Hot-melt type pavement marking paint and method for preparing the same

Abstract

This invention relates to the field of coatings, and proposes a hot-melt road marking coating and its preparation method. The hot-melt road marking coating comprises the following components by weight: 20-24 parts petroleum resin, 4-6 parts binder resin, 9-11 parts abrasion-resistant functional additives, 18-22 parts glass microspheres, 40-45 parts calcium carbonate, and 4-6 parts pigment; the abrasion-resistant functional additives include acrylic-modified nanocellulose and hard fillers. This technical solution solves the problem of insufficient abrasion resistance in related technologies for hot-melt road marking coatings.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a hot-melt road marking coating and its preparation method. Background Technology

[0002] Hot-melt pavement marking paint is widely used in the field of road traffic safety signage due to its advantages such as high construction efficiency, good durability, and stable reflective performance. Existing hot-melt marking paints typically use petroleum resin as a base, combined with components such as glass microspheres and calcium carbonate to achieve basic functions such as reflectivity.

[0003] However, road markings are subject to long-term exposure to vehicle pressure, friction, impact, and sun and rain, which can lead to problems such as rapid wear, powdering, cracking, and detachment, resulting in short service life and high maintenance frequency. Furthermore, traditional paints rely on a single wear-resistant filler, which makes the particles prone to slippage and detachment, resulting in insufficient coating density and low compressive strength, making it difficult to meet the long-term use requirements of high-grade roads and heavy-load road sections. Summary of the Invention

[0004] This invention proposes a hot-melt road marking paint and its preparation method to solve or alleviate at least one of the above-mentioned problems.

[0005] The technical solution of the present invention is as follows: This invention proposes a hot-melt road marking paint, comprising the following components by weight: 20-24 parts petroleum resin, 4-6 parts adhesive resin, 9-11 parts wear-resistant functional additives, 18-22 parts glass microspheres, 40-45 parts calcium carbonate, and 4-6 parts pigment; The wear-resistant functional additives include acrylic-modified nanocellulose and hard fillers.

[0006] Preferably, the mass ratio of the acrylic acid-modified nanocellulose to the hard filler is 1:8~14.

[0007] Preferably, the hard filler includes one or more of alumina ceramic microspheres, garnet powder, quartz powder, brown corundum powder, and wollastonite powder.

[0008] Preferably, the hard filler comprises alumina ceramic microspheres and garnet powder.

[0009] Preferably, the mass ratio of the alumina ceramic microspheres to the garnet powder is 1:1.5~3.

[0010] Preferably, the method for preparing the acrylic acid-modified nanocellulose includes the following steps: Nanocellulose was dispersed in water, an initiator was added, and the dispersion was continued while maintaining the pH of the system at 1. Then, acrylic acid was added to carry out the reaction. After filtration, washing, and drying, acrylic acid-modified nanocellulose was obtained.

[0011] Preferably, the adhesive resin includes chloroacetic acid resin and terpene styrene resin.

[0012] Preferably, the mass ratio of the chloroacetic acid resin to the terpene styrene resin is 1:3~4.

[0013] Preferably, it also includes at least one of an antioxidant and an anti-settling agent.

[0014] Preferably, the antioxidant includes one or more of hindered phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and aromatic amine antioxidants; and / or The anti-settling agent includes bentonite and / or fumed silica.

[0015] This invention also proposes a method for preparing a hot-melt road marking paint, comprising the following steps: First, mix the petroleum resin and adhesive resin evenly, then add the remaining components and mix evenly to obtain the hot-melt road marking paint.

[0016] The beneficial effects of this invention are as follows: In this invention, the hot-melt pavement marking paint composition incorporates acrylic-modified nanocellulose and hard fillers as wear-resistant functional additives, thereby improving the wear resistance of the paint film. The acrylic-modified nanocellulose physically entangles and anchors the inorganic hard filler particles. Furthermore, the polar groups on its surface after modification can form intermolecular hydrogen bonds with the hydroxyl groups on the surface of the hard fillers and other inorganic fillers in the system, further restricting the slippage and detachment of the hard fillers during friction. Both synergistically enhance the overall wear resistance of the marking paint film. Detailed Implementation

[0017] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. In the absence of conflict, the following embodiments and features in the embodiments can be combined with each other.

[0018] A specific embodiment of the first aspect of the present invention provides a hot-melt road marking paint, comprising the following components by weight: 20-24 parts of petroleum resin, 4-6 parts of adhesive resin, 9-11 parts of wear-resistant functional additive, 18-22 parts of glass microspheres, 40-45 parts of calcium carbonate and 4-6 parts of pigment; Wear-resistant additives include acrylic-modified nanocellulose and hard fillers.

[0019] In one embodiment of the present invention, the mass ratio of acrylic acid-modified nanocellulose to rigid filler is 1:8~14.

[0020] In one embodiment of the present invention, the hard filler includes one or more of alumina ceramic microspheres, garnet powder, quartz powder, brown corundum powder, and wollastonite powder.

[0021] In this invention, the average particle size of the glass microspheres is 80~200μm, for example, any value or range between any two values ​​from 80μm, 85μm, 90μm, 95μm, 100μm, 105μm, 110μm, 115μm, 120μm, 125μm, 130μm, 135μm, 140μm, 145μm, 150μm, 155μm, 160μm, 165μm, 170μm, 175μm, 180μm, 185μm, 190μm, 195μm, to 200μm. Glass microspheres possess high refractive index optical properties, enabling spherical retroreflection of vehicle headlights at night, significantly improving the nighttime visibility of road markings and ensuring driving safety. They are the core functional aggregate for achieving the reflective function of road markings.

[0022] In this invention, the average particle size of the hard filler is 10~80μm, for example, it can be any point value or the range between any two points from 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, 55μm, 60μm, 65μm, 70μm, 75μm, 80μm. When the average particle size of the hard filler is within this range, it ensures that the hard filler is uniformly dispersed in the resin matrix and does not easily agglomerate and settle, while also forming a dense and wear-resistant skeleton.

[0023] In one embodiment of the present invention, the hard filler includes alumina ceramic microspheres and garnet powder.

[0024] In this invention, the wear resistance of the prepared coating film is further improved through the synergistic effect of acrylic-modified nanocellulose, alumina ceramic microspheres, and garnet powder. The presumed reason is that the alumina ceramic microspheres, with their ultra-high hardness and regular spherical structure, can construct a rigid, wear-resistant support framework within the coating, directly bearing friction and load, significantly reducing wear damage to the resin matrix. Garnet powder, a high-hardness, irregularly shaped hard powder, can fill the gaps formed by the accumulation of ceramic microspheres, optimizing particle size distribution, improving coating density, and reducing micro-peeling and surface loss during wear. Simultaneously, the surface of the acrylic-modified nanocellulose can form polar bonds and physical entanglement with the active hydroxyl groups on the surfaces of the alumina ceramic microspheres and garnet powder, binding the hard particles and preventing slippage, detachment, and peeling.

[0025] In one embodiment of the present invention, the mass ratio of alumina ceramic microspheres to garnet powder is 1:1.5~3.

[0026] In one embodiment of the invention, the pigment includes a white pigment or a yellow pigment.

[0027] In this invention, the white pigment may be, for example, one or more of titanium dioxide, lithopone, and zinc oxide; the yellow pigment may be, for example, one or more of iron oxide yellow, medium chrome yellow, and benzidine yellow.

[0028] In one embodiment of the present invention, a method for preparing acrylic acid-modified nanocellulose includes the following steps: Nanocellulose was dispersed in water, an initiator was added, and the dispersion was continued while maintaining the pH of the system at 1. Then, acrylic acid was added to carry out the reaction. After filtration, washing, and drying, acrylic acid-modified nanocellulose was obtained.

[0029] In this invention, the mass ratio of nanocellulose to initiator is 5:0.3~0.35.

[0030] In this invention, the mass-to-volume ratio of initiator to acrylic acid is 0.3~0.35g:100mL.

[0031] In this invention, the dispersion and reaction temperatures are each independently set at 40~50°C.

[0032] In one embodiment of the present invention, the adhesive resin includes vinyl chloride resin and terpene styrene resin.

[0033] In this invention, the compressive strength of the hot-melt marking paint film is improved by compounding chloroacetic acid resin and terpene styrene resin. The reason is presumably that terpene styrene resin has excellent compatibility and melt blending properties with the main petroleum resin, ensuring a uniform and stable structure after coating formation. The chloroacetic acid resin and acrylic-modified nanocellulose exhibit polar interactions, which strengthen the interfacial bonding between the resin phase and the inorganic functional phase, further reducing micropores and interfacial defects within the coating. Therefore, the compounding of these two resins significantly improves the overall uniformity and density of the coating.

[0034] In one embodiment of the present invention, the mass ratio of chloroacetic acid resin to terpene styrene resin is 1:3~4.

[0035] In this invention, by limiting the above-mentioned ratio range, the composite bonding resin achieves an optimal balance between rigidity and toughness. Using terpene styrene resin as the main component ensures excellent melt compatibility between the bonding resin and the petroleum resin matrix, avoiding excessive hardness and brittleness of the coating and cracking defects. A small amount of chloroacetic acid resin, as a polar modifying component, can effectively improve the interfacial bonding strength with modified nanocellulose without compromising the system compatibility.

[0036] In one embodiment of the present invention, the components of a hot-melt road marking paint further include at least one of an antioxidant and an anti-settling agent.

[0037] In this invention, by weight, the components of a hot-melt road marking paint also include 0.3 to 0.8 parts of antioxidant and 0.2 to 0.4 parts of anti-settling agent.

[0038] In one embodiment of the present invention, the antioxidant includes one or more of hindered phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and aromatic amine antioxidants.

[0039] In this invention, the hindered phenolic antioxidant may be one or more of antioxidants 1010, 1076, and 264; the phosphite antioxidant may be one or more of antioxidants 168 and 618; and the thioether antioxidant may be one or more of DLTDP and DSTDP. The antioxidants can capture free radicals generated by the thermo-oxidative aging of the resin, inhibiting the oxidative degradation, yellowing, and embrittlement of petroleum resin during high-temperature melting processing and long-term outdoor exposure; simultaneously, they delay coating aging and chalking, extending the service life of hot-melt road markings.

[0040] In one embodiment of the present invention, the anti-settling agent comprises bentonite and / or fumed silica.

[0041] In this invention, the anti-settling agent can improve the thixotropy and structural stability of the coating in the molten state, improve the leveling properties during construction, prevent sagging and uneven thickness during coating application, and improve the overall uniformity of the marking coating.

[0042] A second aspect of the present invention provides a method for preparing a hot-melt road marking paint, used to prepare the hot-melt road marking paint provided in the first aspect of the present invention, comprising the following steps: First, mix the petroleum resin and adhesive resin evenly, then add wear-resistant functional additives, glass microspheres, calcium carbonate, pigments, antioxidants and anti-settling agents, mix evenly, and obtain hot-melt road marking paint.

[0043] To make the objectives, technical solutions, and advantages of the present invention clearer, the following will be described through embodiments.

[0044] In the following examples and comparative examples, the petroleum resin is designated Pht. ®-R1100; the terpene styrene resin is model D610; the chloroacetic acid resin is model VINNOL E 15 / 45; the average particle size of nanocellulose is 100nm; the average particle size of alumina ceramic microspheres is 60μm; the average particle size of calcium carbonate is 15μm; the average particle size of fumed silica is 10μm; and the average particle size of garnet powder is 20μm.

[0045] Example 1 The hot-melt road marking paint comprises the following components by weight: 20 parts petroleum resin, 4 parts terpene styrene resin, 1 part acrylic modified nanocellulose, 8 parts alumina ceramic microspheres, 18 parts glass microspheres, 40 parts calcium carbonate, 4 parts titanium dioxide, 0.3 parts antioxidant 1076, and 0.2 parts fumed silica. The preparation method of acrylic acid modified nanocellulose includes the following steps: 5g of nanocellulose was dispersed in 500mL of water, and 0.3g of potassium persulfate was added as an initiator. The mixture was continuously dispersed at 50℃ for 10min. The pH of the reaction system was maintained at 1 using a 0.1mol / L dilute nitric acid solution. Then, 100mL of acrylic acid was added and the reaction was carried out at 50℃ for 2h. The mixture was filtered, washed, and dried to obtain acrylic acid-modified nanocellulose. A method for preparing hot-melt road marking paint includes the following steps: First, petroleum resin and terpene styrene resin are mixed evenly. Then, modified nanocellulose, alumina ceramic microspheres, glass microspheres, calcium carbonate, titanium dioxide, antioxidant 1076 and fumed silica are added and mixed evenly to obtain hot-melt road marking paint.

[0046] Example 2 The hot-melt road marking paint comprises the following components by weight: 24 parts petroleum resin, 6 parts terpene styrene resin, 0.6 parts acrylic modified nanocellulose, 8.4 parts alumina ceramic microspheres, 22 parts glass microspheres, 45 parts calcium carbonate, 6 parts medium chrome yellow, 0.8 parts antioxidant 1076, and 0.4 parts fumed silica. The preparation method of acrylic acid modified nanocellulose includes the following steps: 5g of nanocellulose was dispersed in 500mL of water, and 0.35g of potassium persulfate was added as an initiator. The dispersion was carried out at 40℃ for 10min. The pH of the reaction system was maintained at 1 using a 0.1mol / L dilute nitric acid solution. Then, 100mL of acrylic acid was added and the reaction was carried out at 40℃ for 2h. After filtration, washing and drying, acrylic acid-modified nanocellulose was obtained. A method for preparing hot-melt road marking paint includes the following steps: First, petroleum resin and terpene styrene resin are mixed evenly. Then, modified nanocellulose, alumina ceramic microspheres, glass microspheres, calcium carbonate, medium chrome yellow, antioxidant 1076 and fumed silica are added and mixed evenly to obtain hot-melt road marking paint.

[0047] Example 3 Hot-melt road marking paint comprises the following components by weight: 22 parts petroleum resin, 6 parts terpene styrene resin, 1 part acrylic modified nanocellulose, 10 parts alumina ceramic microspheres, 20 parts glass microspheres, 42 parts calcium carbonate, 4 parts titanium dioxide, 0.4 parts antioxidant 1076, and 0.3 parts fumed silica. The preparation method of acrylic acid modified nanocellulose includes the following steps: 5g of nanocellulose was dispersed in 500mL of water, and 0.3g of potassium persulfate was added as an initiator. The mixture was continuously dispersed at 50℃ for 10min. The pH of the reaction system was maintained at 1 using a 0.1mol / L dilute nitric acid solution. Then, 100mL of acrylic acid was added and the reaction was carried out at 50℃ for 2h. The mixture was filtered, washed, and dried to obtain acrylic acid-modified nanocellulose. A method for preparing hot-melt road marking paint includes the following steps: First, petroleum resin and terpene styrene resin are mixed evenly. Then, modified nanocellulose, alumina ceramic microspheres, glass microspheres, calcium carbonate, titanium dioxide, antioxidant 1076 and fumed silica are added and mixed evenly to obtain hot-melt road marking paint.

[0048] Example 4 Except for replacing 10 parts of alumina ceramic microspheres in the hot-melt road marking paint components with 10 parts of garnet powder, the rest is the same as in Example 3.

[0049] Example 5 Except for replacing 10 parts of alumina ceramic microspheres in the hot-melt road marking paint components with 4 parts of alumina ceramic microspheres and 6 parts of garnet powder, the rest is the same as in Example 3.

[0050] Example 6 Except for replacing 10 parts of alumina ceramic microspheres in the hot-melt road marking paint components with 2.5 parts of alumina ceramic microspheres and 7.5 parts of garnet powder, the rest is the same as in Example 3.

[0051] Example 7 Except for replacing 6 parts of terpene styrene resin in the hot-melt road marking paint component with 6 parts of chloroacetic acid resin, the rest is the same as in Example 5.

[0052] Example 8 Except for replacing 6 parts of terpene styrene resin in the hot-melt road marking paint components with 4.5 parts of terpene styrene resin and 1.5 parts of chloroacetic acid resin, the rest is the same as in Example 5.

[0053] Example 9 Except for replacing 6 parts of terpene styrene resin in the hot-melt road marking paint components with 4.8 parts of terpene styrene resin and 1.2 parts of chloroacetic acid resin, the rest is the same as in Example 5.

[0054] Example 10 Except for replacing 6 parts of terpene styrene resin in the hot-melt road marking paint components with 4 parts of terpene styrene resin and 2 parts of chloroacetic acid resin, the rest is the same as in Example 5.

[0055] Example 11 Except for replacing 6 parts of terpene styrene resin in the hot-melt road marking paint components with 5 parts of terpene styrene resin and 1 part of chloroacetic acid resin, the rest is the same as in Example 5.

[0056] Comparative Example 1 Except for replacing acrylic acid-modified nanocellulose with nanocellulose, the rest is the same as in Example 3.

[0057] Comparative Example 2 Except for replacing acrylic acid-modified nanocellulose with alumina ceramic microspheres, the rest is the same as in Example 3.

[0058] Comparative Example 3 Except for replacing the alumina ceramic microspheres with acrylic acid-modified nanocellulose, the rest is the same as in Example 3.

[0059] Experimental Example The following performance tests were conducted on the hot-melt road marking paints of Examples 1-11 and Comparative Examples 1-3: (1) Abrasion resistance: The abrasion value of the paint film was tested in accordance with JT / T 280-2022 "Road Marking Paint"; (2) Compressive strength: The compressive strength of the paint film was tested in accordance with JT / T 280-2022 "Road Marking Paint"; The test results are shown in Tables 1 and 2 below.

[0060] Table 1 Abrasion resistance test results

[0061] Table 2 Compressive strength test results

[0062] In Comparative Examples 1-3, the hot-melt pavement marking paint components did not achieve the desired combination of acrylic-modified nanocellulose and hard fillers. Therefore, the abrasion values ​​of the resulting paint films were higher than those in Examples 1-4. This indicates that the abrasion resistance of the paint film can be improved through the synergistic effect of acrylic-modified nanocellulose and hard fillers. Furthermore, in Examples 5-6, by adding alumina ceramic microspheres and garnet powder as hard fillers, the abrasion value of the resulting paint films was further reduced through the synergistic effect of acrylic-modified nanocellulose, alumina ceramic microspheres, and garnet powder. This demonstrates that the abrasion resistance of the paint film can be further improved through the synergistic effect of these three components.

[0063] In Examples 5 and 7, a single binder resin was added; therefore, the compressive strength of the resulting paint film was lower than that of Examples 8-11. This indicates that the combination of chloroacetic acid resin and terpene styrene resin as a binder resin can improve the compressive strength of the paint film. Furthermore, in Examples 8-9, by adding chloroacetic acid resin and terpene styrene resin in a mass ratio of 1:3-4, the compressive strength of the resulting paint film was further improved.

[0064] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. 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 hot-melt road marking paint, characterized in that, It includes the following components by weight: 20-24 parts petroleum resin, 4-6 parts adhesive resin, 9-11 parts wear-resistant functional additives, 18-22 parts glass microspheres, 40-45 parts calcium carbonate, and 4-6 parts pigment; The wear-resistant functional additives include acrylic-modified nanocellulose and hard fillers.

2. The hot-melt road marking paint according to claim 1, characterized in that, The mass ratio of the acrylic acid-modified nanocellulose to the hard filler is 1:8~14.

3. The hot-melt road marking paint according to claim 2, characterized in that, The hard filler includes one or more of alumina ceramic microspheres, garnet powder, quartz powder, brown corundum powder, and wollastonite powder.

4. The hot-melt road marking paint according to claim 3, characterized in that, The hard filler includes alumina ceramic microspheres and garnet powder; The mass ratio of alumina ceramic microspheres to garnet powder is 1:1.5~3.

5. The hot-melt road marking paint according to claim 1, characterized in that, The preparation method of the acrylic acid modified nanocellulose includes the following steps: Nanocellulose was dispersed in water, an initiator was added, and the dispersion was continued while maintaining the pH of the system at 1. Then, acrylic acid was added to carry out the reaction. After filtration, washing, and drying, acrylic acid-modified nanocellulose was obtained.

6. The hot-melt road marking paint according to claim 1, characterized in that, The adhesive resin includes chloroacetic acid resin and terpene styrene resin.

7. A hot-melt road marking paint according to claim 6, characterized in that, The mass ratio of the chloroacetic acid resin to the terpene styrene resin is 1:3~4.

8. A hot-melt road marking paint according to claim 1, characterized in that, It also includes at least one of antioxidants and anti-settling agents.

9. A hot-melt road marking paint according to claim 8, characterized in that, The antioxidant includes one or more of hindered phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and aromatic amine antioxidants; and / or The anti-settling agent includes bentonite and / or fumed silica.

10. A method for preparing a hot-melt road marking paint, used to prepare the hot-melt road marking paint according to any one of claims 1 to 9, characterized in that, Includes the following steps: First, mix the petroleum resin and adhesive resin evenly, then add the remaining components and mix evenly to obtain the hot-melt road marking paint.

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