Continuous reflective hot melt coating and preparation method thereof

Abstract

The invention belongs to the technical field of hot-melt road marking coatings, and particularly relates to a continuous reflective hot-melt coating and a preparation method thereof. The continuous reflective hot melt coating is prepared from the following raw material components in parts by weight: 140 to 150 parts of petroleum resin, 50 to 60 parts of titanium dioxide, 300 to 350 parts of modified glass beads, 10 to 12 parts of a composite coupling agent, 8 to 10 parts of DOP (Dioctyl-Phthalate), 10 to 15 parts of polyethylene wax, 12 to 16 parts of SEBS (Styrene-Ethylene-Butylene-Styrene), 250 to 300 parts of rodlike calcium carbonate, 100 to 150 parts of silica powder, 8 to 10 parts of an antioxidant 1010 and 5 to 8 parts of nano zinc oxide. The composite coupling agent comprises a silane coupling agent, a phosphate coupling agent and an aluminate coupling agent in a mass ratio of 1: (1-2): (1-3). By optimizing the ratio of the raw materials of the coating and the preparation method, the obtained hot-melt coating is used for road marking, not only is good in adhesive force and lasting in light reflection, but also is good in weather resistance, does not change color and does not crack, and can meet the requirements of modern road marking.

Description

Technical Field

[0001] The present invention belongs to the technical field of hot-melt road marking coatings, and particularly relates to a continuously reflective hot-melt coating and a preparation method thereof. Background Art

[0002] Highway traffic markings, as an important carrier for transmitting road traffic information, play roles such as guiding, diverting, prompting, or restricting during vehicle driving. They are a very important part of traffic management, playing crucial roles in channelizing traffic, guiding the road alignment, correctly guiding vehicle passage, and ensuring driving safety. With the continuous and vigorous development of the transportation industry, highway transportation has become increasingly busy, and driving under complex climatic conditions has been increasing day by day, putting higher and higher requirements on traffic markings. The functions and importance of traffic markings are also self-evident. Traffic markings mainly provide functions such as guiding, diverting, prompting, or restricting vehicle driving to ensure the normal and high-speed driving of vehicles on the road and avoid traffic accidents. Therefore, it is required that the markings be complete, clear, distinct, and beautiful, not only eye-catching during the day but also having high directional reflectivity at night, enabling drivers to recognize various pattern symbols of the markings and improving driving safety.

[0003] Currently, road traffic marking coatings are generally divided into: solvent-based coatings, water-based coatings, and hot-melt coatings. Solvent-based coatings are the earliest used road marking coatings, containing more than 30% organic solvents. A large amount of organic solvents will volatilize during construction, causing relatively large pollution to the environment. At the same time, their wear resistance is relatively poor and their service life is short, which gradually limits their production and use. Water-based coatings have strong all-weather visibility, stability, adhesion, wear resistance, and anti-slip safety. They also have a simple construction process, excellent recoatability, low maintenance costs, and a friendly construction environment. However, they have problems such as poor adhesion, wettability, and weather resistance for coatings on asphalt roads and concrete roads. Hot-melt coatings are widely used in traffic road marking coatings due to their strong wear resistance, high solid content, and short film-forming time. They are mainly made of petroleum resin and rosin resin as film-forming substances, and are processed by adding pigments, fillers, and additives. However, with long-term sunlight and rain, many problems have also emerged during the use of hot-melt coatings, such as a significant decrease in the reflective effect, easy discoloration, easy cracking, and easy high-temperature flow. Therefore, it is extremely urgent to develop a new type of hot-melt coating that can reflect light persistently and is stable without cracking to meet the needs of modern road markings. Summary of the Invention

[0004] Aiming at the above deficiencies mentioned in the background art, the purpose of the present invention is to provide a continuously reflective hot-melt coating and a preparation method thereof. The obtained hot-melt coating is used as a road marking, which not only has good adhesion, persistent reflectivity, but also has good weather resistance, does not discolor or crack, and can meet the needs of modern road markings.

[0005] To achieve the above object, the present invention provides a continuously reflective hot-melt coating, which comprises the following raw material components by weight: 140 - 150 parts of petroleum resin, 50 - 60 parts of titanium dioxide, 300 - 350 parts of modified glass beads, 10 - 12 parts of composite coupling agent, 8 - 10 parts of DOP, 10 - 15 parts of polyethylene wax, 12 - 16 parts of SEBS, 250 - 300 parts of rod-shaped calcium carbonate, 100 - 150 parts of silica powder, 8 - 10 parts of antioxidant 1010, 5 - 8 parts of nano zinc oxide; the composite coupling agent comprises silane coupling agent, phosphate ester coupling agent, and aluminate coupling agent with a mass ratio of 1:1 - 2:1 - 3.

[0006] By optimizing the raw materials, the present invention modifies the petroleum resin with a composite coupling agent, SEBS, etc., effectively improving the weather resistance, antioxidant property, temperature resistance, and anti-cracking property of the petroleum resin. At the same time, by selecting glass beads with high refractive index and different particle sizes and modifying them, the binding property with the coating matrix is strong, and the purpose of continuous reflection can be achieved.

[0007] Further, in the above technical solution, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin with a mass ratio of 2 - 3:1. Petroleum resin is used in hot-melt road marking coatings due to its excellent adhesion, drying speed, water resistance, and low cost advantages. Among them, C5 petroleum resin has good tackifying effect, fast drying speed, strong adhesion, and good compatibility, but its light aging resistance and high temperature resistance are poor, while C9 petroleum resin has good weather resistance and light aging resistance, but its bonding force is low and its compatibility is limited. By combining C5 and C9 petroleum resins, the present invention makes their properties complementary and improves the overall performance advantages of the resin.

[0008] Further, in the above technical solution, the modified glass beads are obtained by coating and curing titanium dioxide-coated glass beads with a silane coupling agent. Titanium dioxide-coated glass beads are obtained by coating a thin layer of titanium dioxide on the surface of ordinary glass beads. It not only has a high refractive index but also can greatly extend the reflection life; at the same time, coating with a silane coupling agent can improve its interfacial bonding force with the resin matrix.

[0009] Further, in the above technical solution, in the titanium dioxide-coated glass beads, those with a particle size of 100 - 200 μm account for 10 - 20%, those with a particle size of 200 - 500 μm account for 50 - 60%, and those with a particle size greater than 500 - 800 μm account for 20 - 30%, and the refractive index is ≥1.8. The present invention selects glass beads with different particle size ranges to fill each other, improving the compactness of the overall structure of the glass beads. Among them, large particle glass beads provide the main reflective structure, medium particle glass beads fill the voids to improve the coating compactness, and small particles can enhance the surface flatness, reduce light scattering loss, and ensure the reflection effect.

[0010] Furthermore, in the above technical solution, the silane coupling agent is KH-580 (Hangzhou Jessica), the phosphate coupling agent is peroxy phosphate 651 (BYK of Germany), and the aluminate coupling agent is LZ-101 (Shandong Zibo Sunchuang). In the composite coupling agent of the present invention, the mercapto group (-SH) provided by the silane coupling agent reacts with the resin carboxyl group (-COOH) to form a covalent bond, enhancing the interfacial binding force; the phosphate group in the phosphate coupling agent can capture free radicals, provide antioxidant properties, inhibit high-temperature oxidation, and delay resin aging; the thermal stability of the aluminate coupling agent can inhibit the thermal degradation of the coupling agent, maintain the high-temperature stability of the interface, and at the same time, it can cooperate with the phosphate ester to form a dense interfacial layer, reducing the penetration of oxygen and moisture, and improving the long-term weather resistance.

[0011] The present invention also provides a preparation method of a continuously reflective hot-melt coating, comprising the following steps: (1) Pretreatment of the composite coupling agent: According to the ratio, first mix the silane coupling agent with absolute ethanol in a certain proportion, add a pH regulator to adjust the pH to 4-5, stir at 50-60 °C for 30-40 min, then add the phosphate coupling agent and the aluminate coupling agent, perform ultrasonic dispersion for 20-30 min, and at the same time perform vacuum degassing treatment; (2) Preparation of modified glass beads: First dry the titanium dioxide-coated glass beads at 100-120 °C for 2-3 h, then immerse them in the ethanol solution of the silane coupling agent, cure at 70-80 °C for 2-3 h, and then perform plasma treatment to obtain modified glass beads; (3) Petroleum resin mixing and modification process: Add the petroleum resin to a high-speed kneader and heat it to 130-140 °C. First add the pretreated composite coupling agent and stir for 30-40 min, then add SEBS and nano-zinc oxide and stir for 20-30 min. Then sequentially add titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, and antioxidant 1010, and perform high-speed shearing for 15-20 min; (4) Molding process: Lower the temperature of the resin molten system in step (3) to below 130 °C, add the modified glass beads, perform low-speed mixing for 10-15 min, and perform vacuum degassing treatment to obtain the continuously reflective hot-melt coating.

[0012] The present invention uses a pre-pretreated composite coupling agent to modify the petroleum resin, improving the antioxidant, high-temperature resistance performance and interfacial binding ability of the resin. Then, SEBS and nano-zinc oxide are used to modify the elasticity and anti-ultraviolet performance of the resin, improving the crack resistance and anti-aging performance of the resin. Then, after mixing with other auxiliary materials and low-temperature mixing with the glass beads that have been doubly modified, the obtained continuously reflective hot-melt coating not only has excellent antioxidant, anti-aging, anti-cracking, and high-temperature stability performance, but also has a strong binding force with the glass beads and can reflect light persistently.

[0013] Further, in step (1) of the above technical solution, the mass ratio of the silane coupling agent to absolute ethanol is 1:3 - 5; the power of the ultrasonic dispersion is 200 - 500 W, with an intermittent period of 2 minutes every 5 minutes.

[0014] Further, in step (2) of the above technical solution, the ethanol solution of the silane coupling agent is a mixture with a mass ratio of KH - 580 to 10% ethanol of 1:2 - 3; the power of the plasma treatment is 50 - 60 W, in an Ar atmosphere.

[0015] Further, 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.

[0016] Further, in the above technical solution, the vacuum degree of the vacuum degassing treatment is - 0.08 MPa.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: By optimizing the raw material ratio of the hot - melt coating, the present invention makes full use of the characteristics of each raw material, which can effectively improve the overall performance of the hot - melt coating; by using a composite coupling agent, SEBS, and nano - zinc oxide to modify the petroleum resin, it can not only improve the weather resistance, antioxidant property, heat - resistant property, anti - cracking property, and anti - aging property of the petroleum resin, prevent white yellowing from affecting the reflective effect, but also enhance its interfacial bonding ability with glass beads; adding titanium dioxide to increase whiteness, adding DOP to increase low - temperature flexibility, adding polyethylene wax to increase dispersibility and anti - cracking property, adding rod - shaped calcium carbonate and silica powder as fillers to improve the compressive strength and wear resistance of the coating, and adding an antioxidant to further delay the heat - oxygen aging property; finally, adding glass beads treated by double modification, the obtained continuously reflective hot - melt coating not only has excellent antioxidant, anti - aging, anti - cracking, and high - temperature stability properties, but also has a strong bonding force with glass beads and can reflect light persistently.

[0018] The present invention selects glass beads with different particle size ranges. Large - particle glass beads provide the main reflective structure, medium - particle glass beads fill the voids to improve the coating density, and small - particle glass beads can enhance the surface flatness. Different particle sizes complement each other, reducing light scattering loss while improving the overall structural density of the glass beads, ensuring the reflective effect and durability.

[0019] The present invention modifies petroleum resin using a composite coupling agent. The mercapto group (-SH) in the silane coupling agent reacts with the carboxyl group of the petroleum resin to enhance interfacial chemical bonding. Meanwhile, the silane can condense with the hydroxyl groups on the surface of glass beads to construct a "resin-silane-glass bead" three-dimensional network structure, achieving the purpose of firmly adhering the resin film to the glass beads. The phosphate ester group of the phosphate ester coupling agent can capture free radicals, inhibit the thermal oxidation aging of the resin, and improve the high-temperature dispersibility at the same time. The aluminate coupling agent has high thermal stability, which can inhibit the degradation of the coupling agent itself while maintaining interfacial stability. It can also synergistically act with the phosphate ester to form a dense interface, further enhancing the long-term weather resistance.

[0020] The present invention selects titanium dioxide-coated glass beads as the glass beads, which have a high refractive index and a long reflective life. At the same time, surface treatment with a silane coupling agent is carried out on them to improve the interfacial bonding force with the resin, which can further prevent cracking and shedding, and ultimately achieve the purpose of persistent reflection.

[0021] By separately pretreating each raw material and adding each raw material in stages, the present invention can not only ensure the modification effect, but also prevent the uneven mixing of the raw materials at one time and prevent the titanium dioxide layer on the surface of the glass beads from being damaged. Detailed implementation mode

[0022] The experimental methods in the following examples are all conventional methods unless otherwise specified. The raw materials involved in the following examples are all ordinary commercially available products and can be obtained through market purchase unless otherwise specified.

[0023] All the above technical features of the present invention can be combined with the technical features specifically described below (such as in the examples) to form new or preferred technical solutions.

[0024] The raw materials involved in the embodiments of the present invention are either existing commercially available products or can be prepared according to existing methods.

[0025] The following further explains the specific content of the present invention in conjunction with the examples.

[0026] Example 1 A continuously reflective hot-melt coating, by weight, includes the following raw material components: 140 parts of petroleum resin, 60 parts of titanium dioxide, 325 parts of modified glass beads, 10 parts of composite coupling agent, 10 parts of DOP, 10 parts of polyethylene wax, 15 parts of SEBS, 265 parts of rod-shaped calcium carbonate, 150 parts of silica powder, 10 parts of antioxidant 1010, and 5 parts of nano zinc oxide.

[0027] Among them, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin with a mass ratio of 3:1; The composite coupling agent comprises a silane coupling agent KH-580, a phosphate coupling agent peroxy phosphate 651, and an aluminate coupling agent LZ-101 in a mass ratio of 1:2:3; Among the titanium dioxide-coated glass beads, those with a particle size of 100 - 200 μm account for 20%, those with a particle size of 200 - 500 μm account for 55%, and those with a particle size greater than 500 - 800 μm account for 25%, and the refractive index is ≥1.8 for all.

[0028] Its preparation method comprises the following steps: (1) Pretreatment of the composite coupling agent: According to the ratio, first mix the silane coupling agent and absolute ethanol in a mass ratio of 1:5, add acetic acid to adjust the pH to 4 - 5, stir at 50 °C for 40 min, then add the phosphate coupling agent and the aluminate coupling agent, and perform ultrasonic dispersion for 20 min (500 W, intermittent for 2 min every 5 min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08 MPa); (2) Preparation of the modified glass beads: First dry the titanium dioxide-coated glass beads at 100 °C for 3 h, then immerse them in a silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol with a mass ratio of 1:2), cure at 70 °C for 3 h, and then perform plasma treatment (50 W, Ar atmosphere) to obtain the modified glass beads; (3) Petroleum resin mixing and modification process: Add the petroleum resin into a high-speed kneader and heat to 140 °C. First add the pretreated composite coupling agent, stir at 300 rpm for 40 min, then add SEBS and nano-zinc oxide, stir for 30 min, and then successively add titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, and antioxidant 1010, and perform high-speed shearing at 600 rpm for 20 min; (4) Molding process: Lower the temperature of the resin molten system in step (3) to below 130 °C, add the modified glass beads, mix at a low speed of 100 rpm for 15 min, and perform vacuum degassing treatment (vacuum degree is -0.08 MPa) to obtain the continuously reflective hot-melt coating.

[0029] Example 2 A continuously reflective hot-melt coating, by weight, comprises the following raw material components: 145 parts of petroleum resin, 55 parts of titanium dioxide, 350 parts of modified glass beads, 11 parts of composite coupling agent, 9 parts of DOP, 12 parts of polyethylene wax, 16 parts of SEBS, 258 parts of rod-shaped calcium carbonate, 130 parts of silica powder, 8 parts of antioxidant 1010, and 6 parts of nano-zinc oxide.

[0030] Among them, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin with a mass ratio of 2.5:1; The composite coupling agent comprises silane coupling agent KH-580, phosphate ester coupling agent peroxy phosphate 651, and aluminate coupling agent LZ-101 with a mass ratio of 1:2:2; In the titanium dioxide coated glass beads, those with a particle size of 100-200 μm account for 15%, those with a particle size of 200-500 μm account for 60%, and those with a particle size greater than 500-800 μm account for 25%, and the refractive index is ≥1.8.

[0031] Its preparation method comprises the following steps: (1) Pretreatment of the composite coupling agent: According to the ratio, first mix the silane coupling agent and absolute ethanol at a mass ratio of 1:3-5, add acetic acid to adjust the pH to 4-5, stir at 55 °C for 35 min, then add the phosphate ester coupling agent and the aluminate coupling agent, and perform ultrasonic dispersion for 25 min (300 W, intermittent for 2 min every 5 min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08 MPa); (2) Preparation of the modified glass beads: First dry the titanium dioxide coated glass beads at 120 °C for 2 h, then immerse them in a silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol with a mass ratio of 1:3), cure at 80 °C for 2 h, and then perform plasma treatment (55 W, Ar atmosphere) to obtain the modified glass beads; (3) Petroleum resin mixing and modification process: Add the petroleum resin into a high-speed kneader and heat it to 135 °C. First add the pretreated composite coupling agent, stir at 350 rpm for 35 min, then add SEBS and nano zinc oxide, stir for 25 min, and then sequentially add titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, and antioxidant 1010, and perform high-speed shearing at 700 rpm for 18 min; (4) Molding process: Lower the temperature of the resin melt system in step (3) to below 130 °C, add the modified glass beads, mix at a low speed of 150 rpm for 12 min, and perform vacuum degassing treatment (vacuum degree is -0.08 MPa) to obtain the continuously reflective hot melt coating.

[0032] Example 3 A continuously reflective hot melt coating, by weight, comprises the following raw material components: 150 parts of petroleum resin, 50 parts of titanium dioxide, 300 parts of modified glass beads, 12 parts of composite coupling agent, 8 parts of DOP, 15 parts of polyethylene wax, 16 parts of SEBS, 300 parts of rod-shaped calcium carbonate, 130 parts of silica powder, 9 parts of antioxidant 1010, and 8 parts of nano zinc oxide.

[0033] Among them, the petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin with a mass ratio of 2:1; The composite coupling agent comprises silane coupling agent KH-580, phosphate coupling agent peroxyphosphate 651, and aluminate coupling agent LZ-101 with a mass ratio of 1:1:2. In the titanium dioxide coated glass beads, those with a particle size of 100 - 200 μm account for 20%, those with a particle size of 200 - 500 μm account for 50%, and those with a particle size greater than 500 - 800 μm account for 30%, and the refractive index is ≥1.8 for all.

[0034] Its preparation method includes the following steps: (1) Pretreatment of the composite coupling agent: According to the ratio, first mix the silane coupling agent and absolute ethanol at a mass ratio of 1:3 - 5, add acetic acid to adjust the pH to 4 - 5, stir at 60 °C for 30 min, then add the phosphate coupling agent and aluminate coupling agent, and perform ultrasonic dispersion for 30 min (200 W, intermittent for 2 min every 5 min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08 MPa); (2) Preparation of the modified glass beads: First dry the titanium dioxide coated glass beads at 120 °C for 2 h, then immerse them in a silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol with a mass ratio of 1:2), cure at 70 °C for 3 h, and then perform plasma treatment (60 W, Ar atmosphere) to obtain the modified glass beads; (3) Petroleum resin mixing and modification process: Add the petroleum resin into a high-speed kneader and heat to 130 °C. First add the pretreated composite coupling agent, stir at 400 rpm for 30 min, then add SEBS and nano-zinc oxide, stir for 20 min, and then successively add titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, and antioxidant 1010, and perform high-speed shearing at 800 rpm for 15 min; (4) Molding process: Lower the temperature of the resin molten system in step (3) below 130 °C, add the modified glass beads, mix at low speed of 200 rpm for 10 min, and perform vacuum degassing treatment (vacuum degree is -0.08 MPa) to obtain the continuously reflective hot-melt coating.

[0035] Comparative Example 1 A continuously reflective hot-melt coating, which is different from Example 1 in that the resin used is petroleum resin C5.

[0036] Comparative Example 2 A continuously reflective hot-melt coating, which is different from Example 1 in that the coupling agent used is a silane coupling agent.

[0037] Comparative Example 3 A continuously reflective hot-melt coating, which is different from Example 1 in that the composite coupling agent is a silane coupling agent and a phosphate coupling agent with a mass ratio of 1:2.

[0038] Comparative Example 4 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that the compound coupling agent is a silane coupling agent and an aluminate coupling agent with a mass ratio of 1:2.

[0039] Comparative Example 5 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that the compound coupling agent is a phosphate ester coupling agent and an aluminate coupling agent with a mass ratio of 1:1.

[0040] Comparative Example 6 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that the glass beads are ordinary glass beads.

[0041] Comparative Example 7 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that the particle size of the modified glass beads is 200 - 500 μm.

[0042] Comparative Example 8 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that the glass beads are not modified with a silane coupling agent.

[0043] Comparative Example 9 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that the compound coupling agent is not pretreated during the preparation process.

[0044] Comparative Example 10 A kind of continuously reflective hot-melt coating, which is different from Example 1 in that its preparation method includes the following steps: (1) Compound coupling agent pretreatment: According to the ratio, first mix the silane coupling agent and absolute ethanol in a mass ratio of 1:5, add acetic acid to adjust the pH to 4 - 5, stir at 50°C for 40 min, then add the phosphate ester coupling agent and aluminate coupling agent, and perform ultrasonic dispersion for 20 min (500 W, intermittent for 2 min every 5 min), and at the same time perform vacuum degassing treatment (vacuum degree is -0.08 MPa); (2) Preparation of modified glass beads: First dry the titanium dioxide-coated glass beads at 100°C for 3 h, then immerse them in a silane coupling agent ethanol solution (a mixture of KH-580 and 10% ethanol with a mass ratio of 1:2), cure at 70°C for 3 h, and then perform plasma treatment (50 W, Ar atmosphere) to obtain modified glass beads; (3) Molding process: Add petroleum resin into a high-speed kneader and heat to 140°C, add the pretreated compound coupling agent, SEBS, nano-zinc oxide, titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, antioxidant 1010, and modified glass beads, perform high-speed shearing at 600 - 800 rpm for 15 - 20 min, and perform vacuum degassing treatment (vacuum degree is -0.08 MPa) to obtain the continuously reflective hot-melt coating.

[0045] Test Example The hot-melt coatings obtained in Examples 1-3 and Comparative Examples 1-10 were applied as follows: First, the road surface was preheated to 60-70 °C, and the hot-melt coating was heated to 190 °C. Then the hot-melt coating was sprayed on the road surface with a thickness of 2.5 mm. Performance tests were carried out according to the relevant methods in Standard JT / T 280-2022 Surface Marking Coatings and GB / T 21383-2008. The results are shown in Tables 1-3.

[0046] Table 1 Test Results of Examples 1-3

[0047] Table 2 Test Results of Comparative Examples 1-5

[0048] Table 3 Test Results of Comparative Examples 6-10

[0049] From the results in Table 1, it can be seen that the continuous reflective hot-melt coating prepared by using the formula and preparation method of the present invention has excellent overall performance, with a bonding strength of more than 6.8 MPa and good adhesion; especially, it does not crack after 16 freeze-thaw cycles and has excellent low-temperature anti-cracking performance; it does not change color or crack after accelerated aging, and has good weather resistance and high-temperature resistance; the retroreflective coefficient reaches more than 490 mcd / (lx·m 2 ), and more than 75% of the retroreflective coefficient remains after one year, with good and durable reflective effects.

[0050] It can be seen from the results of Table 2 and Table 3 that in Comparative Example 1, due to the absence of appropriate C9 petroleum resin, its weather resistance, temperature resistance and light aging resistance are relatively poor; in Comparative Example 2, only silane coupling agent is used, and in Comparative Examples 3 to 5, two kinds of coupling agent combinations out of the three are used, and all their properties show a certain decline compared with those of Example 1, indicating that the three combinations are more conducive to the modification of petroleum resin and improve its comprehensive properties; in Comparative Example 6, ordinary glass beads are used instead of titanium dioxide coated glass beads. Although it has little impact on other properties, due to its low refractive index, its retroreflective effect is poor and not lasting; in Comparative Example 7, glass beads with a single particle size are used. Since the gaps between the glass beads cannot be filled, the structure is not dense, the surface is uneven, and the light scattering loss is large, seriously affecting the reflective effect and durability; in Comparative Example 8, the surface of the titanium dioxide coated glass beads is not modified, and its binding ability with other base materials of the coating is poor, and cracking is likely to occur after use, also affecting the reflective effect; in Comparative Example 9, the composite coupling agent is not pretreated in advance, but directly mixed with petroleum resin, resulting in poor modification effect, poor weather resistance and high temperature resistance, and the binding force with glass beads is also affected; in Comparative Example 10, all materials are mixed at one time, which is not conducive to the modification of resin materials, and the titanium dioxide layer is easily damaged and the glass beads are broken during the high-speed mixing process, not only affecting the weather resistance and adhesion, but also the reflective effect.

[0051] In summary, by optimizing the raw material ratio and preparation method, the hot-melt coating obtained in the present invention is used as a road marking. It not only has good adhesion and long-lasting reflectivity, but also has good weather resistance. After low-temperature and heating treatments, it does not change color, crack or flow, and can meet the requirements of modern road markings.

[0052] Finally, it should be emphasized that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A continuous reflective hot melt coating, characterized in that, By weight, it includes the following raw material components: 140 - 150 parts of petroleum resin, 50 - 60 parts of titanium dioxide, 300 - 350 parts of modified glass beads, 10 - 12 parts of composite coupling agent, 8 - 10 parts of DOP, 10 - 15 parts of polyethylene wax, 12 - 16 parts of SEBS, 250 - 300 parts of rod-shaped calcium carbonate, 100 - 150 parts of silica powder, 8 - 10 parts of antioxidant 1010, 5 - 8 parts of nano zinc oxide; the composite coupling agent includes silane coupling agent, phosphate ester coupling agent, and aluminate coupling agent with a mass ratio of 1:1 - 2:1 - 3.

2. The persistent reflective hot-melt paint according to claim 1, wherein, The petroleum resin is a mixture of C5 petroleum resin and C9 petroleum resin with a mass ratio of 2 - 3:

1.

3. The sustained-reflective hot-melt coating according to claim 1, wherein The modified glass beads are coated and cured with silane coupling agent from titanium dioxide-coated glass beads.

4. A kind of continuously reflective hot melt coating according to claim 3, characterized in that, Among the titanium dioxide-coated glass beads, those with a particle size of 100 - 200μm account for 10 - 20%, those with a particle size of 200 - 500μm account for 50 - 60%, and those with a particle size greater than 500 - 800μm account for 20 - 30%, and the refractive index is ≥1.

8.

5. A kind of continuously reflective hot-melt coating according to claim 1, characterized in that, The silane coupling agent is KH-580, the phosphate ester coupling agent is peroxy phosphate ester, and the aluminate coupling agent is LZ-101.

6. The preparation method of a continuously reflective hot-melt coating according to any one of claims 1-5, characterized in that, It includes the following steps: (1) Pretreatment of composite coupling agent: According to the ratio, first mix the silane coupling agent and absolute ethanol in a certain proportion, add a pH regulator to adjust the pH to 4 - 5, stir at 50 - 60°C for 30 - 40 min, then add the phosphate ester coupling agent and aluminate coupling agent, ultrasonically disperse for 20 - 30 min, and simultaneously perform vacuum degassing treatment; (2) Preparation of modified glass beads: First dry the titanium dioxide-coated glass beads at 100 - 120°C for 2 - 3 h, then immerse them in the silane coupling agent ethanol solution, cure at 70 - 80°C for 2 - 3 h, and then perform plasma treatment to obtain modified glass beads; (3) Petroleum resin mixing and modification process: Add the petroleum resin into a high-speed kneader and heat to 130 - 140°C, first add the pretreated composite coupling agent, stir for 30 - 40 min, then add SEBS and nano zinc oxide, stir for 20 - 30 min, and then sequentially add titanium dioxide, DOP, polyethylene wax, rod-shaped calcium carbonate, silica powder, antioxidant 1010, and perform high-speed shearing for 15 - 20 min; (4) Molding process: Lower the temperature of the resin molten system in step (3) below 130°C, add the modified glass beads, mix at low speed for 10 - 15 min, and perform vacuum degassing treatment to obtain a continuously reflective hot-melt coating.

7. The preparation method of a continuously reflective hot-melt coating according to claim 6, characterized in that, In step (1), the mass ratio of the silane coupling agent to absolute ethanol is 1:3 - 5; the power of the ultrasonic dispersion is 200 - 500 W, and there is an intermittent period of 2 min every 5 min.

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

9. The preparation method of a continuously reflective hot-melt coating according to claim 6, 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.

10. The preparation method of a continuously reflective hot melt coating according to claim 6, characterized in that, The degree of vacuum for vacuum degassing treatment is -0.08 MPa for all cases.

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