Durable high-brightness marking paint and preparation method thereof

Abstract

The invention relates to the field of road marking coatings, in particular to a durable high-brightness marking coating and a preparation method thereof, which are used for solving the problems that the existing road marking coating is poor in durability, the color fading and damage of a marking are easily caused, the light reflecting performance is reduced, and the driving safety is further influenced. The durable high-brightness marking coating takes the high-performance durable emulsion as a film forming substance, endows a coating film with good wear resistance and weather resistance, enables marking lines not to be easily damaged in a long-term use process and can keep the definition and integrity of the marking lines for a long time, and the modified glass microspheres are added into the coating film, so that the coating film has excellent light reflection performance and is not easy to damage. The modified glass microspheres are easily and uniformly dispersed in the coating, so that the road marking can be clearly identified even at night or in a weak light environment, the visibility of the marking is remarkably improved, and the driving safety is improved; in addition, the preparation method is simple in process and easy to realize industrial production.

Description

Technical Field

[0001] The present invention relates to the field of road marking coatings, and particularly to a durable and high-brightness marking coating and a preparation method thereof. Background Art

[0002] With the continuous increase in traffic flow and the improvement of vehicle driving speed, the performance requirements for road marking coatings are also getting higher and higher. Road marking coatings are mainly applied to concrete or asphalt roads and play a crucial role in road traffic. They can guide vehicle driving, standardize traffic order, and ensure traffic safety.

[0003] Currently, the road marking coatings on the market mainly consist of reflective glass microspheres, road surface adhesive resins, and additives. As the key reflective material in the marking coating, the performance of reflective glass microspheres directly affects the reflective effect of the marking. However, the bonding force between traditional reflective glass microspheres and road surface adhesive resins is not strong, resulting in easy shedding during the coating process, which limits the service life and reflective performance of the marking coating. Moreover, during long-term use, the road surface adhesive resin is easily affected by factors such as vehicle rolling, rain washing, and ultraviolet radiation, leading to marking fading, wear, and a decline in reflective performance, which affects driving safety.

[0004] Therefore, developing a durable and high-brightness marking coating and a preparation method thereof has important practical significance for improving the durability of road marking coatings and maintaining the reflective effect for a long time. Summary of the Invention

[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide a durable and high-brightness marking coating and a preparation method thereof, which solves the problems that the existing road marking coatings have poor durability, are prone to marking fading, damage, and a decline in reflective performance, thereby affecting driving safety.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A durable and high-brightness marking coating, comprising the following components in parts by weight:

[0008] 25 - 30 parts of high-performance durable emulsion, 5 - 13 parts of modified glass microspheres, 1.1 - 1.5 parts of sodium dodecyl sulfate, 0.5 - 0.7 parts of anti-settling thickening thixotropic agent, 0.2 - 0.6 parts of defoaming agent, 0.2 - 0.6 parts of leveling agent, and 0.1 - 0.3 parts of thickening agent;

[0009] Among them, the high-performance durable emulsion is prepared by the following steps:

[0010] Step a1: Paraformaldehyde, potassium tert-butoxide, and tert-butanol are added to a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Nitrogen protection is introduced. The mixture is stirred and reacted for 30 - 35 min at a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then, 2,6-di-tert-butylphenol is added and the mixture is continuously stirred and reacted for 4 - 5 h. After the reaction ends, the reaction product is poured into distilled water, and then the solvent is removed by rotary evaporation. Then, it is recrystallized with n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0011] Step a2: The hydroxymethyl hindered phenol intermediate, triethylamine, and dichloromethane are added to a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel. The mixture is stirred and reacted for 10 - 15 min at a temperature of -5 - 0 °C and a stirring rate of 200 - 300 r / min. Then, an acryloyl chloride solution is added dropwise while stirring, controlling the dropping rate at 1 - 2 drops / s. After the dropping is completed, the temperature is raised to 25 - 30 °C and the mixture is continuously stirred and reacted for 7 - 8 h. After the reaction ends, the reaction product is vacuum filtered. The filtrate is washed 3 - 5 times successively with distilled water, hydrochloric acid solution, and sodium bicarbonate solution, then dried with anhydrous magnesium sulfate, and then vacuum filtered. The solvent in the filtrate is removed by rotary evaporation, and then it is recrystallized with absolute ethanol to obtain a hindered phenol polymer monomer;

[0012] Step a3: Methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, the hindered phenol polymer monomer, a composite emulsifier, sodium bicarbonate, and deionized water are added to a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel. Nitrogen protection is introduced. The mixture is stirred and reacted for 20 - 30 min at a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then, the temperature is raised to 85 - 90 °C and an ammonium persulfate solution is added dropwise while stirring, controlling the dropping rate at 1 - 2 drops / s. After the dropping is completed, the mixture is continuously stirred and reacted for 4 - 5 h. After the reaction ends, the reaction product is cooled to room temperature, and then passed through a 200 - 300 mesh sieve to obtain a high-performance durable emulsion.

[0013] As a further scheme of the present invention: The dosage ratio of the paraformaldehyde, potassium tert-butoxide, tert-butanol, and 2,6-di-tert-butylphenol in step a1 is 2.5 - 3.1 g: 0.13 - 0.17 g: 40 - 50 mL: 30 mmol.

[0014] As a further scheme of the present invention: The dosage ratio of the hydroxymethyl hindered phenol intermediate, triethylamine, dichloromethane, and acryloyl chloride solution in step a2 is 10 mmol: 13 - 15 mmol: 40 - 50 mL: 10 mL.

[0015] As a further solution of the present invention: the acryloyl chloride solution in step a2 is a solution formed by dissolving acryloyl chloride at 11 - 12 mmol: 10 mL in dichloromethane; the molar concentrations of the hydrochloric acid solution and the sodium bicarbonate solution are 1 mol / L.

[0016] As a further solution of the present invention: the dosage ratio of methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate, deionized water and ammonium persulfate solution in step a3 is 15 - 20 g: 15 - 20 g: 2.3 - 2.9 g: 5.2 - 7.6 g: 3.6 - 8.2 g: 1.5 - 4.5 g: 1.3 - 2.7 g: 0.3 - 0.5 g: 50 - 55 mL: 10 - 15 mL.

[0017] As a further solution of the present invention: the mass fraction of the ammonium persulfate solution in step a3 is 2.5%; the composite emulsifier is a mixture of OP - 10 emulsifier and AEO - 7 emulsifier in a mass ratio of 2:1.

[0018] As a further solution of the present invention: the modified glass microspheres are prepared by the following steps:

[0019] Step b1: Add glass microspheres and deionized water into a beaker, stir and mix for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, then let it stand for 2 - 3 h, collect the upper - layer glass microspheres and place them in a vacuum drying oven, and dry them for 2 - 3 h under the condition of a temperature of 90 - 100 °C to obtain flotation glass microspheres;

[0020] Step b2: Add the flotation glass microspheres, sodium hydroxide and deionized water into a three - necked flask equipped with a stirrer and a thermometer, stir and react for 5 - 10 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, then raise the temperature to 45 - 50 °C and continue to stir and react for 4 - 5 h. After the reaction is completed, cool the reaction product to room temperature, then carry out vacuum filtration, wash the filter cake with deionized water and absolute ethanol 3 - 5 times in sequence, and then place it in a vacuum drying oven and dry it for 3 - 4 h under the condition of a temperature of 90 - 100 °C to obtain pretreated glass microspheres;

[0021] Step b3: Add γ-mercaptopropyltriethoxysilane and ethanol solution into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 10 - 15 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then add the pretreated glass microspheres and continue to stir and react for 4 - 5 h under the condition of heating to 65 - 70 °C. After the reaction is completed, cool the reaction product to room temperature, then perform vacuum filtration. Wash the filter cake with deionized water and absolute ethanol 3 - 5 times successively, and then place it in a vacuum drying oven and dry it for 2 - 3 h under the condition of a temperature of 70 - 75 °C to obtain modified glass microspheres.

[0022] As a further scheme of the present invention: The dosage ratio of the glass microspheres to deionized water in step b1 is 20 g: 100 - 120 mL.

[0023] As a further scheme of the present invention: The glass microspheres in step b1 are 3M hollow glass microspheres S28HS.

[0024] As a further scheme of the present invention: The dosage ratio of the flotation glass microspheres, sodium hydroxide and deionized water in step b2 is 10 g: 1.2 - 1.5 g: 100 - 110 mL.

[0025] As a further scheme of the present invention: The dosage ratio of the γ-mercaptopropyltriethoxysilane, ethanol solution and pretreated glass microspheres in step b3 is 0.5 - 3.9 g: 100 - 120 mL: 10 g.

[0026] As a further scheme of the present invention: The volume fraction of the ethanol solution in step b3 is 85 - 90%.

[0027] As a further scheme of the present invention: A preparation method of a durable high-brightness marking paint includes the following steps:

[0028] Step 1: Weigh 25 - 30 parts of high-performance durable emulsion, 5 - 13 parts of modified glass microspheres, 1.1 - 1.5 parts of sodium dodecyl sulfate, 0.5 - 0.7 parts of anti-settling thickening thixotropic agent, 0.2 - 0.6 parts of defoaming agent, 0.2 - 0.6 parts of leveling agent and 0.1 - 0.3 parts of thickening agent by weight, and set aside;

[0029] Step 2: Add the high-performance durable emulsion, modified glass microspheres and sodium dodecyl sulfate into a stirring kettle, stir and react for 10 - 15 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then continue to stir and react for 3 - 5 h under the condition of heating to 85 - 90 °C. After the reaction is completed, cool the reaction product to room temperature to obtain a durable high-brightness emulsion;

[0030] Step 3: Add the anti-settling, thickening and thixotropic agent, defoamer, leveling agent and thickening agent into the durable high-brightness emulsion, and stir and react for 30 - 50 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min to obtain the durable high-brightness marking paint.

[0031] As a further scheme of the present invention: The anti-settling, thickening and thixotropic agent is a polyamide wax paste 4310-20X solvent-based paint anti-settling, thickening and thixotropic agent.

[0032] As a further scheme of the present invention: The defoamer is a tego810 water-based defoamer.

[0033] As a further scheme of the present invention: The leveling agent is a water-based leveling agent BYK-333.

[0034] As a further scheme of the present invention: The thickening agent is a DEURHEO WT-105A thickening agent.

[0035] Advantages of the present invention:

[0036] A durable high-brightness marking paint and a preparation method thereof according to the present invention, by adding a high-performance durable emulsion, modified glass microspheres and sodium dodecyl sulfate into a stirring kettle for stirring and reacting, cooling the reaction product after the reaction is completed to obtain a durable high-brightness emulsion, and adding an anti-settling, thickening and thixotropic agent, a defoamer, a leveling agent and a thickening agent into the durable high-brightness emulsion for stirring and reacting to obtain a durable high-brightness marking paint; The durable high-brightness marking paint uses a high-performance durable emulsion as a film-forming substance, endowing the coating film with good abrasion resistance and weather resistance, being able to withstand the repeated rolling and friction of vehicles and the erosion of light, oxygen and corrosive media, so that the marking is not easily damaged during long-term use and can maintain the clarity and integrity of the marking for a long time. Adding modified glass microspheres thereto makes the coating film have excellent reflective performance, and the modified glass microspheres are easily and uniformly dispersed in the paint, so that the marking can clearly identify the road marking even at night or in a weak light environment, significantly improving the visibility of the marking and enhancing driving safety; Moreover, the preparation method has a simple process and is easy to realize industrial production.

[0037] In the process of preparing a durable high-brightness marking paint, a high-performance durable emulsion was first prepared. First, paraformaldehyde and 2,6-di-tert-butylphenol were reacted to introduce a hydroxymethyl group onto the benzene ring of 2,6-di-tert-butylphenol, obtaining a hydroxymethyl hindered phenol intermediate. Then, the hydroxymethyl hindered phenol intermediate and acryloyl chloride were reacted, and the hydroxymethyl group on the hydroxymethyl hindered phenol intermediate reacted with the acyl chloride group on acryloyl chloride to introduce an alkenyl group, obtaining a hindered phenol polymer monomer. Finally, methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, and the hindered phenol polymer monomer were used as polymerization monomers for polymerization to obtain a high-performance durable emulsion. The polymer molecular structure of this high-performance durable emulsion contains a large number of hindered phenol structures, which can endow it with excellent antioxidant properties, prevent the coating film from being oxidized and aged by light and oxygen, and avoid the coating film from affecting the reflective effect of the coating film due to excessive color difference. At the same time, the polymer molecular structure of this high-performance durable emulsion contains a large number of fluorine-containing groups, which endow the coating film with excellent water and corrosion resistance, and improve the lubricity of the coating film, reducing friction loss. Therefore, under the action of the high-performance durable emulsion, the clarity and integrity of the marking can be maintained for a long time, and the durability is greatly improved.

[0038] In the process of preparing a durable high-brightness marking paint, a modified glass microsphere was also prepared. First, the glass microspheres were flotated to screen out impurities, solid and damaged glass microspheres, thereby improving the uniformity and integrity of the glass microspheres, and then improving the reflective effect of the coating film. Then, the glass microspheres were pretreated with sodium hydroxide to introduce a large number of hydroxyl groups on their surfaces, facilitating further modification in the follow-up. Finally, they were modified with γ-mercaptopropyltriethoxysilane. After γ-mercaptopropyltriethoxysilane was hydrolyzed, the silanol was subjected to a condensation grafting reaction with the hydroxyl groups on the surface of the glass microspheres, thereby greatly improving the dispersion performance of the glass microspheres, enabling them to be uniformly dispersed in the coating film, and the introduced mercapto group can undergo a click chemical reaction and then be connected to the polymer molecular structure of the high-performance durable emulsion in the form of a chemical bond, further improving the compatibility effect between the two, and enhancing the interfacial bonding force between the two, improving the mechanical properties of the coating film. Therefore, under the action of the modified glass microspheres, the marking can be endowed with excellent reflective properties, improving the visibility of the marking and enhancing driving safety. Detailed implementation manners

[0039] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0040] Example 1:

[0041] This embodiment is a preparation method of a durable high-brightness marking paint, which includes the following steps:

[0042] Step S1: Add 2.5 g of paraformaldehyde, 0.13 g of potassium tert-butoxide, and 40 mL of tert-butanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min. Then add 30 mmol of 2,6-di-tert-butylphenol and continue to stir and react for 4 h. After the reaction is completed, pour the reaction product into distilled water, then rotate and evaporate to remove the solvent, and then recrystallize with n-hexane to obtain a hydroxymethyl hindered phenol intermediate.

[0043] Step S2: Add 10 mmol of hydroxymethyl hindered phenol intermediate, 13 mmol of triethylamine, and 40 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel. Stir and react for 10 min under the conditions of a temperature of -5 °C and a stirring rate of 200 r / min. Then, while stirring, gradually dropwise add 10 mL of an acryloyl chloride solution formed by dissolving 11 mmol of acryloyl chloride in 10 mL of dichloromethane. Control the dropping rate to be 1 drop / s. After the dropping is completed, continue to stir and react for 7 h under the condition of heating to 25 °C. After the reaction is completed, vacuum filter the reaction product. Wash the filtrate successively with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L three times. Then dry with anhydrous magnesium sulfate, and then vacuum filter. Rotate and evaporate the filtrate to remove the solvent, and then recrystallize with absolute ethanol to obtain a hindered phenol polymer monomer.

[0044] Step S3: Add 15 g of methyl methacrylate, 15 g of butyl acrylate, 2.3 g of ethylene glycol diacrylate, 5.2 g of lauryl methacrylate, 3.6 g of dodecafluoroheptyl methacrylate, 1.5 g of hindered phenol polymer monomer, 1.3 g of OP-10 emulsifier, a composite emulsifier formed by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.3 g of sodium bicarbonate, and 50 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 20 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min. Then, while stirring, gradually dropwise add 10 mL of an ammonium persulfate solution with a mass fraction of 2.5% under the condition of heating to 85 °C. Control the dropping rate to be 1 drop / s. After the dropping is completed, continue to stir and react for 4 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 200-mesh sieve to obtain a high-performance durable emulsion.

[0045] Step S4: Add 20 g of 3M hollow glass microspheres S28HS and 100 mL of deionized water into a beaker, stir and mix for 20 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min, then let it stand for 2 h, collect the upper-layer glass microspheres and place them in a vacuum drying oven, and dry them for 2 h under the condition of a temperature of 90 °C to obtain flotation glass microspheres;

[0046] Step S5: Add 10 g of flotation glass microspheres, 1.2 g of sodium hydroxide and 100 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 5 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min, then raise the temperature to 45 °C and continue to stir and react for 4 h. After the reaction is completed, cool the reaction product to room temperature, then carry out vacuum filtration, wash the filter cake with deionized water and absolute ethanol three times in sequence, and then place it in a vacuum drying oven and dry it for 3 h under the condition of a temperature of 90 °C to obtain pretreated glass microspheres;

[0047] Step S6: Add 0.5 g of γ-mercaptopropyltriethoxysilane and 100 mL of an ethanol solution with a volume fraction of 85% into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 10 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min, then add 10 g of pretreated glass microspheres and raise the temperature to 65 °C and continue to stir and react for 4 h. After the reaction is completed, cool the reaction product to room temperature, then carry out vacuum filtration, wash the filter cake with deionized water and absolute ethanol three times in sequence, and then place it in a vacuum drying oven and dry it for 2 h under the condition of a temperature of 70 °C to obtain modified glass microspheres;

[0048] Step S7: Weigh 25 parts of high-performance durable emulsion, 5 parts of modified glass microspheres, 1.1 parts of sodium dodecyl sulfate, 0.5 part of anti-settling thickening thixotropic agent, 0.2 part of defoaming agent, 0.2 part of leveling agent and 0.1 part of thickening agent according to weight parts for standby; the anti-settling thickening thixotropic agent is polyamide wax paste 4310-20X solvent-based coating anti-settling thickening thixotropic agent; the defoaming agent is tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; the thickening agent is DEURHEO WT-105A thickening agent;

[0049] Step S8: Add the high-performance durable emulsion, modified glass microspheres and sodium dodecyl sulfate into a stirring kettle, stir and react for 10 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min, then raise the temperature to 85 °C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0050] Step S9: Add the anti-settling thickening thixotropic agent, defoamer, leveling agent, and thickening agent into the durable high-brightness emulsion, and stir and react for 30 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min to obtain the durable high-brightness marking paint.

[0051] Example 2:

[0052] This example is a preparation method of a durable high-brightness marking paint, including the following steps:

[0053] Step S1: Add 2.8 g of paraformaldehyde, 0.15 g of potassium tert-butoxide, and 45 mL of tert-butanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, introduce nitrogen protection, stir and react for 32 min under the conditions of a temperature of 28°C and a stirring rate of 250 r / min, then add 30 mmol of 2,6-di-tert-butylphenol and continue to stir and react for 4.5 h. After the reaction is completed, pour the reaction product into distilled water, then rotate and evaporate to remove the solvent, and then recrystallize with n-hexane to obtain the hydroxymethyl hindered phenol intermediate;

[0054] Step S2: Add 10 mmol of the hydroxymethyl hindered phenol intermediate, 14 mmol of triethylamine, and 45 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube, and a constant pressure dropping funnel, stir and react for 12 min under the conditions of a temperature of -3°C and a stirring rate of 250 r / min, then gradually add dropwise 10 mL of an acryloyl chloride solution formed by dissolving 11 mmol of acryloyl chloride in 10 mL of dichloromethane while stirring, control the dropping rate at 1 drop / s, and continue to stir and react for 7.5 h under the condition of heating to 28°C after the dropping is completed. After the reaction is completed, vacuum filter the reaction product, wash the filtrate 4 times successively with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L, then dry with anhydrous magnesium sulfate, then vacuum filter, rotate and evaporate the filtrate to remove the solvent, and then recrystallize with absolute ethanol to obtain the hindered phenol polymer monomer;

[0055] Step S3: Add 18 g of methyl methacrylate, 18 g of butyl acrylate, 2.6 g of ethylene glycol diacrylate, 6.4 g of lauryl methacrylate, 5.9 g of dodecafluoroheptyl methacrylate, 3 g of hindered phenol polymerization monomer, 2 g of OP-10 emulsifier, a composite emulsifier formed by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.4 g of sodium bicarbonate, and 52 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection and stir and react for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, while stirring, gradually add 12 mL of an ammonium persulfate solution with a mass fraction of 2.5% dropwise under the condition of raising the temperature to 88 °C, control the dropping rate to be 1 drop / s. After the dropping is completed, continue to stir and react for 4.5 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 250-mesh sieve to obtain a high-performance durable emulsion;

[0056] Step S4: Add 20 g of 3M hollow glass microspheres S28HS and 110 mL of deionized water into a beaker, stir and mix for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, let it stand for 2.5 h, collect the upper-layer glass microspheres and place them in a vacuum drying oven, and dry them for 2.5 h under the condition of a temperature of 95 °C to obtain flotation glass microspheres;

[0057] Step S5: Add 10 g of flotation glass microspheres, 1.4 g of sodium hydroxide, and 105 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 8 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 4.5 h under the condition of raising the temperature to 48 °C. After the reaction is completed, cool the reaction product to room temperature, and then perform vacuum filtration. Wash the filter cake with deionized water and absolute ethanol 4 times in sequence, and then place it in a vacuum drying oven and dry it for 3.5 h under the condition of a temperature of 95 °C to obtain pretreated glass microspheres;

[0058] Step S6: Add 2.2 g of γ-mercaptopropyltriethoxysilane and 110 mL of an ethanol solution with a volume fraction of 88% into a three-necked flask equipped with a stirrer and a thermometer, stir and react for 12 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, add 10 g of pretreated glass microspheres and raise the temperature to 68 °C and continue to stir and react for 4.5 h. After the reaction is completed, cool the reaction product to room temperature, and then perform vacuum filtration. Wash the filter cake with deionized water and absolute ethanol 4 times in sequence, and then place it in a vacuum drying oven and dry it for 2.5 h under the condition of a temperature of 72 °C to obtain modified glass microspheres;

[0059] Step S7: Weigh 28 parts by weight of a high-performance durable emulsion, 9 parts of modified glass microspheres, 1.3 parts of sodium dodecyl sulfate, 0.6 part of an anti-settling thickening thixotropic agent, 0.4 part of an anti-foaming agent, 0.4 part of a leveling agent, and 0.2 part of a thickening agent for standby; the anti-settling thickening thixotropic agent is a polyamide wax paste 4310-20X solvent-based paint anti-settling thickening thixotropic agent; the anti-foaming agent is a tego810 water-based anti-foaming agent; the leveling agent is a water-based leveling agent BYK-333; the thickening agent is a DEURHEO WT-105A thickening agent;

[0060] Step S8: Add the high-performance durable emulsion, modified glass microspheres, and sodium dodecyl sulfate into a stirring kettle, stir and react for 12 min under the conditions of a temperature of 28°C and a stirring rate of 250 r / min, then continue to stir and react for 4 h under the condition of heating to 88°C, and after the reaction is completed, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0061] Step S9: Add the anti-settling thickening thixotropic agent, anti-foaming agent, leveling agent, and thickening agent into the durable and high-brightness emulsion, stir and react for 40 min under the conditions of a temperature of 28°C and a stirring rate of 250 r / min to obtain a durable and high-brightness marking paint.

[0062] Example 3:

[0063] This example is a preparation method of a durable and high-brightness marking paint, including the following steps:

[0064] Step S1: Add 3.1 g of paraformaldehyde, 0.17 g of potassium tert-butoxide, and 50 mL of tert-butanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, introduce nitrogen protection, stir and react for 35 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min, then add 30 mmol of 2,6-di-tert-butylphenol and continue to stir and react for 5 h. After the reaction is completed, pour the reaction product into distilled water, then rotate and evaporate to remove the solvent, and then recrystallize with n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0065] Step S2: Add 10 mmol of hydroxymethyl hindered phenol intermediate, 15 mmol of triethylamine, and 50 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Stir and react for 15 min at a temperature of 0 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise an acryloyl chloride solution formed by dissolving 12 mmol of acryloyl chloride in 10 mL of dichloromethane, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react at 30 °C for 8 h. After the reaction is completed, vacuum filter the reaction product. Wash the filtrate successively with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L for 5 times. Then dry it with anhydrous magnesium sulfate, and then vacuum filter. Rotate and evaporate the filtrate to remove the solvent, and then recrystallize with absolute ethanol to obtain the hindered phenol polymer monomer;

[0066] Step S3: Add 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluoroheptyl methacrylate, 4.5 g of the hindered phenol polymer monomer, 2.7 g of OP-10 emulsifier, a composite emulsifier formed by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.5 g of sodium bicarbonate, and 55 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection and stir and react for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise 15 mL of an ammonium persulfate solution with a mass fraction of 2.5% at 90 °C, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 300-mesh sieve to obtain the high-performance durable emulsion;

[0067] Step S4: Add 20 g of 3M hollow glass microspheres S28HS and 120 mL of deionized water into a beaker. Stir and mix at a temperature of 30 °C and a stirring rate of 300 r / min for 30 min. Then let it stand for 3 h. Collect the upper-layer glass microspheres and place them in a vacuum drying oven to dry at 100 °C for 3 h to obtain the flotation glass microspheres;

[0068] Step S5: Add 10 g of flotation glass microspheres, 1.5 g of sodium hydroxide, and 110 mL of deionized water into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 10 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to 50 °C and continue stirring and reacting for 5 h. After the reaction ends, cool the reaction product to room temperature. Then, perform vacuum filtration. Wash the filter cake with deionized water and absolute ethanol 5 times in sequence. Then, place it in a vacuum drying oven and dry it at a temperature of 100 °C for 4 h to obtain pretreated glass microspheres;

[0069] Step S6: Add 3.9 g of γ-mercaptopropyltriethoxysilane and 120 mL of an ethanol solution with a volume fraction of 90% into a three-necked flask equipped with a stirrer and a thermometer. Stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, add 10 g of pretreated glass microspheres and raise the temperature to 70 °C and continue stirring and reacting for 5 h. After the reaction ends, cool the reaction product to room temperature. Then, perform vacuum filtration. Wash the filter cake with deionized water and absolute ethanol 5 times in sequence. Then, place it in a vacuum drying oven and dry it at a temperature of 75 °C for 3 h to obtain modified glass microspheres;

[0070] Step S7: Weigh 30 parts of high-performance durable emulsion, 13 parts of modified glass microspheres, 1.5 parts of sodium dodecyl sulfate, 0.7 part of anti-settling thickening thixotropic agent, 0.6 part of defoaming agent, 0.6 part of leveling agent, and 0.3 part of thickening agent by weight for standby; the anti-settling thickening thixotropic agent is polyamide wax paste 4310-20X solvent-based paint anti-settling thickening thixotropic agent; the defoaming agent is tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; the thickening agent is DEURHEO WT-105A thickening agent;

[0071] Step S8: Add the high-performance durable emulsion, modified glass microspheres, and sodium dodecyl sulfate into a stirring kettle. Stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to 90 °C and continue stirring and reacting for 5 h. After the reaction ends, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0072] Step S9: Add the anti-settling thickening thixotropic agent, defoaming agent, leveling agent, and thickening agent into the durable and high-brightness emulsion. Stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min to obtain a durable and high-brightness marking paint.

[0073] Comparative Example 1:

[0074] This comparative example is a preparation method of a durable and high-brightness marking paint, including the following steps:

[0075] Step S1: Add 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 2.7 g of OP-10 emulsifier, a composite emulsifier prepared by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.5 g of sodium bicarbonate, and 55 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection and stir and react for 30 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min. Then, while stirring, gradually add 15 mL of an ammonium persulfate solution with a mass fraction of 2.5% dropwise at 90°C, control the dropping rate to be 2 drops / s. After the dropping is completed, continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 300-mesh sieve to obtain a high-performance durable emulsion;

[0076] Step S2: Weigh 30 parts of the high-performance durable emulsion, 13 parts of 3M hollow glass microspheres S28HS, 1.5 parts of sodium dodecyl sulfate, 0.7 part of an anti-settling thickening thixotropic agent, 0.6 part of an anti-foaming agent, 0.6 part of a leveling agent, and 0.3 part of a thickening agent by weight and set aside; the anti-settling thickening thixotropic agent is a polyamide wax paste 4310-20X solvent-based paint anti-settling thickening thixotropic agent; the anti-foaming agent is a tego810 water-based anti-foaming agent; the leveling agent is a water-based leveling agent BYK-333; the thickening agent is a DEURHEO WT-105A thickening agent;

[0077] Step S3: Add the high-performance durable emulsion, 3M hollow glass microspheres S28HS, and sodium dodecyl sulfate into a stirring kettle and stir and react for 15 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min. Then, continue to stir and react for 5 h under the condition of heating to 90°C. After the reaction is completed, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0078] Step S4: Add the anti-settling thickening thixotropic agent, the anti-foaming agent, the leveling agent, and the thickening agent into the durable and high-brightness emulsion and stir and react for 50 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min to obtain a durable and high-brightness marking paint.

[0079] Comparative Example 2:

[0080] This comparative example is a preparation method of a durable and high-brightness marking paint, including the following steps:

[0081] Step S1: Add 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluoroheptyl methacrylate, 2.7 g of OP-10 emulsifier, a composite emulsifier prepared by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.5 g of sodium bicarbonate, and 55 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube, and a constant-pressure dropping funnel. Introduce nitrogen for protection, and stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 15 mL of an ammonium persulfate solution with a mass fraction of 2.5% dropwise at 90 °C, control the dropping rate to be 2 drops / s. After the dropping is completed, continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 300-mesh sieve to obtain a high-performance durable emulsion;

[0082] Step S2: Weigh 30 parts of the high-performance durable emulsion, 13 parts of 3M hollow glass microspheres S28HS, 1.5 parts of sodium dodecyl sulfate, 0.7 part of an anti-settling thickening thixotropic agent, 0.6 part of an antifoaming agent, 0.6 part of a leveling agent, and 0.3 part of a thickening agent by weight and set aside; the anti-settling thickening thixotropic agent is a polyamide wax paste 4310-20X solvent-based paint anti-settling thickening thixotropic agent; the antifoaming agent is a tego810 water-based antifoaming agent; the leveling agent is a water-based leveling agent BYK-333; the thickening agent is a DEURHEO WT-105A thickening agent;

[0083] Step S3: Add the high-performance durable emulsion, 3M hollow glass microspheres S28HS, and sodium dodecyl sulfate into a stirring kettle, and stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 5 h under the condition of raising the temperature to 90 °C. After the reaction is completed, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0084] Step S4: Add the anti-settling thickening thixotropic agent, the antifoaming agent, the leveling agent, and the thickening agent into the durable and high-brightness emulsion, and stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min to obtain a durable and high-brightness marking paint.

[0085] Comparative Example 3:

[0086] This comparative example is a preparation method of a durable and high-brightness marking paint, including the following steps:

[0087] Step S1: Add 3.1 g of paraformaldehyde, 0.17 g of potassium tert-butoxide, and 50 mL of tert-butanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 35 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then add 30 mmol of 2,6-di-tert-butylphenol and continue to stir and react for 5 h. After the reaction is completed, pour the reaction product into distilled water, then remove the solvent by rotary evaporation, and then recrystallize with n-hexane to obtain the hydroxymethyl hindered phenol intermediate;

[0088] Step S2: Add 10 mmol of the hydroxymethyl hindered phenol intermediate, 15 mmol of triethylamine, and 50 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel. Stir and react for 15 min at a temperature of 0 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise 10 mL of an acryloyl chloride solution formed by dissolving 12 mmol of acryloyl chloride in 10 mL of dichloromethane, controlling the dropping rate at 2 drops / s. After the addition is completed, continue to stir and react at a temperature of 30 °C for 8 h. After the reaction is completed, vacuum filter the reaction product. Wash the filtrate successively with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L for 5 times, then dry with anhydrous magnesium sulfate, then vacuum filter, remove the solvent from the filtrate by rotary evaporation, and then recrystallize with absolute ethanol to obtain the hindered phenol polymer monomer;

[0089] Step S3: Add 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluorooctyl methacrylate, 4.5 g of the hindered phenol polymer monomer, 2.7 g of OP-10 emulsifier, a composite emulsifier formed by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.5 g of sodium bicarbonate, and 55 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant pressure dropping funnel. Introduce nitrogen for protection. Stir and react for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise 15 mL of an ammonium persulfate solution with a mass fraction of 2.5% at a temperature of 90 °C, controlling the dropping rate at 2 drops / s. After the addition is completed, continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 300-mesh sieve to obtain the high-performance durable emulsion;

[0090] Step S4: Weigh 30 parts of high-performance durable emulsion, 13 parts of 3M hollow glass microspheres S28HS, 1.5 parts of sodium dodecyl sulfate, 0.7 part of anti-settling thickening thixotropic agent, 0.6 part of defoamer, 0.6 part of leveling agent, and 0.3 part of thickening agent for standby; the anti-settling thickening thixotropic agent is polyamide wax paste 4310-20X solvent-based coating anti-settling thickening thixotropic agent; the defoamer is tego810 water-based defoamer; the leveling agent is water-based leveling agent BYK-333; the thickening agent is DEURHEO WT-105A thickening agent;

[0091] Step S5: Add the high-performance durable emulsion, 3M hollow glass microspheres S28HS, and sodium dodecyl sulfate into a stirring kettle, stir and react for 15 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min, then raise the temperature to 90°C and continue to stir and react for 5 h. After the reaction ends, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0092] Step S6: Add the anti-settling thickening thixotropic agent, defoamer, leveling agent, and thickening agent into the durable and high-brightness emulsion, stir and react for 50 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min to obtain a durable and high-brightness marking paint.

[0093] Comparative Example 4:

[0094] This comparative example is a preparation method of a durable and high-brightness marking paint, including the following steps:

[0095] Step S1: Add 3.1 g of paraformaldehyde, 0.17 g of potassium tert-butoxide, and 50 mL of tert-butanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, introduce nitrogen for protection, stir and react for 35 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min, then add 30 mmol of 2,6-di-tert-butylphenol and continue to stir and react for 5 h. After the reaction ends, pour the reaction product into distilled water, then rotate and evaporate to remove the solvent, and then recrystallize with n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0096] Step S2: Add 10 mmol of hydroxymethyl hindered phenol intermediate, 15 mmol of triethylamine, and 50 mL of dichloromethane into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Stir and react for 15 min at a temperature of 0 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise an acryloyl chloride solution formed by dissolving 12 mmol of acryloyl chloride in 10 mL of dichloromethane, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react at a temperature of 30 °C for 8 h. After the reaction is completed, vacuum filter the reaction product. Wash the filtrate successively with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L for 5 times. Then dry it with anhydrous magnesium sulfate, and then vacuum filter. Rotate and evaporate the filtrate to remove the solvent, and then recrystallize with absolute ethanol to obtain the hindered phenol polymer monomer;

[0097] Step S3: Add 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluorooctyl methacrylate, 4.5 g of the hindered phenol polymer monomer, 2.7 g of OP-10 emulsifier, a composite emulsifier formed by mixing AEO-7 emulsifier in a mass ratio of 2:1, 0.5 g of sodium bicarbonate, and 55 mL of deionized water into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a constant-pressure dropping funnel. Introduce nitrogen for protection and stir and react for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise 15 mL of an ammonium persulfate solution with a mass fraction of 2.5% at a temperature of 90 °C, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then pass it through a 300-mesh sieve to obtain a high-performance durable emulsion;

[0098] Step S4: Add 20 g of 3M hollow glass microspheres S28HS and 120 mL of deionized water into a beaker. Stir and mix for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then let it stand for 3 h. Collect the upper-layer glass microspheres and place them in a vacuum drying oven to dry for 3 h at a temperature of 100 °C to obtain flotation glass microspheres;

[0099] Step S5: Weigh 30 parts of high-performance durable emulsion, 13 parts of flotation glass microspheres, 1.5 parts of sodium dodecyl sulfate, 0.7 part of anti-settling thickening thixotropic agent, 0.6 part of defoaming agent, 0.6 part of leveling agent, and 0.3 part of thickening agent for standby; the anti-settling thickening thixotropic agent is polyamide wax paste 4310-20X solvent-based paint anti-settling thickening thixotropic agent; the defoaming agent is tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; the thickening agent is DEURHEO WT-105A thickening agent;

[0100] Step S6: Add the high-performance durable emulsion, flotation glass microspheres, and sodium dodecyl sulfate into a stirring kettle, stir and react for 15 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min, then raise the temperature to 90°C and continue to stir and react for 5 h. After the reaction ends, cool the reaction product to room temperature to obtain a durable and high-brightness emulsion;

[0101] Step S7: Add the anti-settling thickening thixotropic agent, defoaming agent, leveling agent, and thickening agent into the durable and high-brightness emulsion, stir and react for 50 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min to obtain a durable and high-brightness marking paint.

[0102] Spray the durable and high-brightness marking paints of Examples 1-3 and Comparative Examples 1-4 onto the surface of tinplate, cure to form a coating film, and the thickness of the coating film is 50±2 μm. Then test the performance of the coating film, and the test results are shown in the following table:

[0103] Sample Pencil hardness Water resistance (7d) Color difference Example 1 3H No blistering, wrinkling, cracking, or peeling 0.86 Example 2 3H No blistering, wrinkling, cracking, or peeling 0.81 Example 3 3H No blistering, wrinkling, cracking, or peeling 0.77 Comparative Example 1 H There are blistering, wrinkling, and cracking phenomena, but no peeling 3.81 Comparative Example 2 H There are blistering, wrinkling, and cracking phenomena, but no peeling 1.56 Comparative Example 3 2H There is blistering, but no wrinkling, cracking, or peeling 1.29 Comparative Example 4 3H No blistering, wrinkling, cracking, or peeling 1.02

[0104] Among them, the pencil hardness of the test sample is tested according to GB / T 6739-2022; the water resistance (7d) of the test sample is tested according to GB / T 5209-1985; the color difference of the test sample after 1000 h of ultraviolet aging is tested according to GB / T 1865-2009.

[0105] Referring to the data in the above table, according to the comparison between Examples 1-3 and Comparative Examples 1-4, it can be known that the durable and high-brightness marking paint of the present application has excellent water resistance and color difference retention performance.

[0106] In the description of this specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0107] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications, supplements, or use similar methods to substitute for the specific embodiments described, as long as they do not deviate from the invention or exceed the scope defined by this application, they shall fall within the protection scope of the present invention.

Claims

1. A durable high-brightness road marking paint, characterized in that: It comprises the following components in parts by weight: 25-30 parts of high-performance durable emulsion, 5-13 parts of modified glass microspheres, 1.1-1.5 parts of sodium lauryl sulfate, 0.5-0.7 parts of anti-settling thickening thixotropic agent, 0.2-0.6 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 0.1-0.3 parts of thickener; Wherein, the high performance durable emulsion is prepared by the following steps: Step a1: stirring paraformaldehyde, potassium tert-butoxide and tert-butanol for reaction, then adding 2,6-di-tert-butylphenol and continuing stirring for reaction, and after the reaction is completed, pouring the reaction product into distilled water, then rotary evaporating, and then recrystallizing to obtain a hydroxymethyl hindered phenol intermediate; Step a2: stirring a hydroxymethyl hindered phenol intermediate, triethylamine and dichloromethane for reaction, then adding acryloyl chloride solution dropwise while stirring, continuing to stir the reaction after the addition is complete, vacuum filtering the reaction product after the reaction is complete, washing and drying the filtrate, vacuum filtering the filtrate, rotary evaporating the filtrate, and then recrystallizing to obtain a hindered phenol polymerization monomer; Step a3: stirring methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate and deionized water for reaction, then adding ammonium persulfate solution dropwise while stirring, and continuing to stir the reaction after the addition is completed. After the reaction is completed, the reaction product is cooled and then sieved to obtain a high-performance durable emulsion.

2. A durable high-brightness road marking paint according to claim 1, characterized in that: The amount ratio of the paraformaldehyde, potassium tert-butoxide, tert-butanol and 2,6-di-tert-butylphenol in step a1 is 2.5-3.1 g: 0.13-0.17 g: 40-50 mL: 30 mmol.

3. The durable high-brightness road marking paint according to claim 1, characterized in that: The usage ratio of the hydroxymethyl hindered phenol intermediate, triethylamine, dichloromethane and acryloyl chloride solution in step a2 is 10mmol:13-15mmol:40-50mL:10mL; the acryloyl chloride solution is a solution formed by dissolving acryloyl chloride in dichloromethane at a ratio of 11-12mmol:10mL.

4. The durable high-brightness road marking paint according to claim 1, characterized in that: The dosage ratio of the methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate, deionized water and ammonium persulfate solution in step a3 is 15-20g: 15-20g: 2.3-2.9g: 5.2-7.6g: 3.6-8.2g: 1.5-4.5g: 1.3-2.7g: 0.3-0.5g: 50-55mL: 10-15mL; the mass fraction of the ammonium persulfate solution is 2.5%; the composite emulsifier is a mixture of OP-10 emulsifier and AEO-7 emulsifier in a mass ratio of 2:

1.

5. The durable high-brightness road marking paint according to claim 1, characterized in that: The modified glass microspheres are prepared by the following steps: Step b1: stirring and mixing glass microspheres and deionized water, and then standing the mixture, collecting the upper layer of glass microspheres and drying them to obtain flotation glass microspheres; Step b2: stirring the flotation glass microspheres, sodium hydroxide and deionized water to react, cooling the reaction product after the reaction is completed, and then vacuum filtering, washing and drying the filter cake to obtain pretreated glass microspheres; Step b3: Stir and react γ-mercaptopropyltriethoxysilane and ethanol solution, then add pretreated glass microspheres and continue stirring and reacting. After the reaction is completed, cool the reaction product, then vacuum filter, wash and dry the filter cake to obtain modified glass microspheres.

6. A durable high-brightness road marking paint according to claim 5, characterized in that: The usage ratio of the glass microspheres and deionized water in step b1 is 20 g: 100-120 mL; the glass microspheres are 3M hollow glass microspheres S28HS.

7. The durable high-brightness road marking paint according to claim 5, characterized in that: The usage ratio of the flotation glass microspheres, sodium hydroxide and deionized water in step b2 is 10g:1.2-1.5g:100-110mL.

8. The durable high-brightness road marking paint according to claim 5, characterized in that: The usage ratio of the γ-mercaptopropyltriethoxysilane, ethanol solution and pretreated glass microspheres in step b3 is 0.5-3.9 g: 100-120 mL: 10 g; The volume fraction of the ethanol solution is 85-90%.

9. A method for preparing a durable high-brightness road marking paint, characterized in that: The following steps are involved: Step 1: Weigh 25-30 parts of high-performance durable emulsion, 5-13 parts of modified glass microspheres, 1.1-1.5 parts of sodium dodecyl sulfate, 0.5-0.7 parts of anti-settling thickening thixotropic agent, 0.2-0.6 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 0.1-0.3 parts of thickener according to weight parts, and set aside; Step 2: Add high-performance durable emulsion, modified glass microspheres and sodium dodecyl sulfate into a stirring kettle, stir and react for 10-15 minutes at a temperature of 25-30°C and a stirring rate of 200-300 r / min, then heat to 85-90°C and continue stirring and reacting for 3-5 hours. After the reaction is completed, cool the reaction product to room temperature to obtain a durable high-brightness emulsion; Step 3: Add anti-settling thickening thixotropic agent, defoaming agent, leveling agent and thickener to the durable high-gloss emulsion, stir and react for 30-50 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min to obtain a durable high-gloss marking paint.

10. The method for preparing a durable high-brightness road marking paint according to claim 9, characterized in that: The anti-settling thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling thickening thixotropic agent; the defoaming agent is tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener.