Acrylic acid modified coating for durable road marking as well as preparation method and application of acrylic acid modified coating

Abstract

The invention discloses a durable acrylic modified coating for road marking. The durable acrylic modified coating comprises a component A and a component B, the component A comprises modified acrylic resin, a filler, coated glass beads and an auxiliary agent; and the component B comprises isocyanate, a filler and an auxiliary agent. Wherein the modified acrylic resin is acrylic copolymer resin modified by 4-amino-1-hydroxyadamantane. According to the invention, specially prepared modified acrylic resin is adopted as coating matrix resin, carbocyclic rings of 1, 2-epoxy-4-vinylcyclohexane and 4-amino-1-hydroxyadamantane are utilized to improve the hardness and wear resistance of the road marking coating, and a long carbon chain of oleylamine improves the dispersibility between the resin and glass beads and various assistants, so that the service life of the road marking coating is prolonged, and the service life of the road marking coating is prolonged. Meanwhile, the modified acrylic resin has strong adhesive force to the glass beads, so that when the acrylic modified coating is used for road marking, the acrylic modified coating has durable highlighting performance and good wear resistance, and still has good compression resistance, cold resistance and cracking resistance in a low-temperature environment.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to an acrylic modified coating for durable road markings, a preparation method thereof, and an application thereof. Background Art

[0003] Road traffic markings are facilities that are drawn on the road surface or other facilities with specified lines, arrows, words, elevation markings, raised road markers or other guiding devices to control and guide traffic and disperse traffic flow. It conveys various fixed basic information of the road to vehicles and pedestrians, and is particularly important for drivers. Traffic markings are mainly drawn on the road surface, exposed to sunlight, rain, snow, ice, and subjected to the impact and abrasion of vehicles. Therefore, strict requirements are imposed on their performance. First, it is required to have a short drying time and simple operation to reduce traffic interference; second, it is required to have strong reflection ability, distinct color, and high reflectivity to ensure good visibility during both day and night; third, it should have anti-slip and wear-resistant properties to ensure driving safety and service life.

[0004] However, there are still many problems with the coatings for road markings on the existing market, mainly reflected in the following aspects: the adhesion between the coating and the coated glass beads is poor, resulting in poor reflective effect of the markings; the hot melt markings are prone to softening at high temperatures in summer, cracking in winter, and aging easily; the road surface dust, tire marks of cars, vehicle emissions, etc. are likely to contaminate the markings, causing the safety color range and retroreflective coefficient of the markings to decay rapidly, the clarity of the markings to decrease, and affecting their indication and guiding functions for traffic; the anti-slip performance of the markings is not emphasized, making the markings a potential hazard for accidents such as vehicle skidding and fishtailing. Therefore, there is an urgent need to seek a road marking coating with excellent cold resistance, anti-cracking performance, continuous high brightness, anti-slip and wear resistance. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, the main object of the present invention is to provide an acrylic modified coating for durable road markings and a preparation method thereof, and the coating has excellent cold resistance, anti-cracking property, and properties such as continuous high brightness, anti-slip and wear resistance.

[0006] The main object of the present invention also provides the application of the acrylic modified coating in road markings, especially suitable for application in high altitude and high cold regions.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] On the one hand, the present invention provides an acrylic modified coating for durable road markings, which comprises component A and component B; component A comprises a modified acrylic resin, a filler, coated glass beads, and an auxiliary agent; component B comprises an isocyanate, a filler, and an auxiliary agent.

[0009] In some embodiments, the modified acrylic resin is an acrylic copolymer resin modified with 4-amino-1-hydroxyadamantane; the structural formula of 4-amino-1-hydroxyadamantane is shown in Formula 1, and the CAS number is: 20098-19-5.

[0010]

[0011] In some embodiments, the preparation method of the modified acrylic resin comprises the following steps:

[0012] Step 1: Add acrylic acid, oleylamine, and 1,2-epoxy-4-vinylcyclohexane into a reactor, mix evenly, add catalyst A, control the reaction temperature at 60-80 °C for reaction, the reaction time is 4-8 h, and after the reaction is completed, obtain a polymerization product through solvent extraction, filtration, and drying;

[0013] Step 2: Dissolve the polymerization product and 4-amino-1-hydroxyadamantane in an organic solvent, stir evenly, add catalyst B, heat to 80-100 °C for reaction, the reaction time is 8-16 h, and after the reaction is completed, obtain the modified acrylic resin through extraction, crystallization, and drying.

[0014] In some embodiments, the molar ratio of the addition of acrylic acid, oleylamine, and 1,2-epoxy-4-vinylcyclohexane is 6-10:3-8:1-5;

[0015] Further, the molar ratio of the addition of acrylic acid, oleylamine, and 1,2-epoxy-4-vinylcyclohexane is 6-8:3-4:1-3.

[0016] In some embodiments, catalyst A can be selected from one or more combinations of benzoyl peroxide, di-tert-butyl peroxide, methyl ethyl ketone peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), ammonium persulfate, or potassium persulfate.

[0017] In some embodiments, the organic solvent can be selected from one or more combinations of dimethylformamide or dimethylformamide dihydroxide.

[0018] In some embodiments, the molar ratio of the addition of acrylic acid and 4-amino-1-hydroxyadamantane is 1:1-3.

[0019] In some embodiments, catalyst B is dimethyl carbonate.

[0020] In some embodiments, the filler type of component A may be the same as the filler type of component B, or may be different from the filler type of component B; specifically, the filler may be selected from one or more combinations of heavy calcium, mica powder, whisker silicon powder, titanium dioxide, black iron oxide, red iron oxide, talcum powder and silicon powder;

[0021] Furthermore, the filler is talcum powder, which has better compatibility with modified acrylic resin and is not easy to crack or age under severe low temperature conditions. The filler can be 325 mesh, and the addition of the filler can improve the wear resistance of the coating after film formation and reduce the cost.

[0022] In some embodiments, the type of the auxiliary agent of component A may be the same as that of component B, or may be different from that of component B; specifically, the auxiliary agent is selected from any one or more combinations of defoaming agents, leveling agents, rheological additives, anti-settling agents, and light stabilizers.

[0023] In some embodiments, the coated glass beads are glass microbeads commonly used in the art, and specifically, can be selected from commercially available glass microbeads with a particle size of 0.6-2 mm and a refractive index of ≥1.5.

[0024] In some embodiments, the component A includes 40-80 parts of modified acrylic resin, 24-40 parts of filler, 10-17 parts of coated glass beads and 5-15 parts of additives, by mass; the component B includes 40-80 parts of isocyanate, 15-30 parts of filler and 5-15 parts of additives; and the mass ratio of component A to component B is 1:2-3.

[0025] In another aspect, the present invention also provides a method for preparing the above-mentioned durable acrylic modified coating for road marking, comprising the following steps:

[0026] Preparation of component A: according to the mass ratio, acrylic resin, filler, coated glass beads and additives are put into a mixer in sequence and fully mixed, then transferred to a dispersing emulsifier for dispersion, and filtered and packaged after dispersion and grinding;

[0027] Preparation of component B: according to the mass ratio, put isocyanate, filler and additive into a mixer in turn and mix them thoroughly, then transfer them into a dispersing emulsifier for dispersion, filter and package after the dispersion and grinding is completed;

[0028] The prepared acrylic modified coating components A and B are packaged separately to obtain a two-component durable acrylic modified coating for road marking.

[0029] In another aspect, the present invention also provides the use of the above-mentioned durable acrylic modified paint for road marking in the preparation of road markings.

[0030] Compared with the prior art, the present invention has at least the following advantages:

[0031] 1. The preparation method of the present invention is simple. A specially prepared modified acrylic resin is used as the coating matrix resin. The cycloalkanes of 1,2-epoxy-4-vinylcyclohexane and 4-amino-1-hydroxyadamantane are used to improve the hardness and wear resistance of the road marking paint. The long carbon chain of oleylamine improves the dispersibility between the resin, glass beads, fillers and various additives, avoiding the problem that the marking is prone to cracking in cold environments.

[0032] 2. The prepared modified acrylic resin of the present invention contains epoxy and amino polar groups. The epoxy and amino groups can produce dipole interaction with the oxygen atoms in the molecular structure of glass beads, enabling the modified acrylic resin to have strong adhesion to glass beads. During the use of the marking, even after being rubbed by tires and exposed to wind, sun and rain, the glass beads are not easily detached, thus having a persistent high-brightness performance.

[0033] 3. When the acrylic modified paint for durable road markings provided by the present invention is used for road markings, it has a persistent high-brightness performance, good wear resistance, still has good compressive performance in low-temperature environments, and good cold resistance and anti-cracking properties. Detailed Embodiments

[0034] The present invention will be further described in detail below with reference to specific embodiments. The following embodiments are only descriptive and not restrictive, and the protection scope of the present invention cannot be limited thereby.

[0035] When a quantity, concentration, or other value or parameter is expressed in the form of a range, a preferred range, or a preferred upper and lower limit of a value, it should be understood that any range is specifically disclosed by combining any pair of upper limits of the range or preferred values with any lower limit of the range or preferred values, regardless of whether the range is specifically disclosed. Unless otherwise indicated, the numerical range values listed herein include the endpoints of the range and all integers and fractions within the range.

[0036] Unless otherwise stated, all percentages, parts, ratios, etc. in this article are by weight.

[0037] The materials, methods, and examples in this article are all exemplary and should not be construed as restrictive unless otherwise specified.

[0038] In the following embodiments, the coated glass beads used are purchased from Anhui Tuoli Company, and the model is: AASHTO M247 TYPE 3.

[0039] The modified acrylic used is prepared by the following preparation method:

[0040] Preparation of Modified Acrylic Resin 1

[0041] Step 1: Add 6 mol of acrylic acid, 3 mol of oleylamine, and 1 mol of 1,2-epoxy-4-vinylcyclohexane into a reactor and mix evenly. Then add 0.15 mol of benzoyl peroxide, control the reaction temperature at 60 °C for reaction, and the reaction time is 4 h. After the reaction, obtain the polymerization product through solvent extraction, filtration, and drying.

[0042] Step 2: Dissolve the obtained polymerization product and 6 mol of 4-amino-1-hydroxyadamantane in 100 ml of dimethylformamide, stir evenly, add 0.12 mol of dimethyl carbonate, heat to 90 °C for reaction, and the reaction time is 10 h. After the reaction, obtain the modified acrylic resin 1 through extraction, crystallization, and drying.

[0043] Its infrared data are as follows: 2500 - 3300 cm -1 : -OH exists; 3300 - 3500 cm -1 : -NH exists; 800 - 900 cm -1 : epoxy exists; 1100 - 1300 cm -1 : ester group exists; 1600 - 1650 m -1 Disappearance: -C=C- disappears, indicating that acrylic acid, oleylamine, and 1,2-epoxy-4-vinylcyclohexane are polymerized, and 4-amino-1-hydroxyadamantane is successfully grafted to obtain the modified acrylic resin 1.

[0044] Preparation of modified acrylic resin 2

[0045] The operation steps for preparing modified acrylic resin 2 are basically the same as those for preparing modified acrylic resin 1, with the only difference being that the added molar masses of acrylic acid, oleylamine, 1,2-epoxy-4-vinylcyclohexane, and 4-amino-1-hydroxyadamantane are 10 mol, 8 mol, 5 mol, and 10 mol respectively.

[0046] Preparation of modified acrylic resin 3

[0047] The operation steps for preparing modified acrylic resin 3 are basically the same as those for preparing modified acrylic resin 1, with the only difference being that the added molar masses of acrylic acid, oleylamine, 1,2-epoxy-4-vinylcyclohexane, and 4-amino-1-hydroxyadamantane are 8 mol, 4 mol, 3 mol, and 8 mol respectively.

[0048] Preparation of modified acrylic resin 4

[0049] The operation steps for preparing modified acrylic resin 4 are basically the same as those for preparing modified acrylic resin 1, with the only difference being that step 2 is omitted.

[0050] Preparation of modified acrylic resin 5

[0051] The operating steps for preparing modified acrylic resin 5 are basically the same as those for preparing modified acrylic resin 1, with the only difference being that 1,2-epoxy-4-vinylcyclohexane is not added in step 1. Step 1 is specifically as follows:

[0052] Step 1: Add 6 mol of acrylic acid and 3 mol of oleylamine into a reactor and mix evenly. Then add 0.15 mol of benzoyl peroxide, control the reaction temperature at 60 °C for reaction, with a reaction time of 4 h. After the reaction, obtain the polymerization product through solvent extraction, filtration, and drying.

[0053] Modified acrylic resin 6

[0054] The polyacrylic resin obtained by the double-bond polymerization of 10 mol of acrylic acid is denoted as modified acrylic resin 6.

[0055] Example

[0056] This example provides a preparation method for an acrylic-modified coating for durable road markings, which includes the following steps:

[0057] Preparation of component A: According to the mass ratio in Table 1, sequentially add the modified acrylic resin, filler, coated glass beads, and additives into a mixer and mix thoroughly. Then transfer to a dispersion emulsifier and disperse at 500 r / min. After the dispersion and grinding are completed, filter and package.

[0058] Preparation of component B: According to the mass ratio in Table 1, sequentially add isocyanate, filler (talc powder), and additives (defoamer - isooctanol, leveling agent - BYK306) into a mixer and mix thoroughly. Then transfer to a dispersion emulsifier and disperse at 500 r / min. After the dispersion and grinding are completed, filter and package.

[0059] Package the prepared acrylic-modified coating components A and B separately in a mass ratio of 1:2 to obtain a two-component acrylic-modified coating for durable road markings.

[0060] Table 1 Raw material table for each example (unit: mass part)

[0061]

[0062] Comparative examples 1 - 5

[0063] This comparative example provides a preparation method for an acrylic-modified coating for durable road markings. Its preparation method is basically the same as that of Example 1, with the only difference being that the raw material ratios of the comparative examples are as shown in Table 2.

[0064] Table 2 Raw material table for each comparative example (unit: mass part)

[0065]

[0066]

[0067] Performance Test

[0068] The present application conducts performance tests on the acrylic modified coatings prepared in the above-mentioned examples and comparative examples, specifically as follows:

[0069] The acrylic modified coatings obtained in the above-mentioned examples and comparative examples are applied to a treated base plate to obtain markings. The base plate imitates a road surface, and the marking thickness is controlled at 2 mm. After the markings are dried, the following performance tests are carried out on the markings:

[0070] 1. Luminance factor: The sample is applied on a cement asbestos board substrate of 150 mm×100 mm×5 mm with a 300-μm film applicator, making it parallel to the short side of the cement asbestos board, and a strip-shaped film with a width of 50 mm at the center of the long side is formed. After being fully dried, the luminance factor is tested. A luminance factor greater than 0.8 indicates good luminance effect.

[0071] 2. Abrasion resistance: The JM-1V film abrasion tester is used to test the abrasion resistance of the test. The sum of the weights at both ends of the abrasion tester is 1000 g. The JM-100 rubber grinding wheel is used, and the number of test times is set to 100 times. The percentage of mass loss of the material after the test is measured. The lower the percentage, the better the abrasion resistance; the luminance factor is tested again after testing the abrasion resistance.

[0072] 3. Compressive strength: The compressive strength is tested through an electronic universal testing machine; the sample is placed in an environment of 23°C for 24 h and then placed in an environment of -50°C for freezing for 24 h, and then tested again.

[0073] The specific test results are shown in Table 3:

[0074] Table 3 Performance parameters of acrylic coatings in each example and comparative example

[0075]

[0076] It can be seen from the test results shown in the table that by comparing Example 1 with Comparative Example 1 and Comparative Example 2, in Comparative Example 1, the filler is replaced with heavy calcium carbonate, and in Comparative Example 2, the filler is replaced with mica powder. Due to the change in the properties of the filler, the dispersibility and friction resistance in the coating are lower than those in the example, indicating that the selection of talc powder as the filler can maintain good long-term abrasion resistance and compressive strength, and still has good compressive strength after being frozen in an environment of -50°C for 24 h. Therefore, it has good cold resistance and anti-cracking performance.

[0077] Comparative Examples 3, 4 and 5 replaced the modified acrylic resin with modified acrylic resins 4, 5 and 6. The mass of wear loss in Comparative Examples 3, 4 and 5 increased significantly. At the same time, the compressive strength and the brightness factor after friction also decreased to a certain extent. This shows that using a single 1,2-epoxy-4-vinylcyclohexane or 4-amino-1-hydroxyadamantane to modify the acrylic resin can improve the hardness and wear resistance of the acrylic resin, thereby improving the durability of glass beads in acrylic. At the same time, by using 1,2-epoxy-4-vinylcyclohexane and 4-amino-1-hydroxyadamantane to modify acrylic simultaneously, active groups such as amino groups and epoxy groups are introduced, greatly improving the dispersibility of fillers, glass beads, etc. in the modified acrylic, and thus providing technical support for improving the comprehensive performance of acrylic coatings. That is, the special structure of the modified acrylic resin in the present invention can improve the dispersibility between fillers, glass beads and the resin, and at the same time, the special structure enables the modified acrylic resin to have a strong adhesion to glass beads, thus having a persistent high-brightness performance.

[0078] From the comparison of Examples 1 - 3, it can be seen that the acrylic modified coating for durable road markings provided by the present invention has high-brightness performance, good wear resistance, still has good compressive performance, cold resistance and anti-cracking performance in low-temperature environments.

[0079] The above examples are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing examples, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be covered by the scope of the claims and the description of the present invention.

Claims

1. An acrylic modified coating for durable road markings, which comprises component A and component B; characterized in that, The component A includes a modified acrylic resin, a filler, coated glass beads and an auxiliary agent; the component B includes an isocyanate, a filler and an auxiliary agent.

2. The acrylic modified coating according to claim 1, wherein The modified acrylic resin is an acrylic copolymer resin modified with 4-amino-1-hydroxyadamantane.

3. The acrylic modified coating according to claim 1, characterized in that, The preparation method of the modified acrylic resin includes the following steps: Step 1: Add acrylic acid, oleylamine and 1,2-epoxy-4-vinylcyclohexane into a reactor and mix evenly. Add catalyst A, control the reaction temperature at 60-80 °C for reaction, the reaction time is 4-8 h. After the reaction, obtain the polymerization product through solvent extraction, filtration and drying; Step 2: Dissolve the polymerization product and 4-amino-1-hydroxyadamantane in an organic solvent, stir evenly, add catalyst B, heat to 80-100 °C for reaction, the reaction time is 8-16 h. After the reaction, obtain the modified acrylic resin through extraction, crystallization and drying.

4. The acrylic modified coating according to claim 3, characterized in that, The added molar ratio of the acrylic acid, oleylamine and 1,2-epoxy-4-vinylcyclohexane is 6-10:3-8:1-5.

5. The acrylic modified coating according to claim 3, characterized in that, The added molar amount ratio of the acrylic acid and 4-amino-1-hydroxyadamantane is 1:1-3.

6. The acrylic modified coating according to claim 1, wherein The filler is selected from one or more combinations of heavy calcium carbonate, mica powder, whisker silica powder, titanium dioxide, iron oxide black, iron oxide red, talc powder and silica powder.

7. The acrylic modified coating according to claim 6, characterized in that, The filler is talc powder.

8. The acrylic modified coating according to claim 1, characterized in that, By mass, the component A includes 40-80 parts of modified acrylic resin, 24-40 parts of filler, 10-17 parts of coated glass beads and 5-15 parts of auxiliary agent; the component B includes 40-80 parts of isocyanate, 15-30 parts of filler and 5-15 parts of auxiliary agent; and the mass ratio of the component A to the component B is 1:2-3.

9. The preparation method of the acrylic modified coating according to any one of claims 1-8, characterized in that, It includes the following steps: Preparation of component A: According to the mass ratio, sequentially put the acrylic resin, filler, coated glass beads and auxiliary agent into a mixer and mix evenly, then transfer to a dispersion emulsifier for dispersion. After the dispersion and grinding are completed, filter and package; Preparation of component B: According to the mass ratio, sequentially put the isocyanate, filler and auxiliary agent into a mixer and mix evenly, then transfer to a dispersion emulsifier for dispersion. After the dispersion and grinding are completed, filter and package; Pack the prepared component A and component B of the acrylic modified coating separately to obtain a two-component durable road marking acrylic modified coating.

10. Use of the acrylic modified coating according to any one of claims 1-8 in the preparation of road markings.

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