A road marking material containing a photo-oxidation synergistic protective layer and its construction process

Abstract

The application provides a road marking material containing a light-oxygen synergistic protective layer and a construction process thereof, and belongs to the technical field of road marking materials, and comprises a coating and glass beads, wherein the coating comprises the following components in percentage by weight: 25-35wt% film forming substances, 5-15wt% pigments, 45-55wt% fillers, 2-4wt% functional additives, and 1-2wt% curing agents; the film forming substances comprise the following components in percentage by weight: 60-75wt% aliphatic polyurethane acrylate resins, 15-25wt% methyl methacrylate, and 10-15wt% phenyl methacrylate; and the functional additives comprise one or more than two combinations of leveling agents, dispersants, stabilizers and reinforcing agents. The application provides a road marking material containing a light-oxygen synergistic protective layer and a construction process thereof, and achieves the purposes of improving durability, preventing mechanical strength and reflective performance from deteriorating, and accelerating construction efficiency.

Description

Technical Field

[0001] This invention relates to the field of road marking materials technology, specifically to a road marking material containing a photo-oxidation synergistic protective layer and its construction process. Background Technology

[0002] Road markings are traffic signs applied to road surfaces to guide and regulate the movement of vehicles and pedestrians. Road markings are an important component of traffic safety facilities; reflective paint can improve road visibility at night or in low-visibility conditions, thereby reducing traffic accidents. Traditional reflective paints often use glass microspheres as the reflective material, but these suffer from problems such as rapid reflectivity decay, poor durability, and environmental pollution. Therefore, developing a reflective paint for road markings with high reflectivity, durability, and environmental friendliness is of great significance.

[0003] In the field of photo-oxidation stabilization, the existing protective layer technology has the following problems: (1) A single protective mechanism cannot meet the durability requirements in practical applications, especially under the influence of complex external environments (such as ultraviolet rays, oxidation, moisture, etc.), the protective effect is significantly reduced; (2) Traditional photo-oxidation stabilization methods have a significant impact on the physical properties of materials, leading to the deterioration of their mechanical strength and reflective properties; (3) Existing protective technologies are difficult to balance the requirements of rapid construction with the formation of high-performance surfaces, and there is a contradiction between construction efficiency and material performance. Summary of the Invention

[0004] In view of this, the present invention provides a road marking material containing a photo-oxygen synergistic protective layer and its construction process, which aims to improve durability, prevent the deterioration of mechanical strength and reflective performance, and accelerate construction efficiency.

[0005] To achieve the above objectives, the present invention provides a road marking material containing a photo-oxidation synergistic protective layer, comprising a paint and glass beads. The paint comprises the following components by weight percentage: 25-35 wt% film-forming substance, 5-15 wt% pigment, 45-55 wt% filler, 2-4 wt% functional additives, and 1-2 wt% curing agent. The film-forming substance comprises the following components by weight: 60-75 wt% aliphatic polyurethane acrylate resin, 15-25 wt% methyl methacrylate, and 10-15 wt% phenyl methacrylate. The functional additives comprise one or more combinations of leveling agents, dispersants, stabilizers, and reinforcing agents.

[0006] Optionally, when the functional additive is a combination of leveling agent, dispersant, stabilizer and reinforcing agent, the stabilizer accounts for 0.8 to 1.2 wt% of the coating by mass, and the reinforcing agent accounts for 0.4 to 0.5 wt% of the coating by mass.

[0007] Optionally, the stabilizer is one or a combination of two or more of ultraviolet absorbers, hindered amine light stabilizers, and organobentonite; the reinforcing agent is one or a combination of two of nano-SiO2 and silicon carbide micropowder.

[0008] Optionally, when the reinforcing agent is a combination of nano-SiO2 and silicon carbide micro powder, the mass ratio of nano-SiO2 to silicon carbide micro powder is 3:(1~2).

[0009] Optionally, the pigment is titanium dioxide; the filler is heavy calcium carbonate powder; the curing agent is TPO photoinitiator and TMS-X siloxane; in the TMS-X siloxane, X is one of -(CH2)3OCOCH=CH2, -(CH2)3OCOC(CH3)=CH2, and -CH=CH2.

[0010] Optionally, the glass beads are surface-sprayed glass beads, with a spreading rate of 500-700 g / m². 2 .

[0011] To achieve the above objectives, the present invention also provides a construction process for road marking materials containing a photo-oxidation synergistic protective layer, comprising the following steps:

[0012] The film-forming substance, functional additives, pigments and fillers are added in sequence according to the formula ratio and mixed to obtain the initial mixture;

[0013] The initial mixture and curing agent are thoroughly mixed and then loaded into the synchronous spraying equipment. Glass beads are loaded separately into the synchronous spraying equipment, and finally spraying is performed.

[0014] Optionally, the initial mixture and the curing agent are thoroughly stirred in the dark for 2-3 minutes.

[0015] Optionally, the synchronous spraying equipment is configured such that the paint nozzle is in front and the glass bead nozzle is behind.

[0016] The above-described technical solution of the present invention has at least the following beneficial effects:

[0017] 1. The technical solution of this invention significantly improves the durability of the material through a triple protection system (light-oxygen-water). Even after 600 hours of QUV aging, its performance still meets traffic standards, and its reflective properties still meet the requirements of highways and first-class roads: retroreflective brightness coefficient R... L The minimum value reaches ≥150mcd / m 2 / lx (white) and ≥100mcd / m 2 / lx (yellow).

[0018] 2. Optimized substrate design: By copolymerizing phenyl methacrylate (MAPA) and methyl methacrylate (MMA) in the film-forming material, the balance between the rigidity and flexibility of the material is improved.

[0019] 3. Dynamic cross-linking technology is employed to balance construction efficiency and material performance. The surface layer uses UV curing for rapid curing, while the deeper layers utilize heat-assisted cross-linking technology, significantly enhancing mechanical strength (tensile strength up to 6.5 MPa). This shortens construction time while improving the material's mechanical strength and anti-aging properties. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0021] Example 1

[0022] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: 210g of aliphatic polyurethane acrylate resin, 52.5g of phenyl methacrylate (MAPA), and 87.5g of methyl methacrylate (MMA) as film-forming substances; 150g of titanium dioxide, 450g of fine-mesh heavy calcium carbonate powder, 8g of leveling agent BYK110, 9g of dispersant BYK 410, 2g of stabilizer organic bentonite, 6g of UV-320, 5g of nano-SiO2, 10g of TMS-(CH2)3OCOCH=CH2 siloxane, and 10g of TPO photoinitiator. The glass beads are surface-spread glass beads, with a spreading rate of 500g / m². 2 .

[0023] This invention provides a construction process for a road marking material containing a photo-oxidation synergistic protective layer, comprising the following steps: adding and mixing film-forming substances, functional additives, pigments and fillers in a specific ratio to obtain a preliminary mixture;

[0024] The initial mixture and curing agent are thoroughly mixed and loaded into the synchronous spraying equipment. The glass beads are loaded separately into the synchronous spraying equipment. The initial mixture and curing agent are thoroughly mixed in the dark for 2-3 minutes. The synchronous spraying equipment is configured with the paint nozzle in front and the glass bead nozzle behind, and the spraying is performed last.

[0025] Example 2

[0026] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: 187.5g of aliphatic polyurethane acrylate resin, 25g of phenyl methacrylate (MAPA), and 37.5g of methyl methacrylate (MMA) as film-forming substances; 150g of titanium dioxide, 550g of fine-mesh heavy calcium carbonate powder, 10g of organobentonite stabilizer, 10g of UV-320, 10g of HALS-940, 10g of nano-SiO2, 5g of TMS-(CH2)3OCOC(CH3)=CH2 siloxane, and 5g of TPO photoinitiator. The glass beads are surface-spread glass beads, with a spreading rate of 700g / m². 2 .

[0027] The construction process in this embodiment is the same as that in Embodiment 1.

[0028] Example 3

[0029] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: 195g of aliphatic polyurethane acrylate resin, 30g of phenyl methacrylate (MAPA), and 75g of methyl methacrylate (MMA) as film-forming substances; 100g of titanium dioxide, 542g of fine-mesh heavy calcium carbonate powder, 1108g of leveling agent BYK, 8g of dispersant BYK 410, 13g of stabilizer organic bentonite, 6g of UV-320, 3g of nano-SiO2, 10g of TMS-CH=CH2 siloxane, and 10g of TPO photoinitiator. The glass beads are surface-sprayed glass beads, with a spreading rate of 500g / m². 2 .

[0030] The construction process in this embodiment is the same as that in Embodiment 1.

[0031] Example 4

[0032] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: film-forming substances are aliphatic polyurethane acrylate resin 195g, MAPA 30g, and MMA 75g; titanium dioxide 100g, fine-mesh heavy calcium carbonate powder 542g, leveling agent BYK 110 8g, dispersant BYK 410 9g, stabilizer organic bentonite 13g, UV-320 6g, nano-SiO2 3g, silicon carbide micro powder 1g, TMS-(CH2)3OCOCH=CH2 siloxane 10g, TPO photoinitiator 10g, and the glass beads are surface-spread glass beads with a spreading rate of 500g / m². 2 .

[0033] The construction process in this embodiment is the same as that in Embodiment 1.

[0034] Example 5

[0035] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: film-forming substances are aliphatic polyurethane acrylate resin 195g, MAPA 30g, and MMA 75g; titanium dioxide 100g, fine-mesh heavy calcium carbonate powder 542g, leveling agent BYK 110 8g, dispersant BYK 410 9g, stabilizer organic bentonite 13g, UV-320 6g, HALS-940 6g, nano-SiO2 3g, silicon carbide micro powder 1g, TMS-(CH2)3OCOCH=CH2 siloxane 10g, TPO photoinitiator 10g, and the glass beads are surface-spread glass beads with a spreading rate of 500g / m². 2 .

[0036] The construction process in this embodiment is the same as that in Embodiment 1.

[0037] Comparative Example 1

[0038] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: 195g of aliphatic polyurethane acrylate resin, 30g of phenyl methacrylate (MAPA), and 75g of methyl methacrylate (MMA) as film-forming substances; 100g of titanium dioxide, 542g of fine-mesh heavy calcium carbonate powder, 8g of leveling agent BYK 110, 8g of dispersant BYK 410, 13g of stabilizer organic bentonite, 6g of UV-320, 3g of nano-SiO2, and 10g of TMS-CH=CH2 siloxane. The glass beads are surface-spread glass beads, with a spreading rate of 500g / m². 2 The difference from Example 3 is that only one curing agent is used, and no photoinitiator is used.

[0039] The only difference between the construction process in this comparative example and that in Example 3 is the use of a single curing agent.

[0040] Comparative Example 2

[0041] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: 300g of aliphatic polyurethane acrylate resin as the film-forming substance; 100g of titanium dioxide; 542g of fine-mesh heavy calcium carbonate powder; 8g of leveling agent BYK 110; 8g of dispersant BYK 410; 13g of stabilizer organic bentonite; 6g of UV-320; 10g of TMS-CH=CH2 siloxane; 10g of TPO photoinitiator; and the glass beads are surface-sprayed glass beads, with a spreading rate of 500g / m². 2 The difference from Example 3 is that only aliphatic polyurethane acrylate resin is used as the film-forming material.

[0042] The construction process for this comparative example is the same as that for Example 3.

[0043] Comparative Example 3

[0044] This embodiment provides a road marking material containing a photo-oxidation synergistic protective layer, comprising paint and glass beads. The paint comprises the following components by weight: 300g of aliphatic polyurethane acrylate resin as the film-forming substance; 100g of titanium dioxide; 542g of fine-mesh heavy calcium carbonate powder; 8g of leveling agent BYK 110; 8g of dispersant BYK 410; 13g of stabilizer organic bentonite; 6g of UV-320; 3g of nano-SiO2; 10g of TMS-CH=CH2 siloxane; 10g of TPO photoinitiator; and the glass beads are surface-sprayed glass beads, with a spreading rate of 500g / m². 2 The difference from Example 3 is that only aliphatic polyurethane acrylate resin is used as the film-forming material.

[0045] The construction process for this comparative example is the same as that for Example 3.

[0046] The road marking materials prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to performance tests, and the test results are shown in Table 1.

[0047] The water resistance, artificially accelerated weathering resistance, non-stick drying time, and abrasion resistance were tested according to the test methods for two-component coatings in JT / T 280-2022 "Road Marking Coatings"; the test results were in accordance with the performance requirements of two-component coatings, namely, qualified water resistance, qualified artificially accelerated weathering resistance, non-stick drying time ≤60min, and abrasion resistance ≤40mg.

[0048] Tensile strength was tested using a tensile testing machine, referring to the dumbbell type I standard specimen preparation in GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0049] The surface curing time was tested according to the standard GB / T 1728-2020 "Determination of Drying Time of Paint Film and Putty Film".

[0050] Hardness was tested using a hardness tester.

[0051] Table 1. Performance results of road marking materials prepared in Examples 1-5 and Comparative Examples 1-3

[0052]

[0053] As shown in Table 1, the difference between Comparative Example 1 and Example 3 lies in the curing agent, TMS-CH=CH2 siloxane, and the absence of a photoinitiator. Comparative Example 1 exhibits significantly longer surface curing and non-stick drying times compared to Example 3, with a slight decrease in tensile strength. Comparative Example 2, compared to Example 3, uses only aliphatic polyurethane acrylate resin as the film-forming material and omits a reinforcing agent. Comparative Example 2 shows weaker abrasion resistance than Example 3, and its surface curing and non-stick drying times are also inferior, with a significant decrease in tensile strength. Comparative Example 3, compared to Example 3, uses only aliphatic polyurethane acrylate resin as the film-forming material. Comparative Example 3 exhibits reduced abrasion resistance and hardness, increased surface curing time, and a significant decrease in tensile strength. Example 5, compared to Example 4, adds HALS-940 as a stabilizer. Combined with the remaining components, Example 5 further optimizes abrasion resistance, hardness, surface curing time, and non-stick drying time performance.

[0054] Artificial accelerated weathering was conducted according to GB / T 1865-2009 "Artificial Climate Aging and Artificial Radiation Exposure to Filtered Xenon Arc Radiation for Paints and Varnishes," using a xenon lamp aging chamber with a daylight filter. Cyclic mode A (continuous operation) was employed, with a wetting time of 18 minutes per cycle and a drying time of 102 minutes. The relative humidity during drying was controlled at 40-60%. The xenon lamp aging chamber provided a coupled light-oxygen-water environment. According to JT / T 280-2022 "Road Marking Paints," the standard test time for artificial accelerated weathering of the paint was 600 hours. Based on the test conditions and time, the chromaticity (luminance factor) and photometric properties (retroreflective luminance coefficient) of the material before and after aging were tested.

[0055] Table 2 Performance results of road marking materials prepared in Examples 1-5 and Comparative Examples 1-3

[0056]

[0057] Based on the above results, it can be seen that the retroreflective brightness coefficients of Examples 2 and 5, which contain the light stabilizer HALS 940, are significantly higher than those of other examples and comparative examples after 600 hours of accelerated artificial climate aging, indicating superior aging resistance. Furthermore, the brightness factors of the embodiments of the present invention are all higher than those of the comparative examples after 600 hours of accelerated artificial climate aging. It can be seen that the embodiments of the present invention significantly improve the durability of the material and exhibit good reflective performance.

[0058] In summary, the technical solution provided by this invention enhances the physical properties and durability of road marking materials containing photo-oxygen synergistic protective layers, and, combined with construction techniques, ensures the simultaneous improvement of construction efficiency and material performance.

[0059] The above are preferred embodiments of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A road marking material comprising a photo-oxi synergic protective layer, characterized in that, The coating and glass beads, the coating comprises the following weight percentage of components: 25-35wt% film forming material, 5-15wt% pigment, 45-55wt% filler, 2-4.6wt% functional aid, 1-2wt% curing agent; the film forming material comprises the following weight fraction of ingredients: 60~75wt% aliphatic polyurethane acrylate resin, 15~25wt% methyl methacrylate and 10~15wt% phenyl methacrylate; The functional aid is a combination of leveling agent, dispersant, stabilizer and reinforcing agent, the stabilizer accounts for 0.8~1.9wt% of the mass percentage of the coating, and the reinforcing agent accounts for 0.3~0.5wt% of the mass percentage of the coating; The stabilizer is one or more than two combinations of ultraviolet absorber, hindered amine light stabilizer and organic bentonite; the reinforcing agent is one or two combinations of nano SiO2 and silicon carbide powder; When the reinforcing agent is a combination of nano SiO2 and silicon carbide powder, the mass ratio of nano SiO2 and silicon carbide powder is 3: (1~2); The pigment is titanium white; the filler is heavy calcium powder; the curing agent is TPO photoinitiator and TMS-X siloxane; X in the TMS-X siloxane is one of -(CH2)3OCOCH=CH2, -(CH2)3OCOC(CH3)=CH2, -CH=CH2.

2. The photo-oxygen synergistic shielded pavement marking material of claim 1, wherein, The glass beads are surface glass beads, the spreading amount is 500-700g / m 2 .

3. A process for applying a road marking material comprising a photo-oxi synergic protective layer according to claim 1 or 2, characterized in that, The steps include: The film forming material, functional aid, pigment and filler are added and mixed according to the ratio to obtain the initial mixture; The initial mixture and curing agent are fully stirred and uniformly loaded into the synchronous spraying equipment, and the glass beads are separately loaded into the synchronous spraying equipment, and finally sprayed.

4. The process for applying a road marking material comprising a photo- oxygen synergic protective layer according to claim 3, characterized in that, When the initial mixture and curing agent are fully stirred, light-proof stirring is adopted, and the stirring time is 2~3min.

5. The process for applying the road marking material with the photo-oxygen synergic protective layer according to claim 3, characterized in that, The configuration of the synchronous spraying equipment is that the coating nozzle is in front and the glass bead nozzle is in the rear.

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