A continuous reflective hot melt coating and its preparation method

Abstract

This invention belongs to the technical field of hot-melt road marking paint, specifically relating to a continuous reflective hot-melt paint and its preparation method. The continuous reflective hot-melt paint, by weight, comprises the following raw material components: 140-150 parts petroleum resin, 50-60 parts titanium dioxide, 300-350 parts modified glass beads, 10-12 parts composite coupling agent, 8-10 parts DOP, 10-15 parts polyethylene wax, 12-16 parts SEBS, 250-300 parts rod-shaped calcium carbonate, 100-150 parts silica powder, 8-10 parts antioxidant 1010, and 5-8 parts nano zinc oxide; the composite coupling agent includes a silane coupling agent, a phosphate coupling agent, and an aluminate coupling agent in a mass ratio of 1:1-2:1-3. This invention optimizes the formulation and preparation method of the coating raw materials, resulting in a hot-melt coating that, when used for road markings, not only has good adhesion and long-lasting reflectivity, but also good weather resistance, does not discolor or crack, and can meet the needs of modern road markings.

Description

Technical Field

[0001] This invention belongs to the technical field of hot-melt road marking paint, specifically relating to a continuous reflective hot-melt paint and its preparation method. Background Technology

[0002] As a crucial carrier of road traffic information, road markings play a vital role in guiding, diverting, reminding, or restricting vehicles during travel. They are a critical component of traffic management, playing a vital role in channeling traffic, guiding lanes, correctly directing vehicle flow, and ensuring driving safety. With the continuous and vigorous development of the transportation industry, highway traffic is becoming increasingly busy, and driving in complex weather conditions is becoming more frequent, placing increasingly higher demands on road markings. The function and importance of road markings are self-evident. Road markings primarily provide guidance, diversion, reminders, or restrictions to ensure the normal high-speed travel of vehicles on highways and prevent traffic accidents. Therefore, markings must be complete, clear, bright, and aesthetically pleasing, not only highly visible during the day but also with high directional reflectivity at night, enabling drivers to recognize the various symbols and patterns on the markings and improving driving safety.

[0003] Currently, road marking paints are broadly classified into solvent-based paints, water-based paints, and hot-melt paints. Solvent-based paints were the earliest type of road marking paints used. They contain more than 30% organic solvents, resulting in significant environmental pollution due to the volatilization of large amounts of organic solvents during application. Furthermore, they have poor abrasion resistance and a short service life, gradually limiting their production and use. Water-based paints offer strong all-weather visibility, stability, adhesion, abrasion resistance, and anti-skid safety. They also feature simple application processes, excellent recoatability, low maintenance costs, and a friendly application environment. However, they suffer from poor adhesion, poor wetting properties, and poor weather resistance on asphalt and concrete pavements. Hot-melt coatings are widely used in traffic road marking paints due to their high wear resistance, high solids content, and short film-forming time. They primarily use petroleum resin and rosin resin as film-forming substances, with added pigments, fillers, and additives. However, with prolonged exposure to sunlight and rain, hot-melt coatings exhibit numerous problems during use, such as a significant decrease in reflectivity, easy discoloration, cracking, and high-temperature flow. Therefore, developing a new type of hot-melt coating that provides durable reflectivity and is stable and crack-free to meet the needs of modern road markings is extremely urgent. Summary of the Invention

[0004] In view of the above-mentioned shortcomings mentioned in the background art, the purpose of this invention is to provide a continuous reflective hot melt coating and its preparation method. The obtained hot melt coating, when used as road marking, not only has good adhesion and long-lasting reflectivity, but also has good weather resistance, does not change color or crack, and can meet the needs of modern road marking.

[0005] To achieve the above objectives, the present invention provides a continuous reflective hot-melt coating, comprising the following raw material components by weight:

[0006] The composition includes 140-150 parts petroleum resin, 50-60 parts titanium dioxide, 300-350 parts modified glass beads, 10-12 parts composite coupling agent, 8-10 parts DOP, 10-15 parts polyethylene wax, 12-16 parts SEBS, 250-300 parts rod-shaped calcium carbonate, 100-150 parts silica powder, 8-10 parts antioxidant 1010, and 5-8 parts nano zinc oxide; the composite coupling agent includes silane coupling agent, phosphate coupling agent, and aluminate coupling agent in a mass ratio of 1:1-2:1-3.

[0007] This invention optimizes raw materials and modifies petroleum resin using composite coupling agents, SEBS, etc., effectively improving the weather resistance, oxidation resistance, temperature resistance, and crack resistance of petroleum resin. At the same time, by selecting and modifying high-refractive-index glass beads of different particle sizes, the resin exhibits strong adhesion to the coating matrix, achieving continuous reflectivity.

[0008] Furthermore, in the above technical solution, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin in a mass ratio of 2-3:1. Petroleum resins are used in hot-melt road marking paints due to their excellent adhesion, drying speed, water resistance, and low cost. C5 petroleum resin has good tackifying effect, fast drying speed, strong adhesion, and good compatibility, but its resistance to light aging and high temperature is poor. C9 petroleum resin, on the other hand, has good weather resistance and light aging resistance, but its adhesion is lower and its compatibility is limited. This invention combines C5 and C9 petroleum resins, achieving complementary properties and improving the overall performance advantages of the resins.

[0009] Furthermore, in the above technical solution, the modified glass bead is a titanium dioxide coated glass bead coated and cured with a silane coupling agent. The titanium dioxide coated glass bead is obtained by coating a thin layer of titanium dioxide onto the surface of ordinary glass beads. It not only has a high refractive index but also significantly extends the reflective life; simultaneously, the use of a silane coupling agent for coating improves its interfacial bonding with the resin matrix.

[0010] Furthermore, in the above technical solution, the titanium dioxide coated glass beads contain 10-20% glass beads with a particle size of 100-200 μm, 50-60% with a particle size of 200-500 μm, and 20-30% with a particle size greater than 500-800 μm, all with a refractive index ≥1.8. This invention selects glass beads of different particle size ranges, which fill each other to improve the overall density of the glass bead structure. Large glass beads provide the main reflective structure, medium-sized glass beads fill the gaps to enhance the coating density, and small particles enhance surface smoothness, reduce light scattering loss, and ensure reflective effect.

[0011] Furthermore, in the above technical solution, the silane coupling agent is KH-580 (Hangzhou Jessica), the phosphate coupling agent is peroxyphosphate 651 (BYK, Germany), and the aluminate coupling agent is LZ-101 (Shandong Zibo Suchuang). In the composite coupling agent of this invention, the thiol groups (-SH) provided by the silane coupling agent react with the carboxyl groups (-COOH) of the resin to form covalent bonds, enhancing interfacial bonding; the phosphate groups in the phosphate coupling agent can capture free radicals, providing antioxidant properties, inhibiting high-temperature oxidation, and delaying resin aging; the thermal stability of the aluminate coupling agent can inhibit the thermal degradation of the coupling agent, maintain high-temperature interfacial stability, and at the same time, it can synergistically work with the phosphate ester to form a dense interfacial layer, reducing oxygen and moisture penetration and improving long-term weather resistance.

[0012] This invention also provides a method for preparing a continuously reflective hot-melt coating, comprising the following steps:

[0013] (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol in a certain proportion, add pH adjuster to adjust pH to 4-5, stir at 50-60℃ for 30-40min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 20-30min, and at the same time vacuum degassing treatment.

[0014] (2) Preparation of modified glass beads: The titanium dioxide coated glass beads are first dried at 100-120℃ for 2-3h, then immersed in silane coupling agent ethanol solution, cured at 70-80℃ for 2-3h, and then subjected to plasma treatment to obtain modified glass beads.

[0015] (3) Petroleum resin mixing and modification process: Petroleum resin is added into a high-speed kneader and heated to 130-140℃. First, the pretreated composite coupling agent is added and stirred for 30-40 min. Then, SEBS and nano zinc oxide are added and stirred for 20-30 min. Then, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder and antioxidant 1010 are added in sequence and sheared at high speed for 15-20 min.

[0016] (4) Molding process: Reduce the temperature of the resin melting system in step (3) to below 130°C, add modified glass beads, mix at low speed for 10-15 minutes, and degas under vacuum to obtain a continuous reflective hot melt coating.

[0017] This invention uses a pre-treated composite coupling agent to modify petroleum resin, improving its antioxidant properties, high-temperature resistance, and interfacial bonding ability. Then, SEBS and nano zinc oxide are used to modify the resin's elasticity and UV resistance, improving its crack resistance and aging resistance. After being mixed with other additives, it is then mixed at low temperature with glass beads that have undergone double modification treatment. The resulting continuously reflective hot melt coating not only has excellent antioxidant, anti-aging, crack resistance, and high-temperature stability, but also has strong bonding with glass beads, enabling it to reflect light for a long time.

[0018] Furthermore, in step (1) of the above technical solution, the mass ratio of the silane coupling agent to anhydrous ethanol is 1:3-5; the power of the ultrasonic dispersion is 200-500W, with a 2min interval every 5min.

[0019] Furthermore, in step (2) of the above technical solution, the silane coupling agent ethanol solution is a mixture of KH-580 and 10% ethanol in a mass ratio of 1:2-3; the plasma treatment power is 50-60W, and the atmosphere is Ar.

[0020] Furthermore, in step (3) of the above technical solution, the stirring speed is 300-400 rpm and the high-speed shearing speed is 600-800 rpm; in step (4), the low-speed stirring speed is 100-200 rpm.

[0021] Furthermore, in the above technical solutions, the vacuum degree of the vacuum degassing process is -0.08MPa.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] This invention optimizes the raw material ratio of hot-melt coatings, fully utilizing the characteristics of each raw material to effectively improve the overall performance of the hot-melt coating. By modifying petroleum resin with composite coupling agents, SEBS, and nano-zinc oxide, it not only improves the weather resistance, oxidation resistance, temperature resistance, crack resistance, and aging resistance of the petroleum resin, preventing yellowing from affecting the reflective effect, but also enhances its interfacial bonding ability with glass beads. Adding titanium dioxide increases whiteness, adding DOP increases low-temperature flexibility, adding polyethylene wax increases dispersibility and crack resistance, adding rod-shaped calcium carbonate and silica powder as fillers improves the compressive strength and wear resistance of the coating, and adding antioxidants further delays thermo-oxidative aging performance. Finally, adding double-modified glass beads results in a continuously reflective hot-melt coating that not only has excellent anti-oxidation, anti-aging, crack resistance, and high-temperature stability, but also has strong bonding with glass beads, enabling long-lasting reflectivity.

[0024] This invention selects glass beads of different particle sizes. Large glass beads provide the main reflective structure, medium glass beads fill the gaps to improve the density of the coating, and small beads can enhance the surface smoothness. Different particle sizes complement each other, which can reduce light scattering loss while improving the overall density of the glass bead structure, thus ensuring reflective effect and durability.

[0025] This invention uses composite coupling agents to modify petroleum resin. The thiol (-SH) groups in the silane coupling agent react with the carboxyl groups of the petroleum resin to enhance interfacial chemical bonding. Simultaneously, the silane can condense with the hydroxyl groups on the surface of glass beads, constructing a three-dimensional network structure of "resin-silane-glass bead," achieving a strong bond between the resin film and the glass beads. The phosphate ester coupling agent captures free radicals, inhibiting the thermo-oxidative aging of the resin and improving high-temperature dispersibility. The aluminate coupling agent's high thermal stability inhibits its own degradation while maintaining interfacial stability. It also synergistically works with the phosphate ester to form a dense interface, further enhancing long-term weather resistance.

[0026] This invention uses titanium dioxide coated glass beads as the glass beads, which have a high refractive index and a long reflective life. At the same time, the surface of the beads is treated with a silane coupling agent to improve their interfacial bonding with the resin, which can further prevent cracking and peeling, and ultimately achieve the purpose of long-lasting reflection.

[0027] This invention, by pretreating each raw material separately and adding them in stages, not only ensures the modification effect but also prevents uneven mixing of raw materials at once and avoids damage to the titanium dioxide layer on the surface of the glass beads. Detailed Implementation

[0028] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the raw materials used in the following examples are all commercially available products and can be purchased from the market.

[0029] The above-described technical features of the present invention and the technical features specifically described below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions.

[0030] The raw materials involved in the various embodiments of the present invention are either commercially available products or can be prepared according to existing methods.

[0031] The specific content of the present invention will be further explained and described below with reference to the embodiments.

[0032] Example 1

[0033] A continuous reflective hot-melt coating, comprising the following raw material components by weight:

[0034] 140 parts petroleum resin, 60 parts titanium dioxide, 325 parts modified glass beads, 10 parts composite coupling agent, 10 parts DOP, 10 parts polyethylene wax, 15 parts SEBS, 265 parts rod-shaped calcium carbonate, 150 parts silica powder, 10 parts antioxidant 1010, and 5 parts nano zinc oxide.

[0035] Among them, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin in a mass ratio of 3:1;

[0036] The composite coupling agent includes silane coupling agent KH-580, phosphate coupling agent peroxyphosphate 651, and aluminate coupling agent LZ-101 in a mass ratio of 1:2:3.

[0037] Among the titanium dioxide coated glass beads, 20% have a particle size of 100-200μm, 55% have a particle size of 200-500μm, and 25% have a particle size greater than 500-800μm, with a refractive index ≥1.8 for all of them.

[0038] Its preparation method includes the following steps:

[0039] (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol at a mass ratio of 1:5, add acetic acid to adjust the pH to 4-5, stir at 50℃ for 40min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 20min (500W, 2min interval every 5min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08MPa).

[0040] (2) Preparation of modified glass beads: The titanium dioxide coated glass beads were first dried at 100°C for 3 hours, then immersed in silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol in a mass ratio of 1:2), cured at 70°C for 3 hours, and then subjected to plasma treatment (50W, Ar atmosphere) to obtain modified glass beads.

[0041] (3) Petroleum resin mixing and modification process: Petroleum resin is added into a high-speed kneader and heated to 140°C. First, the pretreated composite coupling agent is added and stirred at 300 rpm for 40 min. Then, SEBS and nano zinc oxide are added and stirred for 30 min. Then, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder and antioxidant 1010 are added in sequence and sheared at 600 rpm for 20 min.

[0042] (4) Molding process: Reduce the temperature of the resin melting system in step (3) to below 130°C, add modified glass beads, mix at a low speed of 100 rpm for 15 min, and degas under vacuum (vacuum degree is -0.08 MPa) to obtain a continuous reflective hot melt coating.

[0043] Example 2

[0044] A continuous reflective hot-melt coating, comprising the following raw material components by weight:

[0045] 145 parts petroleum resin, 55 parts titanium dioxide, 350 parts modified glass beads, 11 parts composite coupling agent, 9 parts DOP, 12 parts polyethylene wax, 16 parts SEBS, 258 parts rod-shaped calcium carbonate, 130 parts silica powder, 8 parts antioxidant 1010, and 6 parts nano zinc oxide.

[0046] The petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin in a mass ratio of 2.5:1.

[0047] The composite coupling agent includes silane coupling agent KH-580, phosphate coupling agent peroxyphosphate 651, and aluminate coupling agent LZ-101 in a mass ratio of 1:2:2.

[0048] The titanium dioxide coated glass beads have a particle size of 100-200μm, 60% have a particle size of 200-500μm, and 25% have a particle size greater than 500-800μm. All of them have a refractive index ≥1.8.

[0049] Its preparation method includes the following steps:

[0050] (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol at a mass ratio of 1:3-5, add acetic acid to adjust the pH to 4-5, stir at 55℃ for 35min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 25min (300W, 2min interval every 5min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08MPa).

[0051] (2) Preparation of modified glass beads: The titanium dioxide coated glass beads were first dried at 120°C for 2 hours, then immersed in a silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol in a mass ratio of 1:3), cured at 80°C for 2 hours, and then subjected to plasma treatment (55W, Ar atmosphere) to obtain modified glass beads.

[0052] (3) Petroleum resin mixing and modification process: Petroleum resin is added into a high-speed kneader and heated to 135°C. First, the pretreated composite coupling agent is added and stirred at 350 rpm for 35 min. Then, SEBS and nano zinc oxide are added and stirred for 25 min. Then, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder and antioxidant 1010 are added in sequence and sheared at 700 rpm for 18 min.

[0053] (4) Molding process: Reduce the temperature of the resin melting system in step (3) to below 130°C, add modified glass beads, mix at low speed of 150 rpm for 12 min, and degas under vacuum (vacuum degree is -0.08 MPa) to obtain a continuous reflective hot melt coating.

[0054] Example 3

[0055] A continuous reflective hot-melt coating, comprising the following raw material components by weight:

[0056] 150 parts petroleum resin, 50 parts titanium dioxide, 300 parts modified glass beads, 12 parts composite coupling agent, 8 parts DOP, 15 parts polyethylene wax, 16 parts SEBS, 300 parts rod-shaped calcium carbonate, 130 parts silica powder, 9 parts antioxidant 1010, and 8 parts nano zinc oxide.

[0057] Among them, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin in a mass ratio of 2:1;

[0058] The composite coupling agent includes silane coupling agent KH-580, phosphate coupling agent peroxyphosphate 651, and aluminate coupling agent LZ-101 in a mass ratio of 1:1:2.

[0059] In the titanium dioxide coated glass beads, 20% have a particle size of 100-200μm, 50% have a particle size of 200-500μm, and 30% have a particle size greater than 500-800μm, and all have a refractive index ≥1.8.

[0060] Its preparation method includes the following steps:

[0061] (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol at a mass ratio of 1:3-5, add acetic acid to adjust the pH to 4-5, stir at 60℃ for 30min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 30min (200W, 2min interval every 5min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08MPa).

[0062] (2) Preparation of modified glass beads: The titanium dioxide coated glass beads were first dried at 120°C for 2 hours, then immersed in silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol in a mass ratio of 1:2), cured at 70°C for 3 hours, and then subjected to plasma treatment (60W, Ar atmosphere) to obtain modified glass beads.

[0063] (3) Petroleum resin mixing and modification process: Petroleum resin is added into a high-speed kneader and heated to 130°C. First, the pretreated composite coupling agent is added and stirred at 400 rpm for 30 min. Then, SEBS and nano zinc oxide are added and stirred for 20 min. Then, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder and antioxidant 1010 are added in sequence and sheared at 800 rpm for 15 min.

[0064] (4) Molding process: Reduce the temperature of the resin melting system in step (3) to below 130°C, add modified glass beads, mix at a low speed of 200 rpm for 10 min, and degas under vacuum (vacuum degree is -0.08 MPa) to obtain a continuous reflective hot melt coating.

[0065] Comparative Example 1

[0066] A continuous reflective hot melt coating differs from Example 1 in that the resin used is petroleum resin C5.

[0067] Comparative Example 2

[0068] A continuous reflective hot melt coating differs from Example 1 in that the coupling agent used is a silane coupling agent.

[0069] Comparative Example 3

[0070] A continuous reflective hot melt coating differs from Example 1 in that the composite coupling agent is a silane coupling agent and a phosphate ester coupling agent in a mass ratio of 1:2.

[0071] Comparative Example 4

[0072] A continuous reflective hot melt coating differs from Example 1 in that the composite coupling agent is a silane coupling agent and an aluminate coupling agent in a mass ratio of 1:2.

[0073] Comparative Example 5

[0074] A continuous reflective hot melt coating differs from Example 1 in that the composite coupling agent is a phosphate ester coupling agent and an aluminate ester coupling agent in a mass ratio of 1:1.

[0075] Comparative Example 6

[0076] A continuous reflective hot melt coating, which differs from Example 1 in that the glass beads are ordinary glass beads.

[0077] Comparative Example 7

[0078] A continuous reflective hot melt coating differs from Example 1 in that the modified glass beads have a particle size of 200-500 μm.

[0079] Comparative Example 8

[0080] A continuous reflective hot melt coating differs from Example 1 in that the glass beads are not modified with a silane coupling agent.

[0081] Comparative Example 9

[0082] A continuous reflective hot melt coating differs from Example 1 in that the composite coupling agent is not pretreated during the preparation process.

[0083] Comparative Example 10

[0084] A continuous reflective hot-melt coating differs from Example 1 in that its preparation method includes the following steps:

[0085] (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol at a mass ratio of 1:5, add acetic acid to adjust the pH to 4-5, stir at 50℃ for 40min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 20min (500W, 2min interval every 5min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08MPa).

[0086] (2) Preparation of modified glass beads: The titanium dioxide coated glass beads were first dried at 100°C for 3 hours, then immersed in silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol in a mass ratio of 1:2), cured at 70°C for 3 hours, and then subjected to plasma treatment (50W, Ar atmosphere) to obtain modified glass beads.

[0087] (3) Molding process: Petroleum resin is added to a high-speed kneader and heated to 140°C. Pretreated composite coupling agent, SEBS, nano zinc oxide, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, antioxidant 1010, and modified glass beads are added. The mixture is sheared at 600-800 rpm for 15-20 minutes and then degassed under vacuum (vacuum degree is -0.08MPa) to obtain a continuously reflective hot melt coating.

[0088] Test case

[0089] The hot-melt coatings obtained in Examples 1-3 and Comparative Examples 1-10 were applied as follows: the road surface was preheated to 60-70℃, the hot-melt coating was heated to 190℃, and then sprayed onto the road surface to a thickness of 2.5mm. Performance tests were conducted according to the relevant methods in standard JT / T280-2022 Surface Marking Coatings and GB / T 21383-2008, and the results are shown in Tables 1-3.

[0090] Table 1 Test results of Examples 1-3

[0091]

[0092] Table 2 Test results of Comparative Examples 1-5

[0093]

[0094] Table 3 Test results of Comparative Examples 6-10

[0095]

[0096] As can be seen from the results in Table 1, the continuously reflective hot-melt coating prepared using the formulation and preparation method of this invention exhibits excellent overall performance, with a bonding strength exceeding 6.8 MPa and good adhesion. In particular, it showed no cracking after 16 freeze-thaw cycles, demonstrating excellent low-temperature crack resistance. It also showed no discoloration or cracking after accelerated aging, exhibiting good weather resistance and high-temperature resistance. The retroreflectivity reached 490 mcd / (lx·m). 2 It has a retroreflectivity of over 75% even after one year, and the reflectivity is good and long-lasting.

[0097] As can be seen from the results in Tables 2 and 3, Comparative Example 1, due to the lack of appropriate C9 petroleum resin, exhibited relatively poor weather resistance, temperature resistance, and light aging resistance. Comparative Example 2, using only silane coupling agents, and Comparative Examples 3 to 5, using combinations of two of the three coupling agents, all showed a decrease in performance compared to Example 1, indicating that the three combinations were more beneficial for modifying petroleum resin and improving its overall performance. Comparative Example 6 used ordinary glass beads instead of titanium dioxide coated glass beads. Although other properties were not significantly affected, its low refractive index resulted in poor and short-lasting retroreflective effects. Comparative Example 7 used glass beads of a single particle size; due to the intermittent nature of the glass beads, the structure was not dense. The uneven surface of the glass beads resulted in significant light scattering loss, severely impacting the reflective effect and durability. In Comparative Example 8, the surface of the titanium dioxide-coated glass beads was not modified, leading to poor adhesion with other base materials in the coating and a tendency to crack after use, which also affected the reflective effect. In Comparative Example 9, the composite coupling agent was not pretreated beforehand and was directly mixed with petroleum resin, resulting in poor modification, poor weather resistance and high-temperature resistance, and also affecting the adhesion with the glass beads. In Comparative Example 10, all materials were mixed at once, which was not conducive to the modification of the resin material. Furthermore, the high-speed mixing process easily damaged the titanium dioxide layer and caused the glass beads to break, affecting not only weather resistance and adhesion but also the reflective effect.

[0098] In summary, the hot-melt coating obtained by this invention through optimized raw material ratio and preparation method not only has good adhesion and long-lasting reflectivity, but also has good weather resistance. It does not change color, crack, or flow after low-temperature or heat treatment, thus meeting the needs of modern road markings.

[0099] Finally, it should be emphasized that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A continuously reflective hot-melt coating, characterized in that, By weight, it includes the following raw material components: The composition includes 140-150 parts petroleum resin, 50-60 parts titanium dioxide, 300-350 parts modified glass beads, 10-12 parts composite coupling agent, 8-10 parts DOP, 10-15 parts polyethylene wax, 12-16 parts SEBS, 250-300 parts rod-shaped calcium carbonate, 100-150 parts silica powder, 8-10 parts antioxidant 1010, and 5-8 parts nano zinc oxide; the composite coupling agent includes silane coupling agent, phosphate coupling agent, and aluminate coupling agent in a mass ratio of 1:1-2:1-3. The petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin in a mass ratio of 2-3:1; The preparation method of the continuously reflective hot-melt coating includes the following steps: (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol in a certain proportion, add pH adjuster to adjust pH to 4-5, stir at 50-60℃ for 30-40min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 20-30min, and at the same time vacuum degassing treatment. (2) Preparation of modified glass beads: Titanium dioxide coated glass beads are first dried at 100-120℃ for 2-3 hours, then immersed in silane coupling agent ethanol solution, cured at 70-80℃ for 2-3 hours, and then subjected to plasma treatment to obtain modified glass beads; the titanium dioxide coated glass beads have a particle size of 100-200μm accounting for 10-20%, 200-500μm accounting for 50-60%, and larger than 500-800μm accounting for 20-30%; (3) Petroleum resin mixing and modification process: Petroleum resin is added into a high-speed kneader and heated to 130-140℃. First, the pretreated composite coupling agent is added and stirred for 30-40 min. Then, SEBS and nano zinc oxide are added and stirred for 20-30 min. Then, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder and antioxidant 1010 are added in sequence and sheared at high speed for 15-20 min. (4) Molding process: Reduce the temperature of the resin melting system in step (3) to below 130°C, add modified glass beads, mix at low speed for 10-15 minutes, and degas under vacuum to obtain a continuous reflective hot melt coating.

2. The continuously reflective hot-melt coating according to claim 1, characterized in that, The refractive index of the titanium dioxide coated glass beads is ≥1.

8.

3. The continuously reflective hot-melt coating according to claim 1, characterized in that, The silane coupling agent is KH-580, the phosphate coupling agent is peroxyphosphate, and the aluminate coupling agent is LZ-101.

4. A method for preparing a continuous reflective hot-melt coating as described in any one of claims 1-3, characterized in that, Includes the following steps: (1) Pretreatment of composite coupling agent: According to the ratio, first mix silane coupling agent and anhydrous ethanol in a certain proportion, add pH adjuster to adjust pH to 4-5, stir at 50-60℃ for 30-40min, then add phosphate coupling agent and aluminate coupling agent, ultrasonically disperse for 20-30min, and at the same time vacuum degassing treatment. (2) Preparation of modified glass beads: The titanium dioxide coated glass beads are first dried at 100-120℃ for 2-3h, then immersed in silane coupling agent ethanol solution, cured at 70-80℃ for 2-3h, and then subjected to plasma treatment to obtain modified glass beads. (3) Petroleum resin mixing and modification process: Petroleum resin is added into a high-speed kneader and heated to 130-140℃. First, the pretreated composite coupling agent is added and stirred for 30-40 min. Then, SEBS and nano zinc oxide are added and stirred for 20-30 min. Then, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder and antioxidant 1010 are added in sequence and sheared at high speed for 15-20 min. (4) Molding process: Reduce the temperature of the resin melting system in step (3) to below 130°C, add modified glass beads, mix at low speed for 10-15 minutes, and degas under vacuum to obtain a continuous reflective hot melt coating.

5. The method for preparing a continuously reflective hot-melt coating according to claim 4, characterized in that, In step (1), the mass ratio of the silane coupling agent to anhydrous ethanol is 1:3-5; the ultrasonic dispersion power is 200-500W, with a 2min interval every 5min.

6. The method for preparing a continuously reflective hot-melt coating according to claim 4, characterized in that, In step (2), the silane coupling agent ethanol solution is a mixture of KH-580 and 10% ethanol in a mass ratio of 1:2-3; the plasma treatment power is 50-60W, and the atmosphere is Ar.

7. The method for preparing a continuously reflective hot-melt coating according to claim 4, characterized in that, In step (3), the stirring speed is 300-400 rpm and the high-speed shearing speed is 600-800 rpm; in step (4), the low-speed stirring speed is 100-200 rpm.

8. The method for preparing a continuously reflective hot-melt coating according to claim 4, characterized in that, The vacuum degree of the vacuum degassing process is -0.08MPa.

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