Pavement marking material for enhancing perception and preparation method thereof

Abstract

The invention provides a pavement marking material capable of enhancing perception, and relates to the technical field of road traffic marking. The pavement marking material capable of enhancing perception comprises 20-30% of C5 petroleum resin, 10-15% of hydrogenated rosin, 3-7% of composite wax, 45-60% of a magnetic composite material, 2-5% of a pigment filler, 0-10% of a filler and 0.5-2% of an antioxidant. The magnetic composite material comprises anisotropic neodymium iron boron magnetic powder and a soft magnetic material. A magnetic material is combined with the road marking, so that the road marking has magnetism, and after a vehicle is loaded with matched magnetic sensing equipment, the vehicle can stably and continuously recognize the road marking under any weather condition and road environment, and the lane keeping function of the vehicle is assisted.

Description

Technical Field

[0001] This invention relates to the field of road traffic marking technology, and more specifically, to a road marking material for enhancing perception and its preparation method. Background Technology

[0002] In the current "human-vehicle-road-cloud" collaborative system, the level of road intelligence lags significantly behind the development of vehicle technology. Level 3 and above autonomous vehicles rely on high-precision road environment perception, but traditional road markings only serve a basic guidance function and cannot provide digital interaction capabilities, causing the vehicle's advanced perception system to be constrained by the defects of the road environment.

[0003] Intelligent vehicles often use visual recognition of road markings to partially perceive the road environment. However, when vehicle cameras are dirty, rain, snow, or sand covers the markings, the vehicle is driving in backlight, or it is passing through curves or tunnels at night, the vehicle's cameras may not be able to accurately recognize the markings, creating blind spots, causing the vehicle to deviate from its lane, and easily leading to safety hazards. Summary of the Invention

[0004] To address the aforementioned issues, this invention proposes an enhanced perception road marking material. The aim is to combine magnetic materials with road markings, giving the road markings magnetism. When a vehicle is equipped with a matching magnetic sensing device, it can stably and continuously identify road markings under any weather conditions and road environment, thus assisting the vehicle's lane-keeping function.

[0005] The inventors discovered that by using neodymium iron boron magnetic powder to replace fillers such as quartz sand in hot-melt road markings, and preparing road marking samples with a neodymium iron boron magnetic powder content of 20%-80%, and then using a large magnetizer to magnetize them, the results showed that the surface magnetic strength of the sample with the highest neodymium iron boron content was only 200GS, which was completely undetectable at long distances. In order to solve the problem that existing neodymium iron boron magnetic powder has low magnetic strength and weak long-distance magnetic navigation ability when directly applied to hot-melt road marking paint, the researchers found that the sample with the highest neodymium iron boron content had a magnetic strength of only 200GS, which was completely undetectable at long distances.

[0006] The first aspect of this invention provides a road marking material for enhanced perception, wherein, by mass fraction, the road marking material for enhanced perception comprises 20-30% C5 petroleum resin, 10-15% hydrogenated rosin, 3-7% composite wax, 45-60% magnetic composite material, 2-5% pigments and fillers, 0-10% filler, and 0.5-2% antioxidant; Among them, magnetic composite materials include anisotropic neodymium iron boron magnetic powder and soft magnetic materials.

[0007] The enhanced perception road marking material of this application uses anisotropic neodymium iron boron magnetic powder, with the addition of soft magnetic materials. The anisotropic neodymium iron boron magnetic powder is chosen because it is oriented by a magnetic field during the production process. The soft magnetic materials themselves do not possess permanent magnetism, but have extremely high magnetic permeability, which can further improve the intensity of long-distance magnetic signals. Composite wax is used as a leveling agent.

[0008] Optionally, the mass ratio of anisotropic NdFeB magnetic powder to soft magnetic material is (1-2):1.

[0009] Optionally, the D50 of the anisotropic NdFeB magnetic powder is not higher than 100 μm.

[0010] In an exemplary embodiment of the present invention, the method for preparing the magnetic composite material includes the following steps: (1) Dry-mix anisotropic neodymium iron boron magnetic powder and soft magnetic material; dissolve low-temperature curing epoxy resin and curing agent in solvent to form a dilute solution; (2) Add the dilute solution to the dry mixture and mix to obtain a mixed wet material. Pour the mixed wet material into a polytetrafluoroethylene mold and place it in a strong pulsed magnetic field environment for pre-orientation treatment. (3) The pre-oriented material is cured at a certain temperature and then crushed and sieved to obtain a magnetic composite material.

[0011] Furthermore, the orientation and curing pretreatment of anisotropic NdFeB magnetic powder and soft magnetic materials involves coating the magnetic powder with low-temperature curing epoxy resin, followed by pre-orientation and preliminary curing under a strong pulsed magnetic field to form magnetic "microspheres" or "microchains" aggregates with consistent orientation. The directional arrangement of the anisotropic magnetic powder can further solve the problem of magnetic moment cancellation caused by random distribution of magnetic powder, and further improve the intensity of long-distance magnetic signals.

[0012] Optionally, by mass fraction, the magnetic composite material comprises 60-70% anisotropic NdFeB magnetic powder, 20-30% soft magnetic material, and 8-15% low-temperature curing epoxy resin.

[0013] Optionally, the curing temperature of the low-temperature curing epoxy resin is below 120℃, and the cured Tg is above 170℃. For example, the low-temperature curing epoxy resin is phenolic epoxy resin.

[0014] Optionally, the curing temperature of low-temperature curing epoxy resin is 80-120℃.

[0015] Optionally, in step (2), the magnetic field strength is ≥3T and the number of pulses is 3-5 in the strong pulsed magnetic field environment.

[0016] Optionally, the curing temperature in step (3) is 90-110℃.

[0017] In one exemplary embodiment of the present invention, the method further includes grafting the magnetic composite material, comprising the following steps: The magnetic composite material was immersed in the hydrolysate of silane coupling agent, stirred at a certain temperature, and then cooled, washed with anhydrous ethanol, and vacuum dried to obtain the pretreated magnetic composite material.

[0018] Surface grafting with silane coupling agents can improve the interfacial bonding force between materials, significantly enhancing mechanical properties, wear resistance, and anti-stripping properties. The vinyl functional groups in the silane coupling agent create physical entanglement and potential chemical cross-linking with the C5 resin matrix, transforming the magnetic particles from simple "fillers" into "reinforcing phases" of the resin matrix. Furthermore, the grafted magnetic composite material is less prone to agglomeration in the molten resin, exhibiting a more uniform distribution, which contributes to the uniformity and stability of the magnetic field.

[0019] Optionally, the amount of silane coupling agent added is 0.5%-1.5% of the mass of the magnetic composite material.

[0020] Optionally, the silane coupling agent is one or both of vinyltriethoxysilane or vinyltrimethoxysilane.

[0021] Optionally, the temperature should be 70-80℃.

[0022] Optionally, the pigment / filler is titanium dioxide; Optionally, the filler may be calcium carbonate or quartz sand; Optionally, the antioxidant is one or more of the following: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010), tris[2,4-di-tert-butylphenyl] phosphite (antioxidant 168), and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV-327); Optionally, the soft magnetic material is one or both of reduced iron powder or carbonyl iron powder.

[0023] A second aspect of the present invention provides a method for preparing a road marking material with enhanced perception, the method comprising the following steps: S1: C5 petroleum resin, hydrogenated rosin, and composite wax are melt-blended at a certain temperature to obtain a mixture; S2: Magnetic composite materials, pigments, fillers, and antioxidants are added to the mixture and mixed at a certain temperature to obtain a melt-mixed coating. S3: Apply the molten mixed coating to the road surface by scraping, and at the same time sprinkle glass microbeads evenly on the coated surface; S4: After cooling, saturate magnetization is performed to obtain road marking material with enhanced perception.

[0024] Optionally, in step S1, the temperature is 170-190℃; Optionally, in step S2, the temperature is no higher than 190℃.

[0025] Optionally, in step S4, the magnetic field strength is ≥3T.

[0026] Compared with the prior art, the present invention achieves at least one of the following beneficial effects: (1) The road marking material for enhanced perception of the present invention adopts the synergistic effect of anisotropic neodymium iron boron magnetic powder and soft magnetic materials, and is compounded with other materials. This can solve the problem that the existing neodymium iron boron magnetic powder has low magnetic strength and weak long-distance magnetic navigation capability when directly applied to hot melt marking paint.

[0027] (2) The road marking material for enhanced perception of the present invention first performs orientation curing pretreatment on magnetic composite materials, then coats magnetic powder with epoxy resin under low temperature curing, and then performs pre-orientation and preliminary curing under strong pulsed magnetic field to form magnetic "microspheres" or "microchains" aggregates with consistent orientation. The anisotropic magnetic powder is oriented, which can further solve the problem of magnetic moment cancellation caused by random distribution of magnetic powder and further improve the intensity of long-distance magnetic signal. Detailed Implementation

[0028] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0029] Unless otherwise specified, the raw materials used in the embodiments and comparative examples of this application were all purchased commercially.

[0030] Unless otherwise specified, the methods used in the embodiments and comparative examples of this application are conventional methods in the prior art. The composite waxes used in the following embodiments and comparative examples are all commercially available products, and the preparation methods of the composite waxes are also existing methods in the prior art. They can be purchased directly or prepared directly by referring to the prior art, for example, referring to patent CN201810974837.4.

[0031] Example 1 In an exemplary embodiment of the present invention, the enhanced perception road marking material comprises 20% C5 petroleum resin, 15% hydrogenated rosin, 7% composite wax, and 45% magnetic composite material. The magnetic composite material comprises anisotropic NdFeB magnetic powder D50 80μm and reduced iron powder, 2% titanium dioxide pigment and filler, 10% quartz sand filler, and 1% antioxidant 1010. The mass ratio of anisotropic NdFeB magnetic powder to reduced iron powder is 1:1.

[0032] The preparation method includes the following steps: S1: In a heated stirring vessel, add C5 petroleum resin, hydrogenated rosin, and composite wax in sequence, heat to 180°C, and stir until a completely molten mixture is formed.

[0033] S2: While stirring, add the magnetic composite material, titanium dioxide, quartz sand and antioxidant 1010 in batches, maintain the temperature at 180℃, and shear stir at high speed for 45 minutes to ensure that all components are evenly dispersed and free of lumps, and obtain a melt-mixed coating.

[0034] S3: Apply the molten mixed coating to the road surface by scraping, and at the same time sprinkle glass microbeads evenly on the coated surface.

[0035] S4: After the road markings have completely cooled to room temperature, a large magnetizer is used with a magnetic field strength of 3T and 3 pulses to perform final saturation magnetization on the road markings, resulting in road marking materials that enhance perception.

[0036] Example 2 In an exemplary embodiment of the present invention, the enhanced perception road marking material comprises 20% C5 petroleum resin, 10% hydrogenated rosin, 7% composite wax, and 60% magnetic composite material. The magnetic composite material comprises anisotropic NdFeB magnetic powder D50 100μm and carbonyl iron powder, 2% titanium dioxide pigment and filler, 0% filler, and 1% antioxidant 1010. The mass ratio of anisotropic NdFeB magnetic powder to carbonyl iron powder is 1:1.

[0037] The preparation method includes the following steps: S1: In a heated stirring vessel, add C5 petroleum resin, hydrogenated rosin, and composite wax in sequence, heat to 190°C, and stir until a completely molten mixture is formed.

[0038] S2: While stirring, add the magnetic composite material, titanium dioxide and antioxidant 1010 in batches, maintain the temperature at 180℃, and shear stir at high speed for 60 minutes to ensure that all components are evenly dispersed and free of lumps, thus obtaining a melt-mixed coating.

[0039] S3: Apply the molten mixed coating to the road surface by scraping, and at the same time sprinkle glass microbeads evenly on the coated surface.

[0040] S4: After the road markings have completely cooled to room temperature, a large magnetizer is used with a magnetic field strength of 3T and 3 pulses to perform final saturation magnetization on the road markings, resulting in road marking materials that enhance perception.

[0041] Example 3 In an exemplary embodiment of the present invention, the enhanced perception road marking material comprises 25% C5 petroleum resin, 11% hydrogenated rosin, 5% composite wax, and 50% magnetic composite material. The magnetic composite material comprises anisotropic NdFeB magnetic powder D50 50μm and reduced iron powder, 3% titanium dioxide pigment and filler, 5% quartz sand filler, and 1% antioxidant 1010. The mass ratio of anisotropic NdFeB magnetic powder to reduced iron powder is 2:1.

[0042] The preparation method includes the following steps: S1: In a heated stirring vessel, add C5 petroleum resin, hydrogenated rosin, and composite wax in sequence, heat to 180°C, and stir until a completely molten mixture is formed.

[0043] S2: While stirring, add the magnetic composite material, titanium dioxide, quartz sand and antioxidant 1010 in batches, maintain the temperature at 180℃, and shear stir at high speed for 45 minutes to ensure that all components are evenly dispersed and free of lumps, and obtain a melt-mixed coating.

[0044] S3: Apply the molten mixed coating to the road surface by scraping, and at the same time sprinkle glass microbeads evenly on the coated surface.

[0045] S4: After the road markings have completely cooled to room temperature, a large magnetizer is used with a magnetic field strength of 4T and 5 pulses to perform final saturation magnetization on the road markings, resulting in road marking materials that enhance perception.

[0046] Example 4 Based on Example 3, the main difference lies in the orientation curing pretreatment of the magnetic composite material, which includes the following steps: (1) Dry mix anisotropic NdFeB magnetic powder and reduced iron powder in a low-speed mixer for 20 minutes until uniformly mixed. Dissolve phenolic epoxy resin and its matching curing agent in ethyl acetate and stir until completely dissolved to form a dilute solution. The curing temperature of phenolic epoxy resin is 120℃, and the Tg after curing is higher than 180℃.

[0047] (2) Slowly add the dilute solution to the mixture of anisotropic NdFeB magnetic powder and reduced iron powder, and stir at low speed to make it uniformly coat the powder surface to obtain a mixed wet material. The mixed wet material is then introduced into a polytetrafluoroethylene mold and placed in a strong pulsed magnetic field environment with a magnetic field strength of 4T and 3 pulses to perform pre-orientation treatment. (3) Immediately transfer the pre-oriented mold to the drying oven and cure it at 90°C for 60 minutes to completely cure the epoxy resin, firmly fix the anisotropic NdFeB magnetic powder and reduced iron powder after orientation, and then sieve the cured block material after coarse crushing and fine crushing to obtain pre-treated magnetic composite material particles with a particle size distribution similar to the original magnetic powder. (4) The pretreated magnetic composite material particles were immersed in a solution of vinyltriethoxysilane. The amount of silane coupling agent added was 0.5% of the mass of the magnetic composite material. The reaction was carried out at 70°C for 4 hours, and then washed and vacuum dried to obtain the pretreated magnetic composite material.

[0048] Example 5 In an exemplary embodiment of the present invention, the enhanced perception road marking material comprises 25% C5 petroleum resin, 11% hydrogenated rosin, 5% composite wax, and 50% magnetic composite material. The magnetic composite material comprises anisotropic NdFeB magnetic powder D50 50μm and carbonyl iron powder, 3% titanium dioxide pigment and filler, 5% calcium carbonate filler, and 1% antioxidant 1010. The mass ratio of anisotropic NdFeB magnetic powder to carbonyl iron powder is 2:1.

[0049] The orientation curing pretreatment of magnetic composite materials includes the following steps: (1) Dry-mix anisotropic NdFeB magnetic powder and carbonyl iron powder in a low-speed mixer for 15 minutes until uniformly mixed. Dissolve phenolic epoxy resin and its matching curing agent in ethyl acetate and stir until completely dissolved to form a dilute solution. The curing temperature of phenolic epoxy resin is 120℃, and the Tg after curing is higher than 180℃.

[0050] (2) Slowly add the dilute solution to the mixture of anisotropic NdFeB magnetic powder and carbonyl iron powder, and stir at low speed to make it uniformly coat the powder surface to obtain a mixed wet material. The mixed wet material is then introduced into a polytetrafluoroethylene mold and placed in a strong pulsed magnetic field environment with a magnetic field strength of 4T and 3 pulses to perform pre-orientation treatment. (3) Immediately transfer the pre-oriented mold to the drying oven and cure it at 110°C for 60 minutes to completely cure the epoxy resin, firmly fix the anisotropic NdFeB magnetic powder and carbonyl iron powder after orientation, and then sieve the cured block material after coarse crushing and fine crushing to obtain pre-treated magnetic composite material particles with a particle size distribution similar to the original magnetic powder. (4) The pretreated magnetic composite material particles were immersed in a solution of vinyltrimethoxysilane. The amount of silane coupling agent added was 1.5% of the mass of the magnetic composite material. The reaction was carried out at 80°C for 4 hours, and then washed and vacuum dried to obtain the pretreated magnetic composite material.

[0051] The preparation method includes the following steps: S1: In a heated stirring vessel, add C5 petroleum resin, hydrogenated rosin, and composite wax in sequence, heat to 180°C, and stir until a completely molten mixture is formed.

[0052] S2: While stirring, add the magnetic composite material, titanium dioxide, calcium carbonate and antioxidant 1010 in batches, maintain the temperature at 180℃, and shear stir at high speed for 45 minutes to ensure that all components are evenly dispersed and free of lumps, and obtain a melt-mixed coating.

[0053] S3: Apply the molten mixed coating to the road surface by scraping, and at the same time sprinkle glass microbeads evenly on the coated surface.

[0054] S4: After the road markings have completely cooled to room temperature, a large magnetizer is used with a magnetic field strength of 4T and 5 pulses to perform final saturation magnetization on the road markings, resulting in road marking materials that enhance perception.

[0055] Comparative Example 1 The main difference from Example 1 is that the magnetic composite material is isotropic neodymium iron boron magnetic powder and reduced iron powder.

[0056] Comparative Example 2 The main difference from Example 1 is that no soft magnetic material was added.

[0057] Test case The enhanced perception road marking materials prepared in the examples and comparative examples were subjected to performance tests, as shown in Table 1.

[0058] Table 1

[0059] Referring to Table 1, the enhanced sensing road markings prepared by this invention have a magnetic induction intensity of no less than 900GS at 1m, a viscosity of no more than 2300 / mPa·s at 180℃, and a mass loss of no more than 25mg after 200 rpm / 1000g.

[0060] Comparing Example 1 and Comparative Example 2, with similar magnetic powder content, Example 1, which added soft magnetic material, had a significantly higher magnetic strength than Comparative Example 2, which did not add it, demonstrating that adding soft magnetic material can further improve the strength of long-distance magnetic signals.

[0061] The above description is merely an embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims

1. An enhanced perception pavement marking material, characterized by, The pavement marking material for enhancing perception comprises, by mass fraction, C5 petroleum resin 20-30%, hydrogenated rosin 10-15%, compound wax 3-7%, magnetic composite material 45-60%, pigment and filler 2-5%, filler 0-10%, and antioxidant 0.5-2%. The magnetic composite material comprises anisotropic neodymium-iron-boron magnetic powder and soft magnetic material.

2. The enhanced awareness pavement marking material of claim 1, wherein, The mass ratio of the anisotropic neodymium-iron-boron magnetic powder and the soft magnetic material is (1-2):1:.

3. The enhanced perception pavement marking material of claim 1, wherein, The preparation method of the magnetic composite material comprises the following steps: (1) dry mixing the anisotropic neodymium-iron-boron magnetic powder and the soft magnetic material; dissolving the low-temperature curing epoxy resin and the curing agent in a solvent to form a dilute solution; (2) adding the dilute solution into the dry-mixed material for mixing to obtain mixed wet material, and introducing the mixed wet material into a polytetrafluoroethylene mold and placing it in a strong pulsed magnetic field environment for pre-orientation treatment; (3) curing the pre-orientation treated material at a certain temperature, and then performing crushing and screening to obtain the magnetic composite material.

4. The enhanced perception pavement marking material of claim 3, wherein, The magnetic composite material comprises, by mass fraction, anisotropic neodymium-iron-boron magnetic powder 60-70%, soft magnetic material 20-30%, and low-temperature curing epoxy resin 8-15%.

5. The enhanced perception pavement marking material of claim 3, wherein, The curing temperature of the low-temperature curing epoxy resin is 80-120℃.

6. The enhanced perception pavement marking material of claim 3, wherein, In the strong pulsed magnetic field environment in step (2), the magnetic field strength is ≥3T, and the pulse number is 3-5 times.

7. The enhanced perception pavement marking material of claim 3, wherein, The curing temperature in step (3) is 90-110℃.

8. The perception-augmented pavement marking material of claim 1, wherein, The pigment and filler is titanium white powder; The filler is calcium carbonate or quartz sand; The antioxidant is one or more of antioxidant 1010, antioxidant 168, and UV-327; The soft magnetic material is one or both of reduced iron powder and carbonyl iron powder.

9. A method of producing a pavement marking material for enhanced perception as claimed in any one of claims 1 to 8, characterised in that, The preparation method comprises the following steps: S1: melt blending C5 petroleum resin, hydrogenated rosin, and compound wax at a certain temperature to obtain a mixture; S2: adding the magnetic composite material, pigment and filler, filler, and antioxidant to the mixture and mixing at a certain temperature to obtain a melt mixed coating; S3: scraping the melt mixed coating on the pavement and uniformly scattering glass beads on the coated surface; S4: after cooling, saturating the magnetization to obtain the pavement marking material for enhancing perception.

10. The method of claim 9, wherein, In step S1, the certain temperature is 170-190℃; And / or in step S2, the certain temperature is not higher than 190℃.

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