All-weather double-component reflective ceramic crystal marking coating as well as preparation method and application thereof

Abstract

The invention relates to the technical field of marking coatings, and discloses an all-weather double-component reflective porcelain crystal marking coating as well as a preparation method and application thereof. The marking paint comprises a first component, a second component and a modified nano titanium dioxide component, wherein the first component comprises poly (alpha-cyanomethyl acrylate); the second component comprises polymethylacrylic acid; the modified nano titanium dioxide component is modified through a silane coupling agent, so that poly (alpha-cyanomethyl acrylate) and polymethylacrylic acid are bonded together through chemical bonds. The marking paint can be naturally dried and hardened at the temperature of 0-30 DEG C, and the drying and hardening time is 20-30 min. The marking paint is simple in preparation process, integrates multiple properties, does not need heating equipment during use, and has a wide market prospect.

Description

Technical Field

[0001] The invention relates to the technical field of road marking paints, in particular to an all-weather two-component reflective ceramic crystal road marking paint and a preparation method and application thereof. Background Art

[0002] With the progress of urbanization, the traffic volume on domestic urban roads far exceeds the speed of road construction. Traditional solvent-based road markings have a short service life, and a large amount of organic solvents evaporate in the paint during construction, which seriously pollutes the environment and endangers the health of construction workers. Later, hot-melt paint was widely used on urban roads. The solvent volatilization of this type of paint has been reduced, but special heating equipment is required during construction, and the construction efficiency is low; moreover, this type of marking is difficult to repaint, easy to get dirty, and generally has problems such as blackening and graying. This type of marking is not clear and anti-fouling during the day, and does not reflect light at night, which is not only not conducive to driving safety, but also affects the civilized and tidy image of the city.

[0003] Two-component road marking paint is a new type of solvent-free environmentally friendly road marking material. The basic principle is that the base material and the curing agent are mixed in a certain proportion, and the two react chemically and solidify into a tough paint film in a relatively short time. Now two-component road marking materials have been successfully used in Western countries such as the United States and Germany, and are a new trend in the development of road marking materials. In recent years, two-component road markings in my country have also begun to gradually rise, but due to unreasonable factors such as resin selection and formula design by various paint manufacturers, most of the domestic two-component road markings are still simply mixed with each component, so there are still performance defects.

[0004] A Chinese patent with publication number CN 117304807A discloses a water-based two-component road marking paint. The paint is mixed with component A and component B, wherein component A is mainly mixed with water-based quick-drying acrylic emulsion, pH adjuster, dispersant, defoamer, deaerator, thickener, wetting dispersant, water-based amine curing agent, film-forming aid, rutile titanium dioxide, filler, antifreeze agent and water; component B is acrylic epoxy hybrid emulsion. The two-component road marking paint has the characteristics of excellent durability, strong adhesion, good early water resistance, strong resistance to chloride ion corrosion, and strong bonding with glass beads. However, the two-component road marking paint is still obtained by simply mixing the components, and its process is not simple enough, and there is still room for improvement in performance. Summary of the invention

[0005] In summary, the present invention aims to provide an all-weather two-component reflective ceramic crystal road marking paint and its preparation method and application. Through a unique formula and simple process, two different components are compounded to prepare a road marking paint that combines high reflectivity, self-cleaning, high anti-fouling properties, and does not require heating equipment when used.

[0006] In order to achieve the above objectives, this application adopts the following technical solutions:

[0007] In the first aspect, the present application provides an all-weather two-component reflective ceramic crystal road marking paint. The all-weather two-component reflective ceramic crystal road marking paint comprises a first component, a second component and a modified nano titanium dioxide component; the first component comprises poly α-methyl cyanoacrylate; the second component comprises poly methacrylic acid; the modified nano titanium dioxide component is modified by a silane coupling agent; the poly α-methyl cyanoacrylate and poly methacrylic acid are chemically bonded together by the modified nano titanium dioxide component.

[0008] In a second aspect, the present application provides a method for preparing an all-weather two-component reflective ceramic crystal road marking paint, the preparation method comprising:

[0009] Weighing poly(methyl α-cyanoacrylate) and adding it into the first reaction kettle, and then introducing nitrogen for a first set time to remove the poly(methyl α-cyanoacrylate) and air in the first reaction kettle;

[0010] Then, the curing agent and bentonite are added to the first reaction kettle, and stirred for a second set time under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the first reaction kettle, and stirring is continued for a third set time under nitrogen protection. The first component is obtained by discharging the material;

[0011] Then, polymethacrylic acid is weighed and added into the second reaction kettle, and then nitrogen is introduced for a first set time to remove air from the polymethacrylic acid and the second reaction kettle;

[0012] Then, the curing agent and bentonite are added to the second reaction kettle, and stirred for a second set time under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the second reaction kettle, and stirring is continued for a third set time under nitrogen protection. The second component is obtained by discharging the material;

[0013] The first component, the second component and the modified nano titanium dioxide are mixed in a third reaction kettle under nitrogen protection, and after stirring for a fourth set time at a set temperature, the all-weather two-component reflective ceramic crystal road marking paint is obtained.

[0014] In a third aspect, the present application provides an application of an all-weather two-component reflective ceramic crystal marking paint, which is used to prepare road markings.

[0015] Beneficial technical effects

[0016] The present application uses a unique formula and a simple process to chemically bond two different components together using modified nano-titanium dioxide as a bridge to prepare an all-weather two-component reflective ceramic crystal road marking paint.

[0017] The all-weather two-component reflective ceramic crystal road marking paint prepared by the present application, under the action of the preferred curing agent in the first component and the second component, first makes the first component and the second component undergo free radical polymerization reaction respectively, cross-linking occurs, and a high molecular weight polymer with a network structure is formed. Finally, the high molecular weight polymer forms a film to produce an organic silicon coating. The low surface energy organic silicon coating makes it difficult for the road marking paint to be mixed with stains, which gives the surface of the road marking paint a high anti-fouling ability. The introduction of modified nano titanium dioxide, the organic groups on its surface bond the first component and the second component together through chemical bonds, and also promotes the uniform dispersion of tempered glass beads. This can improve the reflectivity of the road marking paint on the one hand, and greatly improve the curing efficiency of the road marking paint on the other hand; the road marking paint can be naturally dried at 0-30°C when in use, and the drying time is 20-30 minutes; therefore, it can be cured without heating equipment, greatly improving the construction efficiency.

[0018] At the same time, the presence of modified nano-titanium dioxide makes the electrons on the valence band of the modified nano-titanium dioxide jump to the conduction band when the road marking paint is irradiated by ultraviolet light, and the electrons are excited and ionized, and positive holes are generated, forming electron-hole pairs. The electron-hole pairs will react with the oxygen and water adsorbed and dissolved on its surface to produce ·OH free radicals. The presence of ·OH free radicals can oxidize most organic and inorganic pollutants. Therefore, the road marking paint with uniformly dispersed modified nano-titanium dioxide has a special self-cleaning function, which can effectively reduce the pollution and dirt adhesion on the surface of the paint, and keep the paint surface clean and beautiful.

[0019] In addition, other additives are added to make the road marking paint non-slip and have certain anti-icing properties in winter.

[0020] The all-weather two-component reflective ceramic crystal road marking paint prepared in this application has a simple preparation process, integrates various performances in one, and does not require heating equipment when used, and has broad market prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the components of the all-weather two-component reflective ceramic crystal road marking paint.

[0022] Figure 2 It is a schematic diagram of the preparation process of all-weather two-component reflective ceramic crystal road marking paint.

[0023] Figure 3 The invention discloses an all-weather two-component reflective ceramic road marking paint prepared in Example 1.

[0024] Figure 4 The road marking is prepared by using the all-weather two-component reflective ceramic crystal marking paint in Example 1. DETAILED DESCRIPTION

[0025] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application clearer, the present application is further described in detail below in conjunction with the embodiments. However, this should not be understood as the scope of the present application being limited to the following examples. Without departing from the above-mentioned method ideas of the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0026] In this application, the terms used in this application are for the purpose of describing specific embodiments only and are not intended to limit the application.

[0027] The terms “first”, “second” and “third” are used for descriptive purposes only and should not be understood as indicating or implying relative importance.

[0028] Furthermore, as used in this application and the appended claims, the singular forms "for," "or," "an," "any," and "said" are intended to include the plural forms unless the context clearly indicates otherwise.

[0029] In a first aspect, the present application provides an all-weather two-component reflective ceramic crystal road marking paint. Figure 1 As shown, the all-weather two-component reflective ceramic crystal marking paint includes a first component, a second component and a modified nano titanium dioxide component; the first component includes poly methyl α-cyanoacrylate; the second component includes poly methacrylic acid; the modified nano titanium dioxide component is modified by a silane coupling agent; the poly methyl α-cyanoacrylate and poly methacrylic acid are chemically bonded together through the modified nano titanium dioxide component.

[0030] Preferably, in the first component, the mass ratio of poly-α-cyanoacrylate, curing agent, anti-icing agent, bentonite, titanium dioxide, tempered glass beads and double fly ash is (25-35): (0.5-1): (0.5-1): (0.5-1): (5-10): (20-30): (30-40).

[0031] Preferably, in the second component, the mass ratio of polymethacrylic acid, curing agent, anti-icing agent, bentonite, titanium dioxide, tempered glass beads and double fly ash is (30-40): (0.5-1): (0.5-1): (0.5-2): (5-10): (20-30): (25-35).

[0032] Preferably, in the first component and the second component, the mesh size of the tempered glass beads is 40-50 meshes, and the softening temperature is 950° C.; the mesh size of the double fly ash is 1000 meshes.

[0033] Preferably, in the first component and the second component, the curing agent is one or more of benzoin dimethyl ether, 2-isopropylthioxanthone and 2-hydroxy-2-methylacetophenone.

[0034] Preferably, the silane coupling agent used in the modified nano-titanium dioxide includes one or more of KH550, KH792, and KH960.

[0035] Preferably, the particle size of the modified nano titanium dioxide is in the range of 50 to 100 nm; the mass ratio of the nano titanium dioxide to the silane coupling agent is: 100:(1 to 2).

[0036] In a second aspect, the present application provides a method for preparing an all-weather two-component reflective ceramic crystal road marking paint, the preparation method being as follows Figure 2 As shown, including:

[0037] Weighing poly(methyl α-cyanoacrylate) and adding it into the first reaction kettle, and then introducing nitrogen for a first set time to remove the poly(methyl α-cyanoacrylate) and air in the first reaction kettle;

[0038] Then, the curing agent and bentonite are added to the first reaction kettle, and stirred for a second set time under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the first reaction kettle, and stirring is continued for a third set time under nitrogen protection. The first component is obtained by discharging the material;

[0039] Then, polymethacrylic acid is weighed and added into the second reaction kettle, and then nitrogen is introduced for a first set time to remove air from the polymethacrylic acid and the second reaction kettle;

[0040] Then, the curing agent and bentonite are added to the second reaction kettle, and stirred for a second set time under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the second reaction kettle, and stirring is continued for a third set time under nitrogen protection. The second component is obtained by discharging the material;

[0041] The first component, the second component and the modified nano titanium dioxide are mixed in a third reaction kettle under nitrogen protection, and after stirring for a fourth set time at a set temperature, the all-weather two-component reflective ceramic crystal road marking paint is obtained.

[0042] Preferably, the first setting time is 0.5 to 1 hour; the second setting time is 2 to 3 hours, the third setting time is 1 to 2 hours; the fourth setting time is 1 to 2 hours; and the set temperature is 80 to 100°C.

[0043] Preferably, the mass ratio of the first component, the second component and the modified nano titanium dioxide is (40-50): (40-50): (5-10).

[0044] In a third aspect, the present application provides an application of an all-weather two-component reflective ceramic crystal marking paint, which is used to prepare road markings.

[0045] Specific application methods include:

[0046] The all-weather two-component reflective ceramic crystal road marking paint is applied on the road surface by scraping to form road markings. The height of the raised part of the edge of the road marking is 1.8 to 2 mm. The road marking formed by the construction is naturally dried at 0 to 30 degrees Celsius.

[0047] Or the all-weather two-component reflective ceramic crystal marking paint can be applied to the road surface by extrusion to form road markings. The road marking height is 2 to 3 mm. The formed road markings are naturally dried at 0 to 30°C.

[0048] The following will combine different examples to specifically describe an all-weather two-component reflective ceramic crystal road marking paint provided by the present application, as well as its preparation method and application.

[0049] Embodiment 1:

[0050] like Figure 2 As shown, a method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0051] 1. Weigh poly(α-methyl cyanoacrylate) and add it into the first reaction kettle, then introduce nitrogen for 0.5 hours to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0052] 2. Then, a curing agent (benzoin dimethyl ether) and bentonite were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. Titanium dioxide, tempered glass beads, anti-icing agent and double fly ash were added to the first reaction kettle, and the mixture was stirred for 1 hour under nitrogen protection. The first component was obtained by discharging the mixture.

[0053] In steps 1 and 2, the mass ratio of poly-α-cyanoacrylate, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:1:1:1:7:25:35;

[0054] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 0.5 hours to remove the air in the polymethacrylic acid and the second reactor;

[0055] 4. Then add the curing agent (benzoin dimethyl ether) and bentonite into the second reactor, stir for 2 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reactor, continue to stir for 1 hour under nitrogen protection, and discharge to obtain the second component;

[0056] In steps 3 and 4, the mass ratio of polymethacrylic acid, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:1:1:1:7:25:35;

[0057] 5. Under nitrogen protection, the first component, the second component, and the modified nano titanium dioxide (the mass ratio of nano titanium dioxide to KH550 is 100:1) are mixed in the third reaction kettle, and stirred at 80°C for 1 hour. The all-weather two-component reflective ceramic crystal road marking paint is obtained. The mass ratio of the first component, the second component, and the modified nano titanium dioxide is 45:45:10. The obtained all-weather two-component reflective ceramic crystal road marking paint is as follows: Figure 3 shown.

[0058] The prepared all-weather two-component reflective ceramic crystal road marking paint was applied to the road surface by scraping. The height of the raised part of the road marking edge was 1.8-2 mm. The formed road marking was naturally dried at 15°C, and the drying time was recorded. Figure 4 shown.

[0059] Embodiment 2:

[0060] like Figure 2 As shown, a method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0061] 1. Weigh poly(α-methyl cyanoacrylate) and add it to the first reaction kettle, then introduce nitrogen for 0.5 hours to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0062] 2. Then, a curing agent (2-isopropylthioxanthone) and bentonite were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. Titanium dioxide, tempered glass beads, anti-icing agent and double fly ash were added to the first reaction kettle, and the mixture was stirred for 1 hour under nitrogen protection. The first component was obtained by discharging the mixture.

[0063] In steps 1 and 2, the mass ratio of poly-α-cyanoacrylate, 2-isopropylthioxanthone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 25:0.5:1:0.5:10:30:33;

[0064] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 0.5 hours to remove the air in the polymethacrylic acid and the second reactor;

[0065] 4. Then add the curing agent (2-isopropylthioxanthone) and bentonite into the second reactor, stir for 2 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reactor, continue to stir for 1 hour under nitrogen protection, and discharge the material to obtain the second component;

[0066] In steps 3 to 4, the mass ratio of polymethacrylic acid, 2-isopropylthioxanthone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 25:0.5:1:0.5:10:30:33;

[0067] 5. Under nitrogen protection, the first component, the second component and modified nano titanium dioxide (the mass ratio of nano titanium dioxide to KH792 is 100:1) are mixed in the third reactor. After stirring at 80°C for 1 hour, the all-weather two-component reflective ceramic crystal marking paint is obtained. The mass ratio of the first component, the second component and the modified nano titanium dioxide is 46:46:8.

[0068] The prepared all-weather two-component reflective ceramic crystal road marking paint is constructed on the road surface by extrusion. The road marking height is 2-3 mm. The constructed marking is naturally dried at 15°C, and the drying time is recorded.

[0069] Embodiment 3:

[0070] like Figure 2 As shown, a method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0071] 1. Weigh poly(α-methyl cyanoacrylate) and add it into the first reaction kettle, then introduce nitrogen for 1 hour to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0072] 2. Then, a curing agent (benzoin dimethyl ether) and bentonite were added to the first reaction kettle, and the mixture was stirred for 2.5 hours under nitrogen protection. Titanium dioxide, tempered glass beads, anti-icing agent and double fly ash were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. The first component was obtained by discharging the mixture.

[0073] In steps 1 and 2, the mass ratio of the poly-α-cyanoacrylate, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:0.5:1:0.5:8:30:30;

[0074] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 1 hour to remove the air in the polymethacrylic acid and the second reactor;

[0075] 4. Then add the curing agent (2-hydroxy-2-methyl acetophenone) and bentonite into the second reaction kettle, stir for 2.5 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reaction kettle, continue to stir for 2 hours under nitrogen protection, and discharge to obtain the second component;

[0076] In steps 3 to 4, the mass ratio of the polymethacrylic acid, 2-hydroxy-2-methylpropiophenone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:0.5:1:0.5:8:30:30;

[0077] 5. Under nitrogen protection, the first component, the second component and modified nano titanium dioxide (the mass ratio of nano titanium dioxide to KH960 is 100:1) are mixed in the third reactor. After stirring at 100°C for 1 hour, the all-weather two-component reflective ceramic crystal marking paint is obtained. The mass ratio of the first component, the second component and the modified nano titanium dioxide is 45:45:10.

[0078] The prepared all-weather two-component reflective ceramic crystal road marking paint is constructed on the road surface by extrusion. The road marking height is 2-3 mm. The constructed marking is naturally dried at 15°C, and the drying time is recorded.

[0079] Embodiment 4:

[0080] like Figure 2 As shown, a method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0081] 1. Weigh poly(α-methyl cyanoacrylate) and add it to the first reaction kettle, then introduce nitrogen for 0.75 hours to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0082] 2. Then, a curing agent (2-hydroxy-2-methylpropiophenone) and bentonite were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. Titanium dioxide, tempered glass beads, anti-icing agent and double fly ash were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. The first component was obtained by discharging the mixture.

[0083] In steps 1 and 2, the mass ratio of the poly-α-cyanoacrylate, 2-hydroxy-2-methylacetophenone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:1:1:1:7:25:35;

[0084] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 0.75 hours to remove the air in the polymethacrylic acid and the second reactor;

[0085] 4. Then add the curing agent (2-hydroxy-2-methyl acetophenone) and bentonite into the second reaction kettle, stir for 2 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reaction kettle, continue to stir for 2 hours under nitrogen protection, and discharge the material to obtain the second component;

[0086] In steps 3 to 4, the mass ratio of the polymethacrylic acid, 2-hydroxy-2-methylpropiophenone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:0.5:1:0.5:8:30:30;

[0087] 5. Under nitrogen protection, the first component, the second component and modified nano titanium dioxide (nano titanium dioxide and KH550 mass ratio of 100:2) were mixed in the third reactor. After stirring at 100°C for 1 hour, the all-weather two-component reflective ceramic crystal marking paint was obtained. The mass ratio of the first component, the second component and the modified nano titanium dioxide was 47:47:6.

[0088] The prepared all-weather two-component reflective ceramic crystal marking paint was applied to the road surface by scraping. The height of the raised portion of the edge of the road marking was 1.8-2 mm. The constructed marking was dried naturally at 15° C., and the drying time was recorded.

[0089] Embodiment 5:

[0090] like Figure 2 As shown, a method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0091] 1. Weigh poly(α-methyl cyanoacrylate) and add it into the first reaction kettle, then introduce nitrogen for 1 hour to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0092] 2. Then, a curing agent (2-isopropylthioxanthone) and bentonite were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. Titanium dioxide, tempered glass beads, anti-icing agent and double fly ash were added to the first reaction kettle, and the mixture was stirred for 1.5 hours under nitrogen protection. The first component was obtained by discharging the mixture.

[0093] In steps 1 and 2, the mass ratio of poly-α-cyanoacrylate, 2-isopropylthioxanthone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:0.5:0.5:0.5:8.5:20:40;

[0094] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 1 hour to remove the air in the polymethacrylic acid and the second reactor;

[0095] 4. Then add the curing agent (benzoin dimethyl ether) and bentonite into the second reactor, stir for 2 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reactor, continue to stir for 1.5 hours under nitrogen protection, and discharge the material to obtain the second component;

[0096] In steps 3 and 4, the mass ratio of polymethacrylic acid, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 40:0.5:1:0.5:8:20:30;

[0097] 5. Under nitrogen protection, the first component, the second component and modified nano titanium dioxide (the mass ratio of nano titanium dioxide to KH792 is 100:2) are mixed in the third reactor. After stirring at 90°C for 1 hour, the all-weather two-component reflective ceramic crystal marking paint is obtained. The mass ratio of the first component, the second component and the modified nano titanium dioxide is 48:48:4.

[0098] The prepared all-weather two-component reflective ceramic crystal marking paint was applied to the road surface by scraping. The height of the raised portion of the edge of the road marking was 1.8-2 mm. The constructed marking was dried naturally at 15° C., and the drying time was recorded.

[0099] Embodiment 6:

[0100] like Figure 2 As shown, a method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0101] 1. Weigh poly(α-methyl cyanoacrylate) and add it into the first reaction kettle, then introduce nitrogen for 1 hour to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0102] 2. Then, a curing agent (benzoin dimethyl ether) and bentonite are added to the first reaction kettle, and stirred for 2 hours under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the first reaction kettle, and stirring is continued for 2 hours under nitrogen protection. The first component is obtained by discharging the material;

[0103] In steps 1 and 2, the mass ratio of poly-α-cyanoacrylate, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 35:0.5:0.5:0.5:8.5:20:35;

[0104] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 1 hour to remove the air in the polymethacrylic acid and the second reactor;

[0105] 4. Then add the curing agent (2-hydroxy-2-methyl acetophenone) and bentonite into the second reaction kettle, stir for 2 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reaction kettle, continue to stir for 2 hours under nitrogen protection, and discharge the material to obtain the second component;

[0106] In steps 3 and 4, the mass ratio of polymethacrylic acid, 2-hydroxy-2-methylpropiophenone, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 35:0.5:1:0.5:8:20:35;

[0107] 5. Under nitrogen protection, the first component, the second component and modified nano titanium dioxide (the mass ratio of nano titanium dioxide to KH960 is 100:2) are mixed in the third reactor. After stirring at 90°C for 2 hours, the all-weather two-component reflective ceramic crystal marking paint is obtained. The mass ratio of the first component, the second component and the modified nano titanium dioxide is 45:45:10.

[0108] The prepared all-weather two-component reflective ceramic crystal road marking paint is constructed on the road surface by extrusion. The road marking height is 2-3 mm. The constructed marking is naturally dried at 15°C, and the drying time is recorded.

[0109] Comparative Example 1:

[0110] A method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0111] 1. Weigh poly(α-methyl cyanoacrylate) and add it to the first reaction kettle, then introduce nitrogen for 0.5 hours to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0112] 2. Then, a curing agent (benzoin dimethyl ether) and bentonite were added to the first reaction kettle, and the mixture was stirred for 2 hours under nitrogen protection. Titanium dioxide, tempered glass beads, anti-icing agent and double fly ash were added to the first reaction kettle, and the mixture was stirred for 1 hour under nitrogen protection. The first component was obtained by discharging the mixture.

[0113] In steps 1 and 2, the mass ratio of poly-α-cyanoacrylate, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:1:1:1:7:25:35;

[0114] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 0.5 hours to remove the air in the polymethacrylic acid and the second reactor;

[0115] 4. Then add the curing agent (benzoin dimethyl ether) and bentonite into the second reactor, stir for 2 hours under nitrogen protection, then add titanium dioxide, tempered glass beads, anti-icing agent and double fly ash into the second reactor, continue to stir for 1 hour under nitrogen protection, and discharge to obtain the second component;

[0116] In steps 3 and 4, the mass ratio of polymethacrylic acid, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is 30:1:1:1:7:25:35;

[0117] 5. Mix the first component and the second component in the third reaction kettle under nitrogen protection, stir at 80°C for 1 hour, and then obtain the all-weather two-component reflective ceramic crystal marking paint. The mass ratio of the first component to the second component is 50:50.

[0118] The prepared all-weather two-component reflective ceramic crystal marking paint was applied to the road surface by scraping. The height of the raised portion of the edge of the road marking was 1.8-2 mm. The constructed marking was dried naturally at 15° C., and the drying time was recorded.

[0119] Comparative Example 2:

[0120] A method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0121] 1. Weigh poly(α-methyl cyanoacrylate) and add it into the first reaction kettle, then introduce nitrogen for 0.5 hours to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0122] 2. Then, the curing agent (2-isopropylthioxanthone) and bentonite were added to the first reaction kettle, and stirred for 2 hours under nitrogen protection. Titanium dioxide, anti-icing agent and double fly ash were added to the first reaction kettle, and stirring was continued for 1 hour under nitrogen protection. The first component was obtained by discharging the material;

[0123] In steps 1 and 2, the mass ratio of the poly-α-cyanoacrylate, 2-isopropylthioxanthone, anti-icing agent, bentonite, titanium dioxide, and double fly ash is 25:0.5:1:0.5:10:63;

[0124] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 0.5 hours to remove the air in the polymethacrylic acid and the second reactor;

[0125] 4. Then add the curing agent (2-isopropylthioxanthone) and bentonite into the second reactor, stir for 2 hours under nitrogen protection, then add titanium dioxide, anti-icing agent and double fly ash into the second reactor, continue to stir for 1 hour under nitrogen protection, and discharge to obtain the second component;

[0126] In steps 3 and 4, the mass ratio of polymethacrylic acid, 2-isopropylthioxanthone, anti-icing agent, bentonite, titanium dioxide and double fly ash is 25:0.5:1:0.5:10:63;

[0127] 5. Under nitrogen protection, the first component, the second component and modified nano titanium dioxide (the mass ratio of nano titanium dioxide to KH792 is 100:1) are mixed in the third reactor. After stirring at 80°C for 1 hour, the all-weather two-component reflective ceramic crystal marking paint is obtained. The mass ratio of the first component, the second component and the modified nano titanium dioxide is 46:46:8.

[0128] The prepared all-weather two-component reflective ceramic crystal road marking paint is constructed on the road surface by extrusion. The road marking height is 2-3 mm. The constructed marking is naturally dried at 15°C, and the drying time is recorded.

[0129] Comparative Example 3:

[0130] A method for preparing an all-weather two-component reflective ceramic crystal road marking paint comprises the following steps:

[0131] 1. Weigh poly(α-methyl cyanoacrylate) and add it into the first reaction kettle, then introduce nitrogen for 1 hour to remove the air in the poly(α-methyl cyanoacrylate) and the first reaction kettle;

[0132] 2. Then add the curing agent (benzoin dimethyl ether) and bentonite into the first reaction kettle, stir for 2 hours under nitrogen protection, then add titanium dioxide, anti-icing agent and double fly ash into the first reaction kettle, continue to stir for 2 hours under nitrogen protection, and discharge to obtain the first component;

[0133] In steps 1 and 2, the mass ratio of poly-α-cyanoacrylate, benzoin dimethyl ether, anti-icing agent, bentonite, titanium dioxide, and double fly ash is 35:0.5:0.5:0.5:8.5:55;

[0134] 3. Weigh polymethacrylic acid and add it to the second reactor, then introduce nitrogen for 1 hour to remove the air in the polymethacrylic acid and the second reactor;

[0135] 4. Then add the curing agent (2-hydroxy-2-methyl propiophenone) and bentonite into the second reaction kettle, stir for 2 hours under nitrogen protection, then add titanium dioxide, anti-icing agent and double fly ash into the second reaction kettle, continue to stir for 2 hours under nitrogen protection, and discharge the material to obtain the second component;

[0136] In steps 3 and 4, the mass ratio of polymethacrylic acid, 2-hydroxy-2-methylpropiophenone, anti-icing agent, bentonite, titanium dioxide and double fly ash is 35:0.5:1:0.5:8:55;

[0137] 5. Mix the first component and the second component in the third reaction kettle under nitrogen protection, stir for 2 hours at 90°C, and then obtain the all-weather two-component reflective ceramic crystal marking paint. The mass ratio of the first component to the second component is 50:50.

[0138] The prepared all-weather two-component reflective ceramic crystal road marking paint is constructed on the road surface by extrusion. The road marking height is 2-3 mm. The constructed marking is naturally dried at 15°C, and the drying time is recorded.

[0139] Refer to GB / T 21383-2008 and use a retroreflective marking measuring instrument to test the initial retroreflective brightness coefficient of the all-weather two-component reflective ceramic crystal marking paint.

[0140] Refer to JT / T 690-2022 and use a retroreflective marking measuring instrument to test the retroreflective brightness coefficient of all-weather two-component reflective ceramic crystal marking paint during normal use.

[0141] The combination of the initial retroreflective brightness coefficient and the retroreflective brightness coefficient during normal use reflects the reflective performance of the all-weather two-component reflective ceramic crystal marking paint.

[0142] According to the actual situation of road construction, the drying time of the all-weather two-component reflective ceramic crystal marking paint is tested and recorded to reflect its curing performance.

[0143] Referring to GB / T 9780-2013, the anti-fouling performance of all-weather two-component reflective ceramic crystal road marking paint was tested using a paint anti-fouling tester.

[0144] With reference to GB / T 31815-2015, the decomposition test of organic matter (methyl red) was used to test the self-cleaning performance of the all-weather two-component reflective ceramic crystal road marking paint.

[0145] Table 1 Test results of reflective properties and curing properties of road marking paint in different embodiments

[0146]

[0147] As can be seen from Table 1, the initial retroreflective brightness coefficient and the retroreflective brightness coefficient during normal use of Examples 1 to 6 are higher than those of Comparative Examples 1 to 3, and the drying time of Examples 1 to 6 is shorter than that of Comparative Examples 1 to 3. This is because the introduction of modified nano-titanium dioxide in the all-weather two-component reflective ceramic crystal road marking paint of Examples 1 to 6 causes the organic groups on its surface to bond the first component and the second component together through chemical bonds, and also promotes the uniform dispersion of tempered glass beads. On the one hand, this can improve the reflectivity of the road marking paint, and on the other hand, it can greatly improve the curing efficiency of the road marking paint; thereby, the road marking paint can be cured without the need for heating equipment during use, greatly improving the construction efficiency. In Comparative Examples 1 to 3, there is either no modified nano-titanium dioxide or no tempered glass beads, so the initial retroreflective brightness coefficient and the retroreflective brightness coefficient during normal use are lower, and the drying time is longer.

[0148] Table 2 Test results of anti-fouling performance and self-cleaning performance of road marking paint in different embodiments

[0149]

[0150] As can be seen from Table 2, the anti-fouling grade and discoloration degree of Examples 1 to 6 are better than those of Comparative Examples 1 to 3. This is because, under the action of the preferred curing agent in the first component and the second component, the first component and the second component are firstly subjected to free radical polymerization reaction, cross-linked, and a high molecular weight polymer with a network structure is formed, and finally the high molecular weight polymer forms a film to produce an organic silicon coating. The low surface energy organic silicon coating makes it difficult for the road marking paint to be mixed with stains, which gives the road marking paint surface a high anti-fouling ability.

[0151] The presence of modified nano titanium dioxide makes the electrons in the valence band of the modified nano titanium dioxide jump to the conduction band when the road marking paint is exposed to ultraviolet light, and the electrons are excited and ionized, and positive holes are generated to form electron-hole pairs. The electron-hole pairs react with the oxygen and water adsorbed and dissolved on their surfaces to produce ·OH free radicals. The presence of ·OH free radicals can oxidize most organic and inorganic pollutants. Therefore, the road marking paint with uniformly dispersed modified nano titanium dioxide has a special self-cleaning function, which can effectively reduce the pollution and dirt adhesion on the surface of the coating, and keep the coating surface clean and beautiful. However, there is no modified nano titanium dioxide in Comparative Examples 1 and 3, so the anti-fouling performance and self-cleaning performance are poor.

[0152] The above results show and describe the basic principles and main features of the present invention as well as the advantages of the present invention.

[0153] Those skilled in the art should understand that the present invention is not limited by the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the equivalents of the appended claims.

Claims

1. An all-weather two-component reflective ceramic crystal road marking paint, characterized in that: The all-weather two-component reflective ceramic crystal road marking paint includes a first component, a second component and a modified nano titanium dioxide component; the first component includes poly methyl α-cyanoacrylate; the second component includes poly methacrylic acid; the modified nano titanium dioxide component is modified by a silane coupling agent; the poly methyl α-cyanoacrylate and poly methacrylic acid are chemically bonded together through the modified nano titanium dioxide component.

2. The all-weather two-component reflective ceramic crystal road marking paint according to claim 1, characterized in that: The first component also includes a curing agent, an anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash. The mass ratio of the poly-α-cyanoacrylate, curing agent, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is (25-35): (0.5-1): (0.5-1): (0.5-1): (5-10): (20-30): (30-40).

3. The all-weather two-component reflective ceramic crystal road marking paint according to claim 2, characterized in that: The second component also includes a curing agent, an anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash. The mass ratio of the polymethyl methacrylate, curing agent, anti-icing agent, bentonite, titanium dioxide, tempered glass beads, and double fly ash is (30-40): (0.5-1): (0.5-1): (0.5-2): (5-10): (20-30): (25-35).

4. The all-weather two-component reflective ceramic crystal road marking paint according to claim 3, characterized in that: The mesh number of the tempered glass beads is 40-50 meshes, and the softening temperature is 950° C.; the mesh number of the double fly ash is 1000 meshes.

5. The all-weather two-component reflective ceramic crystal road marking paint according to claim 3, characterized in that: The curing agent is one or more of benzoin dimethyl ether, 2-isopropylthioxanthone, and 2-hydroxy-2-methylacetophenone.

6. The all-weather two-component reflective ceramic crystal road marking paint according to claim 1, characterized in that: The silane coupling agent used in the modified nano titanium dioxide includes one or more of KH550, KH792 and KH960; the particle size of the modified nano titanium dioxide is in the range of 50 to 100 nm; the mass ratio of the nano titanium dioxide to the silane coupling agent is 100:(1 to 2).

7. A method for preparing an all-weather two-component reflective ceramic crystal road marking paint according to any one of claims 3 to 6, characterized in that: include: Weighing poly(methyl α-cyanoacrylate) and adding it into the first reaction kettle, and then introducing nitrogen for a first set time to remove the poly(methyl α-cyanoacrylate) and air in the first reaction kettle; Then, the curing agent and bentonite are added to the first reaction kettle, and stirred for a second set time under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the first reaction kettle, and stirring is continued for a third set time under nitrogen protection. The first component is obtained by discharging the material; Then, polymethacrylic acid is weighed and added into the second reaction kettle, and then nitrogen is introduced for a first set time to remove air from the polymethacrylic acid and the second reaction kettle; Then, the curing agent and bentonite are added to the second reaction kettle, and stirred for a second set time under nitrogen protection. Then, titanium dioxide, tempered glass beads, anti-icing agent and double fly ash are added to the second reaction kettle, and stirring is continued for a third set time under nitrogen protection. The second component is obtained by discharging the material; The first component, the second component and the modified nano titanium dioxide are mixed in a third reaction kettle under nitrogen protection, and after stirring for a fourth set time at a set temperature, the all-weather two-component reflective ceramic crystal road marking paint is obtained.

8. The method for preparing an all-weather two-component reflective ceramic crystal road marking paint according to claim 7, characterized in that: The first setting time is 0.5 to 1 hour; the second setting time is 2 to 3 hours, the third setting time is 1 to 2 hours; the fourth setting time is 1 to 2 hours; the setting temperature is 80 to 100°C; the mass ratio of the first component, the second component and the modified nano titanium dioxide is (40 to 50): (40 to 50): (5 to 10).

9. The use of an all-weather two-component reflective ceramic crystal road marking paint as claimed in any one of claims 1 to 6, characterized in that: Used in the preparation of road markings.

10. The use of an all-weather two-component reflective ceramic crystal road marking paint according to claim 9, characterized in that: include: The all-weather two-component reflective ceramic crystal road marking paint is applied on the road surface by scraping to form road markings. The height of the raised part of the edge of the road marking is 1.8 to 2 mm. The road marking formed by the construction is naturally dried at 0 to 30 degrees Celsius. Or the all-weather two-component reflective ceramic crystal marking paint can be applied to the road surface by extrusion to form road markings. The road marking height is 2 to 3 mm. The formed road markings are naturally dried at 0 to 30°C.

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