Wear-resistant hot-melt pavement marking paint and preparation method thereof

Abstract

The present application relates to the field of paint, and propose a kind of wear-resistant hot melt pavement marking paint and preparation method thereof, wear-resistant hot melt pavement marking paint includes the following weight parts of component: petroleum resin 14~20 parts, functional filler 45~55 parts, SEBS resin 4~8 parts, glass bead 20~30 parts, antioxidant 0.1~0.5 parts, ultraviolet absorber 0.2~0.4 parts, processing aid 0.1~0.5 parts;Functional filler includes quartz sand and calcium carbonate, and functional filler is prepared after being pretreated by coupling agent.The technical scheme above, solve the problem of insufficient wear resistance of hot melt pavement marking paint in related art.

Description

Technical Field

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

[0002] Hot-melt pavement marking paint is one of the most widely used marking materials in road traffic marking engineering. Hot-melt paint is a powder at room temperature, containing no solvent volatiles. During construction, it is melted by heating and applied to the road surface using specialized equipment, where it solidifies into a film through physical cooling. This paint has excellent properties such as complete and clear lines, high sharpness, and fast drying speed, theoretically guaranteeing a long service life.

[0003] However, in actual use, hot-melt pavement marking paint has insufficient abrasion resistance, affecting the service life and traffic function of the markings. Abrasion resistance is directly related to traffic volume; in road sections with high traffic volume, many large vehicles, and frequent lane changes, the wear rate of the markings is significantly accelerated. At the same time, dirty road surfaces, the presence of sand and small stones further accelerate the wear of the markings, placing higher demands on the abrasion resistance of pavement markings.

[0004] The reasons for insufficient wear resistance are mainly related to several aspects: substandard raw material quality, inferior resin or filler will lead to poor wear resistance; unreasonable ratio of wear-resistant filler in the formula will also affect the final wear resistance.

[0005] To address the aforementioned problems, existing technologies typically improve wear resistance by adding wear-resistant fillers such as quartz sand to the coating. However, the improvement effect is limited and cannot fundamentally solve the problem of insufficient wear resistance in hot-melt pavement marking coatings. Therefore, it is necessary to develop a technical solution that can effectively improve the wear resistance of hot-melt pavement marking coatings. Summary of the Invention

[0006] This invention proposes a wear-resistant hot-melt road marking paint and its preparation method to solve or alleviate at least one of the above-mentioned problems.

[0007] The technical solution of the present invention is as follows: This invention proposes a wear-resistant hot-melt pavement marking coating, comprising the following components in parts by weight: 14-20 parts petroleum resin, 45-55 parts functional filler, 4-8 parts SEBS resin, 20-30 parts glass beads, 0.1-0.5 parts antioxidant, 0.2-0.4 parts ultraviolet absorber, and 0.1-0.5 parts processing aid; the functional filler comprises quartz sand and calcium carbonate, and the functional filler is prepared after pretreatment with a coupling agent.

[0008] Preferably, by weight, the functional filler comprises 30-35 parts of quartz sand and 15-20 parts of calcium carbonate.

[0009] Preferably, the coupling agent comprises a titanate coupling agent and 3-(phenylamino)propyltrimethoxysilane.

[0010] Preferably, the mass ratio of the titanate coupling agent to 3-(phenylamino)propyltrimethoxysilane is 1:3 to 3:1.

[0011] Preferably, the SEBS resin includes at least one of YH-561, YH-602, G1652 and G1651.

[0012] Preferably, the SEBS resin includes models YH-561 and G1652.

[0013] Preferably, the glass beads have a particle size of 0.1~0.8mm; The particle size of the quartz sand is 300~500 mesh; The calcium carbonate has a particle size of 200-300 mesh.

[0014] Preferably, the processing aid includes an antifoaming agent; The antioxidants include chain-terminated antioxidants and hydroperoxide decomposition antioxidants; The ultraviolet absorbers include benzotriazole ultraviolet absorbers and / or benzophenone ultraviolet absorbers.

[0015] Preferably, the defoamer includes at least one of SN-327 and SN-345.

[0016] This invention also proposes a method for preparing wear-resistant hot-melt pavement marking paint, which includes the following steps: A1. Stir and mix petroleum resin and SEBS resin to obtain a preliminary mixture; A2. Add functional fillers to the initial mixture and stir. Add antioxidants, UV absorbers, glass beads and processing aids and continue stirring and mixing. Extrude and crush to obtain wear-resistant hot-melt road marking paint.

[0017] The beneficial effects of this invention are as follows: In this invention, SEBS resin is introduced into a petroleum resin-based hot-melt pavement marking paint, and the original quartz sand / calcium carbonate filler is pretreated with a coupling agent, significantly improving the wear resistance of the paint. Petroleum resin, as the main film-forming base, is relatively brittle. SEBS, a triblock copolymer, forms a physical cross-linked network between the polystyrene (PS) hard segments and the ethylene-butene (EB) soft segments. The PS segments provide rigidity, and the EB segments provide elasticity. When the coating is subjected to impact loads, the soft phase absorbs the impact energy, and the hard phase resists shear stress, effectively reducing the wear rate. The coupling agent, after hydrolysis, connects to the hydroxyl groups on the surface of the functional filler, and at the other end, it binds to the petroleum resin base containing SEBS resin, enhancing the inorganic-organic interfacial bonding force. The filler pretreated with the coupling agent has a tighter and more uniform interface with the SEBS resin-containing matrix, reducing stress concentration points during friction. The synergistic effect of SEBS resin and the coupling agent-pretreated filler improves the wear resistance of the hot-melt pavement marking paint and extends the service life of the markings by reducing the wear rate and stress concentration points, respectively. Detailed Implementation

[0018] 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.

[0019] A specific embodiment of the first aspect of the present invention provides a wear-resistant hot-melt pavement marking coating, comprising the following components in parts by weight: 14-20 parts petroleum resin, 45-55 parts functional filler, 4-8 parts SEBS resin, 20-30 parts glass beads, 0.1-0.5 parts antioxidant, 0.2-0.4 parts ultraviolet absorber, and 0.1-0.5 parts processing aid; the functional filler comprises quartz sand and calcium carbonate, and the functional filler is prepared after pretreatment with a coupling agent.

[0020] In this invention, the functional filler comprises quartz sand and calcium carbonate, and the functional filler is prepared after pretreatment with a coupling agent. Specifically, by weight, the functional filler contains 30-35 parts quartz sand and 15-20 parts calcium carbonate. The quartz sand has a particle size of 300-500 mesh, such as 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, etc., and the calcium carbonate has a particle size of 200-300 mesh, such as 200 mesh, 220 mesh, 240 mesh, 260 mesh, 280 mesh, 300 mesh, etc.

[0021] The preparation method of the above-mentioned pretreated functional filler includes the following steps: hydrolyzing a coupling agent and a solvent to obtain a modified liquid; ultrasonically dispersing the functional filler to obtain a dispersed functional filler; adding the dispersed functional filler to the modified liquid and mixing thoroughly; filtering and drying to obtain the pretreated functional filler; wherein, when preparing the pretreated functional filler, the mass of the titanate coupling agent is 1% to 3% of the mass of the functional filler, preferably 2%; the mass-to-volume ratio of the coupling agent to the solvent is 1g:5~10mL, for example, 1g:5mL, 1g:6mL, 1g:7... The dispersion solvent is ethanol aqueous solution, preferably 70% by volume. The dispersion solvent for ultrasonic dispersion is ethanol, the dispersion power is 200~300W, the dispersion time is 15min, etc., to reduce the agglomeration of the filler. The mass-volume ratio of the functional filler to the dispersion solvent is 1g:2~8mL, for example, it can be 1g:2mL, 1g:3mL, 1g:4mL, 1g:5mL, 1g:6mL, 1g:7mL, 1g:8mL, etc., preferably 1g:3mL. Coupling agents include titanate coupling agents and 3-(phenylamino)propyltrimethoxysilane. The mass ratio of titanate coupling agent to 3-(phenylamino)propyltrimethoxysilane is 1:3 to 3:1, for example, 1:3, 1:2, 1:1, 2:1, 3:1, etc. The long chain of titanate coupling agent can form physical entanglement with the resin. The benzene ring structure in the molecule of 3-(phenylamino)propyltrimethoxysilane has good compatibility with SEBS. Using both together with a relatively single coupling agent or a combination of other types of coupling agents will have better results and further improve wear resistance.

[0022] In this invention, the SEBS resin type includes, but is not limited to, at least one of YH-561, YH-602, G1652 and G1651, preferably YH-561 and G1652. When the SEBS resin type is YH-561 and G1652, the wear resistance of the hot melt pavement marking paint is further improved, and the wear resistance value can be reduced to 9.2mg during the wear resistance test, which is better than the improvement effect of other types or combinations of types on the wear resistance of hot melt pavement marking paint.

[0023] In this invention, the glass beads are hollow glass beads with a particle size of 0.1~0.8mm, such as 0.1mm, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, etc. The hollow glass beads have low density characteristics and can effectively reflect light according to optical principles, thus optimizing the reflective performance of the markings.

[0024] In this invention, the processing aid includes a defoamer, the type of which includes at least one of SN-327 and SN-345. The defoamer achieves its defoaming effect by reducing the surface tension of the foam, causing it to break down. Defoamers such as SN-327 and SN-345, which are silicone or mineral oil-based, can effectively eliminate foam generated during coating processing due to stirring, ensuring good workability and preventing foam from affecting the smoothness and aesthetics of the markings. Antioxidants include chain-terminated antioxidants and hydroperoxide decomposition antioxidants. Chain-terminated antioxidants can be, for example, antioxidants 1010, 1076, 1098, 215, 225, or 264. These antioxidants can effectively capture free radicals generated by materials under heat and light, preventing thermo-oxidative aging and discoloration. Hydroperoxide decomposition antioxidants can be, for example, antioxidants 168, 626, DSTDP, TPP, TNPP, 3114, or 1135. These antioxidants can decompose hydroperoxides generated during thermo-oxidative aging into stable non-free radical substances, preventing thermo-oxidative aging. Preferably, antioxidants 1010 and 168 are used together to produce a synergistic effect and improve the antioxidant effect. Ultraviolet absorbers include benzotriazole ultraviolet absorbers and / or benzophenone ultraviolet absorbers; benzotriazole ultraviolet absorbers may be, for example, UV-P, UV-326, UV-327, UV-366, UV-328, UV-329 or UV-360, etc.; benzophenone ultraviolet absorbers may be, for example, UV-9 or UV-531, etc.

[0025] A second aspect of the present invention provides a method for preparing a wear-resistant hot-melt pavement marking paint, used to prepare the wear-resistant hot-melt pavement marking paint provided in the first aspect of the present invention, comprising the following steps: A1. Stir and mix petroleum resin and SEBS resin at 185~195℃ and 450~550r / min for 15min to obtain a preliminary mixture; A2. Add the pretreated functional filler to the initial mixture and stir and mix evenly at 170~180℃ and 850~950r / min. Then add the remaining components of the road marking paint and continue stirring and mixing evenly at 300~400r / min. Extrude, cool, and crush to a particle size of 3mm to obtain wear-resistant hot-melt road marking paint.

[0026] The present invention will now be described in detail with reference to preferred embodiments and comparative examples. The preferred embodiments of the invention described below can be modified in various ways, and therefore the scope of the invention should not be construed as limited to the preferred embodiments described in detail below. Preferred embodiments are provided to help those skilled in the art to more readily understand the invention.

[0027] Example 1 The wear-resistant hot-melt road marking paint is characterized by comprising the following components in parts by weight: 14 parts of C5 petroleum resin (model B1110), 45 parts of functional filler, 4 parts of SEBS resin (SEBS resin YH-561 and SEBS resin YH-602 in a mass ratio of 3:1), 20 parts of hollow glass beads (particle size of 0.1mm), 0.08 parts of antioxidant 1010, 0.02 parts of antioxidant 168, 0.2 parts of ultraviolet absorber UV-531, and 0.1 parts of defoamer SN-327; The functional filler comprises the following components in parts by weight: 30 parts of quartz sand (average particle size 300 mesh) and 15 parts of calcium carbonate (average particle size 300 mesh); A method for preparing wear-resistant hot-melt pavement marking paint includes the following steps: A1. Stir and mix petroleum resin and SEBS resin at 185℃ and 550r / min for 15min to obtain a preliminary mixture; A2. Add the pretreated functional filler to the initial mixture and stir and mix evenly at 170℃ and 850r / min. Then add the remaining components of the road marking paint and continue stirring and mixing evenly at 300r / min. Extrude, cool, and crush to a particle size of 3mm to obtain wear-resistant hot melt road marking paint. The preparation method of the pretreated functional filler includes the following steps: Adding the titanate coupling agent (model NDZ-201) to a 70% (v / v) ethanol aqueous solution at a mass-to-volume ratio of 1g:5mL, hydrolyzing for 15min to obtain a modified solution; drying the functional filler, dispersing it in anhydrous ethanol (functional filler to anhydrous ethanol mass-to-volume ratio of 1g:3mL) using ultrasonic dispersion at 200W for 15min to obtain a dispersed functional filler; adding the dispersed functional filler to the modified solution and mixing thoroughly for 40min, filtering, and drying at 110℃ for 2h to obtain the pretreated functional filler; the mass of the titanate coupling agent is 2% of the mass of the functional filler.

[0028] Example 2 The wear-resistant hot-melt road marking paint is characterized by comprising the following components in parts by weight: 20 parts of C5 petroleum resin (model B1110), 55 parts of functional filler, 8 parts of SEBS resin (SEBS resin YH-561 and SEBS resin YH-602 in a mass ratio of 3:1), 30 parts of hollow glass beads (particle size of 0.8mm), 0.3 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.4 parts of ultraviolet absorber UV-327, and 0.5 parts of defoamer SN-327; The functional filler comprises the following components in parts by weight: 35 parts of quartz sand (average particle size 500 mesh) and 20 parts of calcium carbonate (average particle size 200 mesh); A method for preparing wear-resistant hot-melt pavement marking paint includes the following steps: A1. Stir and mix petroleum resin and SEBS resin at 195℃ and 450r / min for 15min to obtain a preliminary mixture; A2. Add the pretreated functional filler to the initial mixture and stir and mix evenly at 180℃ and 850r / min. Then add the remaining components of the road marking paint and continue stirring and mixing evenly at 400r / min. Extrude, cool, and crush to a particle size of 3mm to obtain wear-resistant hot melt road marking paint. The preparation method of the pretreated functional filler includes the following steps: Adding the titanate coupling agent (model NDZ-201) to a 70% (v / v) ethanol aqueous solution at a mass-to-volume ratio of 1g:5mL, hydrolyzing for 15min to obtain a modified solution; drying the functional filler, dispersing it in anhydrous ethanol (functional filler to anhydrous ethanol mass-to-volume ratio of 1g:3mL) using ultrasonic dispersion at 300W for 15min to obtain a dispersed functional filler; adding the dispersed functional filler to the modified solution and mixing thoroughly for 40min, filtering, and drying at 110℃ for 2h to obtain the pretreated functional filler; the mass of the titanate coupling agent is 2% of the mass of the functional filler.

[0029] Example 3 This embodiment is the same as Example 1, except that the titanate coupling agent is replaced with 3-(phenylamino)propyltrimethoxysilane.

[0030] Example 4 In this embodiment, the titanate coupling agent is replaced with titanate coupling agent (model NDZ-201) and 3-(phenylamino)propyltrimethoxysilane in a mass ratio of 3:1, and the total mass of titanate coupling agent (model NDZ-201) and 3-(phenylamino)propyltrimethoxysilane is 2% of the mass of the functional filler. Otherwise, it is the same as in Example 1.

[0031] Example 5 In this embodiment, the titanate coupling agent is replaced with titanate coupling agent (model NDZ-201) and 3-(phenylamino)propyltrimethoxysilane in a mass ratio of 1:3, and the total mass of titanate coupling agent (model NDZ-201) and 3-(phenylamino)propyltrimethoxysilane is 2% of the mass of the functional filler. Otherwise, it is the same as in Example 1.

[0032] Example 6 This embodiment is the same as Example 5, except that the SEBS resin (SEBS resin YH-561 and SEBS resin YH-602 in a mass ratio of 3:1) is replaced with SEBS resin (SEBS resin YH-561 and SEBS resin G1652 in a mass ratio of 3:1).

[0033] Example 7 This embodiment is the same as Example 5, except that the SEBS resin (SEBS resin YH-561 and SEBS resin YH-602 in a mass ratio of 3:1) is replaced with SEBS resin (SEBS resin YH-602 and SEBS resin G1652 in a mass ratio of 3:1).

[0034] Example 8 This embodiment is the same as Example 5, except that the SEBS resin (SEBS resin YH-561 and SEBS resin YH-602 in a mass ratio of 3:1) is replaced with SEBS resin (SEBS resin YH-561 and SEBS resin G1651 in a mass ratio of 3:1).

[0035] Comparative Example 1 This comparative example is the same as Example 1 except that SEBS resin is not added.

[0036] Comparative Example 2 This comparative example is the same as Example 1 except that SEBS resin is replaced with EVA resin.

[0037] Comparative Example 3 This comparative example is the same as Example 1, except that the functional filler was not pretreated with a coupling agent.

[0038] The abrasion resistance of the hot-melt pavement marking paints of Examples 1-8 and Comparative Examples 1-3 was tested: the abrasion value was measured according to the abrasion resistance test method in 6.2.6 of the test standard JT / T 280-2022 "Pavement Marking Paints". The load weight was 1000g and the number of revolutions was 200. The result was the average of three parallel tests. The test results are shown in Table 1 below.

[0039] Table 1 Abrasion resistance test results

[0040] By comparing the data in Table 1 above, it can be found that the abrasion value of the hot-melt pavement marking paint prepared using the formulations and preparation methods of Examples 1-8 is lower than that of the hot-melt pavement marking paint prepared in Comparative Examples 1-3. This indicates that the use of SEBS resin and functional fillers in the hot-melt pavement marking paint, after pretreatment with a coupling agent, significantly improves the abrasion resistance of the marking paint. In particular, the use of titanate coupling agent and 3-(phenylamino)propyltrimethoxysilane for pretreatment in Examples 4-5 is more effective in improving the abrasion resistance of the hot-melt pavement marking paint than using a single coupling agent. In addition, Examples 6-8 also explored the effect of different types of SEBS resin on abrasion resistance. Among them, the abrasion resistance is best when SEBS resin YH-561 and SEBS resin G1652 are used together.

[0041] 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 wear-resistant hot-melt road marking paint, characterized in that, The product comprises the following components in parts by weight: 14-20 parts petroleum resin, 45-55 parts functional filler, 4-8 parts SEBS resin, 20-30 parts glass beads, 0.1-0.5 parts antioxidant, 0.2-0.4 parts ultraviolet absorber, and 0.1-0.5 parts processing aid; the functional filler comprises quartz sand and calcium carbonate, and the functional filler is prepared after pretreatment with a coupling agent.

2. The wear-resistant hot-melt pavement marking paint according to claim 1, characterized in that, By weight, the functional filler contains 30-35 parts of quartz sand and 15-20 parts of calcium carbonate.

3. The wear-resistant hot-melt pavement marking paint according to claim 1, characterized in that, The coupling agent includes titanate coupling agent and 3-(phenylamino)propyltrimethoxysilane.

4. The wear-resistant hot-melt pavement marking paint according to claim 3, characterized in that, The mass ratio of the titanate coupling agent to 3-(phenylamino)propyltrimethoxysilane is 1:3 to 3:

1.

5. The wear-resistant hot-melt pavement marking paint according to claim 1, characterized in that, The SEBS resin is of at least one of the following types: YH-561, YH-602, G1652, and G1651.

6. The wear-resistant hot-melt pavement marking paint according to claim 5, characterized in that, The SEBS resins include models YH-561 and G1652.

7. The wear-resistant hot-melt pavement marking paint according to claim 1, characterized in that, The glass beads have a particle size of 0.1~0.8mm; The particle size of the quartz sand is 300~500 mesh; The calcium carbonate has a particle size of 200-300 mesh.

8. The wear-resistant hot-melt pavement marking paint according to any one of claims 1 to 7, characterized in that, The processing aids include defoamers; The antioxidants include chain-terminated antioxidants and hydroperoxide decomposition antioxidants; The ultraviolet absorbers include benzotriazole ultraviolet absorbers and / or benzophenone ultraviolet absorbers.

9. The wear-resistant hot-melt pavement marking paint according to claim 8, characterized in that, The defoamer includes at least one of SN-327 and SN-345.

10. A method for preparing a wear-resistant hot-melt pavement marking paint, used to prepare the wear-resistant hot-melt pavement marking paint according to any one of claims 1 to 9, characterized in that, Includes the following steps: A1. Stir and mix petroleum resin and SEBS resin to obtain a preliminary mixture; A2. Add functional fillers to the initial mixture and stir. Add antioxidants, UV absorbers, glass beads and processing aids and continue stirring and mixing. Extrude and crush to obtain wear-resistant hot-melt road marking paint.

Images