A wear-resistant and stain-resistant hot-melt road marking paint and its preparation method

Abstract

The present invention provides a wear-resistant and stain-resistant hot-melt road marking paint. The paint, by weight, comprises the following raw materials: 30-40 parts of polyurea-modified enhanced petroleum resin, 0.5-1 part of defoamer, 5-8 parts of aliphatic dibasic acid, 80-100 parts of heavy calcium carbonate, 30-40 parts of quartz powder, 10-20 parts of modified glass beads, 10-15 parts of titanium dioxide, 1-2 parts of plasticizer, and 2-4 parts of dispersant. The wear-resistant and stain-resistant hot-melt road marking paint prepared by the present invention has a rapid film drying speed, super wear-resistant performance, long service life, strong adhesion to the base surface, good stain-resistant performance, good low-temperature crack resistance, distinct beauty and good night-time retroreflective performance, and has good film integrity, water resistance and alkali resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of coating manufacturing, and particularly relates to a wear-resistant and stain-resistant hot-melt road marking coating and a preparation method thereof. Background Art

[0002] Road markings are the core part of traffic safety facilities and play an irreplaceable role in traffic control. At present, there are mainly four common road marking coatings on the market, namely solvent-based, hot-melt, two-component and water-based coatings. Among them, solvent-based coatings are seriously polluted during construction, and the operation of construction equipment is complex. Although two-component and water-based coatings are simple in construction and have little pollution, their wear resistance and durability are poor, and their service life is short, making it difficult to be widely promoted and used on a large scale. The hot-melt road marking coating has long occupied the primary position of road marking coatings due to its strong adhesion, wear resistance, long service life, rapid drying during construction, and low project cost. Therefore, it is necessary to develop a hot-melt road marking coating that can solve the problems of poor low-temperature crack resistance, poor wear resistance, short service life, and low adhesion to the base surface of existing road marking coatings. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a wear-resistant and stain-resistant hot-melt road marking coating and a preparation method thereof in view of the above-mentioned deficiencies of the existing technology. The wear-resistant and stain-resistant hot-melt road marking coating provided by the present invention has good low-temperature crack resistance, super wear resistance, long service life, and strong adhesion to the base surface.

[0004] The technical solution adopted by the present invention to solve the above-mentioned problems is as follows:

[0005] A wear-resistant and stain-resistant hot-melt road marking coating, by weight, comprises the following raw materials: 30-40 parts of polyurea-modified enhanced petroleum resin, 0.5-1 part of defoamer, 5-8 parts of aliphatic dibasic acid, 80-100 parts of heavy calcium, 30-40 parts of quartz powder, 10-20 parts of modified glass beads, 10-15 parts of titanium dioxide, 1-2 parts of plasticizer, and 2-4 parts of dispersant.

[0006] The preparation process of the above-mentioned polyurea-modified enhanced petroleum resin is as follows: (1) Octadecylamine and cyclohexylamine are ultrasonically dissolved in absolute ethanol to obtain solution a; (2) The organic amine and diphenylmethane diisocyanate are dissolved in ethyl acetate and then put into a reaction kettle, and then molten petroleum resin is added. Under vacuum conditions, the pressure is increased to 15-20 Mpa, and after heating to 80-90 °C, mechanical stirring is carried out at a speed of 1000-1200 rpm for 30-40 min to obtain mixture b; (3) Solution a and mixture b are mixed and then pressurized to 10-15 mpa under vacuum conditions, and stirred at a speed of 800-1200 rpm at 60-100 °C for 1-2 h to obtain reaction product c; (4) The reaction product c is cooled, dried and then ground into powder to obtain the polyurea-modified enhanced petroleum resin;

[0007] Among them, in step (1), the volume ratio of octadecylamine, cyclohexylamine and absolute ethanol is (5-6):5:(20-24); in step (2), the volume ratio of the organic amine, diphenylmethane diisocyanate and ethyl acetate is 1:(1-1.5):(1-1.5); the solid-liquid ratio of the petroleum resin to the organic amine is 50 g:(15-18) ml; the organic amine is one or more of hexamethylenetetramine, m-ethoxyaniline and p-butylaniline; in step (3), the solid-liquid ratio of mixture b to solution a is 10 g:(3-4) ml.

[0008] The preparation process of the above-mentioned modified glass microspheres is as follows: (1) A 50-100 g / L titanium tetrachloride solution is added to water at 90-95 °C, and then a surfactant is added and stirred for 15-20 min to obtain metatitanic acid slurry a; (2) 6-8 mol / L hydrochloric acid, initiator cumene hydroperoxide, 3-4 g / L chitosan solution, grafting agent methyl methacrylate are mixed with glass microspheres, and after heating to 70-90 °C, stirred for 10-15 min to obtain glass microsphere slurry b; (3) Glass microsphere slurry b is filtered by suction and washed 2-3 times with absolute ethanol, and then dried at 120-130 °C under vacuum to obtain grafted glass microspheres c; (4) Metatitanic acid slurry a and grafted glass microspheres c are mixed and stirred at 12-15 Mpa and 80-100 °C for 1-2 h, then filtered by suction under vacuum, washed clean with absolute ethanol, and dried at 130-150 °C under vacuum to obtain the modified glass microspheres;

[0009] Among them, in step (1), the volume ratio of the titanium tetrachloride solution, water and surfactant is 1:(3-4):(0.1-0.2); the surfactant is one or more of Span-80, OP-10 or TO-3;

[0010] In step (2), the volume ratio of hydrochloric acid, cumene hydroperoxide, chitosan solution, and methyl methacrylate is 5:10:(5 - 10):(1 - 2); the solid-liquid ratio of the glass microspheres to methyl methacrylate is 10 g:(2 - 3) ml; in step (4), the mass ratio of metatitanic acid slurry a to grafted glass microspheres c is 4:(1 - 2).

[0011] As a further improvement of the present invention, the aliphatic dibasic acid is one or a mixture of azelaic acid and dodecanedioic acid.

[0012] As a further improvement of the present invention, the defoamer is an organosilicon defoamer.

[0013] As a further improvement of the present invention, the heavy calcium carbonate is a heavy calcium carbonate powder with a whiteness of more than 95% and a particle size between 600 and 800 mesh.

[0014] As a further improvement of the present invention, the particle size range of the quartz powder is between 300 and 500 mesh.

[0015] As a further improvement of the present invention, the titanium dioxide is anatase titanium dioxide, and the particle size range is between 100 and 5000 mesh.

[0016] As a further improvement of the present invention, the plasticizer is dibutyl phthalate or dibutyl maleate.

[0017] As a further improvement of the present invention, the dispersant is one or a mixture of erucamide and stearamide.

[0018] The present invention also provides a preparation method of the above-mentioned wear-resistant and stain-resistant hot-melt road marking paint, which includes the following steps:

[0019] (1) Weigh each raw material according to the raw material composition, mix polyurea-modified enhanced petroleum resin, defoamer, aliphatic dibasic acid, heavy calcium carbonate, quartz powder, titanium dioxide, plasticizer, and dispersant, and stir at a stirring rate of 500 - 600 r / min for 20 - 30 min;

[0020] (2) Add the mixture obtained in step (1) to modified glass microspheres and then perform sanding at a sanding rate of 600 - 800 r / min for 20 - 30 min to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

[0021] Compared with the existing technology, the beneficial effects of the present invention are:

[0022] (1) The wear-resistant and stain-resistant hot-melt road marking paint provided by the present invention has a rapid film drying speed, super wear-resistant performance, long service life, strong adhesion to the base surface, good stain-resistant performance, good low-temperature crack resistance, distinct beauty and good night-time retroreflective performance, and the film has good integrity, water resistance and alkali resistance.

[0023] (2) The wear-resistant and stain-resistant hot-melt road marking paint provided by the present invention conducts polyurea enhanced modification on petroleum resin in an organic manner. The polyurea is arranged in a staggered polyurea enhanced resin fiber manner within the petroleum resin, changing the resin structure, increasing the crosslinking density inside the resin, enhancing the bonding performance of the resin, and also improving the adhesion of the resin to the base surface. Coupled with the full application of the physical barrier effect of the filler in the coating, the amount of tiny pores in the resin is reduced, and an excellent barrier effect on the external environment is achieved, thereby reducing the probability of fine cracking of the paint and simultaneously enhancing the wear-resistant performance of the resin. At the same time, the polyurea enhanced resin fibers can evenly improve the stress caused by the expansion of the internal products of the paint and reduce coating blistering. Finally, the synergistic effect of these three greatly improves the wear-resistant performance of the paint and also extends the service life of the paint.

[0024] (3) The wear-resistant and stain-resistant hot-melt road marking paint provided by the present invention uses nano-titanium dioxide to modify the surface of glass beads. This not only enhances the surface compatibility between the glass beads and the resin, enables the glass beads to be evenly dispersed in the resin, and improves the interfacial strength, but also the titanium dioxide coated on the surface of the glass beads has excellent stain-resistant performance, which can effectively improve the stain resistance of the paint. Moreover, there are intermolecular hydrogen bonds in the glass beads grafted with methyl methacrylate. The composite material composed of the modified glass beads forms a thixotropic fluid effect in the molten state. By controlling the hydrogen bond concentration in the molecular chain, the thixotropic strength of the fluid can be adjusted. During heating and stirring, it can protect the hollow glass microspheres from being easily broken, better ensure the surface uniformity of the prepared paint, obtain a good appearance, and at the same time, this can also effectively improve the retroreflective coefficient of the glass beads, thereby enhancing the night-time luminous and reflective performance and reducing the occurrence of night-time traffic accidents. And by enhancing the overall strength of the glass beads, the wear-resistant performance of the paint can also be improved.

[0025] (4) The wear-resistant and stain-resistant hot-melt road marking paint provided by the present invention has good water resistance and alkali resistance. This is because the molar ratio of the aliphatic dibasic acids azelaic acid and dodecanedioic acid selected in the present invention is relatively low, resulting in a lower glass transition temperature point of the resin, the best impact resistance of the resin. At the same time, due to the relatively small particle sizes of heavy calcium and quartz powder, the covering efficiency of anatase titanium dioxide is not affected after mixing, and the fillers cooperate with each other, which is beneficial to improving the integrity, wear resistance, water resistance and alkali resistance of the paint film. Detailed implementation mode

[0026] The technical solution of the present invention will be fully and clearly described below in conjunction with embodiments, but the described embodiments are only some embodiments of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention.

[0027] The petroleum resin used in the embodiments of the present invention and the comparative examples is C5 petroleum resin of R-1100S model sold by Dongguan Yucheng Plastic Co., Ltd.; the glass microspheres are reflective glass microspheres with a mesh size of 325 mesh sold by Huizhou Juncai Chemical Co., Ltd.; the aliphatic dibasic acid is azelaic acid and lauric acid analytical reagent sold by Aladdin reagent manufacturer; the defoamer is Dow Corning AFE-1410 silicone defoamer; the heavy calcium is heavy calcium powder with a whiteness of more than 95% and a particle size range of 600-800 mesh sold by Jiangxi Guangyuan Chemical Co., Ltd.; the quartz powder is quartz powder with a particle size range of 300-500 mesh sold by Shijiazhuang Dengfeng Building Materials Co., Ltd.; the titanium dioxide is anatase titanium dioxide sold by Jiangxi Guangyuan Chemical Co., Ltd., with a particle size range of 100-5000 mesh; the plasticizer is dibutyl phthalate analytical reagent sold by Aladdin reagent manufacturer; the dispersant is erucamide analytical reagent sold by Aladdin reagent manufacturer.

[0028] A wear-resistant and anti-fouling hot-melt road marking paint comprises the following raw materials, measured by weight: 30-40 parts of polyurea modified enhanced petroleum resin, 0.5-1 parts of defoaming agent, 5-8 parts of aliphatic dibasic acid, 80-100 parts of heavy calcium, 30-40 parts of quartz powder, 10-20 parts of modified glass microbeads, 10-15 parts of titanium dioxide, 1-2 parts of plasticizer, and 2-4 parts of dispersant.

[0029] The preparation process of the above-mentioned polyurea modified enhanced petroleum resin is as follows: (1) 30 ml of octadecylamine and 25 ml of cyclohexylamine are ultrasonically dissolved in 100 ml of anhydrous ethanol to obtain solution a; (2) 15 ml of hexamethylenetetramine and 22 ml of diphenylmethane diisocyanate are dissolved in 20 ml of ethyl acetate and then put into a reaction kettle, and then 50 g of molten petroleum resin is added, and the mixture is pressurized to 15 MPa under vacuum conditions, heated to 80° C. and mechanically stirred at a speed of 1000 rpm for 30 minutes to obtain a mixture b; (3) 30 ml of solution a is mixed with 100 g of mixture b, and then pressurized to 12 MPa under vacuum conditions, and stirred at 60° C. and 800 rpm for 1 hour to obtain a reaction product c; (4) The reaction product c is cooled, dried, and ground into powder to obtain a polyurea modified enhanced petroleum resin.

[0030] The preparation process of the above-mentioned modified glass microspheres is as follows: (1) Add 30 ml of 50 g / L titanium tetrachloride solution to 100 ml of water at 190 °C, then add 3 ml of surfactant span-80 and stir for 15 min to obtain metatitanic acid slurry a; (2) Mix 5 ml of 8 mol / L hydrochloric acid, 10 ml of initiator cumene hydroperoxide, 8 ml of 4 g / L chitosan solution, 2 ml of grafting agent methyl methacrylate with 10 g of glass microspheres, heat up to 90 °C and stir for 10 min to obtain glass microsphere slurry b; (3) Filter the glass microsphere slurry b by suction, wash it twice with absolute ethanol, and dry it at 120 °C under vacuum to obtain grafted glass microspheres c; (4) Mix 40 g of metatitanic acid slurry a with 10 g of grafted glass microspheres c, stir at 15 Mpa and 90 °C for 1 h, then filter by suction under vacuum, wash it clean with absolute ethanol, and dry it at 150 °C under vacuum to obtain the modified glass microspheres.

[0031] The preparation method of the above-mentioned wear-resistant and stain-resistant hot-melt road marking paint includes the following steps:

[0032] (1) Weigh each raw material according to the raw material composition, mix polyurea-modified enhanced petroleum resin, defoamer, aliphatic dibasic acid, heavy calcium, quartz powder, titanium dioxide, plasticizer and dispersant, and stir at a stirring rate of 500 - 600 r / min for 1 - 2 h;

[0033] (2) Add modified glass microspheres to the mixture obtained in step (1) and then carry out sanding at a sanding rate of 500 - 600 r / min for 20 - 30 min to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

[0034] Example 1

[0035] The preparation method of a wear-resistant and stain-resistant hot-melt road marking paint includes the following steps:

[0036] (1) Take 30 parts of polyurea-modified enhanced petroleum resin, 1 part of Dow Corning AFE-1410 defoamer, 5 parts of azelaic acid, 100 parts of heavy calcium, 30 parts of quartz powder, 15 parts of titanium dioxide, 2 parts of plasticizer dibutyl phthalate and 3 parts of dispersant erucamide, mix them and put them into a blender for grinding. The stirring rate of the blender is controlled at 500 revolutions per minute, and the stirring time is controlled at 1 hour.

[0037] (2) Take out the stirred and mixed powder from the blender and put it into a sand mill. At the same time, add 15 parts of modified glass microspheres to the sand mill, and sand the mixed powder at a speed of 600 revolutions per minute for 20 min to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

[0038] Example 2

[0039] A preparation method of a wear-resistant and stain-resistant hot-melt road marking paint, comprising the following steps:

[0040] (1) Take 35 parts of polyurea-modified enhanced petroleum resin, 0.5 part of Dow Corning AFE-1410 defoamer, 6 parts of azelaic acid, 100 parts of heavy calcium, 40 parts of quartz powder, 15 parts of titanium dioxide, 2 parts of plasticizer dibutyl phthalate and 2 parts of dispersant erucamide, mix them and put them into a blender for grinding. The stirring rate of the blender is controlled at 500 revolutions per minute, and the stirring time is controlled at 1 hour.

[0041] (2) Take out the stirred and mixed powder from the blender and put it into a sand mill. At the same time, add 20 parts of modified glass microspheres into the sand mill, and grind the mixed powder at a speed of 700 revolutions per minute for 20 minutes to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

[0042] Example 3

[0043] A preparation method of a wear-resistant and stain-resistant hot-melt road marking paint, comprising the following steps:

[0044] (1) Take 30 parts of polyurea-modified enhanced petroleum resin, 1 part of Dow Corning AFE-1410 defoamer, 8 parts of azelaic acid, 100 parts of heavy calcium, 40 parts of quartz powder, 15 parts of titanium dioxide, 2 parts of plasticizer dibutyl phthalate and 2 parts of dispersant erucamide, mix them and put them into a blender for grinding. The stirring rate of the blender is controlled at 600 revolutions per minute, and the stirring time is controlled at 1 hour.

[0045] (2) Take out the stirred and mixed powder from the blender and put it into a sand mill. At the same time, add 20 parts of modified glass microspheres into the sand mill, and grind the mixed powder at a speed of 800 revolutions per minute for 30 minutes to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

[0046] Comparative Example 1

[0047] (1) Take 30 parts of ordinary resin, 1 part of Dow Corning AFE-1410 defoamer, 5 parts of azelaic acid, 100 parts of heavy calcium, 30 parts of quartz powder, 15 parts of titanium dioxide, 2 parts of plasticizer dibutyl phthalate and 3 parts of dispersant erucamide, mix them and put them into a blender for grinding. The stirring rate of the blender is controlled at 500 revolutions per minute, and the stirring time is controlled at 1 hour.

[0048] (2) Take out the stirred and mixed powder from the blender and put it into a sand mill. At the same time, add 15 parts of modified glass microspheres into the sand mill, and grind the mixed powder at a speed of 800 revolutions per minute for 30 minutes to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

[0049] Comparative Example 2

[0050] (1) Take 30 parts of polyurea-modified enhanced petroleum resin, 1 part of Dow Corning AFE-1410 defoamer, 5 parts of azelaic acid, 100 parts of heavy calcium, 30 parts of quartz powder, 15 parts of titanium dioxide, 2 parts of plasticizer dibutyl phthalate, and 3 parts of dispersant erucamide. Mix them and put them into a blender for grinding. The stirring rate of the blender is controlled at 500 revolutions per minute, and the stirring time is controlled at 1 hour.

[0051] (2) Take out the stirred and mixed powder from the blender and put it into a sand mill. At the same time, add 15 parts of glass beads to the sand mill. Grind the mixed powder at a speed of 800 revolutions per minute for 30 minutes to obtain a wear-resistant and stain-resistant hot-melt road marking paint.

[0052] Comparative Example 3

[0053] (1) Take 30 parts of ordinary resin, 1 part of Dow Corning AFE-1410 defoamer, 5 parts of azelaic acid, 100 parts of heavy calcium, 30 parts of quartz powder, 15 parts of titanium dioxide, 2 parts of plasticizer dibutyl phthalate, and 3 parts of dispersant erucamide. Mix them and put them into a blender for grinding. The stirring rate of the blender is controlled at 500 revolutions per minute, and the stirring time is controlled at 1 hour.

[0054] (2) Take out the stirred and mixed powder from the blender and put it into a sand mill. At the same time, add 15 parts of glass beads to the sand mill. Grind the mixed powder at a speed of 800 revolutions per minute for 30 minutes to obtain a wear-resistant and stain-resistant hot-melt road marking paint.

[0055] The formulations of the wear-resistant and stain-resistant hot-melt road marking paints prepared in Examples 1-3 and Comparative Examples 1-3 are shown in Table 1 as follows:

[0056] Table 1

[0057]

[0058] Carry out the following relevant tests on the samples of the wear-resistant and stain-resistant hot-melt road marking paints prepared in Examples 1-3 and Comparative Examples 1-3, including abrasion resistance, alkali resistance, low-temperature crack resistance, retroreflection coefficient, film drying time, compressive strength, etc.:

[0059] Abrasion resistance test: The rotating rubber grinding wheel method is adopted, in accordance with GB / T1768-2006. First, apply a layer of glycerin on the film cavity of the sample preparation device. After it dries, inject the molten sample into the cavity and let it level (if it cannot level, preheat the test mold first), and punch a test hole with a diameter of about 7 mm at the center while it is still soft and hot. Three test plates should be made from the same sample. After being placed for 24 h under standard test conditions, under a load of 1000 g and a rotation speed of 200 revolutions, accurately weigh the weight loss of the test plate after the test (accurate to 0.1 mg), and take the average weight loss mass of the three tests as the abrasion resistance value of the sample. This index is an important basic physical and chemical index and an important strength index of the hot-melt marking paint, evaluating the ability of the paint to resist repeated wear loads.

[0060] Alkali resistance test: For the alkali resistance of the hot-melt marking paint, in accordance with GB / T9265-2009, inject the molten sample into the water resistance sample preparation device (size: 60 mm×60 mm×5 mm), let it level, cool to room temperature, take it out for use as a test piece, soak it in saturated calcium hydroxide solution for 24 h, and observe whether there are any abnormal phenomena. This index is a durability index of the hot-melt marking paint, evaluating the alkali resistance ability of the paint.

[0061] Low-temperature crack resistance test: Make test plates according to the method of film appearance, and observe whether there are cracks with a five-fold magnifying glass. If there are cracks, remake the plates; place the prepared test plates flat in a low-temperature chamber at -20℃±2℃ for 4 h, take them out and place them at room temperature for 4 h as one cycle, and do ten cycles continuously; observe with a five-fold magnifying glass after taking them out and there should be no cracks. This index is one of the durability indexes of the hot-melt marking paint, evaluating the low-temperature crack resistance ability of the paint.

[0062] Determination of retroreflective coefficient: It is determined in accordance with the national standard GB / T18833-2002 "Reflective Sheeting for Road Traffic Signs".

[0063] Determination of film drying time: It is determined with reference to GB6753.2-86.

[0064] Compressive strength test: It is tested by an electronic universal testing machine with reference to GB 5768.3-2009.

[0065] The relevant test results such as abrasion resistance, alkali resistance, low-temperature crack resistance, retroreflective coefficient, film drying time, and compressive strength of the samples of the wear-resistant and anti-fouling hot-melt road marking paint prepared in Examples 1-3 and Comparative Examples 1-3 are shown in Table 2:

[0066] Table 2

[0067]

[0068] As can be seen from Table 2, the hot-melt road marking paint prepared in the examples has the advantages of short drying time, appropriate softening point, good flexibility, excellent wear resistance, good retroreflective performance, strong water and alkali resistance, while the comparative examples have the disadvantages of high abrasion loss, rust spots and poor demoulding effect.

[0069] In summary, the hot-melt road marking paint provided by the present invention has a rapid drying film, super wear resistance, long service life, strong adhesion to the base surface, good anti-fouling performance, good low-temperature crack resistance, distinct beauty and good night-time reflective performance, and the film has good integrity, water resistance and alkali resistance.

[0070] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and its improvement concept of the present invention, with equivalent replacement or change, should be covered by the protection scope of the present invention.

Claims

1. A wear-resistant and stain-resistant hot-melt road marking paint, characterized in that, By weight, it includes the following raw materials: 30-40 parts of polyurea-modified enhanced petroleum resin, 0.5-1 part of defoamer, 5-8 parts of aliphatic dibasic acid, 80-100 parts of heavy calcium carbonate, 30-40 parts of quartz powder, 10-20 parts of modified glass microspheres, 10-15 parts of titanium dioxide, 1-2 parts of plasticizer, and 2-4 parts of dispersant; Among them, the preparation process of the polyurea-modified enhanced petroleum resin is as follows: (1) Dissolve octadecylamine and cyclohexylamine in absolute ethanol to obtain solution a; (2) Dissolve organic amine and diphenylmethane diisocyanate in ethyl acetate, then add molten petroleum resin, and then stir for 30-40 min under vacuum conditions of 15-20 Mpa and 80-90 °C to obtain mixture b; (3) Mix solution a and mixture b and stir for 1-2 h under vacuum conditions of 10-15 mpa and 60-100 °C to obtain reaction product c; (4) Cool and dry the reaction product c and grind it into powder to obtain polyurea-modified enhanced petroleum resin; Among them, in step (1), the volume ratio of octadecylamine, cyclohexylamine and absolute ethanol is (5-6):5:(20-24); In step (2), the volume ratio of organic amine, diphenylmethane diisocyanate and ethyl acetate is 1:(1-1.5):(1-1.5); the solid-liquid ratio of the petroleum resin to the organic amine is 50 g:(15-18) ml; the organic amine is one or more of hexamethylenetetramine, m-ethoxyaniline and p-butylaniline; In step (3), the solid-liquid ratio of mixture b to solution a is 10 g:(3-4) ml.

2. The wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, wherein The preparation process of the modified glass microspheres is as follows: (1) Add 50-100 g / L titanium tetrachloride solution to water at 90-95 °C, then add a surfactant and stir for 15-20 min to obtain metatitanic acid slurry a; (2) Mix 6-8 mol / L hydrochloric acid, initiator cumene hydroperoxide, 3-4 g / L chitosan solution, grafting agent methyl methacrylate with glass microspheres, heat up to 70-90 °C and stir for 10-15 min to obtain glass microsphere slurry b; (3) Filter glass microsphere slurry b, wash it with absolute ethanol, and then dry it at 120-130 °C under vacuum to obtain grafted glass microspheres c; (4) Mix metatitanic acid slurry a and grafted glass microspheres c, stir at 12-15 Mpa and 80-100 °C for 1-2 h, then filter under vacuum, wash with absolute ethanol, and dry at 130-150 °C under vacuum to obtain modified glass microspheres; Among them, in step (1), the volume ratio of titanium tetrachloride solution, water and surfactant is 1:(3-4):(0.1-0.2); the surfactant is one or more of Span-80, OP-10 or TO-3; In step (2), the volume ratio of hydrochloric acid, cumene hydroperoxide, chitosan solution, methyl methacrylate is 5:10: (5-10): (1-2); the solid-liquid ratio of the glass microspheres to methyl methacrylate is 10 g:(2-3) ml; In step (4), the mass ratio of metatitanic acid slurry a to grafted glass beads c is 4:(1 - 2).

3. A wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, characterized in that, The aliphatic dibasic acid is one or a mixture of azelaic acid and dodecanedioic acid.

4. The wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, wherein, The defoamer is a silicone defoamer.

5. A wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, characterized in that, The heavy calcium carbonate is heavy calcium carbonate powder with a whiteness of over 95% and a particle size range of 600 - 800 mesh; the particle size range of the quartz powder is 300 - 500 mesh.

6. A wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, characterized in that, The titanium dioxide is anatase titanium dioxide with a particle size range of 100 - 5000 mesh.

7. A wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, characterized in that, The plasticizer is dibutyl phthalate or dibutyl maleate.

8. A wear-resistant and stain-resistant hot-melt road marking paint according to claim 1, characterized in that, The dispersant is one or a mixture of erucamide and stearamide.

9. The preparation method of the wear-resistant and stain-resistant hot-melt road marking paint according to any one of claims 1-8, characterized in that, It includes the following steps: (1) Weigh each raw material according to the raw material composition, mix and stir polyurea-modified enhanced petroleum resin, defoamer, aliphatic dibasic acid, heavy calcium carbonate, quartz powder, titanium dioxide, plasticizer and dispersant, with a stirring rate of 500 - 600 r / min and a stirring time of 1 - 2 h; (2) Add modified glass beads to the mixture obtained in step (1) and then carry out sanding at a sanding rate of 600 - 800 r / min for 20 - 30 min to obtain the wear-resistant and stain-resistant hot-melt road marking paint.

Images