modifier A is a modified SBS polymer, introducing polar groups and a cross-linked structure. This imparts excellent flexibility and cohesion to the coating. Under vehicle load, it adapts to stress changes through deformation and sliding of its molecular chains, reducing permanent deformation and improving the coating's rutting resistance. For example, the flexibility of its molecular chains allows for elastic deformation under the pressure of a vehicle tire and then returns to its original shape after the vehicle leaves, reducing rutting. Toughening modifier B incorporates rigid particles such as nanocellulose and nanosilica. These nanoparticles act as a reinforcing framework within the coating, hindering relative sliding of polymer chains, inhibiting plastic deformation, and increasing the material's rigidity and strength. Under vehicle load, the nanoparticles can partially absorb the pressure, limiting deformation of the coating and enhancing its rutting resistance. Furthermore, the good interfacial bonding between the surface-modified nanocellulose and the polymer matrix facilitates efficient stress transfer, further enhancing rutting resistance. The combination of toughening modifiers A and B achieves an excellent combination of flexibility and rigidity. The flexible molecular chains of Toughening Modifier A buffer some of the stress when the coating is subjected to rutting forces, dissipating energy through deformation and initially deforming flexibly. Meanwhile, the nanoparticles in Toughening Modifier B, after reaching a certain deformation level, act as a deformation inhibitor, preventing the coating from over-deforming. The two synergistically enhance impact resistance. This synergistic effect allows the coating to better maintain its shape and structural integrity under long-term vehicle loads, effectively improving its rollover resistance and making the marking less susceptible to fatigue failure under long-term cyclic loading. The antioxidant properties of Toughening Modifier A combined with the heat resistance of Toughening Modifier B enhance the composite's weatherability over long-term use. This composite maintains stable performance in harsh environments such as high temperatures and UV rays. The raw material costs of Toughening Modifiers A and B are relatively low, and their optimal combination can significantly improve the composite's performance without significantly increasing costs. Toughening Modifier A provides excellent elasticity and impact resistance, while Toughening Modifier B enhances the material's toughness and wear resistance. The combination of the two achieves complementary performance, enabling the composite material to excel in a variety of applications. The polar groups of toughening modifier A form chemical bonds with fillers (such as nano-titanium dioxide and glass microspheres), while the nanocellulose of toughening modifier B enhances interfacial bonding through physical entanglement. The combination of the two further reduces filler agglomeration, improves stress transfer efficiency, and avoids cracking caused by localized stress concentration. Toughening modifier A maintains stability at high temperatures, while toughening modifier B improves low-temperature brittleness, allowing the coating to maintain excellent performance across a wide temperature range. In summary, toughening modifier B offers advantages such as high strength, good dispersibility, heat resistance, and environmental friendliness. When combined with toughening modifier A, it can achieve beneficial effects such as synergistic toughening, improved compatibility, and enhanced weather resistance.

[0024] The method for preparing the above-mentioned road marking composite coating comprises the following steps:

[0025] Step a, adding petroleum resin, raising the temperature to 160-170° C., rotating at 30-40 rpm, and stirring for 5-8 minutes; then adding toughening modifier A, heating at 170-175° C., mixing for 3-5 minutes, then adding toughening modifier B, heating at 175-180° C., mixing for 4-6 minutes, then sequentially adding filler and glass microbeads, rotating at 50-60 rpm, stirring for 8-10 minutes, finally adding antioxidant, nano-titanium dioxide, compatibilizer, and dispersant, lowering the temperature to 165-170° C., and mixing for 3-5 minutes to obtain a composite coating material;

[0026] Step b: heating the composite coating material to 180-190° C., spraying and curing at a speed of 1.5-2.5 m / s under a pressure of 12-18 MPa to obtain the composite coating material.

[0027] Application of the above-mentioned road marking composite coating.

[0028] Preferably, the method includes sequentially laying a primer layer, a graphene electrothermal carbon slurry layer, and an interface protection layer in the road marking area, and then spraying a road marking composite coating.

[0029] The present invention has the following beneficial effects:

[0030] The composite road marking coating of the present invention utilizes petroleum resin as its base resin, exhibiting excellent film-forming properties and capable of forming a tough coating. Fillers increase the coating's hardness and wear resistance. The addition of a toughening modifier further enhances the coating's impact resistance and toughness, allowing it to remain intact despite frequent vehicle traffic and extending its service life. The use of a compatibilizer improves the compatibility of the various components, resulting in a tighter bond between the coating and the road surface. The proper selection and proportioning of fillers also enhances the coating's adhesion to the road surface. The addition of glass microbeads is key to improving the reflective properties of road markings. Nano-titanium dioxide pigments possess excellent optical properties and enhance the coating's refractive index and reflectivity. The uniform coating formed by the petroleum resin and toughening modifier provides excellent fixation and protection for the glass microbeads, enabling them to better reflect light at night or in low-light conditions. The toughening modifier and compatibilizer enhance the coating's stability and durability, preventing the glass microbeads from falling off, thereby ensuring that the road marking maintains a good reflective effect over long-term use. Petroleum resin also has good weather resistance and can resist the erosion of environmental factors such as ultraviolet rays. The addition of antioxidants further improves the antioxidant capacity of the coating, slows down the aging rate of the coating, and enables it to maintain good performance even when exposed to the natural environment for a long time. The coating formed by components such as petroleum resin and compatibilizer has a certain chemical stability and can resist the erosion of acidic and alkaline substances, oil stains, etc. on the road surface, and maintains the clarity and integrity of the markings. In summary, the road marking composite coating of the present invention is tightly combined with the road surface, has strong adhesion, is not easy to fall off, and can maintain good adhesion performance even under adverse weather and traffic conditions. It has good toughness, wear resistance, and weather resistance, can withstand the rolling and friction of vehicles for a long time, is not easy to crack or fall off, will not break even in low temperature environments, and will not soften in high temperature environments. It can also effectively resist ultraviolet rays, ensure that there is no aging phenomenon during use, and improve the overall performance of the coating.

[0031] The preparation method of the present invention achieves overall optimization of coating performance and high production efficiency through precise control of process parameters (temperature, rotation speed, pressure), optimization of component addition sequence and spraying technology. The obtained coating has stable performance and is suitable for road marking applications on various roads and in complex environments. DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the embodiments described are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0033] The raw materials used in the following examples are all common commercially available products. The petroleum resin is C5 / C9 copolymer resin, Shenzhen Yoshida Chemical Co., Ltd.; the compatibilizer is maleic anhydride grafted SEBS, model sebs7126, Dongguan Xiuzhisheng Plastic Co., Ltd.; calcium carbonate, 1250 mesh, Lingshou County Zhan Teng Mineral Products Processing Plant; glass microbeads, particle size 80-100 mesh, Lingshou County Yaoyang Mineral Products Processing Plant; rutile nano-titanium dioxide, particle size 50-100nm, Dongguan Metron Plastic Chemical Co., Ltd.; dispersant BYK-110, Dongguan Hongrui Chemical Co., Ltd.; SBS is linear SBS particles, Dongguan Suwei New Materials Co., Ltd.; sulfur, brand: Fisher; zinc stearate, active ingredient content 99%, Henan Xinzhiyuan Chemical Products Co., Ltd.; nanocellulose, diameter 1-20nm, Hubei Kemaidi Chemical Co., Ltd.; polybutadiene, using end-hydroxyl polybutadiene liquid, active ingredient content 99%, Hubei Xinyuhong Biomedical Technology Co., Ltd.; nano-silica, 20nm, Nanjing Tianxing New Materials Co., Ltd. Example 1

[0034] A road marking composite coating comprises the following components in parts by weight: a base resin of 40 parts hydrogenated C5 / C9 copolymer resin, 22 parts of a toughening modifier, 4 parts of a compatibilizer, 26 parts of calcium carbonate, 20 parts of glass microspheres, 0.5 parts of an antioxidant, 6 parts of rutile nano-titanium dioxide, and 0.4 parts of a dispersant, BYK-110. The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1.

[0035] The toughening modifier is a mixture of toughening modifier A and toughening modifier B, wherein the weight ratio of toughening modifier A to toughening modifier B is 58:40. The preparation method of the toughening modifier A comprises the following steps:

[0036] Step 1: 100 parts by weight of linear SBS was dissolved in 360 parts of toluene, 2.8 parts of acrylic acid and 0.9 parts of potassium persulfate were added at a speed of 220 rpm under nitrogen protection, and the mixture was reacted at 80° C. for 6 hours. The toluene was removed by distillation under reduced pressure, and then the mixture was alkaline washed twice with 5% sodium carbonate solution at 60° C. (solid-to-liquid ratio of 1:3), and then washed with deionized water to pH = 7, and vacuum dried at 80° C. to constant weight to obtain product 1;

[0037] Step 2, 100 parts of product 1, 0.40 parts of sulfur, and 0.20 parts of zinc stearate were dynamically vulcanized in a twin-screw extruder at 180° C. and a screw speed of 320 rpm for 5 minutes, and Soxhlet extraction was performed with acetone as a solvent for 7 hours until the acetone extract was colorless and transparent, followed by ultrasonic cleaning with a mixed solution of ethanol and water in a ratio of 1:1 at 40 kHz for 30 minutes, and vacuum drying at 60° C. to constant weight to obtain product 2;

[0038] Step 3: 100 parts of product 2 were mixed with 20 parts of methyl methacrylate, and then 1.2 parts of sodium lauryl sulfate were added as an emulsifier and 0.35 parts of ammonium persulfate were added as an initiator. The reaction temperature was 80°C for 5.2 hours, and a 5% calcium chloride solution was added for demulsification for 12 minutes. The weight ratio of product 2 to calcium chloride solution was 1:5, and then filtered through a 200-mesh filter. After filtration, the product was washed with methanol 3 times and then vacuum dried at 50°C to constant weight.

[0039] The preparation method of the toughening modifier B comprises the following steps:

[0040] Step A: 3.5 parts of nanocellulose were dispersed in a mixture of 100 parts of ethanol and water at a ratio of 4:1 (weight ratio), 1.2 parts of silane coupling agent KH-570 were added, and the mixture was stirred at 60°C and 350 rpm for 2 hours. After the reaction was completed, the mixture was cooled to 25°C and 9000 rpm, and centrifuged for 18 minutes (to separate unreacted KH-570 and solvent). The mixture was washed with an ethanol / water (1:1) mixture at a solid-liquid ratio of 1:5 and ultrasonically cleaned at 40 kHz for 10 minutes. The mixture was then washed twice with ethanol, centrifuged at 5000 rpm for 10 minutes after each wash, and then vacuum dried at 60°C to constant weight to obtain surface-modified nanocellulose.

[0041] In step B, 87 parts of linear SBS and 2.5 parts of polybutadiene (LPB) are added to an internal mixer and mixed at 160° C. for 5 minutes; 4.5 parts of the surface-modified nanocellulose prepared in step A and 2.5 parts of nano-silica are added, the temperature is raised to 180° C., the mixture is mixed at 75 rpm for 8 minutes, and the temperature is maintained constant. The melt is filtered through a 200-mesh metal filter to remove undispersed silica and surface-modified nanocellulose agglomerates, and then vacuum devolatilization is performed at 200° C. and -0.08 MPa for 2 minutes, and the mixture is cooled to room temperature to obtain the product.

[0042] The method for preparing the above-mentioned road marking composite coating comprises the following steps:

[0043] Step a, adding hydrogenated C5 / C9 resin, raising the temperature to 165°C, rotating at 35 rpm, and stirring for 7 minutes; then adding toughening modifier A, mixing at 172°C for 4 minutes, then adding toughening modifier B, mixing at 178°C for 5 minutes, then sequentially adding calcium carbonate and glass beads, raising the speed to 55 rpm, and stirring for 9 minutes; finally, adding antioxidant, rutile nano-titanium dioxide, compatibilizer, and dispersant, lowering the temperature to 167°C, mixing for 4 minutes, and granulating by twin-screw extrusion (die temperature 182°C), and cooling the granules to room temperature to obtain a composite coating material;

[0044] Step b: heat the composite coating material to 185° C., use high-pressure airless spraying equipment, spray at a pressure of 15 MPa, at a speed of 2 m / s, with the nozzle 40 cm away from the road surface for spraying and curing, and obtain the product.

[0045] The application of the above-mentioned road marking composite coating is specifically as follows: a primer (road marking coating agent) is applied to the marking area on the road surface. The construction environment temperature is between 10-32°C. After the primer is evenly applied, the graphene electrothermal carbon slurry is sprayed. After the graphene electrothermal carbon slurry is formed and stabilized, an interface protective agent is sprayed on its surface to ensure the insulation effect and improve the adhesion performance with the coating layer. After the interface protective agent is sprayed, the road marking composite coating is sprayed. When self-luminescence at night is required, as well as in key areas and special sections, the electroluminescent material and protective layer are sprayed. Example 2

[0046] A road marking composite coating comprises the following components in parts by weight: a base resin: 35 parts of a hydrogenated C5 / C9 copolymer resin, 25 parts of a toughening modifier, 3 parts of a compatibilizer, 28 parts of calcium carbonate, 25 parts of glass microspheres, 0.3 parts of an antioxidant, 4 parts of rutile nano-titanium dioxide, and 0.5 parts of a dispersant (BYK-110). The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1.

[0047] The toughening modifier is a mixture of toughening modifier A and toughening modifier B, and the weight ratio of the toughening modifier A to the toughening modifier B is 50:45.

[0048] The preparation method of the toughening modifier A comprises the following steps:

[0049] Step 1: 100 parts by weight of SBS was dissolved in 350 parts of toluene. 2.5 parts of acrylic acid and 1.0 part of potassium persulfate were added at a speed of 200 rpm under nitrogen protection, and the mixture was reacted at 78° C. for 6.2 hours. The toluene was removed by distillation under reduced pressure, and then the mixture was alkaline washed twice with 5% sodium carbonate solution at 60° C. (solid-to-liquid ratio of 1:3), and then washed with deionized water until the pH was 7. The mixture was vacuum dried at 80° C. to constant weight to obtain product 1.

[0050] Step 2, 100 parts of product 1, 0.35 parts of sulfur, and 0.15 parts of zinc stearate were dynamically vulcanized in a twin-screw extruder at 175° C. and a screw speed of 350 rpm for 5.5 minutes, and Soxhlet extraction was performed with acetone as a solvent for 8 hours until the acetone extract was colorless and transparent, followed by ultrasonic cleaning with a mixed solution of ethanol and water in a ratio of 1:1 at 40 kHz for 30 minutes, and vacuum drying at 60° C. to constant weight to obtain product 2;

[0051] Step 3, 100 parts of product 2 were mixed with 22 parts of methyl methacrylate, and then 1.0 parts of sodium lauryl sulfate were added as an emulsifier, 0.4 parts of ammonium persulfate were added as an initiator, the reaction temperature was 82 ° C, the time was 5 hours, and a 5% concentration of calcium chloride solution was added for demulsification for 10 minutes. The weight ratio of product 2 to calcium chloride solution was 1:5, and then filtered through a 200 mesh filter. After filtration, the product was washed with methanol 3 times and then vacuum dried at 50 ° C to constant weight.

[0052] The preparation method of the toughening modifier B comprises the following steps:

[0053] Step A: 3 parts of nanocellulose were dispersed in a mixture of 100 parts of ethanol and water (4:1 (weight ratio), 1.0 part of silane coupling agent KH-570 was added, and the mixture was stirred at 55°C and 400 rpm for 1.8 hours. After the reaction was completed, the mixture was cooled to 25°C and 9000 rpm, and centrifuged for 18 minutes (to separate unreacted KH-570 and solvent). The mixture was washed with an ethanol / water (1:1) mixture at a solid-liquid ratio of 1:5 and ultrasonically cleaned at 40 kHz for 10 minutes. The mixture was then washed twice with ethanol, centrifuged at 5000 rpm for 10 minutes after each wash, and then vacuum dried at 60°C to constant weight to obtain surface-modified nanocellulose.

[0054] In step B, 90 parts of linear SBS and 2 parts of polybutadiene (LPB) are added to an internal mixer and mixed at 155° C. for 5.5 minutes; 4 parts of the surface-modified nanocellulose prepared in step A and 2 parts of nano-silica are added, the temperature is raised to 175° C., the temperature is maintained at 80 rpm, and the mixture is mixed for 8.5 minutes. The melt is filtered through a 200-mesh metal filter to remove undispersed silica and surface-modified nanocellulose agglomerates, and then vacuum devolatilization is performed at 200° C. and -0.08 MPa for 2 minutes, and the mixture is cooled to room temperature to obtain the product.

[0055] The method for preparing the above-mentioned road marking composite coating comprises the following steps:

[0056] Step a, adding hydrogenated C5 / C9 resin, raising the temperature to 160°C, rotating at 40 rpm, and stirring for 5 minutes; then first adding toughening modifier A, mixing at 170°C for 5 minutes, then adding toughening modifier B, mixing at 175°C for 6 minutes, then sequentially adding calcium carbonate and glass beads, raising the speed to 50 rpm, and stirring for 10 minutes, finally adding antioxidant, rutile nano-titanium dioxide, compatibilizer, and dispersant, lowering the temperature to 165°C, mixing for 5 minutes, and granulating by twin-screw extrusion (die temperature 180°C), and cooling the granules to room temperature to obtain a composite coating material;

[0057] Step b: heat the composite coating material to 180° C., use high-pressure airless spraying equipment, spray at a pressure of 12 MPa, at a speed of 2.5 m / s, with the nozzle 30 cm away from the road surface, spray and cure, and obtain the product.

[0058] The specific application of the above-mentioned road marking composite coating is the same as that in Example 1. Example 3

[0059] A road marking composite coating comprises the following components in parts by weight: a base resin: 45 parts of a hydrogenated C5 / C9 copolymer resin, 18 parts of a toughening modifier, 6 parts of a compatibilizer, 25 parts of calcium carbonate, 15 parts of glass microspheres, 0.8 parts of an antioxidant, 8 parts of rutile nano-titanium dioxide, and 0.2 parts of a dispersant (BYK-110). The antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1.

[0060] The toughening modifier is a mixture of toughening modifier A and toughening modifier B, wherein the weight ratio of toughening modifier A to toughening modifier B is 65:35. The preparation method of the toughening modifier A comprises the following steps:

[0061] Step 1: 100 parts by weight of SBS was dissolved in 380 parts of toluene, 3.2 parts of acrylic acid and 0.8 parts of potassium persulfate were added at a speed of 250 rpm under nitrogen protection, and the mixture was reacted at 82° C. for 5.8 hours. The toluene was removed by distillation under reduced pressure, and then the mixture was alkaline washed twice with 5% sodium carbonate solution at 60° C. (solid-to-liquid ratio of 1:3), and then washed with deionized water to pH = 7, and vacuum dried at 80° C. to constant weight to obtain product 1;

[0062] Step 2, 100 parts of product 1, 0.45 parts of sulfur, and 0.25 parts of zinc stearate were dynamically vulcanized in a twin-screw extruder at 185° C. and a screw speed of 300 rpm for 4.5 minutes, and Soxhlet extraction was performed with acetone as a solvent for 6 hours until the acetone extract was colorless and transparent, followed by ultrasonic cleaning with a mixed solution of ethanol and water in a ratio of 1:1 at 40 kHz for 30 minutes, and vacuum drying at 60° C. to constant weight to obtain product 2;

[0063] Step 3: 100 parts of product 2 were mixed with 22 parts of methyl methacrylate, and then 1.3 parts of sodium lauryl sulfate were added as an emulsifier and 0.3 parts of ammonium persulfate were added as an initiator. The reaction temperature was 78 ° C. and the time was 5.5 hours. A 5% calcium chloride solution was added for demulsification for 15 minutes. The weight ratio of product 2 to calcium chloride solution was 1:5. The mixture was then filtered through a 200-mesh filter. After filtration, the mixture was washed with methanol 3 times and then vacuum-dried at 50 ° C. to constant weight.

[0064] The preparation method of the toughening modifier B comprises the following steps:

[0065] Step A: 4 parts of nanocellulose were dispersed in a mixture of 100 parts of ethanol and water (4:1 (weight ratio), 1.5 parts of silane coupling agent KH-570 were added, and the mixture was stirred at 65°C and 300 rpm for 2.2 hours. After the reaction was completed, the mixture was cooled to 25°C and 9000 rpm, and centrifuged for 18 minutes (to separate unreacted KH-570 and solvent). The mixture was then washed with an ethanol / water (1:1) mixture at a solid-liquid ratio of 1:5 and ultrasonically cleaned at 40 kHz for 10 minutes. The mixture was then washed twice with ethanol, centrifuged at 5000 rpm for 10 minutes after each wash, and then vacuum dried at 60°C to constant weight to obtain surface-modified nanocellulose.

[0066] In step B, 85 parts of linear SBS and 3 parts of polybutadiene (LPB) are added to an internal mixer and mixed at 165° C. for 4.5 minutes; 5 parts of the surface-modified nanocellulose prepared in step A and 3 parts of nano-silica are added, the temperature is raised to 185° C., the temperature is maintained at 70 rpm, and the mixture is mixed for 7.5 minutes. The melt is filtered through a 200-mesh metal filter to remove undispersed silica and surface-modified nanocellulose agglomerates, and then vacuum devolatilization is performed at 200° C. and -0.08 MPa for 2 minutes, and the mixture is cooled to room temperature to obtain the product.

[0067] The method for preparing the above-mentioned road marking composite coating comprises the following steps:

[0068] Step a, adding hydrogenated C5 / C9 resin, raising the temperature to 170°C, rotating at 30 rpm, and stirring for 8 minutes; then adding toughening modifier A, mixing at 175°C for 3 minutes, then adding toughening modifier B, mixing at 180°C for 4 minutes, then sequentially adding calcium carbonate and glass microbeads, raising the speed to 60 rpm, and stirring for 8 minutes; finally, adding antioxidant, rutile nano-titanium dioxide, compatibilizer, and dispersant, lowering the temperature to 170°C, mixing for 5 minutes, and granulating by twin-screw extrusion (die temperature 185°C), and cooling the pellets to room temperature to obtain a composite coating material;

[0069] Step b: heat the composite coating material to 190° C., use high-pressure airless spraying equipment, spray at a pressure of 18 MPa, at a speed of 1.5 m / s, with the nozzle 50 cm away from the road surface for spraying and curing, and obtain the product.

[0070] The specific application of the above-mentioned road marking composite coating is the same as that in Example 1.

[0071] Comparative Example 1

[0072] A road marking composite coating, wherein the toughening modifier is SBS, and the rest is the same as in Example 1.

[0073] Comparative Example 2

[0074] A road marking composite coating, wherein the toughening modifier is entirely toughening modifier A, and the rest is the same as in Example 1.

[0075] Comparative Example 3

[0076] A road marking composite coating, wherein the toughening modifier is entirely toughening modifier B, and the rest is the same as in Example 1.

[0077] Performance Testing

[0078] Coating flexibility: The coating flexibility was tested in accordance with GB / T1731-2020. The substrate was tinplate with a size of 100×60×0.2 mm. One coat was sprayed, with a dry film thickness of 100 μm. The coating was exposed to direct sunlight for 6 hours and then subjected to standard curing (temperature 23±2°C, 50% RH) for 48 hours before testing.

[0079] The low-temperature crack resistance test was conducted according to JT / T280-2004. One cycle consisted of freezing at (-25±2)℃ for 4 hours and then placing at (23±2)℃ for 4 hours.

[0080] According to GA / T298-2001, the wear resistance and compression resistance are tested.

[0081] Table 1. Performance test results

[0082]

[0083] As can be seen from Table 1, the toughness, low-temperature crack resistance, wear resistance and compressive strength are all improved by the synergistic effect of the toughening modifier A and the toughening modifier B of the present invention.

[0084] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0085] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A road marking composite coating, characterized in that: The following components are included by weight: 35-45 parts of petroleum resin, 18-25 parts of toughening modifier, 3-6 parts of compatibilizer, 25-28 parts of filler, 15-25 parts of glass microspheres, 0.3-0.8 parts of antioxidant, 4-8 parts of nano titanium dioxide, and 0.2-0.5 parts of dispersant; The toughening modifier is a mixture of toughening modifier A and toughening modifier B. The preparation method of the toughening modifier A comprises the following steps: Step 1, dissolve SBS in toluene, add acrylic acid and potassium persulfate under nitrogen protection, react at 78-82°C for 5.8-6.2 hours, and purify to obtain product 1; Step 2, dynamically vulcanizing the product 1 with sulfur and zinc stearate at 175-185° C. and a screw speed of 300-350 rpm for 4.5-5.5 minutes to purify the product 2; Step 3: Mix product 2 with methyl methacrylate, then add sodium lauryl sulfate and ammonium persulfate, react at 78-82° C. for 5-5.5 hours, and purify to obtain toughening modifier A; The preparation method of the toughening modifier B comprises the following steps: Step A, dispersing nanocellulose in a mixed solution of ethanol and water, adding a silane coupling agent, and stirring the mixture at 55-65° C. for 1.8-2.2 hours to obtain surface-modified nanocellulose; Step B: mixing SBS and polybutadiene at 155-165° C. for 4.5-5.5 minutes; adding the surface-modified nanocellulose and nanosilica of step A, raising the temperature to 175-185° C., and mixing for 7.5-8.5 minutes to obtain toughening modifier B.

2. The road marking composite coating according to claim 1, characterized in that: In step 1, the weight ratio of SBS, toluene, acrylic acid and potassium persulfate is 100:350-380:2.5-3.2:0.8-1.

0.

3. The road marking composite coating according to claim 1, characterized in that: In step 2, the weight ratio of the product 1, sulfur, and zinc stearate is 100:0.35-0.45:0.15-0.

25.

4. The road marking composite coating according to claim 1, characterized in that: In step 3, the weight ratio of the product 2, methyl methacrylate, sodium lauryl sulfate, and ammonium persulfate is 100:18-22:1.0-1.3:0.3-0.

4.

5. The road marking composite coating according to claim 1, characterized in that: In step A, the ratio of the nanocellulose to the silane coupling agent is 3-4: 1.0-1.5, in step B, the weight ratio of the SBS, polybutadiene, surface-modified nanocellulose, and nano-silica is 85-90:2-3:4-5:2-3.

6. The road marking composite coating according to claim 1, characterized in that: The weight ratio of the toughening modifier A to the toughening modifier B is 50-65:35-45.

7. The method for preparing a road marking composite coating according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step a, adding petroleum resin, raising the temperature to 160-170° C., rotating at 30-40 rpm, and stirring for 5-8 minutes; then adding toughening modifier A, heating at 170-175° C., mixing for 3-5 minutes, then adding toughening modifier B, heating at 175-180° C., mixing for 4-6 minutes, then sequentially adding filler and glass microbeads, rotating at 50-60 rpm, stirring for 8-10 minutes, finally adding antioxidant, nano-titanium dioxide, compatibilizer, and dispersant, lowering the temperature to 165-170° C., and mixing for 3-5 minutes to obtain a composite coating material; Step b: heating the composite coating material to 180-190° C., spraying and curing at a speed of 1.5-2.5 m / s under a pressure of 12-18 MPa to obtain the composite coating material.

8. Use of the road marking composite coating according to any one of claims 1 to 6.

9. The use of the road marking composite coating according to any one of claims 1 to 6, characterized in that: First, a primer layer, a graphene electrothermal carbon slurry layer, and an interface protection layer are sequentially laid in the road marking area, and then a road marking composite coating is sprayed.

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