High-adhesion and high-toughness hot-melt reflective marking coating

Abstract

The invention belongs to the field of road marking coatings, and particularly relates to a high-adhesion and high-toughness hot-melt reflective marking coating. The marking paint is composed of a component A and a component B, the component A is prepared from the following raw materials in parts by weight: 200 to 300 parts of C5 petroleum resin, 300 to 500 parts of filler, 20 to 100 parts of pigment, 10 to 20 parts of plasticizer, 5 to 10 parts of anti-ultraviolet agent, 200 to 300 parts of modified glass beads and 10 to 50 parts of hydrogen-containing silicone oil; the component B is prepared from the following raw materials in parts by weight: 10 to 50 parts of vinyl alkoxy silane oligomer and 0.02 to 0.5 part of platinum catalyst. The hot-melt reflective marking paint prepared by the invention has excellent toughness, bonding strength and wear resistance, effectively reduces the risks of falling off, cracking and the like of the marking, and remarkably prolongs the service life of the road marking.

Description

Technical Field

[0001] The present invention belongs to the field of road marking coatings, and particularly relates to a hot-melt reflective road marking coating with high adhesion and high toughness. Background Art

[0002] With the continuous increase in traffic flow, the requirements for the safety, economy, and durability of highway traffic facilities are also constantly rising. Hot-melt road marking coatings are widely used in road marking construction due to their long service life, good reflective performance, and environmental protection characteristics. Its main film-forming substance is natural resins such as petroleum resin and rosin resin, supplemented with pigments, fillers, and additives, and forms a coating after heating and melting. Premixed glass microspheres can provide continuous reflective effects, and have a short production cycle, low cost, short drying time, no pollution during the construction process, good adhesion, and environmental friendliness.

[0003] Although hot-melt marking coatings have many advantages in construction, they also face some key problems. First, the cost per unit coating area is relatively high, resulting in an increase in construction costs. Second, the wear resistance of the coating is poor, especially in busy traffic sections, where the markings are easily worn, affecting the durability and effect of the coating. In addition, the adhesion of the coating on aged asphalt pavements and cement pavements is poor, resulting in easy peeling of the coating, further increasing the costs of maintenance and repair. At the same time, the toughness of the marking coating is insufficient, making the coating prone to cracking or peeling in high-temperature or low-temperature environments, affecting its long-term stability. In order to improve the performance of hot-melt road marking coatings, especially to improve their wear resistance, adhesion, and toughness, and extend their service life, has become an important direction in the current research on road marking coatings. Improving the flexibility, adhesion, and durability by improving the formula and construction process to cope with the increasingly harsh road use environment has become the key direction for future research. Summary of the Invention

[0004] Aiming at the problems and deficiencies existing in the prior art, the purpose of the present invention is to provide a hot-melt reflective road marking coating with high adhesion and high toughness.

[0005] Based on the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention provides a hot-melt reflective road marking coating with high adhesion and high toughness, and the marking coating is composed of two components, A and B.

[0007] The component A is composed of the following raw materials in parts by weight: 200 - 300 parts of C5 petroleum resin, 300 - 500 parts of filler, 20 - 100 parts of pigment, 10 - 20 parts of plasticizer, 5 - 10 parts of ultraviolet absorber, 200 - 300 parts of modified glass microspheres, and 10 - 50 parts of hydrogen-containing silicone oil.

[0008] The component B is composed of the following raw materials in parts by weight: 10-50 parts of vinyl alkoxysilane oligomer and 0.02-0.5 part of platinum catalyst.

[0009] Preferably, the average molecular weight of the hydrogen-containing silicone oil is 5,000-20,000, and the hydrogen content is 0.5%-1.5%.

[0010] Preferably, the modified glass microspheres are prepared by modifying glass microspheres with a silane coupling agent.

[0011] Preferably, the silane coupling agent is vinyl silane or methacryloxy silane.

[0012] Further, the modified glass microspheres are prepared by the following method:

[0013] (1) Pretreatment: Place the glass microspheres in anhydrous ethanol and ultrasonically clean for 20-30 min to remove surface impurities, and then dry at 100-110 °C for 2-3 h;

[0014] (2) Preparation of silane coupling agent solution: Dissolve the silane coupling agent in anhydrous ethanol to prepare a silane solution with a mass fraction of 5%-10%;

[0015] (3) Surface modification reaction: Add the glass microspheres treated in step (1) to the silane coupling agent solution in step (2), and the mass ratio of the glass microspheres to the silane coupling agent solution is 1:(1-3), and stir and react at 60-80 °C for 4-6 h;

[0016] (4) Post-treatment: After the reaction is completed, filter, wash, and vacuum dry at 40-60 °C for 6-12 h to obtain the modified glass microspheres.

[0017] Preferably, the vinyl alkoxysilane oligomer is a polysiloxane containing vinyl and C1-C3 alkoxy groups.

[0018] Preferably, the plasticizer is one or more of dioctyl phthalate, dipropylene glycol dibenzoate, and naphthenic oil.

[0019] Preferably, the filler is one or more of quartz sand, talc powder, heavy calcium carbonate, barium sulfate, and fumed silica.

[0020] Preferably, the pigment is one or more of titanium dioxide and medium chrome yellow.

[0021] Preferably, the platinum catalyst is bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum or chloroplatinic acid.

[0022] Preferably, the ultraviolet absorber is a hindered amine light stabilizer.

[0023] Furthermore, the preparation method of the high-adhesion and high-toughness hot-melt reflective marking paint includes the following steps:

[0024] (1) Preparation of Component A: Mix C5 petroleum resin, filler, pigment, plasticizer, anti-ultraviolet agent, modified glass beads, and hydrogen-containing silicone oil evenly, heat to a molten state at 150-200 °C, stir evenly, and cool and pulverize to obtain Component A;

[0025] (2) Preparation of Component B: Stir and mix vinylalkoxysilane oligomer and platinum catalyst evenly to obtain Component B.

[0026] (3) Store the prepared Component A and Component B separately. When in use, mix Component A and Component B evenly to obtain the high-adhesion and high-toughness hot-melt reflective marking paint.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0028] (1) By introducing hydrogen-containing silicone oil into the marking paint, the present invention makes full use of its unique molecular structure and performance advantages: the molecular main chain of hydrogen-containing silicone oil is composed of highly flexible silicon-oxygen bonds (Si-O-Si), which can introduce flexible chain segments into the paint, thereby significantly improving the deformation ability and overall toughness of the material. At the same time, hydrogen-containing silicone oil has excellent wettability and adhesion, which can effectively improve the interfacial state of the material surface, enhance the adhesion between the coating and the substrate, and avoid cracking problems caused by interfacial debonding. In addition, hydrogen-containing silicone oil can form a uniformly distributed silicon-based phase in the paint, helping to disperse external forces and evenly transfer local stress to the whole material, thus significantly reducing the adverse effects of stress concentration on the material performance and providing guarantee for the long-term stability and service life of the paint.

[0029] (2) The structure of the vinylalkoxysilane oligomer used in the present invention contains both vinyl functional groups that can participate in the hydrosilylation reaction and hydrolyzable alkoxy groups. This unique bifunctional design enables it to not only construct a crosslinked network in the system but also form chemical bonds with the substrate. Its long-chain molecular structure not only ensures the thermal stability of the material during construction but also endows the system with flexibility, improving the performance of the paint in terms of adhesion and durability.

[0030] (3) The present invention modifies the surface of glass microspheres with a silane coupling agent, enabling the silanol groups on the surface to form a stable Si-O-Si covalent bond structure with the coupling agent. This modification achieves a dual optimization effect: First, it significantly reduces the surface energy of the microspheres and improves their wetting performance with the resin. Second, through the exposed vinyl / methacryloxy and other reactive functional groups, the interfacial compatibility is greatly enhanced; it can undergo a cross-linking reaction with vinylalkoxysilane oligomers and hydrogen-containing silicone oil to construct a chemical bonding network, replacing the traditional physical adsorption mechanism. This strong interfacial interaction enhances the adhesion and encapsulation of the glass microspheres in the marking paint system, effectively reducing the possibility of glass microsphere shedding, thereby significantly improving the wear resistance and service life of the paint and ensuring that the marking can maintain good functional performance during long-term use.

[0031] (4) During the high-temperature construction process of the marking paint prepared by the present invention, the hydrogen-containing silicone oil in component A, the unsaturated bonds on the surface of the modified glass microspheres, and the vinylalkoxysilane oligomer in component B undergo a hydrosilylation reaction under the action of a catalyst to form a stable cross-linked network structure. This cross-linked network can not only effectively disperse the internal stress of the material but also significantly improve the crack resistance and toughness of the paint. In addition, the alkoxy groups in the vinylalkoxysilane oligomer can form strong chemical bonds with the construction substrate after hydrolysis, thereby further enhancing the adhesion strength between the paint and the substrate and improving the long-term durability of the marking. Detailed implementation manners

[0032] To make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below through examples. It should be understood that the specific examples described herein are only used to explain the present invention and are not used to limit the present invention.

[0033] The reagents used in the following examples are shown as follows:

[0034] UV stabilizer: BASF Tinuvin791, Tinuvin770DF;

[0035] Hydrogen-containing silicone oil: Hydrogen-containing silicone oil with an average molecular weight of 20,000 and a hydrogen content of 0.8%, hydrogen-containing silicone oil with an average molecular weight of 10,000 and a hydrogen content of 0.8%, hydrogen-containing silicone oil with an average molecular weight of 20,000 and a hydrogen content of 1.2%;

[0036] Vinylalkoxysilane oligomer: Evonik 6598, Chenguang CG-081, Chenguang CG-087, Jianghan New Materials JH-VP10, Jianghan New Materials JH-VP12;

[0037] Platinum catalysts: bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane)platinum (Karstedt), chloroplatinic acid (Speier);

[0038] Silane coupling agents: KH-570, A151, A171, KH571.

[0039] (I) Preparation of modified glass microspheres

[0040] Example 1-1

[0041] The modified glass microspheres provided in this example are prepared by the following method:

[0042] (1) Take 500 g of glass microspheres and place them in 2 L of absolute ethanol for ultrasonic cleaning for 25 min, and then dry them in an oven at 105 °C for 2.5 h;

[0043] (2) Add 12 g of KH-570 (3-methacryloxypropyltrimethoxysilane) and 388 g of absolute ethanol to a 1 L three-necked flask equipped with mechanical stirring, and stir for 30 min to form a 3 wt% silane solution;

[0044] (3) Add 400 g of pretreated glass microspheres to the silane solution in step (2), and stir and react at 70 ± 1 °C for 5 h;

[0045] (4) The reaction product is filtered by suction through a Buchner funnel, washed 3 times with absolute ethanol, and then placed in a vacuum drying oven (-0.08 MPa) for vacuum drying at 50 ± 1 °C for 8 h to obtain modified glass microspheres a.

[0046] Example 1-2

[0047] The modified glass microspheres provided in this example are prepared by the following method:

[0048] (1) Take 500 g of glass microspheres and place them in 2 L of absolute ethanol for ultrasonic cleaning for 25 min, and then dry them in an oven at 105 °C for 2.5 h;

[0049] (2) Add 12 g of A151 (vinyltriethoxysilane) and 388 g of absolute ethanol to a 1 L three-necked flask equipped with mechanical stirring, and stir for 30 min to form a 3 wt% silane solution;

[0050] (3) Add 400 g of pretreated glass microspheres to the silane solution in step (2), and stir and react at 70 ± 1 °C for 5 h;

[0051] (4) The reaction product is filtered by suction through a Buchner funnel, washed 3 times with absolute ethanol, and then placed in a vacuum drying oven (-0.08 MPa) for vacuum drying at 50 ± 1 °C for 8 h to obtain modified glass microspheres b.

[0052] Examples 1 - 3

[0053] The modified glass beads provided in this example are prepared by the following method:

[0054] (1) Take 500 g of glass beads and place them in 2 L of absolute ethanol for ultrasonic cleaning for 25 min, and then dry them in an oven at 105 °C for 2.5 h;

[0055] (2) Add 12 g of A171 (vinyltrimethoxysilane) and 388 g of absolute ethanol to a 1 L three-necked flask with mechanical stirring, and stir for 30 min to form a 3 wt% silane solution;

[0056] (3) Add 400 g of pretreated glass beads to the silane solution in step (2), and stir and react at 70 ± 1 °C for 5 h;

[0057] (4) The reaction product is filtered by suction through a Buchner funnel, washed 3 times with absolute ethanol, and then placed in a vacuum drying oven (-0.08 MPa) for vacuum drying at 50 ± 1 °C for 8 h to obtain the modified glass beads c.

[0058] Examples 1 - 4

[0059] The modified glass beads provided in this example are prepared by the following method:

[0060] (1) Take 500 g of glass beads and place them in 2 L of absolute ethanol for ultrasonic cleaning for 25 min, and then dry them in an oven at 105 °C for 2.5 h;

[0061] (2) Add 12 g of KH571 (3-methacryloxypropylmethyldimethoxysilane) and 388 g of absolute ethanol to a 1 L three-necked flask with mechanical stirring, and stir for 30 min to form a 3 wt% silane solution;

[0062] (3) Add 400 g of pretreated glass beads to the silane solution in step (2), and stir and react at 70 ± 1 °C for 5 h;

[0063] (4) The reaction product is filtered by suction through a Buchner funnel, washed 3 times with absolute ethanol, and then placed in a vacuum drying oven (-0.08 MPa) for vacuum drying at 50 ± 1 °C for 8 h to obtain the modified glass beads d.

[0064] (II) Explore the influence of hydrogen-containing silicone oil on the performance of hot-melt reflective road marking coatings

[0065] 1) Preparation of hot-melt reflective road marking coatings

[0066] Example 2 - 1

[0067] A high-adhesion and high-toughness hot-melt reflective road marking coating consists of two components, A and B.

[0068] The component A is composed of the following raw materials in parts by weight: 250 parts of C5 petroleum resin, 420 parts of heavy calcium carbonate, 100 parts of quartz sand, 30 parts of titanium dioxide, 50 parts of medium chrome yellow, 15 parts of dioctyl phthalate, 10 parts of BASF Tinuvin 791 ultraviolet absorber, 250 parts of modified glass beads d, and 50 parts of hydrogen-containing silicone oil (average molecular weight of 20,000 and hydrogen content of 0.8%).

[0069] The component B is composed of the following raw materials in parts by weight: 30 parts of vinylalkoxysilane oligomer (Chenguang CG-081) and 0.2 part of Speier platinum catalyst.

[0070] The preparation method of the above high-adhesion and high-toughness hot-melt reflective road marking paint comprises the following steps:

[0071] (1) Preparation of component A: Mix C5 petroleum resin, heavy calcium carbonate, quartz sand, titanium dioxide, medium chrome yellow, dioctyl phthalate, BASF Tinuvin 791 ultraviolet absorber, modified glass beads d, and hydrogen-containing silicone oil (average molecular weight of 20,000 and hydrogen content of 0.8%) evenly, heat to the molten state at 150-200°C, stir evenly at high speed, and obtain component A after cooling and pulverizing;

[0072] (2) Preparation of component B: Stir and mix vinylalkoxysilane oligomer (Chenguang CG-081) and Speier platinum catalyst evenly to obtain component B;

[0073] (3) Store the prepared component A and component B separately. When in use, mix component A and component B evenly to obtain the high-adhesion and high-toughness hot-melt reflective road marking paint.

[0074] Example 2-2

[0075] A high-adhesion and high-toughness hot-melt reflective road marking paint has basically the same composition as that in Example 2-1, except that the average molecular weight of the hydrogen-containing silicone oil is 10,000 and the hydrogen content is 0.8%.

[0076] The preparation method of the above high-adhesion and high-toughness hot-melt reflective road marking paint is the same as that in Example 2-1.

[0077] Example 2-3

[0078] A high-adhesion and high-toughness hot-melt reflective road marking paint has basically the same composition as that in Example 2-1, except that the average molecular weight of the hydrogen-containing silicone oil is 20,000 and the hydrogen content is 1.2%.

[0079] The preparation method of the above-mentioned hot-melt reflective marking paint with high adhesion and high toughness is the same as that of Example 2-1.

[0080] Comparative Example 2-1

[0081] A kind of hot-melt reflective marking paint, its composition is basically the same as that of Example 2-1, the difference is that: hydrogen-containing silicone oil is not added to component A.

[0082] The preparation method of the above-mentioned hot-melt reflective marking paint is the same as that of Example 2-1.

[0083] 2) Performance test and analysis of the marking paint

[0084] The hot-melt marking paints prepared in Examples 2-1 to 2-3 and Comparative Example 2-1 were melted and sprayed on cement asbestos boards, with a film thickness of 2 mm. Referring to JT / T 280-2022 "Pavement Marking Paint", the softening point, compressive strength (23±1°C), water resistance, alkali resistance, abrasion resistance, and low-temperature crack resistance were measured. Among them, the low-temperature crack resistance test was: maintaining at -10°C for 4 h and placing at room temperature for 4 h was taken as a cycle period, and the number of cycles was recorded when cracks appeared; the water resistance test: the film was immersed in water for 24 h without any abnormal phenomenon; the alkali resistance test: the film was immersed in saturated lime water for 18 h without any abnormal. The adhesion strength was tested according to the test of GB / T 5210—2006 "Pull-off Adhesion Test for Paints and Varnishes", with a film thickness of 2 mm and the substrate being C30 mortar blocks. The test results are shown in Table 1.

[0085] Table 1 Test results of the influence of hydrogen-containing silicone oil on the performance of hot-melt marking paint

[0086]

[0087] As can be seen from Table 1, compared with Comparative Example 2-1, hydrogen-containing silicone oil was added in Examples 2-1 to 2-3, which not only increased the low-temperature crack resistance cycle times and bonding strength of the coating system, but also significantly reduced the wear amount. This is because the highly flexible silicon-oxygen bond (Si-O-Si) segments in the hydrogen-containing silicone oil can effectively buffer external stress through the dynamic adjustment of molecular chain conformation, thereby endowing the coating with excellent deformation ability and overall toughness, making it show more excellent crack resistance performance in low-temperature environments. At the same time, the improvement of the bonding strength and abrasion resistance further indicates that the hydrogen-containing silicone oil participated in the cross-linking reaction in the coating system, constructing a denser and more stable interpenetrating network structure, thereby enhancing the cohesive strength and interfacial bonding force of the coating, and realizing the overall improvement of the coating performance.

[0088] (III) Explore the influence of vinylalkoxysilane oligomers on the performance of hot-melt reflective marking paint

[0089] 1) Preparation of hot-melt reflective marking paint

[0090] Example 3-1

[0091] A hot-melt reflective road marking paint with high adhesion and high toughness has a composition basically the same as that of Example 2-1, except that: the vinylalkoxysilane oligomer is selected from Evonik 6598.

[0092] The preparation method of the above-mentioned hot-melt reflective road marking paint with high adhesion and high toughness is the same as that of Example 2-1.

[0093] Example 3-2

[0094] A hot-melt reflective road marking paint with high adhesion and high toughness has a composition basically the same as that of Example 2-1, except that: the vinylalkoxysilane oligomer is selected from Jianghan New Materials JH-VP10.

[0095] The preparation method of the above-mentioned hot-melt reflective road marking paint with high adhesion and high toughness is the same as that of Example 2-1.

[0096] Comparative Example 3-1

[0097] A hot-melt reflective road marking paint has a composition basically the same as that of Example 2-1, except that: the vinylalkoxysilane oligomer is not added to Component B.

[0098] The preparation method of the above-mentioned hot-melt reflective road marking paint is the same as that of Example 2-1.

[0099] 2) Performance testing and analysis of road marking paint

[0100] The hot-melt road marking paints prepared in Example 3-1, 3-2, and Comparative Example 3-1 were melt-sprayed on a cement asbestos board with a film thickness of 2 mm. The softening point, compressive strength (23 ± 1 °C), water resistance, alkali resistance, abrasion resistance, and low-temperature crack resistance were measured with reference to JT / T 280-2022 "Road Marking Paints". Among them, the low-temperature crack resistance test was: maintaining at -10 °C for 4 h and placing at room temperature for 4 h as a cycle period, and the number of cycles was recorded when cracks appeared; the water resistance test: the film was immersed in water for 24 h without abnormal phenomena; the alkali resistance test: the film was immersed in saturated lime water for 18 h without abnormal. The adhesion strength was tested according to the test of GB / T 5210—2006 "Pull-off Adhesion Test for Paints and Varnishes", with a film thickness of 2 mm and the substrate being a C30 mortar block. The test results are shown in Table 2.

[0101] Table 2 Test results of the influence of vinylalkoxysilane oligomer on the performance of hot-melt road marking paint

[0102]

[0103] As can be seen from Table 2, compared with Comparative Example 3-1, in Examples 2-1, 3-1, and 3-2, Component B prepared from vinylalkoxysilane oligomers was added, resulting in a significant reduction in abrasion loss, an increase in bonding strength, and an increase in the number of low-temperature cycles. This performance optimization stems from the triple action mechanism of vinylalkoxysilane oligomers: First, its reactive siloxane groups form chemical bonds with the substrate, strengthening the interfacial bonding; second, it undergoes a cross-linking reaction with hydrogen-containing silicone oil to construct a three-dimensional network, enhancing the wear resistance; finally, the flexible characteristics of the long molecular chain segments endow the coating with low-temperature deformation ability and enhance the crack resistance. Therefore, this multi-scale synergistic effect comprehensively improves the comprehensive performance of the coating.

[0104] (IV) Explore the influence of modified glass beads on the performance of hot-melt reflective road marking coatings

[0105] 1) Preparation of hot-melt reflective road marking coatings

[0106] Example 4-1

[0107] A high-bonding and high-toughness hot-melt reflective road marking coating has basically the same composition as Example 2-1, except that: the modified glass beads are modified glass beads a.

[0108] The preparation method of the above high-bonding and high-toughness hot-melt reflective road marking coating is the same as that of Example 2-1.

[0109] Example 4-2

[0110] A high-bonding and high-toughness hot-melt reflective road marking coating has basically the same composition as Example 2-1, except that: the modified glass beads are modified glass beads c.

[0111] The preparation method of the above high-bonding and high-toughness hot-melt reflective road marking coating is the same as that of Example 2-1.

[0112] Comparative Example 4-1

[0113] A hot-melt reflective road marking coating has basically the same composition as Example 2-1, except that: unmodified glass beads are selected.

[0114] The preparation method of the above hot-melt reflective road marking coating is the same as that of Example 2-1.

[0115] 2) Performance testing and analysis of road marking coatings

[0116] The hot-melt road marking paints prepared in Example 2-1, 4-1, 4-2 and Comparative Example 4-1 were melt-sprayed on cement asbestos boards with a film thickness of 2 mm. The softening point, compressive strength (23±1°C), water resistance, alkali resistance, abrasion resistance and low-temperature crack resistance were measured with reference to JT / T 280-2022 "Road Marking Paints". Among them, the low-temperature crack resistance test was as follows: maintaining at -10°C for 4 h and placing at room temperature for 4 h was taken as a cycle period, and the number of cycles was recorded when cracks appeared; the water resistance test: the film was immersed in water for 24 h without any abnormal phenomenon; the alkali resistance test: the film was immersed in saturated lime water for 18 h without any abnormal phenomenon. The bond strength was tested according to the test of GB / T 5210—2006 "Pull-off Adhesion Test for Paints and Varnishes", with a film thickness of 2 mm and the substrate being C30 mortar blocks. The test results are shown in Table 3.

[0117] Table 3 Test Results of the Influence of Modified Glass Microspheres on the Performance of Hot-Melt Road Marking Paints

[0118]

[0119]

[0120] As can be seen from Table 3, compared with Comparative Example 4-1, in Examples 2-1, 4-1 and 4-2, due to the addition of modified glass microspheres, the wear loss was significantly reduced and the bond strength was improved. This is mainly attributed to the enhanced surface activity of the modified glass microspheres, which makes them more easily coated by the resin and react and crosslink with the coating system through the functional groups on the surface, thus constructing a stable chemical bonding network.

[0121] (V) Comparison between Traditional Hot-Melt Reflective Road Marking Paint and the Hot-Melt Reflective Road Marking Paint of the Present Invention

[0122] 1) Preparation of Hot-Melt Reflective Road Marking Paint

[0123] Example 5-1

[0124] A kind of hot-melt reflective road marking paint with high adhesion and high toughness is composed of two components, A and B.

[0125] The component A is composed of the following raw materials in parts by weight: 220 parts of C5 petroleum resin, 350 parts of heavy calcium carbonate, 100 parts of quartz sand, 50 parts of titanium dioxide, 10 parts of dioctyl phthalate, 6 parts of BASF Tinuvin791 ultraviolet absorber, 250 parts of modified glass microspheres b, and 40 parts of hydrogen-containing silicone oil (average molecular weight is 10,000 and hydrogen content is 1.5%).

[0126] The component B is composed of the following raw materials in parts by weight: 40 parts of vinylalkoxysilane oligomer (Jianghan New Materials JH-VP10) and 0.3 parts of Karstedt platinum catalyst.

[0127] The preparation method of the above-mentioned hot-melt reflective marking paint with high adhesion and high toughness comprises the following steps:

[0128] (1) Preparation of component A: Mix C5 petroleum resin, heavy calcium carbonate, quartz sand, titanium dioxide, dioctyl phthalate, ultraviolet light absorber, modified glass bead b, and hydrogen-containing silicone oil (average molecular weight of 10,000 and hydrogen content of 1.5%) evenly, heat to the molten state at 150-200 °C, stir evenly at high speed, and obtain component A after cooling and pulverizing;

[0129] (2) Preparation of component B: Stir and mix vinyltrimethoxysilane and Karstedt platinum catalyst evenly to obtain component B.

[0130] (3) Store the prepared component A and component B separately. When in use, mix component A and component B evenly to obtain the hot-melt reflective marking paint with high adhesion and high toughness.

[0131] Example 5-2

[0132] A hot-melt reflective marking paint with high adhesion and high toughness consists of two components, A and B.

[0133] Component A is composed of the following raw materials in parts by weight: 280 parts of C5 petroleum resin, 370 parts of heavy calcium carbonate, 30 parts of quartz sand, 50 parts of talc powder, 30 parts of titanium dioxide, 30 parts of medium chrome yellow, 20 parts of dipropylene glycol dibenzoate, 10 parts of BASF Tinuvin791 ultraviolet light absorber, 280 parts of modified glass bead a, and 50 parts of hydrogen-containing silicone oil (average molecular weight of 15,000 and hydrogen content of 1.2%).

[0134] Component B is composed of the following raw materials in parts by weight: 50 parts of vinylalkoxysilane oligomer (Chenguang CG-087) and 0.3 parts of Karstedt platinum catalyst.

[0135] The preparation method of the above-mentioned hot-melt reflective marking paint with high adhesion and high toughness is the same as that of Example 5-1.

[0136] Example 5-3

[0137] A hot-melt reflective marking paint with high adhesion and high toughness consists of two components, A and B.

[0138] Component A is composed of the following raw materials in parts by weight: 250 parts of C5 petroleum resin, 450 parts of heavy calcium carbonate, 50 parts of talc powder, 50 parts of titanium dioxide, 30 parts of medium chrome yellow, 10 parts of dipropylene glycol dibenzoate, 10 parts of BASF Tinuvin791 ultraviolet light absorber, 260 parts of modified glass bead d, and 40 parts of hydrogen-containing silicone oil (average molecular weight of 5,000 and hydrogen content of 1%).

[0139] The component B is composed of the following raw materials in parts by weight: 20 parts of vinyl alkoxysilane oligomer (Chenguang CG-087) and 0.15 part of Speier platinum catalyst.

[0140] The preparation method of the above high-adhesion and high-toughness hot-melt reflective marking paint is the same as that of Example 5-1.

[0141] Example 5-4

[0142] A high-adhesion and high-toughness hot-melt reflective marking paint is composed of two components, A and B.

[0143] The component A is composed of the following raw materials in parts by weight: 300 parts of C5 petroleum resin, 250 parts of heavy calcium carbonate, 50 parts of talcum powder, 100 parts of titanium dioxide, 15 parts of naphthenic oil, 5 parts of BASF Tinuvin791 ultraviolet absorber, 200 parts of modified glass beads b, and 30 parts of hydrogen-containing silicone oil (average molecular weight is 20,000, hydrogen content is 1.5%).

[0144] The component B is composed of the following raw materials in parts by weight: 30 parts of vinyl alkoxysilane oligomer (Chenguang CG-081) and 0.3 part of Speier platinum catalyst.

[0145] The preparation method of the above high-adhesion and high-toughness hot-melt reflective marking paint is the same as that of Example 5-1.

[0146] Example 5-5

[0147] A high-adhesion and high-toughness hot-melt reflective marking paint is composed of two components, A and B.

[0148] The component A is composed of the following raw materials in parts by weight: 300 parts of C5 petroleum resin, 400 parts of heavy calcium carbonate, 80 parts of titanium dioxide, 20 parts of naphthenic oil, 10 parts of BASF Tinuvin791 ultraviolet absorber, 300 parts of modified glass beads c, and 50 parts of hydrogen-containing silicone oil (average molecular weight is 10,000, hydrogen content is 0.5%).

[0149] The component B is composed of the following raw materials in parts by weight: vinyl alkoxysilane oligomer (Evonik 6598) 10 parts and Speier platinum catalyst 0.1 part.

[0150] The preparation method of the above high-adhesion and high-toughness hot-melt reflective marking paint is the same as that of Example 5-1.

[0151] Comparative Example 5-1

[0152] A traditional hot-melt reflective marking paint is composed of the following raw materials in parts by weight: 250 parts of C5 petroleum resin, 420 parts of heavy calcium carbonate, 100 parts of quartz sand, 30 parts of titanium dioxide, 50 parts of medium chrome yellow, 15 parts of dioctyl phthalate, 10 parts of BASF Tinuvin791 ultraviolet absorber, and 250 parts of glass beads.

[0153] The preparation method of the above-mentioned hot-melt reflective marking paint includes the following steps: Mix C5 petroleum resin, heavy calcium carbonate, quartz sand, titanium dioxide, medium chrome yellow, dioctyl phthalate, ultraviolet absorber, and glass beads evenly, heat to a molten state at 150-200 °C, stir evenly at high speed, and cool and pulverize.

[0154] 2) Performance testing and analysis of marking paint

[0155] The hot-melt marking paints prepared in Examples 5-1 to 5-5 and Comparative Example 5-1 were melt-sprayed on cement asbestos boards with a film thickness of 2 mm. The softening point, compressive strength (23±1 °C), water resistance, alkali resistance, abrasion resistance, and low-temperature crack resistance were measured with reference to JT / T 280-2022 "Pavement Marking Paint". Among them, the low-temperature crack resistance test was as follows: -10 °C for 4 h and room temperature for 4 h was taken as a cycle, and the number of cycles was recorded when cracks appeared; the water resistance test: the film was immersed in water for 24 h without any abnormal phenomenon; the alkali resistance test: the film was immersed in saturated lime water for 18 h without any abnormal. The adhesion strength was tested according to the test of GB / T 5210—2006 "Pull-off adhesion test for paints and varnishes", with a film thickness of 2 mm and the substrate being C30 mortar blocks. The test results are shown in Table 4.

[0156] Table 4 Comparison between traditional hot-melt reflective marking paint and the hot-melt reflective marking paint of the present invention

[0157]

[0158] It can be seen from the test results in Table 4 that compared with the traditional hot-melt marking paint in Comparative Example 5-1, the hot-melt marking paint prepared in Example 2-1 showed significant improvements in flexibility, adhesion strength, and abrasion resistance. In addition, the paints in Examples 5-1 to 5-5 were superior to Comparative Example 5-1 in the above key properties. Among them, the marking paint prepared in Example 5-5 had the best comprehensive performance. This further shows that by optimizing the paint raw materials and their ratios, the overall performance of the marking paint can be effectively improved, overcoming problems such as easy cracking, peeling, and wear, thereby improving the service life and durability.

[0159] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting the protection scope of the present invention. Those skilled in the art can modify or equivalently replace the technical solutions of the present invention according to the idea of the present invention, without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A hot-melt reflective marking paint with high adhesion and high toughness, characterized in that: The road marking paint is composed of two components, A and B; The component A is composed of the following raw materials in parts by weight: 200-300 parts of C5 petroleum resin, 300-500 parts of filler, 20-100 parts of pigment, 10-20 parts of plasticizer, 5-10 parts of anti-ultraviolet agent, 200-300 parts of modified glass microspheres, and 10-50 parts of hydrogen-containing silicone oil; The B component is composed of the following raw materials in parts by weight: 10 to 50 parts of vinyl alkoxysilane oligomer and 0.02 to 0.5 parts of platinum catalyst.

2. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The average molecular weight of the hydrogen-containing silicone oil is 5000-20000, and the hydrogen content is 0.5%-1.5%.

3. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The modified glass microbeads are prepared by modifying glass microbeads with a silane coupling agent; the silane coupling agent is vinyl silane or methacryloxy silane.

4. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The vinyl alkoxysilane oligomer is a polysiloxane containing a vinyl group and a C1-C3 alkoxy group.

5. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The plasticizer is one or more of dioctyl phthalate, dipropylene glycol dibenzoate, and naphthenic oil.

6. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The filler is one or more of quartz sand, talcum powder, heavy calcium carbonate, barium sulfate, and fumed silica.

7. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The pigment is one or more of titanium dioxide and medium chrome yellow.

8. The hot-melt reflective marking paint with high adhesion and high toughness according to claim 1, characterized in that: The platinum catalyst is bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane)platinum or chloroplatinic acid.

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