Self-cleaning reflective paint for highway crash barriers and preparation method thereof

Abstract

The present application relates to a kind of expressway anti-collision wall self-cleaning reflective paint and its preparation method, the expressway anti-collision wall self-cleaning reflective paint includes the component as follows by mass fraction: silicone acrylic resin 10-20 parts, modified polyacrylate 10-20 parts, modified glass microsphere 5-20 parts, photocatalyst 10-20 parts, auxiliary agent 1-10 parts, solvent 1-10 parts;Wherein, the modified polyacrylate is fluorine-containing acrylate, glycidyl acrylate and acrylic alkyl ester reaction obtained;The modified glass microsphere is rare earth material, cellulose, silane coupling agent and glass microsphere reaction obtained.The present application not only improves the reflective effect of reflective paint, but also enhances stability, weather resistance Multiple performance, and give product certain self-cleaning function, can more effectively play the protection effect, ensure the safety of road traffic, solve the problems in the prior art.

Description

Technical Field

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

[0002] Highway crash barrier reflective paint is a high-performance coating specifically designed for traffic safety installations. It's primarily used to enhance the visibility of crash barriers at night or in low-visibility conditions, thereby enhancing road safety. This product requires exceptionally strong reflective properties, capable of reflecting light from headlights, allowing drivers to clearly identify the location and outline of the crash barrier, thereby reducing the risk of traffic accidents.

[0003] Existing reflective paint products usually use high-refractive index glass beads or reflective particles as the core material, combined with a resin base material (such as acrylic resin or epoxy resin) to ensure a certain degree of weather resistance and adhesion to achieve reflective and warning effects. However, conventional glass beads not only have the problem of insufficient reflective effect, but also have less than ideal bonding with the resin material. They are prone to agglomeration and falling off, resulting in inconsistent reflective effects and affecting the driver's judgment. At the same time, conventional resins are also difficult to maintain stability in harsh environments such as long-term sun exposure, rain, high and low temperatures, and are prone to aging, peeling, discoloration, etc. They may also adhere to a large amount of oil and dust, seriously affecting the reflective effect and making it difficult to maintain.

[0004] However, current technical solutions for addressing the aforementioned shortcomings of reflective paint are still not ideal. How to effectively improve the reflective effect of reflective paint and its waterproof, anti-corrosion, UV resistance, weather resistance and other properties to extend the service life of crash barriers remains a challenge 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 its preparation method. This invention utilizes a combination of organic silicone acrylic resin, modified polyacrylate, and modified glass microbeads to not only enhance the reflective effect of the reflective paint, but also improve its stability, weather resistance, and other properties. It also imparts a self-cleaning function, enabling more effective protection and ensuring road traffic safety, resolving the problems existing in the prior art.

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

[0008]

[0009]

[0010] in,

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

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

[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 inhibitor, an antifreeze agent, a dispersant, a wetting agent, a defoaming agent, a film-forming agent, a thickener, an initiator, a curing agent, and a cross-linking agent.

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

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

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

[0018] S1, mixing a rare earth material with a silane coupling agent, heating and reacting to obtain an intermediate product;

[0019] 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;

[0020] S3, mixing fluorinated acrylate, glycidyl acrylate, alkyl acrylate and an initiator, heating and stirring under an inert gas atmosphere to react to obtain a modified polyacrylate;

[0021] S4. Mix the modified glass microbeads, modified polyacrylate, silicone acrylate, photocatalyst, additive and solvent, stir and disperse them evenly, and obtain the highway crash barrier self-cleaning reflective paint.

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

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

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

[0025] Furthermore, 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 silicone acrylic resin, modified polyacrylate, and modified glass microbeads as the main components. The modified glass microbeads are obtained by treating glass microbeads with a silane coupling agent to introduce double bonds, and then reacting with double-bond-containing cellulose and a rare earth material (yttrium oxide). The outer layer of the glass microbeads is coated with cellulose and a rare earth fluorescent material. On the one hand, cellulose has a macromolecular structure and contains abundant active groups, which has a thickening effect, thereby improving the compatibility of the modified glass microbeads with the acrylic resin and preventing the glass microbeads from agglomerating and falling off. On the other hand, the rare earth fluorescent material can chemically cross-link with the glass microbeads and cellulose through double bonds. Cellulose also has excellent adsorption function, which improves the bonding strength with the rare earth material. The modified glass microbeads have better reflective and fluorescent properties. When compounded with a photocatalyst, they can further exert multiple photocatalytic activities, greatly enhancing the product's reflective effect.

[0028] The modified polyacrylate of the present invention is obtained by reacting an alkyl acrylate with hexafluorobutyl acrylate and glycidyl acrylate. Fluorocarbon segments and epoxy groups are introduced into the polyacrylate, which not only reduces the surface energy of the coating, improves water resistance and corrosion resistance, but also has a self-cleaning function when combined with a hydrophobic additive. It can also form a more three-dimensional network structure through cross-linking with modified glass microbeads and other components via the epoxy groups, thereby enhancing the strength and stability of the paint film. This allows the product to adapt to various climatic conditions, has a longer service life, and achieves a more excellent protective effect. DETAILED DESCRIPTION

[0029] In order to more clearly illustrate the technical solutions of the present invention, the following examples are given. Unless otherwise stated, the raw materials, reactions and post-processing methods mentioned in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0030] The terms "preferred," "preferably," "more preferred," and the like, used herein, refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0031] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.

[0032] The organic silicon acrylic resin in the embodiment of the present invention is Budford 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 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 its preparation method 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 added dropwise to solution 1 under a nitrogen atmosphere of -5°C, and then reacted at 25°C for 24 h. The product was precipitated with deionized water and filtered, washed, and dried to obtain the product.

[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 6 hours, filter, wash, and dry to obtain an intermediate product;

[0043] S2. Using ethanol as a solvent, glass microspheres and KH570 in a mass ratio of 2:1 were mixed, reacted at 60° C. for 6 h, filtered, washed, and dried, and then mixed with the intermediate product, cellulose, and an initiator (the mass ratio of glass microspheres, intermediate product, cellulose, and ammonium persulfate was 10:1:2:0.01), using toluene as a solvent, reacted at 80° C. under a nitrogen atmosphere for 2 h, filtered, washed, and dried to obtain modified glass microspheres;

[0044] S3, using ethyl acetate as solvent, mixing hexafluorobutyl acrylate, glycidyl methacrylate, methyl methacrylate, and azobisisobutyronitrile in a mass ratio of 3:5:10:0.9, stirring at 80°C under a nitrogen atmosphere for 4 h, and removing the solvent by distillation under reduced pressure to obtain a modified polyacrylate;

[0045] S4. Mix the modified glass microbeads, modified polyacrylate, silicone acrylate, photocatalyst, additive and solvent according to the above-mentioned parts by mass, stir and disperse them evenly, and obtain the self-cleaning reflective paint for highway crash barrier.

[0046] Example 2

[0047] A self-cleaning reflective paint for a highway crash barrier, comprising the following components in parts by weight:

[0048]

[0049] The method for preparing the self-cleaning reflective paint for the highway crash barrier comprises the following steps:

[0050] S1. Using ethanol as solvent, mix yttrium oxide and KH570 in a mass ratio of 2:1, react at 60°C for 6 hours, filter, wash, and dry to obtain an intermediate product;

[0051] S2. Using ethanol as a solvent, glass microspheres and KH570 in a mass ratio of 2:1 were mixed, reacted at 60° C. for 6 h, filtered, washed, and dried, and then mixed with the intermediate product, cellulose, and an initiator (the mass ratio of glass microspheres, intermediate product, cellulose, and ammonium persulfate was 10:1:2:0.01), using toluene as a solvent, reacted at 80° C. under a nitrogen atmosphere for 2 h, filtered, washed, and dried to obtain modified glass microspheres;

[0052] S3, using ethyl acetate as solvent, mixing hexafluorobutyl acrylate, glycidyl methacrylate, methyl methacrylate, and azobisisobutyronitrile in a mass ratio of 3:5:10:0.9, stirring at 80°C under a nitrogen atmosphere for 4 h, and removing the solvent by distillation under reduced pressure to obtain a modified polyacrylate;

[0053] S4, the modified glass beads, modified polyacrylate, silicone acrylate, photocatalyst, auxiliary and solvent are mixed according to the above mass fraction, and stirred and dispersed uniformly to obtain the self-cleaning reflective paint for the highway crash barrier wall.

[0054] Example 3

[0055] A self-cleaning reflective paint for a highway crash barrier wall comprises the following components in mass fraction:

[0056]

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

[0058] S1, mixing yttrium oxide and KH570 in a mass ratio of 2:1 with ethanol as a solvent, reacting at 60℃ for 6h, filtering, washing and drying to obtain an intermediate product;

[0059] S2, mixing glass beads and KH570 in a mass ratio of 2:1 with ethanol as a solvent, reacting at 60℃ for 6h, filtering, washing and drying, and then mixing the product with yttrium oxide, cellulose and an initiator (the mass ratio of glass beads, intermediate product, cellulose and ammonium persulfate is 10:1:2:0.01), toluene as a solvent, and reacting at 80℃ for 2h under a nitrogen atmosphere, filtering, washing and drying to obtain modified glass beads;

[0060] S3, mixing hexafluorobutyl acrylate, glycidyl methacrylate, methyl methacrylate and azobisisobutyronitrile in a mass ratio of 3:5:10:0.9 with ethyl acetate as a solvent, stirring and reacting at 80 under a nitrogen atmosphere for 4h, and then removing the solvent by distillation under reduced pressure to obtain modified polyacrylate;

[0061] S4, the modified glass beads, modified polyacrylate, silicone acrylate, photocatalyst, auxiliary and solvent are mixed according to the above mass fraction, and stirred and dispersed uniformly to obtain the self-cleaning reflective paint for the highway crash barrier wall.

[0062] Comparative Example 1

[0063] A self-cleaning reflective paint for a highway crash barrier wall, which is different from Example 1 in that steps S1 and S2 are deleted and replaced by: mixing glass beads and KH570 in a mass ratio of 2:1 with ethanol as a solvent, reacting at 60℃ for 6h, filtering, washing and drying, and then mixing the product with yttrium oxide and cellulose in a mass ratio of 10:1:2 to obtain modified glass beads, and other components and preparation methods are the same as those of Example 1.

[0064] Comparative Example 2

[0065] A self-cleaning reflective paint for highway crash barriers. The difference between this comparative example and Example 1 is that step S3 is deleted, and the modified polyacrylate is replaced by silicone acrylic resin. Other ingredients and preparation methods are the same as those in Example 1.

[0066] Test Case

[0067] The performance of the self-cleaning reflective paint for highway crash barriers prepared in Examples 1-3 and Comparative Examples 1-2 was tested.

[0068] The test method is as follows:

[0069] Hardness, adhesion, stain resistance, resistance to artificial climate acceleration and reflectance coefficient tests are carried out with reference to GB / T 6739, GB / T 9286, GB / T 9780, GB / T 14522 and other standards.

[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 Level 1 Level 1 Level 1 Level 2 Level 1 Stain resistance / % 9.4 9.9 9.5 10.2 17.6 Weather resistance / 4000h No bubbles or cracks No bubbles or cracks No bubbles or cracks Bubbles, cracks bubble <![CDATA[反射系数 / mcd / lx·m 2 ]]> ≥500 ≥500 ≥500 421 495

[0073] According to Table 1, the self-cleaning reflective paint for highway crash barriers prepared in Examples 1-3 of the present invention has good strength, excellent adhesion, and weather resistance, and can also achieve a certain self-cleaning function and good stain resistance. In particular, it also has an extremely high reflectivity, which is significantly better than the national standard of 300mcd / lx·m 2 , with excellent comprehensive performance, overcoming the shortcomings of the prior art. However, the compatibility, cross-linking, and bonding strength between the different components of Comparative Examples 1-2, which replaced modified glass microbeads or modified polyacrylate, were significantly reduced. As a result, the reflectivity was significantly reduced, the reflective performance was insufficient, the stability was poor, and the weather resistance was unsatisfactory. The stain resistance of Comparative Example 2 was also greatly reduced, making it difficult to meet the high requirements of practical applications.

[0074] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0075] Furthermore, it should be understood that although the specification is described in terms of embodiments, not every embodiment includes every feature or implementation described herein. The specification can include implicit combinations of explicitly mentioned features and / or implicit combinations of implicitly mentioned features. Such combinations are also expressly included within the scope of the specification and an embodiment.

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: 10-20 parts of silicone acrylic resin 10-20 parts of modified polyacrylate 5-20 parts of modified glass microspheres 10-20 parts of photocatalyst 1-10 parts of additives 1-10 parts of solvent; in, The modified polyacrylate is obtained by reacting fluorinated 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; The preparation method of the self-cleaning reflective paint for highway crash barriers comprises the following steps: S1, mixing a rare earth material with a 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 a modified polyacrylate; S4, mixing the modified glass microbeads, modified polyacrylate, silicone acrylic resin, photocatalyst, additive and solvent, stirring and dispersing them evenly to obtain the highway crash barrier self-cleaning reflective paint; The cellulose is cellulose containing unsaturated double bonds; The silane coupling agent is a silane coupling agent containing unsaturated double bonds.

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 a bactericide, a mildew preventer, an antifreeze agent, a dispersant, a wetting agent, a defoaming agent, a film-forming auxiliary agent, a thickener, an initiator, a curing agent, and a cross-linking agent.

4. The self-cleaning reflective paint for highway crash barriers according to claim 1 is 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).

5. The self-cleaning reflective paint for highway crash barriers according to claim 1 is characterized in that: In step S2, the temperature of the heating reaction is 60-100°C.

6. The self-cleaning reflective paint for highway crash barriers according to claim 1 is 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).

7. The self-cleaning reflective paint for highway crash barriers according to claim 1, characterized in that: In step S3, the temperature of the heating and stirring reaction is 60-100°C.

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