Self-cleaning road marking paint and method for its production

Abstract

The self-cleaning road marking paint is composed of A component and B component, wherein the A component is composed of 50-150 mass parts of modified acrylic resin, 0.1-2 mass parts of accelerator, 1-10 mass parts of inert oil and 10-50 mass parts of low-boiling and low-surface tension solvent; the B component is composed of 50-150 mass parts of modified acrylic resin, 1-10 mass parts of curing agent, 1-10 mass parts of inert oil and 10-50 mass parts of low-boiling and low-surface tension solvent; the modified acrylic resin is a mixture obtained by dissolving solid acrylic resin with active monomers of methyl methacrylate, butyl acrylate and hydroxypropyl methacrylate as dispersion medium, adding inorganic filler and nano titanium dioxide, and modifying the inorganic filler and nano titanium dioxide with silane coupling agent. The paint can realize long-term self-cleaning effect of road marking without increasing the smoothness of the surface of the road marking.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, and relates to a road marking coating, particularly a road marking coating with self-cleaning function, and a method for preparing the road marking coating. Background Technology

[0002] Road markings are an important component of road safety facilities. Because they guide traffic, their visibility affects the driver's experience and thus safety. If road markings get dirty easily, their directional effectiveness will decrease rapidly in a short period, reducing their visibility and creating safety hazards.

[0003] To address the issue of road markings getting dirty easily, a common solution is to improve the surface smoothness of the marking paint coating to enhance its anti-fouling effect.

[0004] However, this method still has two problems: First, the increased surface smoothness will reduce the surface anti-skid coefficient of the road markings, prolonging the braking distance of cars or causing pedestrians to slip and increase safety hazards; second, its anti-fouling effect is related to the surface structure. As the road markings are used for longer periods of time, their surface structure will wear down and become damaged, which will inevitably cause the road markings to lose their anti-fouling effect and become equally prone to getting dirty.

[0005] Therefore, inventing a marking paint with low surface smoothness and continuous stain resistance can effectively solve the above-mentioned problems in the industry. Summary of the Invention

[0006] The purpose of this invention is to provide a self-cleaning road marking paint and a method for preparing the paint, so as to improve the anti-fouling ability of the road marking without increasing the smoothness of the road marking surface.

[0007] The self-cleaning road marking paint of the present invention is composed of 1 part by weight of component A and 1 to 2 parts by weight of component B, each packaged separately.

[0008] Component A is composed of 50-150 parts by weight of modified acrylic resin, 0.1-2 parts by weight of accelerator, 1-10 parts by weight of inert oil, and 10-50 parts by weight of low-boiling-point, low-surface-tension solvent.

[0009] The B component is composed of 50-150 parts by weight of modified acrylic resin, 1-10 parts by weight of curing agent, 1-10 parts by weight of inert oil, and 10-50 parts by weight of low-boiling-point, low-surface-tension solvent.

[0010] The modified acrylic resin is a mixture obtained by dissolving solid acrylic resin with active monomers methyl methacrylate, butyl acrylate, and hydroxypropyl methacrylate as a dispersion medium, adding inorganic fillers and pigment nano-titanium dioxide, and modifying the inorganic fillers and nano-titanium dioxide with a silane coupling agent.

[0011] Furthermore, the dispersion medium is composed of 50-70 parts by weight of methyl methacrylate, 20-30 parts by weight of butyl acrylate, 10-20 parts by weight of hydroxypropyl methacrylate and 70-100 parts by weight of solid acrylic resin.

[0012] Furthermore, the amount of inorganic filler added is 100-200% of the mass of the dispersion medium.

[0013] Furthermore, the amount of pigment nano-titanium dioxide added is 10-30% of the mass of the dispersion medium.

[0014] This invention is based on acrylic resin, the core component for curing road marking paint. Utilizing the fluidity of acrylic resin, it serves as a dispersion medium for inorganic fillers and nano-titanium dioxide modification. The inorganic fillers and nano-titanium dioxide are dispersed within the resin and modified with a silane coupling agent, achieving thorough dispersion of the inorganic fillers and nano-titanium dioxide within the resin and preventing agglomeration. The inorganic fillers and nano-titanium dioxide are distributed more evenly with the resin molecules, allowing for the formation of more and more uniform nanoporous structures during the subsequent resin curing process, thus improving the hydrophobic effect of the road marking coating. Furthermore, this invention avoids the separate modification of inorganic fillers and nano-titanium dioxide, eliminating the drying step for both, simplifying the operation, and saving time and energy consumption.

[0015] In the modified acrylic resin of the present invention, the solid acrylic resin is a polymer obtained by copolymerization of methyl methacrylate with butyl methacrylate, hydroxypropyl methacrylate or styrene.

[0016] The inorganic filler described in this invention is an inorganic material containing hydroxyl functional groups, including but not limited to at least one of porous silica microspheres, silica powder, apatite powder, alumina powder, and hollow glass microspheres.

[0017] Furthermore, the present invention preferably uses porous silica microspheres as inorganic fillers.

[0018] Furthermore, the silane coupling agent described in this invention contains C in its molecular structure. n H 2n+1 (n≥10) Various alkylsilane coupling agents with molecular chain segments, or those containing C in their molecular structure.n F 2n+1 (n≥3) Fluorosilane coupling agents with molecular chain segments.

[0019] Grafting the silane coupling agent onto inorganic fillers and nano-titanium dioxide can significantly reduce the surface free energy of the inorganic fillers and nano-titanium dioxide. Because fluorine has the strongest electronegativity, low atomic polarizability, and high CF bond energy, and fluorine atoms are distributed in a helical pattern along the carbon bonds, it has a shielding effect and weak intermolecular forces, thus more effectively reducing the surface free energy of the coating. Therefore, this invention preferably uses a fluorosilane coupling agent.

[0020] The accelerator added to component A and the curing agent added to component B in this invention are curing agents and accelerators that can initiate the polymerization reaction of acrylic acid at room temperature after mixing.

[0021] Specifically, the accelerator includes, but is not limited to, at least one of N,N-dimethylaniline and N,N-dimethyl-p-toluidine; the curing agent includes, but is not limited to, at least one of cyclohexanone peroxide, methyl ethyl ketone peroxide, and benzoyl peroxide.

[0022] Furthermore, this invention incorporates a certain proportion of inert oil into both component A and component B to adsorb the nanopores formed during the curing process of the modified inorganic filler and nano-titanium dioxide, thereby further improving the hydrophobic properties of the coating. The inert oil includes, but is not limited to, at least one of dimethyl silicone oil, tung oil, castor oil, and linseed oil.

[0023] This invention also incorporates a certain proportion of low-boiling-point, low-surface-tension solvent into components A and B to coat the modified inorganic filler and nano-titanium dioxide, forming a microsphere structure. During the subsequent resin curing process, these microsphere structures adhere to each other, forming a nanoporous structure on the coating surface and inside. This nanoporous structure, in conjunction with the modified inorganic filler and nano-titanium dioxide exposed on the resin exterior, achieves a superhydrophobic effect.

[0024] The low-boiling-point, low-surface-tension solvent includes, but is not limited to, at least one of n-hexane, methanol, ethanol, and low-boiling-point fluorinated liquids. More preferably, the low-boiling-point, low-surface-tension solvent is a low-boiling-point fluorinated liquid.

[0025] Therefore, this invention achieves hydrophobicity by coupling modification of hydroxyl-containing pigments and fillers. Simultaneously, a small amount of low-tension solvent is added to the coating. During coating curing, solvent shrinkage occurs, forming a nano-protrusion-like porous structure. This nanoscale structure exhibits hydrophobicity, and due to the modification of the pigments and fillers, the structure is hydrophobic from the inside out. The addition of inert oil allows it to be easily adsorbed into the pores, providing both filling and protection. Furthermore, the low surface tension of the inert oil expands the hydrophobic area of ​​the coating, thereby enhancing the hydrophobic effect.

[0026] The present invention does not particularly limit the preparation method of the self-cleaning road marking paint. Any conventional mixing method that can mix the components A and B constituting the self-cleaning road marking paint evenly can be used as the preparation method of the self-cleaning road marking paint of the present invention.

[0027] Specifically, 0.1-2 parts by weight of accelerator, 1-10 parts by weight of inert oil, and 10-50 parts by weight of low-boiling-point, low-surface-tension solvent are added to 50-150 parts by weight of modified acrylic resin, and the mixture is stirred at 400-900 r / min for 0.5-1 hour, then sealed to obtain component A of the self-cleaning road marking paint; 1-10 parts by weight of curing agent, 1-10 parts by weight of inert oil, and 10-50 parts by weight of low-boiling-point, low-surface-tension solvent are added to 50-150 parts by weight of modified acrylic resin, and the mixture is stirred at 400-900 r / min for 0.5-1 hour, then sealed to obtain component B of the self-cleaning road marking paint.

[0028] The modified acrylic resin is prepared by the following method: 50-70 parts by weight of methyl methacrylate, 20-30 parts by weight of butyl acrylate and 10-20 parts by weight of hydroxypropyl methacrylate are mixed evenly, 70-100 parts by weight of solid acrylic resin is added and dissolved evenly to obtain a dispersion medium, then 100-200% by weight of inorganic filler and 10-30% by weight of pigment nano-titanium dioxide are added and dispersed evenly, and finally 1-10 parts by weight of silane coupling agent are added, heated to 60-80℃ and stirred under reflux for 1-2 hours to obtain the modified acrylic resin.

[0029] In use, simply mix component A and component B evenly according to the stated mass fraction to initiate a free radical reaction, and a self-cleaning road marking paint can be prepared.

[0030] When component A and component B are mixed, the curing agent generates free radicals under the action of the accelerator. Components containing active double bonds undergo free radical polymerization, forming a cross-linked network and curing into a film. In actual construction, the two components are atomized separately using a device with dual nozzles and mixed on the ground substrate, thereby initiating the free radical polymerization reaction.

[0031] The self-cleaning road marking paint provided by this invention can be applied to various substrates such as asphalt concrete and cement concrete. It is non-toxic, harmless, and environmentally friendly. It can be cured at low temperatures and can enable rapid traffic release.

[0032] The self-cleaning road marking paint of the present invention has high curing efficiency and fast speed, and can be cured even in low temperature conditions in winter. Compared with traditional MMA markings, the application areas are not reduced, and it has higher applicability.

[0033] Furthermore, because the road marking paint of this invention introduces long carbon chains with strong hydrophobic effects into the coating molecules through silane hydrolysis, the pigments and fillers in the paint have low free energy. The low-boiling-point solvent causes the coating to shrink and form a porous nanopore structure during the curing process, increasing the roughness of the coating's internal and external structure. This allows for the formation of nano-protrusions on the coating surface, resulting in excellent hydrophobic properties. Simultaneously, the inert oil added to the coating, under the influence of intermolecular and chemical bonding forces, can fill the nanopores of the pigments and fillers, thereby expanding the low free energy region on the coating surface and enhancing the hydrophobic effect. This constructs the overall hydrophobic properties, achieving a long-lasting self-cleaning effect.

[0034] Road markings prepared with the self-cleaning road marking paint of this invention have low surface tension, are not easily dusty, and water has a large contact angle on the marking surface, allowing water droplets to flow freely on the surface, thereby easily removing dust from the coating surface and achieving a self-cleaning effect. Moreover, the self-cleaning effect of this invention is not only present on the marking surface, but also has low surface energy inside the structure, so the anti-fouling effect is not affected by the wear of the markings. Attached Figure Description

[0035] Figure 1 This is a scanning electron microscope image of the self-cleaning road marking coating sample from Example 1.

[0036] Figure 2 This is a diagram showing the effect of water droplets forming on the surface of the self-cleaning road marking coating sample in Example 1. Detailed Implementation

[0037] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings and examples. The following examples are only used to more clearly illustrate the technical solutions of the present invention, so that those skilled in the art can better understand and utilize the present invention, and are not intended to limit the scope of protection of the present invention.

[0038] The terms such as "upper," "lower," "left," "right," and "middle" used in this specification are merely for clarity of description and are not intended to limit the scope of the invention. Any changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0039] Unless otherwise specified, the raw materials used in the embodiments of this invention are not subject to any special restrictions on their source. Even commercially available materials can be prepared using conventional methods well-known to those skilled in the art.

[0040] The processes and equipment used in this invention are all conventional names in the field. Each name is very clear and specific in the relevant field of application, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment based on the names.

[0041] Example 1.

[0042] Weigh out 60g of methyl methacrylate, 30g of butyl acrylate, 20g of hydroxypropyl methacrylate, and 80g of Liaoning Sanhuan. TM A-02 solid acrylic resin, 180g porous silica microspheres, and 20g nano titanium dioxide (1000 mesh) were added sequentially to a reaction vessel and stirred for 30 minutes. Then, 2g of perfluorodecyltrimethoxysilane coupling agent was added, and the mixture was heated to 80°C and refluxed for 1 hour under continuous stirring to prepare the modified acrylic resin.

[0043] Take 100g of modified acrylic resin, add 0.2g of N,N-dimethylaniline, 10g of dimethyl silicone oil, and 20g of 3M. TM The 7100 fluorinated liquid was stirred at 800 r / min for 1 hour, discharged, sealed and stored to obtain component A of the self-cleaning road marking paint.

[0044] Take 100g of modified acrylic resin, add 3g of benzoyl peroxide, 10g of dimethyl silicone oil, and 20g of 3M. TM The 7100 fluorinated liquid was stirred at 800 r / min for 1 hour, discharged, sealed and stored to obtain component B of the self-cleaning road marking paint.

[0045] Component A and component B were mixed at a weight ratio of 1:1 and stirred for 1 minute to ensure uniform mixing. The mixture was then applied to tinplate using a 600 μm applicator. After the reaction was complete, a self-cleaning road marking coating sample was obtained.

[0046] Figure 1 Scanning electron microscope (SEM) images of the coated samples are provided. The images show that after curing, a porous structure was formed both on the surface and inside the coating, with a small amount of inert oil adsorbed within the pores (the darker areas inside the pores).

[0047] Therefore, these porous structures increase the surface roughness of the coating, and this rough surface structure is the basis for the superhydrophobicity. In addition, the adsorbed inert oil can both protect the porous structure and expand the low free energy region, further enhancing the hydrophobic effect of the coating.

[0048] Using a dropper, slowly drip a few drops of water onto the coating surface; you can then observe... Figure 2 The effect shown indicates that the coating surface is hydrophobic, and water droplets form droplets without wetting the coating surface.

[0049] Example 2.

[0050] Weigh out 50g of methyl methacrylate, 20g of butyl acrylate, 10g of hydroxypropyl methacrylate, and 100g of Liaoning Sanhuan. TM A-04 solid acrylic resin, 110g hollow glass microspheres, and 10g nano titanium dioxide (1000 mesh) were added sequentially to a reaction vessel and stirred for 30 minutes. Then, 10g dodecyltrimethoxysilane coupling agent was added, and the mixture was heated to 60°C and refluxed for 2 hours under continuous stirring to prepare the modified acrylic resin.

[0051] Take 100g of modified acrylic resin, add 1g of N,N-dimethyl-p-toluidine, 8g of tung oil and 30g of n-hexane, stir at 800r / min for 0.5 hours, discharge and seal for storage to obtain component A of self-cleaning road marking paint.

[0052] Take 100g of modified acrylic resin, add 5g of benzoyl peroxide, 8g of tung oil and 30g of n-hexane, stir at 800r / min for 0.5 hours, discharge and seal for storage to obtain component B of self-cleaning road marking paint.

[0053] Component A and component B were mixed at a weight ratio of 1:1 and stirred for 1 minute to ensure uniform mixing. The mixture was then applied to tinplate using a 600 μm applicator. After the reaction was complete, a self-cleaning road marking coating sample was obtained.

[0054] Comparative Example 1.

[0055] MMA road marking paint was prepared according to the "Road Marking Materials and Applications" (Du Limin, Zheng Jiajun, He Yong. People's Communications Press [M]: Beijing, 2005: 85-95.).

[0056] Take 40g of solid acrylic resin Degaroute ® 660, 2g plasticizer Degaroute ®Mix W3, 30g of ultrafine double-flying powder (1000 mesh), 17.5g of ultrafine quartz powder (1000 mesh), and 10g of pigment R902 evenly to form component A.

[0057] Take 40g of solid acrylic resin Degaroute ® 662, 2g plasticizer Degaroute ® Mix W3, 30g of ultrafine double-flying powder (1000 mesh), 17.5g of ultrafine quartz powder (1000 mesh), and 10g of pigment R902 evenly to form component B.

[0058] Mix component A and component B at a weight ratio of 1:1, add 4g of benzoyl peroxide, stir for 1 minute to make it evenly mixed, and apply it to tinplate with a 600μm applicator. After the reaction is complete, the MMA road marking sample is obtained.

[0059] The coating performance of the self-cleaning road marking coating samples from Examples 1 and 2 and the above-mentioned MMA road marking samples were tested respectively.

[0060] Among them, the tensile strength and elongation at break were tested according to the method of GB / T 2567-2008, the gloss index was tested according to the method of GB 1743-1979(1989), the anti-slip coefficient was tested according to the standard method of JT / T 712-2008, and the contact angle was tested according to the method of GB / T 30693-2014.

[0061]

[0062] By comparing the test results of the samples in the comparative example and the embodiment, it can be seen that the samples prepared with the self-cleaning road marking paint of the present invention have similar tensile strength and elongation at break to the samples prepared with traditional MMA road marking paint. Their physical properties are similar, which means that their performance is comparable.

[0063] Meanwhile, the self-cleaning road marking sample exhibits a lower gloss (less than 10 GU), classifying it as a low-gloss coating, while traditional MMA road markings have a gloss greater than 10 GU, classifying them as medium-gloss coatings. Correspondingly, the anti-skid coefficient of the self-cleaning road marking sample can be increased to around 30, while that of traditional MMA road markings is only 11, indicating that the anti-skid effect of the self-cleaning road marking coating of this invention has been improved.

[0064] Furthermore, the water and oil contact angles on the surface of the self-cleaning road marking sample are significantly higher than those of traditional MMA road markings, thus demonstrating the superior anti-fouling effect of this invention. Even after the coating surface is sanded off, the coating sample of this invention still exhibits a high water and oil contact angle, indicating that the coating itself also possesses a self-cleaning effect and has a more durable self-cleaning capability.

[0065] The above embodiments of the present invention do not describe all details exhaustively, nor do they limit the present invention to the embodiments described above. Various changes, modifications, substitutions, and variations made by those skilled in the art to these embodiments without departing from the principles and spirit of the present invention should be included within the scope of protection of the present invention.

Claims

1. A self-cleaning road marking paint, comprising 1 part by weight of component A and 1-2 parts by weight of component B, each individually packaged, wherein: The A component is composed of 50-150 parts by weight of modified acrylic resin, 0.1-2 parts by weight of accelerator, 1-10 parts by weight of dimethyl silicone oil, and 10-50 parts by weight of low-boiling-point, low-surface-tension solvent. Component B is composed of 50-150 parts by weight of modified acrylic resin, 1-10 parts by weight of curing agent, 1-10 parts by weight of dimethyl silicone oil, and 10-50 parts by weight of low-boiling-point, low-surface-tension solvent. The modified acrylic resin is a mixture obtained by dissolving 70-100 parts by weight of solid acrylic resin in 50-70 parts by weight of methyl methacrylate, 20-30 parts by weight of butyl acrylate, and 10-20 parts by weight of hydroxypropyl methacrylate as a dispersion medium, adding 100-200% by weight of inorganic filler and 10-30% by weight of pigment nano-titanium dioxide, and modifying the inorganic filler and nano-titanium dioxide with a silane coupling agent; wherein the solid acrylic resin is a polymer obtained by copolymerizing methyl methacrylate with at least one or more of butyl methacrylate, hydroxypropyl methacrylate, or styrene, and the inorganic filler is an inorganic material containing hydroxyl functional groups. The accelerator is N,N'-dimethylaniline or N,N'-dimethyl-p-toluidine, and the curing agent is cyclohexanone peroxide, methyl ethyl ketone peroxide or benzoyl peroxide; The low-boiling-point, low-surface-tension solvents are n-hexane, methanol, ethanol, and 3M. TM At least one of the 7100 fluorinated liquids.

2. The self-cleaning road marking paint according to claim 1, characterized in that... The inorganic filler is at least one of porous silica microspheres, silica powder, apatite powder, alumina powder, and hollow glass microspheres.

3. The self-cleaning road marking paint according to claim 1, characterized in that... The silane coupling agent contains C in its molecular structure. n H 2n+1 (n≥10) Alkylsilane coupling agents with molecular chain segments, or those containing C in their molecular structure. n F 2n+1 (n≥3) Fluorosilane coupling agents with molecular chain segments.

4. A method for preparing the self-cleaning road marking paint according to claim 1, comprising mixing 50-70 parts by weight of methyl methacrylate, 20-30 parts by weight of butyl acrylate and 10-20 parts by weight of hydroxypropyl methacrylate evenly, adding 70-100 parts by weight of solid acrylic resin and dissolving evenly to obtain a dispersion medium, then adding 100-200% by weight of inorganic filler and 10-30% by weight of pigment nano-titanium dioxide and dispersing evenly, adding 1-10 parts by weight of silane coupling agent, heating to 60-80°C and stirring under reflux for 1-2 hours to obtain modified acrylic resin; Add 0.1-2 parts by weight of accelerator, 1-10 parts by weight of dimethyl silicone oil and 10-50 parts by weight of low boiling point and low surface tension solvent to 50-150 parts by weight of modified acrylic resin, stir and mix at 400-900 r / min for 0.5-1 hour, and seal to obtain component A of self-cleaning road marking paint; Add 1-10 parts by weight of curing agent, 1-10 parts by weight of dimethyl silicone oil and 10-50 parts by weight of low boiling point, low surface tension solvent to 50-150 parts by weight of modified acrylic resin, stir and mix at 400-900 r / min for 0.5-1 hour, and seal to obtain component B of self-cleaning road marking paint.

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