Self-cleaning reflective paint for anti-collision wall of expressway and preparation method of self-cleaning reflective paint

Abstract

The invention relates to self-cleaning reflective paint for an anti-collision wall of an expressway and a preparation method of the self-cleaning reflective paint. The self-cleaning reflective paint for the anti-collision wall of the expressway comprises the following components in parts by mass: 10-20 parts of organosilicon acrylic resin, 10-20 parts of modified polyacrylate, 5-20 parts of modified glass beads, 10-20 parts of a photocatalyst, 1-10 parts of an auxiliary agent and 1-10 parts of a solvent, wherein the modified polyacrylate is obtained by reacting fluorine-containing acrylate, glycidyl acrylate and alkyl acrylate; the modified glass beads are obtained by reacting a rare earth material, cellulose, a silane coupling agent and glass beads. The reflective paint has the advantages that the reflective effect of the reflective paint is improved, the stability, weather resistance and other properties are enhanced, the product is endowed with a certain self-cleaning function, the protective effect can be more effectively exerted, the safety of road traffic is guaranteed, and the problems in the prior art are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and particularly to a self-cleaning reflective paint for highway crash barriers and a preparation method thereof. Background Art

[0002] Highway crash barrier reflective paint is a high-performance coating specifically used for traffic safety facilities, mainly used to improve the visibility of crash barriers at night or under low visibility conditions, thereby enhancing road safety. Such products need to have extremely strong reflective performance, be able to reflect light under the illumination of vehicle lights, enable drivers to clearly identify the position and contour of the crash barrier, and reduce the occurrence of traffic accidents.

[0003] Existing reflective paint products usually use glass microspheres or reflective particles with high refractive indices as the core materials, combined with resin binders (such as acrylic resin or epoxy resin), to ensure certain weather resistance and adhesion, and achieve the reflective and prompting effects. However, conventional glass microspheres not only have insufficient reflective effects, but also have unsatisfactory binding properties with resin materials, are prone to agglomeration and shedding, resulting in defects such as inconsistent reflective effects and affecting driver judgment. At the same time, conventional resins are also difficult to maintain stability under harsh environments such as long-term sunlight, rain, high and low temperatures, are prone to phenomena such as aging, peeling, and discoloration, and may also adhere to a large amount of oil and dust, seriously affecting the reflective effect and being difficult to maintain.

[0004] However, the improvement effects of current technical solutions on the above-mentioned disadvantages of reflective paint are still not ideal. How to effectively improve the reflective effect and various properties such as waterproof, anti-corrosion, anti-ultraviolet, and weather resistance of reflective paint to improve the service life of crash barriers is a problem that needs to be continuously solved in this field.

[0005] In summary, it is necessary to develop a new technical solution to solve the deficiencies in the existing technology. Summary of the Invention

[0006] Based on this, the present invention provides a self-cleaning reflective paint for highway crash barriers and a preparation method thereof. The present invention uses a compound of organosilicon acrylate resin, modified polyacrylate, and modified glass microspheres, etc., which not only improves the reflective effect of the reflective paint, but also enhances various properties such as stability and weather resistance, and endows the product with a certain self-cleaning function, can play a more effective protective role, ensures the safety of road traffic, and solves the problems existing in the prior art.

[0007] An object of the present invention is to provide a self-cleaning reflective paint for highway crash barriers, and the self-cleaning reflective paint for highway crash barriers comprises components in the following parts by mass:

[0008]

[0009]

[0010] Among them,

[0011] The modified polyacrylate is obtained by reacting a fluorinated acrylate, glycidyl acrylate, and an alkyl acrylate;

[0012] The modified glass microspheres are obtained by reacting a rare earth material, cellulose, a silane coupling agent, and glass microspheres.

[0013] Furthermore, the rare earth material is yttrium oxide.

[0014] Furthermore, the auxiliary agent is selected from one or more of a bactericide, a mildew preventive, an antifreeze, a dispersant, a wetting agent, an antifoaming agent, a film-forming auxiliary agent, a thickener, an initiator, a curing agent, and a crosslinking agent.

[0015] Furthermore, the cellulose is cellulose containing an unsaturated double bond.

[0016] Furthermore, the silane coupling agent is a silane coupling agent containing an unsaturated double bond.

[0017] Another object of the present invention is to provide a method for preparing the above-mentioned self-cleaning reflective paint for highway crash barriers, and the method for preparing the self-cleaning reflective paint for highway crash barriers includes the following steps:

[0018] S1. Mix the rare earth material and the silane coupling agent, and after heating and reacting, obtain an intermediate product;

[0019] S2. Mix the glass microspheres and the silane coupling agent, and after heating and reacting, mix with the intermediate product, cellulose, and initiator, and continue to react to obtain modified glass microspheres;

[0020] S3. Mix the fluorinated acrylate, glycidyl acrylate, alkyl acrylate, and initiator, and under an inert gas atmosphere, heat and stir to react to obtain a modified polyacrylate;

[0021] S4. Mix the modified glass microspheres, modified polyacrylate, organosilicon acrylate, photocatalyst, auxiliary agent, and solvent, and stir and disperse evenly to obtain the self-cleaning reflective paint for highway crash barriers.

[0022] Furthermore, in step S2, the mass ratio of the glass microspheres, intermediate product, and cellulose is (5 - 15):(1 - 3):(1 - 5).

[0023] Furthermore, in step S2, the temperature of the heating reaction is 60 - 100 °C.

[0024] Further, in step S3, the mass ratio of the fluoroacrylate, glycidyl acrylate and alkyl acrylate is (1 - 5):(1 - 10):(5 - 10).

[0025] Further, in step S3, the temperature of the heating and stirring reaction is 60 - 100 °C.

[0026] The present invention has the following beneficial effects:

[0027] The self-cleaning reflective paint for highway crash barriers provided by the present invention uses substances such as organosilicon acrylate resin, modified polyacrylate and modified glass beads as the main components. The modified glass beads are obtained by reacting glass beads treated with a silane coupling agent to introduce double bonds with cellulose and rare earth materials (yttrium oxide) containing double bonds, and a cellulose and rare earth fluorescent material are coated on the outer layer of the glass beads. On the one hand, cellulose has a macromolecular structure, contains rich active groups, and has a thickening effect, thereby improving the compatibility between the modified glass beads and the acrylate resin and avoiding the agglomeration and shedding of the glass beads; on the other hand, the rare earth fluorescent material can chemically crosslink with the glass beads and cellulose through double bonds, and cellulose also has excellent adsorption function, improving the binding strength with the rare earth materials. The modified glass beads have better reflective and fluorescent properties. After being compounded with a photocatalyst, they can further exert multiple photocatalytic activities, greatly enhancing the reflective effect of the product.

[0028] The modified polyacrylate of the present invention is obtained by reacting an alkyl acrylate with hexafluorobutyl acrylate and glycidyl acrylate, introducing a fluorocarbon segment and an epoxy group into the polyacrylate. It can not only reduce the surface energy of the coating, improve water and corrosion resistance, and has a self-cleaning function when combined with a hydrophobic aid; it can also crosslink with the modified glass beads and other components through the epoxy group to form a more three-dimensional network structure, thereby enhancing the strength and stability of the paint film, enabling the product to adapt to various climate conditions, having a longer service life, and achieving a more excellent protective effect. Detailed Embodiments

[0029] In order to more clearly illustrate the technical solutions of the present invention, the following examples are listed. The raw materials, reactions and post-treatment means appearing in the examples are all common raw materials on the market and technical means well-known to those skilled in the art, unless otherwise specified.

[0030] The terms "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain cases. However, in the same or other cases, other embodiments may also be preferred. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not available, nor is it intended to exclude other embodiments from the scope of the present invention.

[0031] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0032] The organic silicon acrylic resin in the embodiment of the present invention is Badful RS3788.

[0033] The glass microspheres in the embodiment of the present invention are 500 mesh.

[0034] The additives in the embodiment of the present invention include a mildew preventer (ROCIMA 342) in a mass ratio of 0.1:0.4:0.5:1:2:1, an antifreeze agent (propylene glycol), a defoamer (SI 2292, BASF), a film-forming aid (lauryl alcohol ester), a hydrophobic agent (PTFE, Solvay F5A, USA) and an emulsifier (OP-10, Aladdin).

[0035] The cellulose in the embodiment of the present invention is cellulose containing unsaturated double bonds, and the preparation method thereof comprises the following steps:

[0036] 3 g of cellulose acetate (purchased from Aladdin) was dissolved in 40 mL of N, N-dimethylacetamide, and then 2.5 g of triethylamine was added to obtain solution 1; 1.3 g of methacryloyl chloride was added to 20 mL of N, N-dimethylacetamide to obtain solution 2. Solution 2 was dropped into solution 1 under a nitrogen atmosphere of -5°C, and then reacted at 25°C for 24 hours, precipitated with deionized water, and the product was obtained after filtration, washing, and drying.

[0037] The "parts" in the embodiments of the present invention refer to parts by mass.

[0038] Example 1

[0039] A self-cleaning reflective paint for a highway crash barrier, comprising the following components in parts by weight:

[0040]

[0041] The method for preparing the self-cleaning reflective paint for the highway crash barrier comprises the following steps:

[0042] S1. Using ethanol as solvent, mix yttrium oxide and KH570 in a mass ratio of 2:1, react at 60°C for 6h, filter, wash and dry to obtain an intermediate product;

[0043] S2. Using ethanol as a solvent, mix glass microspheres and KH570 at a mass ratio of 2:1, react at 60 °C for 6 h, after filtration, washing and drying, mix with the intermediate product, cellulose and initiator (the mass ratio of glass microspheres, intermediate product, cellulose and ammonium persulfate is 10:1:2:0.01), using toluene as a solvent, react at 80 °C for 2 h under a nitrogen atmosphere, after filtration, washing and drying, obtain modified glass microspheres;

[0044] S3. Using ethyl acetate as a solvent, mix hexafluorobutyl acrylate, glycidyl methacrylate, methyl methacrylate and azobisisobutyronitrile at a mass ratio of 3:5:10:0.9, under a nitrogen atmosphere, stir and react at 80 °C for 4 h, after removing the solvent by vacuum distillation, obtain modified polyacrylate;

[0045] S4. According to the above mass parts, mix the modified glass microspheres, modified polyacrylate, organosilicon acrylate, photocatalyst, additives and solvent, stir and disperse evenly to obtain the self-cleaning reflective paint for highway crash barriers.

[0046] Example 2

[0047] A self-cleaning reflective paint for highway crash barriers, comprising the following components in mass parts:

[0048]

[0049] The preparation method of the self-cleaning reflective paint for highway crash barriers comprises the following steps:

[0050] S1. Using ethanol as a solvent, mix yttrium oxide and KH570 at a mass ratio of 2:1, react at 60 °C for 6 h, after filtration, washing and drying, obtain an intermediate product;

[0051] S2. Using ethanol as a solvent, mix glass microspheres and KH570 at a mass ratio of 2:1, react at 60 °C for 6 h, after filtration, washing and drying, mix with the intermediate product, cellulose and initiator (the mass ratio of glass microspheres, intermediate product, cellulose and ammonium persulfate is 10:1:2:0.01), using toluene as a solvent, react at 80 °C for 2 h under a nitrogen atmosphere, after filtration, washing and drying, obtain modified glass microspheres;

[0052] S3. Using ethyl acetate as a solvent, mix hexafluorobutyl acrylate, glycidyl methacrylate, methyl methacrylate and azobisisobutyronitrile at a mass ratio of 3:5:10:0.9, under a nitrogen atmosphere, stir and react at 80 °C for 4 h, after removing the solvent by vacuum distillation, obtain modified polyacrylate;

[0053] S4. According to the above mass parts, mix the modified glass microspheres, modified polyacrylate, silicone acrylate, photocatalyst, auxiliary agent and solvent, and stir and disperse them evenly to obtain the self-cleaning reflective paint for highway crash barriers.

[0054] Example 3

[0055] A self-cleaning reflective paint for highway crash barriers, comprising the following components in mass parts:

[0056]

[0057] The preparation method of the self-cleaning reflective paint for highway crash barriers comprises the following steps:

[0058] S1. Using ethanol as a solvent, mix yttrium oxide and KH570 in a mass ratio of 2:1, react at 60°C for 6 h, filter, wash and dry to obtain an intermediate product;

[0059] S2. Using ethanol as a solvent, mix glass microspheres and KH570 in a mass ratio of 2:1, react at 60°C for 6 h, filter, wash and dry, and then mix with the intermediate product, cellulose and initiator (the mass ratio of glass microspheres, intermediate product, cellulose and ammonium persulfate is 10:1:2:0.01). Using toluene as a solvent, react at 80°C for 2 h under a nitrogen atmosphere, filter, wash and dry to obtain modified glass microspheres;

[0060] S3. Using ethyl acetate as a solvent, mix hexafluorobutyl acrylate, glycidyl methacrylate, methyl methacrylate and azobisisobutyronitrile in a mass ratio of 3:5:10:0.9, stir and react at 80°C for 4 h under a nitrogen atmosphere, and remove the solvent by vacuum distillation to obtain modified polyacrylate;

[0061] S4. According to the above mass parts, mix the modified glass microspheres, modified polyacrylate, silicone acrylate, photocatalyst, auxiliary agent and solvent, and stir and disperse them evenly to obtain the self-cleaning reflective paint for highway crash barriers.

[0062] Comparative Example 1

[0063] A self-cleaning reflective paint for highway crash barriers. The difference between this comparative example and Example 1 is that steps S1 and S2 are deleted and replaced with: Using ethanol as a solvent, mix glass microspheres and KH570 in a mass ratio of 2:1, react at 60°C for 6 h, filter, wash and dry, and then mix the product with yttrium oxide and cellulose in a mass ratio of 10:1:2 to obtain modified glass microspheres. The other components and preparation methods are the same as those in Example 1.

[0064] Comparative Example 2

[0065] An anti-collision wall self-cleaning reflective paint for expressways. The difference between this comparative example and Example 1 is as follows: Step S3 is deleted, and the modified polyacrylate is replaced with an organosilicon acrylate resin. Other components and the preparation method are the same as those in Example 1.

[0066] Test example

[0067] Perform performance tests on the anti-collision wall self-cleaning reflective paints prepared in Examples 1-3 and Comparative Examples 1-2.

[0068] The test method is as follows:

[0069] Refer to standards such as GB / T 6739, GB / T 9286, GB / T 9780, and GB / T 14522 to conduct hardness, adhesion, stain resistance, artificial weathering acceleration resistance, and reflectivity tests.

[0070] The test results are shown in Table 1.

[0071] Table 1 Performance test results

[0072] Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hardness HB HB HB HB HB Adhesion Grade 1 Grade 1 Grade 1 Grade 2 Grade 1 Stain resistance / % 9.4 9.9 9.5 10.2 17.6 Weather resistance / 4000h No bubbles, cracks No bubbles, cracks No bubbles, cracks Bubbles, cracks Bubbles <![CDATA[Reflectance / mcd / lx·m 2 > ≥500 ≥500 ≥500 421 495

[0073] It can be concluded from Table 1 that the anti-collision wall self-cleaning reflective paints prepared in Examples 1-3 of the present invention have good strength, excellent adhesion, and weather resistance, can also achieve a certain self-cleaning function, have good stain resistance, and especially have an extremely high reflectivity, significantly superior to the national standard of 300 mcd / lx·m. 2 Moreover, the compatibility, cross-linking, and bonding strength among different components of Comparative Examples 1-2, in which the modified glass beads or modified polyacrylate are replaced, are significantly reduced. Therefore, the reflectivity is significantly reduced, the reflective performance is insufficient, and at the same time, the stability is poor and the weather resistance is not ideal. The stain resistance of Comparative Example 2 also drops greatly, making it difficult to meet the relatively high requirements of practical applications.

[0074] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to embrace all changes falling within the meaning and scope of the equivalent elements of the claims within the present invention.

[0075] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A self-cleaning reflective paint for highway crash barriers, characterized in that: The self-cleaning reflective paint for highway crash barriers comprises the following components in parts by mass: in, The modified polyacrylate is obtained by reacting fluorine-containing acrylate, glycidyl acrylate and alkyl acrylate; The modified glass microspheres are obtained by reacting rare earth materials, cellulose, a silane coupling agent and glass microspheres.

2. The self-cleaning reflective paint for highway crash barriers according to claim 1 is characterized in that: The rare earth material is yttrium oxide.

3. The self-cleaning reflective paint for highway crash barriers according to claim 1 is characterized in that: The auxiliary agent is selected from one or more of bactericides, mildew inhibitors, antifreeze agents, dispersants, wetting agents, defoaming agents, film-forming aids, thickeners, initiators, curing agents, and cross-linking agents.

4. The self-cleaning reflective paint for highway crash barriers according to claim 1 is characterized in that: The cellulose is cellulose containing unsaturated double bonds.

5. The self-cleaning reflective paint for highway crash barriers according to claim 1 is characterized in that: The silane coupling agent is a silane coupling agent containing unsaturated double bonds.

6. The method for preparing the self-cleaning reflective paint for highway crash barriers according to any one of claims 1 to 5, characterized in that: The preparation method of the highway crash barrier self-cleaning reflective paint comprises the following steps: S1, mixing the rare earth material and the silane coupling agent, heating and reacting to obtain an intermediate product; S2, mixing the glass microspheres with the silane coupling agent, heating for reaction, and then mixing with the intermediate product, cellulose and an initiator, and continuing the reaction to obtain modified glass microspheres; S3, mixing fluorinated acrylate, glycidyl acrylate, alkyl acrylate and an initiator, heating and stirring under an inert gas atmosphere to react, to obtain modified polyacrylate; S4, mixing the modified glass microbeads, modified polyacrylate, silicone acrylate, photocatalyst, additive and solvent, stirring and dispersing them evenly, and obtaining the highway crash barrier self-cleaning reflective paint.

7. The method for preparing the self-cleaning reflective paint for highway crash barriers according to claim 6, characterized in that: In step S2, the mass ratio of the glass beads, the intermediate product and the cellulose is (5-15):(1-3):(1-5).

8. The method for preparing the self-cleaning reflective paint for highway crash barriers according to claim 6, characterized in that: In step S2, the temperature of the heating reaction is 60-100°C.

9. The method for preparing the self-cleaning reflective paint for highway crash barriers according to claim 6, characterized in that: In step S3, the mass ratio of the fluorine-containing acrylate, glycidyl acrylate and alkyl acrylate is (1-5):(1-10):(5-10).

10. The method for preparing the self-cleaning reflective paint for highway crash barriers according to claim 6, characterized in that: In step S3, the temperature of the heating and stirring reaction is 60-100°C.

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