Low-carbon marking paint for high-cold region and application

Abstract

The application discloses a low-carbon marking paint for high-cold regions and application, and relates to the technical field of marking paint.The low-carbon marking paint for high-cold regions is composed of the following components in a mass ratio: base resin 45-60 parts, functional filler 25-35 parts, low-carbon plasticizer 2-4 parts, anti-freezing agent 3-5 parts, dispersing agent 1-3 parts, defoaming agent 0.5-1 part and ultraviolet absorber 1-2 parts.The ultraviolet absorber with a specific structure can accurately absorb ultraviolet rays and convert the ultraviolet rays into heat energy for release, thereby blocking the damage of the ultraviolet rays to the base resin of the paint, and remarkably improving the ultraviolet aging resistance of the paint.Through the synergistic effect of the components, the problems of brittle cracking and peeling of the paint film caused by low temperature are effectively avoided, the stability and durability of the paint under harsh weather conditions are enhanced, and the service life of the paint is prolonged.

Description

Technical Field

[0001] This invention relates to the field of road marking paint technology, specifically to a low-carbon road marking paint for use in cold regions and its application. Background Technology

[0002] Road marking paint plays a vital role in modern traffic infrastructure, effectively guiding and regulating vehicles and pedestrians by painting clear lines on the road surface. However, existing road marking paints face numerous challenges and problems when applied in high-altitude and cold regions. The harsh climate conditions in these regions, with their frigid winters and prone to icing and snow accumulation, place extremely high demands on the performance of road marking paints.

[0003] Existing road marking paints are prone to performance degradation in low-temperature environments, such as brittleness, cracking, peeling, and debonding from the road surface. These problems severely impact the service life and safety of road markings. Furthermore, existing paints are prone to accelerated aging under strong ultraviolet radiation, leading to fading and performance failure, failing to meet the needs of long-term use in high-altitude and cold regions. Currently, most road marking paints on the market use traditional high-carbon plasticizers and solvents, which not only increases carbon emissions but also contradicts the current low-carbon and environmentally friendly development concept. At the same time, existing paint formulations are insufficient in adapting to different substrates, making it difficult to meet the needs of various road surface types.

[0004] In summary, existing technologies for road marking paints in cold regions have significant shortcomings in terms of low-temperature performance, UV resistance, and applicability. Therefore, developing a road marking paint that is suitable for cold regions, has stable performance, and is environmentally friendly is of great practical significance. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing road marking paints suitable for cold environments in terms of low-temperature toughness, freeze-thaw resistance, and weather resistance, and to provide a low-carbon road marking paint for cold regions, its preparation method, and its application. This paint exhibits good low-temperature crack resistance, excellent UV resistance, and can meet the requirements for long-term use in harsh environments in cold regions.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A low-carbon road marking paint for high-altitude and cold regions is composed of the following components in the indicated mass ratios: 45-60 parts base resin, 25-35 parts functional filler, 2-4 parts low-carbon plasticizer, 3-5 parts antifreeze agent, 1-3 parts dispersant, 0.5-1 part defoamer, and 1-2 parts ultraviolet absorber.

[0008] The ultraviolet absorber is a compound represented by Formula 1:

[0009] Formula 1: ;

[0010] In Formula 1, R1 is a substituent, and R1 is selected from any one of methyl, phenyl, cyano, nitro, and methoxy.

[0011] Furthermore, the base resin is at least one of epoxy acrylate resin, polyurethane acrylate resin, and polyester acrylate resin.

[0012] Furthermore, the functional filler is composed of quartz sand, heavy calcium carbonate and talc powder, with a mass ratio of 3:2:1, wherein the particle size of the quartz sand is 80-120 mesh and the particle size of the heavy calcium carbonate is 200-300 mesh.

[0013] Furthermore, the low-carbon plasticizer is epoxidized soybean oil.

[0014] Furthermore, the antifreeze is composed of ethylene glycol and glycerol, with a mass ratio of 1:(1-2).

[0015] Furthermore, the dispersant is at least one of sodium polyacrylate or sodium lignosulfonate.

[0016] Furthermore, the defoamer is at least one of tributyl phosphate, methyl silicone oil, BYK-021, and BYK-024.

[0017] Furthermore, the ultraviolet absorber is any one of the compounds with the following structures:

[0018] ;

[0019] ;

[0020] .

[0021] A method for preparing a low-carbon road marking paint for high-altitude and cold regions includes the following steps:

[0022] a. Add the base resin, low-carbon plasticizer, and antifreeze to a mixing tank and stir at 600-800 r / min for 15-20 min at 60-80℃ to obtain a premixed solution;

[0023] b. Add the functional filler, dispersant, and ultraviolet absorber to the premixed liquid, heat to 80-90℃, and stir at high speed for 30-40 minutes to obtain a mixture;

[0024] c. Cool the mixture to 60-70℃, add the defoamer, stir at low speed for 20-30 minutes, cool to room temperature and filter to obtain a low-carbon road marking paint for high-altitude and cold regions.

[0025] Furthermore, the high-speed stirring speed in step b is 1000-1200 r / min.

[0026] Furthermore, in step c, the low-speed stirring speed is 300-500 r / min, and the filtration is carried out using a 200-300 mesh filter.

[0027] A low-carbon road marking paint for high-altitude and cold regions, the paint being suitable for cement concrete pavement or asphalt pavement in high-altitude and cold regions.

[0028] The core mechanism of the UV absorber in this road marking paint is to block the aging and damage of the paint through three steps: selective absorption, energy conversion, and structural stabilization. Selectively absorbing UV light, the molecule contains functional groups such as hydroxyl groups and nitrogen heterocycles, allowing it to precisely absorb UV-B and UV-A rays from sunlight. This prevents direct UV radiation from irradiating the base resin in the paint, thus preventing the resin molecular chains from breaking due to UV energy. After absorbing UV light, the molecule converts high-energy light energy into low-energy heat energy, which is slowly released into the environment through intramolecular vibration and rotation, rather than being transferred to other components of the paint as light energy. This cuts off the energy transfer chain at its source, preventing the paint from fading, cracking, and delamination. Furthermore, the conjugated system in the molecule can disperse the absorbed energy, reducing its own decomposition. Simultaneously, its structure has good compatibility with the paint base and functional fillers, allowing it to remain stably dispersed in the paint for a long time, continuously exerting its UV absorption function. This makes it suitable for the harsh environments of high-altitude and cold regions with both low temperatures and strong UV radiation, extending the service life of the road marking paint.

[0029] This invention comprehensively addresses the problems of low-temperature brittleness, poor freeze-thaw resistance, and insufficient weather resistance encountered in high-altitude and cold environments through the synergistic effect of its components. The base resin, as the coating matrix, provides basic adhesion and structural framework, anchoring the action sites of other components. It works synergistically with a low-carbon plasticizer, which can insert into the resin molecular chains, lowering the resin's glass transition temperature, improving the coating's low-temperature flexibility, and preventing low-temperature cracking. Simultaneously, the low-carbon properties of the plasticizer align with environmental protection requirements. Functional fillers and the base resin form a reinforcing system: large-particle-size quartz sand improves the coating's wear resistance, while small-particle-size heavy calcium carbonate fills the resin gaps, reducing shrinkage. Together with a dispersant, the dispersant ensures uniform dispersion of the fillers, preventing agglomeration and allowing the reinforcing and filling effects to be fully realized, avoiding localized stress concentration that could lead to cracking. Antifreeze agents, in synergy with the plasticizer and resin, lower the freezing point inside the coating, inhibiting the damage to the coating structure caused by the expansion of water freezing at low temperatures, improving freeze-thaw resistance, and preventing the coating from debonding from the road surface. Defoamers eliminate air bubbles during preparation, preventing structural defects caused by bubble rupture, and, in conjunction with the dispersant, ensure coating density and strengthen adhesion.

[0030] A specially structured UV absorber can capture strong ultraviolet radiation in high-altitude and cold regions, preventing it from causing degradation of the resin molecular chain. It works synergistically with the base resin to delay coating aging and fading, ensuring long-term weather resistance. The components complement each other, working together to improve low-temperature toughness, freeze-thaw resistance, abrasion resistance, and weather resistance, meeting the needs of use in high-altitude and cold environments.

[0031] Compared with the prior art, the beneficial effects of the present invention are:

[0032] 1. Significantly improved low-temperature performance: Through the synergistic effect of antifreeze and low-carbon plasticizer, the low-temperature crack resistance of the coating in cold environments is significantly improved, effectively avoiding problems such as coating brittleness and peeling caused by low temperature, and enhancing the stability and durability of the coating under harsh climatic conditions.

[0033] 2. Enhanced UV resistance: UV absorbers with specific structures can accurately absorb UV rays and convert them into heat energy, blocking the destructive effect of UV rays on the coating base resin. This significantly improves the coating's resistance to UV aging, reduces fading and cracking caused by UV radiation, and extends the coating's service life. Attached Figure Description

[0034] Figure 1 This is the NMR spectrum of the ultraviolet absorber 1 described in this invention. Detailed Implementation

[0035] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Preparation Example 1:

[0037] Preparation of UV absorber 1:

[0038] ;

[0039] CAS number for raw material 1: 2440-22-4;

[0040] CAS number for raw material 2: 200290-24-0;

[0041] Under a nitrogen atmosphere, 10.00 g of starter 1, 11.55 g of starter 2, 23.65 g of potassium phosphate trihydrate, 0.42 g of CuI, 0.05 g of pyridine-2-carboxylic acid, and 150 mL of DMSO were added to the reaction system. The reaction mixture was heated at 85 °C for 16 h. After cooling, the reaction mixture was extracted with ammonia solution and methyl tert-butyl ether. The organic phase was washed five times with water, then twice with saturated NaCl aqueous solution. Finally, the combined organic phases were dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography using a mixed solvent of n-heptane and ethyl acetate as the eluent. The mixture was then evaporated to dryness to obtain 13.68 g of starter 3. The mass spectrometry (MS) of starter 3 [M+H] was performed. + :405.

[0042] ;

[0043] CAS number for raw material 4: 183106-15-2;

[0044] Under a nitrogen atmosphere, 13.68 g of starting material 3, 10.39 g of starting material 4, 6.50 g of sodium tert-butoxide, 0.31 g of tris(dibenzylacetone)dipalladium, 0.34 g of tri-tert-butylphosphine, and 200 ml of toluene solution were added to the reaction system. The mixture was stirred thoroughly, heated to 120 °C, and refluxed for 12 h. After the reaction was complete, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth. The filtrate was cooled to room temperature, washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator. The solution was then evaporated to dryness, subjected to column chromatography, and eluted with a mixture of petroleum ether and ethyl acetate. The solution was evaporated to dryness again to obtain 15.12 g of ultraviolet absorber 1. Mass spectrometry (MS) [M+H] of ultraviolet absorber 1 was performed. + :631, NMR of UV absorber 1 is shown in Figure 1 .

[0045] Preparation Examples 2-5:

[0046] In Preparation Examples 2-5, UV absorber 2-UV absorber 5 were prepared sequentially, following the preparation method of Preparation Example 1, except that raw material 2 was replaced, and the rest remained the same as in Preparation Example 1. For details, please refer to Table 1.

[0047] Table 1

[0048]

[0049]

[0050] Example 1:

[0051] Preparation of a low-carbon road marking paint for high-altitude and cold regions:

[0052] 1. Raw material components:

[0053] The base resin, 53 parts, is epoxy acrylic resin with a viscosity of 25,000-35,000 (cps / 25℃), purchased from Nanxiong Ketian Chemical Co., Ltd.

[0054] The functional filler is 30 parts, which is composed of quartz sand (purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.), heavy calcium carbonate (purchased from Jinan Shengfeng Industry and Trade Co., Ltd.) and talc powder (purchased from Shandong Xiya Chemical Co., Ltd.) in a mass ratio of 3:2:1, wherein the particle size of quartz sand is 100 mesh and the particle size of heavy calcium carbonate is 250 mesh.

[0055] Three parts of low-carbon plasticizer, which is epoxidized soybean oil, were purchased from Nantong Herun Biotechnology Co., Ltd.

[0056] The antifreeze agent consists of 4 parts by weight of ethylene glycol (purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd.) and glycerol (purchased from Shandong Xintu Chemical Co., Ltd.).

[0057] Two parts of dispersant, sodium polyacrylate, were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0058] 0.8 parts of defoamer, which is tributyl phosphate, purchased from Wuxi Donghu Chemical Plant;

[0059] 1.5 parts of ultraviolet absorber, which is ultraviolet absorber 1.

[0060] 2. Preparation method:

[0061] a. Add 53 parts of base resin, 3 parts of low-carbon plasticizer, and 4 parts of antifreeze to a mixing tank, and stir at 700 r / min for 17 min at 70℃ to obtain a uniform premix.

[0062] b. Add 30 parts of functional filler, 2 parts of dispersant and 1.5 parts of ultraviolet absorber to the premix, heat to 85°C, and stir at high speed of 1100 r / min for 35 min to fully mix the components and obtain the mixture.

[0063] c. Cool the mixture to 65°C, add 0.8 parts of defoamer, stir at a low speed of 400 r / min for 25 min, then cool to room temperature, and finally filter through a 250 mesh filter to obtain a low-carbon road marking paint for high-altitude and cold regions.

[0064] Examples 2-5:

[0065] The preparation of a low-carbon road marking paint for high-altitude and cold regions is carried out by referring to the preparation method of Example 1, except that the ultraviolet absorber 1 is replaced with ultraviolet absorber 2-ultraviolet absorber 5 in sequence, and the rest is the same as in Example 1.

[0066] Comparative Example 1:

[0067] The preparation of a low-carbon road marking paint for high-altitude and cold regions is carried out by referring to the preparation method of Example 1, except that the ultraviolet absorber 1 is replaced with ultraviolet absorber UV-0 (CAS: 131-56-6), and the rest is the same as in Example 1.

[0068] Comparative Example 2:

[0069] The preparation of a low-carbon road marking paint for high-altitude and cold regions is carried out by referring to the preparation method of Example 1, except that the ultraviolet absorber 1 is replaced with ultraviolet absorber UV-234 (CAS: 70321-86-7), and the rest is the same as in Example 1.

[0070] Comparative Example 3:

[0071] The preparation of a low-carbon road marking paint for high-altitude and cold regions is the same as in Example 1, except that the ultraviolet absorber is not added.

[0072] Comparative Example 4:

[0073] The preparation of a low-carbon road marking paint for high-altitude and cold regions is the same as in Example 1, except that no functional filler is added.

[0074] Comparative Example 5:

[0075] The preparation of a low-carbon road marking paint for high-altitude and cold regions is the same as in Example 1, except that the antifreeze agent is not added.

[0076] Performance testing:

[0077] Test sample preparation: A substrate matching the actual application was used, namely a cement concrete slab (150mm×70mm×50mm). The substrate surface was sanded smooth, free of oil and impurities, and allowed to stand for 24 hours in a 25℃ environment beforehand. The coating was evenly applied to the substrate surface using a scraper, controlling the dry film thickness to 1.2mm. It was then cured for 7 days in a standard environment of 25℃ and 50% relative humidity to ensure complete curing of the coating.

[0078] 1. Low-temperature crack resistance test: Referring to GB / T 9265-2009 "Determination of freeze-thaw cycle resistance of architectural coatings", take 3 cured samples and place them in a low-temperature environment chamber. Set the temperature to -30℃ and keep it at a constant temperature for 24 hours. After taking out the samples, let them stand in an environment of 25℃ for 30 minutes. Then fix both ends of the sample (span 100mm) and apply vertical pressure in the middle (loading speed 5mm / min) until the bending angle of the sample reaches 15°. Observe whether cracks appear on the surface. Repeat the above test 9 times (10 cycles in total). After each cycle, wait 1 hour (to allow the sample to return to room temperature) before the next cycle.

[0079] Result determination: After 10 cycles, the coating is considered qualified if there is no cracking, peeling, or obvious deformation. See Table 2 for the results.

[0080] 2. UV resistance aging test: Referring to GB / T 1865-2009 "Artificial weathering and artificial radiation exposure of paints and varnishes", three cured samples were placed in a xenon lamp aging test chamber with the following parameters set: UVB-313 lamp tube, irradiance 0.71W / (m²). 2 •nm), temperature 60℃, relative humidity 75%, cycle period (8h irradiation + 4h darkness), total test duration 3000h;

[0081] After completion, visually inspect the surface of the markings for signs of fading, peeling, or cracking.

[0082] The CIE LAB color difference value (ΔE) of the sample before and after aging was tested using a colorimeter. The smaller the ΔE, the better the fading resistance. The results are shown in Table 2.

[0083] 3. Adhesion Test: Referring to GB / T 9286-1998 "Paints and Varnishes Cross-cut Test", a cross-cut tester was used to cut a grid on the coating surface with a grid spacing of 1 mm. The grid depth penetrated the coating to the substrate surface, forming 100 1 mm × 1 mm squares. Adhesion tape (viscosity 36 N / 25 mm, conforming to GB / T 2792) was applied tightly to the square area. The tape was pressed with a finger to ensure no air bubbles, and then the tape was quickly peeled off in a 180° direction (peeling speed ≥ 300 mm / min). The test was repeated 3 times (each test area did not overlap). The grades were determined according to GB / T 9286 (Grade 0: no squares peeled off; Grade 1: ≤5% squares peeled off; Grade 2: 5%-15% squares peeled off). The results are shown in Table 2.

[0084] Table 2

[0085]

[0086] The data in Table 2 show that the coatings in the example series exhibit excellent stability in performance indicators such as low-temperature crack resistance, UV aging resistance, and adhesion. In contrast, the comparative coatings showed varying degrees of performance degradation after the absence of key components or the substitution of components. Specifically, the coatings in the examples showed no significant cracking, peeling, or deformation after low-temperature and freeze-thaw cycles, demonstrating good low-temperature toughness. Regarding UV aging resistance, the coatings in the examples showed no significant fading, peeling, or cracking, with a small color difference value ΔE, indicating good weather resistance. Adhesion test results also showed a tight bond between the coatings in the examples and the substrate. In contrast, the comparative coatings showed a significant performance decline when lacking key components such as UV absorbers, functional fillers, or antifreeze agents, exhibiting problems such as fading, slight peeling, and cracking, while also showing a lower adhesion rating. This indicates that the rational combination of components in the coatings of this invention plays a crucial role in improving overall performance, especially in the complex environmental conditions of high-altitude and cold regions, meeting the high standards required for long-term use.

[0087] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A low-carbon road marking paint for use in high-altitude and cold regions, characterized in that, It is composed of the following components in the indicated mass ratios: 45-60 parts base resin, 25-35 parts functional filler, 2-4 parts low-carbon plasticizer, 3-5 parts antifreeze agent, 1-3 parts dispersant, 0.5-1 part defoamer, and 1-2 parts ultraviolet absorber. The ultraviolet absorber is a compound represented by Formula 1: Formula 1: ; In Formula 1, R1 is a substituent, and R1 is selected from any one of methyl, phenyl, cyano, nitro, and methoxy. The functional filler is composed of quartz sand, heavy calcium carbonate and talc powder, with a mass ratio of 3:2:1, wherein the particle size of the quartz sand is 80-120 mesh and the particle size of the heavy calcium carbonate is 200-300 mesh. The antifreeze is composed of ethylene glycol and glycerol, with a mass ratio of 1:(1-2).

2. The low-carbon road marking paint for high-altitude and cold regions according to claim 1, characterized in that, The base resin is at least one of epoxy acrylate resin, polyurethane acrylate resin, and polyester acrylate resin.

3. The low-carbon road marking paint for high-altitude and cold regions according to claim 1, characterized in that, The low-carbon plasticizer is epoxidized soybean oil.

4. The low-carbon road marking paint for high-altitude and cold regions according to claim 1, characterized in that, The dispersant is at least one of sodium polyacrylate or sodium lignosulfonate; the defoamer is at least one of tributyl phosphate, methyl silicone oil, BYK-021, and BYK-024.

5. A method for preparing a low-carbon road marking paint for high-altitude and cold regions as described in any one of claims 1-4, characterized in that, Includes the following steps: a. Add the base resin, low-carbon plasticizer, and antifreeze to a mixing tank and stir at 600-800 r / min for 15-20 min at 60-80℃ to obtain a premixed solution; b. Add the functional filler, dispersant, and ultraviolet absorber to the premixed liquid, heat to 80-90℃, and stir at high speed for 30-40 minutes to obtain a mixture; c. Cool the mixture to 60-70℃, add the defoamer, stir at low speed for 20-30 minutes, cool to room temperature and filter to obtain a low-carbon road marking paint for high-altitude and cold regions.

6. The method for preparing a low-carbon road marking paint for high-altitude and cold regions according to claim 5, characterized in that, In step b, the high-speed stirring speed is 1000-1200 r / min; in step c, the low-speed stirring speed is 300-500 r / min, and filtration is carried out using a 200-300 mesh filter.

7. A low-carbon road marking paint for high-altitude and cold regions as described in any one of claims 1-4, characterized in that, The coating is suitable for cement concrete or asphalt pavements in cold regions.

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