High-adhesion glass microbeads for highway marking and method for preparing the same

Abstract

The application discloses a kind of high adhesive highway marking glass microspheres, and the glass microspheres are surface complexing treated glass microspheres.The glass microspheres prepared by the application are firmly combined with the adhesive component in road marking paint, the prepared road marking paint has strong wear resistance, the glass beads are not easy to fall off, at the same time, the prepared road marking paint has good stain resistance and is not easy to be contaminated with dust.In the preparation process, argon bombardment is used to improve the adhesion of the surface of the glass microspheres, 2-methyl acrylic acid chromium tetrachloride and isopropoxy titanium tristearate are combined to treat, which improves the wear resistance of the glass microspheres;Silane coupling agent KH-550 and silane coupling agent KH-602 are used in combination to improve the stain resistance of the material.

Description

Technical Field

[0001] This invention belongs to the field of highway marking technology, specifically relating to a high-adhesion glass microsphere for highway markings and its preparation method. Background Technology

[0002] Glass microspheres, as the core material for achieving nighttime retroreflective functionality in road markings, suffer from weak adhesion to the paint matrix, a key bottleneck restricting the service life (lack of wear resistance) and reflective durability of the markings. This deficiency stems from the inherent physical and chemical incompatibility between the inorganic silicate properties of glass microspheres and the organic polymer resins in the paint. The surface of glass microspheres exhibits polar hydrophilic properties, while most road marking paints use resins (such as hot-melt petroleum resins, epoxy, or acrylic resins) that are organic hydrophobic systems. The high interfacial tension between the two makes it difficult to form a strong chemical bond, relying primarily on physical interlocking. Under the repeated action of wheel rolling and shear stress, this weak interface is prone to stress concentration, causing the microspheres to peel off from the coating. This not only results in a sharp decrease in the retroreflective coefficient but also renders the markings ineffective. Research indicates that the embedding depth of the glass microspheres is a crucial construction parameter affecting adhesion strength: if embedded too shallowly, the microspheres are easily detached under stress; if embedded too deeply, light cannot be effectively reflected back. Ideally, approximately half the volume of the microspheres should be embedded in the coating. To fundamentally improve interfacial adhesion, the industry commonly employs coupling agents to treat the surface of glass microspheres, a process known as "coating." Increasing the surface roughness of microspheres through acid-base etching to enhance the mechanical "anchoring" effect, or introducing active groups through plasma treatment, are also effective technical approaches to improve compatibility. Therefore, addressing the inherent weakness in the adhesion between glass microspheres and coatings requires a multi-dimensional approach, including interfacial chemical modification, particle size distribution optimization, and construction process control, to achieve a long-term balance between the reflectivity and durability of road markings.

[0003] Increasing the surface roughness of microspheres through acid-base etching or other physical treatments to enhance the mechanical "anchoring" effect and improve adhesion performance also introduces another drawback: reduced anti-fouling properties, making the surface more susceptible to dust or dirt adhesion. Therefore, further surface treatment is necessary, and currently, there is no effective technology to overcome this defect. Summary of the Invention

[0004] The purpose of this invention is to provide a high-adhesion glass microsphere for highway markings and its preparation method.

[0005] A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0006] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the vacuum, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres. (2) Take out the glass microspheres treated in step (1) and boil them in an acidic aqueous solution with a pH of 4-6; (3) Dissolve chromium tetrachloride 2-methacrylate (CAS No.: 15096-41-0) and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 1-3% for chromium tetrachloride 2-methacrylate and a mass concentration of 1-3% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1-2 hours, take them out, and dry them. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 3-6%. Immerse the glass microspheres treated in step (3) in the above solution for 1-3 hours, take them out, and dry them.

[0007] The inert gas in step (1) is argon, and the gas flow rate is 0.5-1.0 L / min.

[0008] The power of the RF power supply in step (1) is 50-300W, and the bombardment time is 80-300s.

[0009] The acidic aqueous solution in step (2) is hydrochloric acid or citric acid aqueous solution.

[0010] The drying temperature in step (3) is 55-75℃ and the drying time is 20-60min.

[0011] The drying temperature in step (4) is 65-85℃ and the drying time is 30-80min.

[0012] The silane coupling agent is one or more of the following: silane coupling agent KH-550, silane coupling agent KH-570, silane coupling agent KH-602, and silane coupling agent KH-171.

[0013] The beneficial effects of this invention are as follows: The glass microspheres prepared by this invention bond firmly with the adhesive components in road marking paint, resulting in road marking paint with strong wear resistance and minimal glass bead detachment. Simultaneously, the prepared road marking paint exhibits good stain resistance and is not easily stained by dust. Argon bombardment during the preparation process improves the adhesion of the glass microsphere surface; combined treatment with chromium tetrachloride 2-methacrylate and isopropoxytetrate titanate enhances the wear resistance of the glass microspheres; and the combined use of silane coupling agents KH-550 and KH-602 improves the material's stain resistance. Detailed Implementation

[0014] To facilitate understanding of the present invention, a more comprehensive description will be given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention. Example 1

[0015] A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0016] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the chamber, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 0.8 L / min; the power of the radio frequency power supply is 180W, and the bombardment time is 120s. (2) Take out the glass microspheres treated in step (1) and boil them in hydrochloric acid aqueous solution with pH 4.5; (3) Dissolve chromium tetrachloride 2-methacrylate and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 2% for chromium tetrachloride 2-methacrylate and a mass concentration of 2% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1.5 hours, take them out, and dry them. The drying temperature is 65°C and the drying time is 40 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 5%. Immerse the glass microspheres treated in step (3) in the above solution for 2 hours, take them out, and dry them. The drying temperature is 75°C and the drying time is 60 minutes. The silane coupling agent is a mixture of silane coupling agent KH-550 and silane coupling agent KH-602 mixed in a mass ratio of 2:1. Example 2

[0017] A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0018] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the chamber, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 0.6L / min; the power of the radio frequency power supply is 80W, and the bombardment time is 120s. (2) Take out the glass microspheres treated in step (1) and boil them in hydrochloric acid aqueous solution with pH 4; (3) Dissolve chromium tetrachloride 2-methacrylate and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 1.5% for chromium tetrachloride 2-methacrylate and a mass concentration of 1.5% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1 hour, take them out, and dry them. The drying temperature is 60°C and the drying time is 30 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 3%. Immerse the glass microspheres treated in step (3) in the above solution for 1 hour, take them out, and dry them. The drying temperature is 70°C and the drying time is 40 minutes. The coupling agent is a mixture of silane coupling agent KH-570 and silane coupling agent KH-171 mixed in a mass ratio of 1:1. Example 3

[0019] A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0020] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate and continuously introduce inert gas, turn on the radio frequency power supply and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 1.0 L / min; the power of the radio frequency power supply is 200W and the bombardment time is 180s. (2) Take out the glass microspheres treated in step (1) and boil them in a citric acid aqueous solution with a pH of 5.5; (3) Dissolve chromium tetrachloride 2-methacrylate and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 2.5% for chromium tetrachloride 2-methacrylate and a mass concentration of 2.5% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 2 hours, take them out, and dry them. The drying temperature is 70°C and the drying time is 50 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 5%. Immerse the glass microspheres treated in step (3) in the above solution for 3 hours, take them out, and dry them. The drying temperature is 80°C and the drying time is 60 minutes. The silane coupling agent is a mixture of silane coupling agent KH-550 and silane coupling agent KH-171 mixed in a mass ratio of 1:2.

[0021] Comparative Example 1 A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0022] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the chamber, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 0.8 L / min; the power of the radio frequency power supply is 180W, and the bombardment time is 120s. (2) Take out the glass microspheres treated in step (1) and boil them in hydrochloric acid aqueous solution with pH 4.5; (3) Dissolve chromium tetrachloride of 2-methacrylate in acetone to prepare a solution with a mass concentration of 4% chromium tetrachloride of 2-methacrylate. Immerse the glass microspheres treated in step (2) in the above solution for 1.5 hours, take them out, and dry them. The drying temperature is 65°C and the drying time is 40 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 5%. Immerse the glass microspheres treated in step (3) in the above solution for 2 hours, take them out, and dry them. The drying temperature is 75°C and the drying time is 60 minutes. The silane coupling agent is a mixture of silane coupling agent KH-550 and silane coupling agent KH-602 mixed in a mass ratio of 2:1.

[0023] Comparative Example 2 A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0024] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the chamber, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 0.8 L / min; the power of the radio frequency power supply is 180W, and the bombardment time is 120s. (2) Take out the glass microspheres treated in step (1) and boil them in hydrochloric acid aqueous solution with pH 4.5; (3) Dissolve isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 4% isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1.5 hours, take them out, and dry them. The drying temperature is 65°C and the drying time is 40 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 5%. Immerse the glass microspheres treated in step (3) in the above solution for 2 hours, take them out, and dry them. The drying temperature is 75°C and the drying time is 60 minutes. The silane coupling agent is a mixture of silane coupling agent KH-550 and silane coupling agent KH-602 mixed in a mass ratio of 2:1.

[0025] Comparative Example 3 A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0026] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the chamber, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 0.8 L / min; the power of the radio frequency power supply is 180W, and the bombardment time is 120s. (2) Take out the glass microspheres treated in step (1) and boil them in hydrochloric acid aqueous solution with pH 4.5; (3) Dissolve chromium tetrachloride 2-methacrylate and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 2% for chromium tetrachloride 2-methacrylate and a mass concentration of 2% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1.5 hours, take them out, and dry them. The drying temperature is 65°C and the drying time is 40 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 5%. Immerse the glass microspheres treated in step (3) in the above solution for 2 hours, take them out, and dry them. The drying temperature is 75°C and the drying time is 60 minutes. The silane coupling agent is silane coupling agent KH-550.

[0027] Comparative Example 4 A type of high-adhesion glass microsphere for road marking, wherein the glass microsphere is a glass microsphere whose surface has undergone complexation treatment.

[0028] The preparation method of the high-adhesion glass microspheres for road markings is carried out according to the following steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the chamber, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres; the inert gas is argon, the gas flow rate is 0.8 L / min; the power of the radio frequency power supply is 180W, and the bombardment time is 120s. (2) Take out the glass microspheres treated in step (1) and boil them in hydrochloric acid aqueous solution with pH 4.5; (3) Dissolve chromium tetrachloride 2-methacrylate and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 2% for chromium tetrachloride 2-methacrylate and a mass concentration of 2% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1.5 hours, take them out, and dry them. The drying temperature is 65°C and the drying time is 40 minutes. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 5%. Immerse the glass microspheres treated in step (3) in the above solution for 2 hours, take them out, and dry them. The drying temperature is 75°C and the drying time is 60 minutes. The silane coupling agent is silane coupling agent KH-602.

[0029] Experimental example: There is no national standard for directly measuring the adhesive properties of glass microspheres. The good adhesive properties of glass microspheres are directly manifested in their wear resistance and resistance to detachment. Using the glass microspheres of this invention, a road marking paint was prepared according to the formulation of Example 1 in the inventor's previous patent 202410124382.2, a novel two-component road marking paint. The prepared paint was tested according to the industry standard JT / T280-2004 for road marking paint. The tested indicators were wear resistance (weight loss after 200 revolutions / 1000g, mg) and stain resistance (coating thickness 1mm, dust was sprinkled on the sample and swept with a broom).

[0030] Each experiment was repeated three times and the average value was taken. SPSS 24.0 software was used for statistical analysis. The results of the continuous data were expressed as x̅±s (mean ± standard deviation). The Kolmogorov-Smirnov test was used to test the normality of the data. For data that conformed to normal distribution, the t-test was used to compare the differences in means between the two groups. P<0.05 was considered to be statistically significant.

[0031] The measurement results are shown in Table 1-2: Table 1

[0032] Note: * indicates P < 0.05 compared to Example 1 group. Table 2

[0033] Note: * indicates P < 0.05 compared to Example 1 group. The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A type of high-adhesion glass microsphere for highway markings, characterized in that, The glass microspheres are glass microspheres whose surface has undergone complexation treatment.

2. The method for preparing the high-adhesion glass microspheres for road markings according to claim 1, characterized in that, Follow these steps: (1) Place the glass microspheres into the reaction chamber of the plasma processor, evacuate the vacuum, continuously introduce inert gas, turn on the radio frequency power supply, and bombard the glass microspheres. (2) Take out the glass microspheres treated in step (1) and boil them in an acidic aqueous solution with a pH of 4-6; (3) Dissolve chromium tetrachloride 2-methacrylate and isopropoxytearyl titanate in acetone to prepare a solution with a mass concentration of 1-3% for chromium tetrachloride 2-methacrylate and a mass concentration of 1-3% for isopropoxytearyl titanate. Immerse the glass microspheres treated in step (2) in the above solution for 1-2 hours, take them out, and dry them. (4) Dissolve the silane coupling agent in ethanol to prepare a solution with a mass concentration of 3-6%. Immerse the glass microspheres treated in step (3) in the above solution for 1-3 hours, take them out, and dry them.

3. The method for preparing high-adhesion glass microspheres for road markings according to claim 2, characterized in that, The inert gas in step (1) is argon, and the gas flow rate is 0.5-1.0 L / min.

4. The method for preparing high-adhesion glass microspheres for road markings according to claim 2, characterized in that, The power of the RF power supply in step (1) is 50-300W, and the bombardment time is 80-300s.

5. The method for preparing high-adhesion glass microspheres for road markings according to claim 2, characterized in that, The acidic aqueous solution in step (2) is hydrochloric acid or citric acid aqueous solution.

6. The method for preparing high-adhesion glass microspheres for highway markings according to claim 2, characterized in that, The drying temperature in step (3) is 55-75℃ and the drying time is 20-60min.

7. The method for preparing high-adhesion glass microspheres for road markings according to claim 2, characterized in that, The drying temperature in step (4) is 65-85℃ and the drying time is 30-80min.

8. The method for preparing high-adhesion glass microspheres for road markings according to claim 2, characterized in that, The silane coupling agent is one or more of the following: silane coupling agent KH-550, silane coupling agent KH-570, silane coupling agent KH-602, and silane coupling agent KH-171.

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