Hydrophobic wear-resistant water-based road marking paint and preparation method thereof

Abstract

The invention discloses a hydrophobic wear-resistant water-based road marking coating and a preparation method thereof, and relates to the technical field of road marking coatings. The water-based road marking paint is mainly prepared from the following raw materials in percentage by mass: 15-45% of water-based acrylic emulsion; 10%-30% of organic silicon modified water-based acrylic emulsion; 5%-23% of a self-crosslinking resin liquid; 20%-55% of a filler; 5%-35% of pigment; 2%-18% of nano titanium dioxide particles; 1%-3% of a dispersing agent; 0.5%-2% of a leveling agent; 0.5%-1.5% of a coalescing agent; 0.2%-1.5% of a defoaming agent; and the balance of deionized water. The organic silicon modified water-based acrylic emulsion is formed by reacting and polymerizing a compound emulsifier, EHA, a silane coupling agent, St and an initiator, and the organic silicon modified water-based acrylic emulsion is used as a coating component and can enhance the hydrophobic property and the mechanical property of acrylic resin; and by introducing the self-crosslinking resin liquid, the wear resistance of the marking line can be obviously improved. The water-based road marking coating disclosed by the invention has better wear resistance, hydrophobicity and covering performance.

Description

Technical Field

[0001] The invention relates to the technical field of road marking paints, and in particular to a hydrophobic and wear-resistant water-based road marking paint and a preparation method thereof. Background Art

[0002] Traditional road marking materials used in asphalt pavement mainly include hot melt materials, solvent materials, and two-component materials. Among them, hot melt and solvent materials are currently the most widely used in my country. (1) The film thickness of hot melt marking is about 1.5 to 2.5 mm, so it has good wear resistance, but it also has problems such as high-temperature heating equipment required during construction, difficult to repair markings, and high construction costs. (2) Solvent-based materials use organic solvents as dispersion media, and the volatile organic compound content can reach 400 to 500 g / L, which will cause certain damage to the surrounding environment and the health of construction workers. At the same time, solvent-based coatings also have disadvantages such as poor wear resistance and durability. Therefore, they are usually not used on roads with heavy traffic. (3) Two-component materials use two components to form road markings through chemical reactions at the construction site. They have good durability and weather resistance, but two-component coatings need to be mixed at the construction site, and the raw material cost and construction cost are high, which limits their promotion and application.

[0003] Compared with traditional solvent-based paint, water-based paint, as a new type of paint, has stronger durability and environmental protection characteristics. Compared with traditional hot-melt paint, the new water-based paint has stronger adhesion and is more convenient to apply. At the same time, because the coating film of water-based paint is thinner during construction, the material cost per square meter is lower than that of hot-melt road markings. In addition, during the maintenance of road markings, water-based road markings can be directly applied on the surface of old road markings, while the use of hot-melt road markings requires additional costs for removing old road markings.

[0004] However, the construction of water-based paint usually requires relatively dry climatic conditions, and humid weather may affect its laying effect. In addition, water-based paint is highly temperature-sensitive. Under high temperature conditions, the balance of the water-based system will be destroyed, causing the performance of water-based paint to deteriorate during storage. Because water-based road markings are thinner, they are often more susceptible to wear than other types of road marking materials after being affected by weather and traffic loads. Especially in the southwest of my country, where the area of ​​mountainous and hilly areas is high and the annual rainfall is high, rain will bring dust in the air to the road surface, reducing the visibility of road markings. The road markings in this area are easily polluted by rain, dust and other factors during service, which greatly affects the use effect and service life of road markings.

[0005] Existing Chinese patent document CN111205726A discloses a water-based acrylic water-resistant road marking paint, which is prepared from the following raw materials in parts by weight: 100-200 parts of modified acrylic resin, 1-3 parts of diacetone acrylamide, 1-3 parts of adipic acid dihydrazine, 5-10 parts of neopentyl glycol, 10-15 parts of maleic anhydride, 3-7 parts of adipic acid ester, 10-20 parts of film-forming aid, 5-10 parts of dispersant and 5-10 parts of defoamer, which can mainly improve its gloss retention, water resistance, acid resistance, chemical corrosion resistance, etc.

[0006] The existing Chinese patent document CN113355001 A discloses a road marking paint, which is composed of 5-60 parts of heavy calcium carbonate, 3-5 parts of coloring material, 20-30 parts of glass beads, 1-2 parts of auxiliary agent, 20-30 parts of water-based acrylic emulsion, 5-10 parts of wood fiber, 1-2 parts of rare earth aluminate luminous powder and 3-5 parts of hydroxyethyl cellulose. The road marking paint mainly solves the problem that the traditional water-based paint has poor toughness and is easily affected by ground deformation and breaks.

[0007] The road marking paints mentioned in the above-mentioned prior art documents have all improved the deformation performance of the marking materials, which can alleviate the cracking and falling off of the road markings caused by the deformation of the road surface to a certain extent. However, in the actual engineering application of water-based road markings, the main form of damage is surface wear. The above-mentioned patent documents have not optimized the wear performance of the markings. Although attempts have been made to extend the service life of the markings by improving water resistance, chemical corrosion resistance and long-lasting reflectivity, if the wear resistance of the marking body is insufficient, it will still directly lead to a rapid decrease in the service life of the markings. Therefore, it is urgent to develop a road marking paint with better wear resistance. Summary of the invention

[0008] The technical problem to be solved by the present invention is: in view of the defects of the prior art, a hydrophobic and wear-resistant water-based road marking paint and a preparation method thereof are provided, wherein the water-based road marking paint has better wear resistance, hydrophobicity and hiding power, and can increase the service life of the marking line.

[0009] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a hydrophobic and wear-resistant water-based road marking paint, which is mainly prepared from the following raw materials in percentage by mass:

[0011] Water-based acrylic emulsion 15% to 45%;

[0012] Silicone modified water-based acrylic emulsion 10% to 30%;

[0013] Self-crosslinking resin liquid 5% to 23%;

[0014] Filler 20%~55%;

[0015] Pigment 5% to 35%;

[0016] Nano titanium dioxide particles 2% to 18%;

[0017] Dispersant 1% to 3%;

[0018] Leveling agent 0.5%~2%;

[0019] Film-forming aid 0.5% to 1.5%;

[0020] Defoaming agent 0.2%~1.5%;

[0021] The balance was deionized water.

[0022] Furthermore, the organosilicon-modified water-based acrylic emulsion is prepared by polymerization of a composite emulsifier, isooctyl acrylate (EHA), a silane coupling agent, styrene (St), and an initiator.

[0023] Furthermore, the preparation process of the silicone-modified acrylic emulsion specifically includes the following steps:

[0024] (1) dissolving the composite emulsifier in deionized water and stirring thoroughly to dissolve, adding the polymer monomer silane coupling agent, EHA, and St, and ultrasonically dispersing for 10 to 13 minutes to prepare a pre-emulsion;

[0025] (2) Then, the pre-emulsion is partially transferred to a container with nitrogen protection and condensation reflux device, and a part of the initiator solution is slowly added dropwise until blue fluorescence appears, indicating that the free radical initiation reaction has started. Then, the remaining pre-emulsion and initiator solution are slowly added dropwise within a preset time, and the temperature is controlled at 75-80°C (to prevent the temperature from being too high and causing polymer degradation). After the addition is completed, the heat preservation reaction is continued for 1-2.5 hours to ensure that the monomer is completely polymerized; after the polymerization is completed, when the emulsion temperature inside the container drops below 50-55°C, a pH adjuster is added to adjust the pH value to 8-8.5 (weakly alkaline) to obtain a silicone-modified acrylic emulsion.

[0026] Furthermore, the composite emulsifier accounts for 2.5% to 3% of the total weight of the organosilicon-modified water-based acrylic emulsion.

[0027] Furthermore, the composite emulsifier consists of polyoxyethylene octylphenol ether (OP-10) and sodium dodecyl sulfate (SDS).

[0028] Preferably, the mass ratio of polyoxyethylene octylphenol ether (OP-10) to sodium dodecyl sulfate (SDS) in the composite emulsifier is 6:4.

[0029] Furthermore, the silane coupling agent is KH570 (γ-methacryloxypropyltrimethoxysilane) or KH550 (γ-aminopropyltriethoxysilane), preferably KH570.

[0030] Preferably, the mass ratio of EHA, St and KH570 monomers is (65-75):(20-25):(3-7).

[0031] Preferably, the initiator is potassium persulfate (KPS), accounting for 0.34% to 1% of the total amount of all polymer monomers.

[0032] Preferably, the pH adjuster is a mixed solution of sodium hydroxide solution and ammonia water.

[0033] Furthermore, the main component of the aqueous acrylic emulsion is a polymer of 2-ethylhexyl acrylate and styrene.

[0034] Furthermore, the main component of the self-crosslinking resin liquid is a polymer of 2-methyl-2-acrylate, 2-butyl acrylate, vinylbenzene and 2-acrylic acid.

[0035] Preferably, the pigment is rutile titanium dioxide (mainly composed of titanium dioxide) with a particle size of 1 to 8 μm.

[0036] Preferably, the particle size of nano titanium dioxide is between 0.05 and 0.1 μm.

[0037] Preferably, the filler is a mixture of 325 mesh silicon micropowder and 800 mesh heavy calcium powder.

[0038] Preferably, the mass ratio of silicon micropowder to heavy calcium powder is (35-55):(45-65).

[0039] Preferably, the leveling agent includes one or two or more of H421, RM2020, and SN612.

[0040] Preferably, the dispersant includes one or two or more of BYK180, BYK190, BYK191, SN5040, and SN5027.

[0041] Preferably, the defoaming agent includes one or two or more of BYK019, BYK024, and BYK028.

[0042] Preferably, the film-forming aid includes one or two or more of DPNB, DPM, alcohol lipid dodecahydrate, and alcohol lipid hexahydrate.

[0043] In a second aspect, the present invention also provides a method for preparing a hydrophobic and wear-resistant water-based road marking paint, the main steps of which are as follows:

[0044] S1, weighing the raw material components of corresponding weight parts for standby use;

[0045] S2, adding nano titanium dioxide particles to part of deionized water, adding part of dispersant at the same time, and ultrasonically dispersing for 30 to 40 minutes at an ultrasonic frequency of 20 to 25 kHz to obtain a nano titanium dioxide dispersion; during the ultrasonic dispersion process, the temperature is controlled below 50° C. to avoid agglomeration of nanoparticles;

[0046] S3, placing the aqueous acrylic emulsion, the silicone-modified acrylic emulsion, the self-crosslinking resin liquid, the remaining deionized water, and the dispersant in a container; stirring and mixing at a speed of 300 to 500 rpm for 10 to 15 minutes to obtain a pre-emulsified emulsion;

[0047] S4. Add the nano titanium dioxide dispersion prepared in S2 to the pre-emulsified emulsion of S3, then slowly add pigments and fillers for multiple times, and then add leveling agent, film-forming aid and defoaming agent in sequence after there are no obvious particles in the solution; stir and mix at a speed of 800-1000 rpm for 15-18 minutes, then adjust the pH value to 9-10, then filter through an 80-mesh filter, transfer to a sealed light-proof container to prevent the acrylic resin from self-crosslinking under ultraviolet irradiation, causing the coating to harden prematurely, and obtain a water-based road marking material.

[0048] The present invention has the following beneficial effects:

[0049] 1. On the basis of conventional water-based acrylic emulsion, the present invention adopts a composite emulsifier, isooctyl acrylate (EHA), a silane coupling agent, styrene (St), and an initiator to polymerize to prepare an organosilicon-modified water-based acrylic emulsion, wherein the organosilicon-modified water-based acrylic emulsion is modified by a silane coupling agent, and a siloxane group is grafted into a polymer chain. The prepared organosilicon-modified water-based acrylic emulsion is used as a coating component to enhance the hydrophobicity and mechanical properties of acrylic resin.

[0050] Compared with the common water-based road markings prepared with water-based acrylic emulsion, the present invention uses silicone-modified acrylic emulsion to partially replace part of the water-based acrylic emulsion, which can simultaneously improve the weather resistance and hydrophobicity of the entire marking.

[0051] 2. The coating provided by the present invention uses nano-titanium dioxide to replace part of the large-particle rutile titanium dioxide pigment. On the one hand, the nano-sized titanium dioxide particles can construct a micro-nano structure on the surface of the marking road, thereby improving the hydrophobicity of the marking road material. On the other hand, titanium dioxide is the main component of the marking road pigment. Adding part of the nano-titanium dioxide with a smaller particle size to the coating of the present invention can make the internal color filler of the coating more densely stacked, which can significantly improve the chromaticity and hiding rate of the marking road.

[0052] 3. The present invention introduces a self-crosslinking emulsion formed by polymerization of 2-methyl-2-methyl methacrylate, 2-butyl methacrylate, vinylbenzene and 2-acrylic acid in a water-based road marking paint, which has a multi-polymer chain structure, wherein: 2-methyl-2-methyl methacrylate can provide steric hindrance and polar enhancement effects, and 2-butyl methacrylate has flexibility. At the same time, the main components of the water-based acrylic emulsion are polymers of 2-ethylhexyl methacrylate and styrene, wherein styrene can enhance the rigidity and stability of the resin. The high acid value characteristic (79) of the self-crosslinking resin liquid enables it to undergo an effective chemical reaction with the carboxyl group in the polymerization system with the water-based acrylic emulsion to form a dense crosslinking network structure. This highly crosslinked three-dimensional structure can effectively disperse the stress applied by the outside world, reduce the wear on the coating surface, and enhance the wear resistance of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 A schematic flow chart of a method for preparing a silicone-modified water-based acrylic emulsion provided in an embodiment of the present invention.

[0054] Figure 2 A schematic flow chart of a method for preparing a water-based road marking material provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0055] As used herein:

[0056] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0057] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0058] When a parameter is expressed as a range, a preferred range, or a range limited by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges of "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5" and the like. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range. In these embodiments, unless otherwise indicated, the parts and percentages described are all by mass.

[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0060] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0061] like Figure 1 As shown, the present invention first provides a silicone-modified water-based acrylic emulsion, which is prepared by the following method:

[0062] (1) Prepare polymer monomers (including isooctyl acrylate (EHA), styrene (St), and silane coupling agent KH570) according to a preset mass ratio, where the mass ratio of EHA, St, and KH570 monomers is (65-75): (20-25): (3-7); 2.5-3% of a composite emulsifier, wherein the composite emulsifier is composed of polyoxyethylene octylphenol ether and sodium dodecyl sulfate. In the following preferred embodiment, the mass ratio of OP-10: SDS is 6:4; deionized water and an initiator solution. The initiator is KPS, and its amount is 0.34-0.1% of the mass of the polymer monomer. Deionized water is used as a solvent to prepare an initiator aqueous solution with a certain mass percentage concentration.

[0063] (2) The composite emulsifier was dissolved in deionized water and stirred thoroughly to dissolve, and then the polymer monomers, silane coupling agents KH570, EHA and St were added, and ultrasonic dispersion was performed for 10 to 13 minutes to prepare a pre-emulsion.

[0064] (3) Then, the pre-emulsion is partially transferred to a container with nitrogen protection and condensation reflux device, and part of the initiator solution is slowly dripped until blue fluorescence appears, and then the remaining pre-emulsion and initiator solution are slowly dripped within a preset time, and the temperature is controlled at 75-80°C. After the dripping is completed, the heat preservation reaction is continued for 1-2.5 hours; after the polymerization is completed, when the emulsion temperature inside the container drops below 50-55°C, a pH regulator is added to adjust the pH value to 8-8.5, and a silicone-modified acrylic emulsion is obtained. In the following preferred embodiment, the pH regulator is a mixture of sodium hydroxide solution and ammonia water in a volume ratio of 1:1, the ammonia solution is commercially available, and the mass percentage concentration is 26%; the sodium bicarbonate solution is prepared using sodium bicarbonate solid, and the mass percentage concentration is 10%.

[0065] In order to further illustrate the scheme of the present invention, the preferred embodiments (embodiments 1-3) of the organosilicon-modified water-based acrylic emulsion of the present invention are given below as examples for illustration. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0066] Example 1 (Preparation Example of Silicone-Modified Water-Based Acrylic Emulsion)

[0067] This embodiment provides a silicone-modified water-based acrylic emulsion, and the preparation method is as follows:

[0068] (1) Prepare polymer monomers (including 29.82% isooctyl acrylate, 10.13% styrene, 2.53% KH570 silane coupling agent), 2.50% composite emulsifier (OP-10: SDS mass ratio is 6:4), 55.02% deionized water and initiator solution according to the mass ratio. KPS is used as the initiator, and its amount is 0.6% of the mass of the polymer monomer. Deionized water is used as the solvent to prepare the initiator aqueous solution with a mass percentage concentration of 3%.

[0069] (2) A certain amount of deionized water and a composite emulsifier were added to a four-necked flask, and the mixture was mixed at 45° C. at 200 rpm for 5 minutes using a stirrer to completely dissolve the composite emulsifier; then isooctyl acrylate, styrene and KH570 were added, and ultrasonic dispersion treatment was performed for 10 minutes to prepare a pre-emulsion of a silicone-modified acrylic resin.

[0070] (3) Transfer part (30%) of the pre-emulsion to another device with nitrogen protection and condensation reflux, heat to 80°C, start to drop part (20%) of the KPS aqueous solution, observe the system during the dropwise addition and see the blue fluorescence, indicating that the free radical initiation reaction has begun, then slowly drop the remaining pre-emulsion and KPS aqueous solution over 90 minutes, and use the condensation reflux device to control the temperature at around 80°C to prevent the polymer from being degraded due to excessive temperature. After the dropwise addition is completed, continue to keep the reaction warm for 1 hour to ensure that the monomer is completely polymerized. After the polymerization is completed, cool to 50°C, add an appropriate amount of pH adjuster (sodium hydroxide solution and ammonia water are mixed in a volume ratio of 1:1), adjust the pH to 8.0, ensure the stability of the emulsion, continue to stir for 10 minutes to ensure that the solution is uniform, and finally cool the emulsion to room temperature, filter with a 120-mesh filter to remove insoluble matter, and transfer to a sealed container for storage for later use.

[0071] Example 2 (Preparation Example of Silicone-Modified Water-Based Acrylic Emulsion)

[0072] This embodiment provides a silicone-modified water-based acrylic emulsion, and the preparation method is as follows:

[0073] (1) Prepare polymer monomers (including 28.5% isooctyl acrylate, 11.5% styrene, 3% KH570 silane coupling agent), 2.8% composite emulsifier (OP-10: SDS mass ratio is 6:4), and 54.2% deionized water according to the mass ratio. KPS is used as the initiator, and its amount is 1.0% of the mass of the polymer monomer. Deionized water is used as the solvent to prepare an initiator aqueous solution with a mass percentage concentration of 3.5%.

[0074] (2) A certain amount of deionized water and a composite emulsifier were added to a four-necked flask, and the mixture was mixed at 45° C. at 220 rpm for 6 minutes using a stirrer to completely dissolve the composite emulsifier; then isooctyl acrylate, styrene and KH570 were added, and ultrasonic dispersion treatment was performed for 10 minutes to prepare a pre-emulsion of a silicone-modified acrylic resin.

[0075] (3) Transfer part (35%) of the pre-emulsion to another device with nitrogen protection and condensation reflux, heat to 75°C, start to drop part (25%) of the KPS aqueous solution, observe the system during the dropwise addition and blue fluorescence appears, indicating that the free radical initiation reaction has begun, then drop the remaining pre-emulsion and KPS aqueous solution within 90 minutes, and use the condensation reflux device to control the temperature at about 75°C to prevent the polymer from being degraded due to excessive temperature. After the dropwise addition is completed, continue to keep the reaction warm for 2.5 hours to ensure that the monomer is completely polymerized. After the polymerization is completed, cool to 50°C, add an appropriate amount of pH adjuster (sodium hydroxide solution and ammonia water are mixed in a volume ratio of 1:1), adjust the pH to 8.0, ensure the stability of the emulsion, continue to stir for 10 minutes to ensure that the solution is uniform, and finally cool the emulsion to room temperature, filter with a 120-mesh filter to remove insoluble matter, and transfer to a sealed container for storage for later use.

[0076] Example 3 (Preparation Example of Silicone-Modified Water-Based Acrylic Emulsion)

[0077] This embodiment provides a silicone-modified water-based acrylic emulsion, and the preparation method is as follows:

[0078] (1) Prepare polymer monomers (including 30.2% isooctyl acrylate, 10.5% styrene, 1.8% silane coupling agent (KH570)), 3% composite emulsifier (the mass ratio of OP-10: SDS is 6:4), and 54.5% deionized water according to the mass ratio. KPS is used as the initiator, and its amount is 0.34% of the mass of the polymer monomer. Deionized water is used as the solvent to prepare an initiator aqueous solution with a concentration of 4%.

[0079] (2) A certain amount of deionized water and a composite emulsifier were added to a four-necked flask, and the mixture was mixed at 50° C. for 5 minutes at 400 rpm using a stirrer to completely dissolve the composite emulsifier; then isooctyl acrylate, styrene and KH570 were added, and ultrasonic dispersion treatment was performed for 13 minutes to prepare a pre-emulsion of a silicone-modified acrylic resin.

[0080] (3) Transfer part (20%) of the pre-emulsion to another device with nitrogen protection and condensation reflux, heat to 80°C, start to drop part (20%) of the KPS aqueous solution, observe the system during the dropwise addition and see the blue fluorescence, indicating that the free radical initiation reaction has begun, then drop the remaining pre-emulsion and KPS aqueous solution within 40 minutes, and use the condensation reflux device to control the temperature at about 80°C to prevent the polymer from being degraded due to excessive temperature. After the dropwise addition is completed, continue to keep the reaction warm for 50 minutes to ensure that the monomer is completely polymerized. After the polymerization is completed, cool to 55°C, add an appropriate amount of pH adjuster (sodium hydroxide solution and ammonia water are mixed in a volume ratio of 1:1), adjust the pH to 8.5, ensure the stability of the emulsion, continue to stir for 10 minutes to ensure that the solution is uniform, and finally cool the emulsion to room temperature, filter with a 120-mesh filter to remove insoluble matter, and transfer to a sealed container for storage for later use.

[0081] like Figure 2 As shown, the present invention further provides a water-based road marking material, and the preparation method thereof is as follows:

[0082] S1. Weigh the following raw material components in mass percentage according to mass ratio: 15%-45% water-based acrylic emulsion; 10%-30% organosilicon-modified water-based acrylic emulsion; 5%-23% self-crosslinking resin liquid; 20%-55% filler; 5%-35% pigment; 2%-18% nano titanium dioxide particles; 1%-3% dispersant; 0.5%-2% leveling agent; 0.5%-1.5% film-forming aid; 0.2%-1.5% defoaming agent; the balance is deionized water.

[0083] In a specific embodiment, the leveling agent includes one or two or more of H421, RM2020, and SN612. The dispersant includes one or two or more of BYK180, BYK190, BYK191, SN5040, and SN5027. The defoamer includes one or two or more of BYK019, BYK024, and BYK028. The film-forming aid includes one or two or more of DPNB, DPM, alcohol lipid twelve, and alcohol lipid sixteen.

[0084] In the following preferred embodiments:

[0085] The water-based acrylic emulsion is a commercially available finished product, the main components of which are a polymer of 2-ethylhexyl 2-acrylate and styrene. The following examples specifically use a water-based acrylic resin liquid RX-20 from Hanwha, South Korea. The self-crosslinking resin liquid is a commercially available finished product, the main components of which are a polymer of 2-methyl-2-acrylate, 2-butyl acrylate, vinylbenzene and 2-acrylic acid. The following examples specifically use a self-crosslinking resin liquid HW-6 from Hanwha, South Korea. The pigment uses rutile titanium dioxide (the main component is titanium dioxide), with a particle size of 1 to 8 μm. The particle size of nano titanium dioxide is 0.05 to 0.1 μm.

[0086] S2. Add nano titanium dioxide particles into part of deionized water and add part of dispersant at the same time, and perform ultrasonic dispersion for 30 to 40 minutes at an ultrasonic frequency of 20 to 25 kHz to ensure that the nano titanium dioxide particles are evenly dispersed to obtain a stable nano titanium dioxide dispersion. During the ultrasonic dispersion process, the equipment temperature needs to be controlled below 50°C to avoid agglomeration of nanoparticles.

[0087] S3. Add the aqueous acrylic emulsion, the silicone-modified acrylic emulsion, the self-crosslinking resin liquid and the remaining deionized water and the dispersant into a container with a sealing device, and stir at a speed of 300-500 rpm for 10-15 minutes to ensure that the components in the emulsion are evenly mixed to obtain a pre-emulsified emulsion.

[0088] S4. After stirring, slowly add the titanium dioxide dispersion in S2 to the pre-emulsified emulsion in S3, then slowly add the pigment and filler several times, and then add the leveling agent, film-forming aid and defoaming agent in sequence after there are no obvious particles in the solution; stir and mix at a speed of 800-1000 rpm for 15-18 minutes, then adjust the pH value to 9-10, then filter through an 80-mesh filter, and transfer to a sealed light-proof container to obtain a water-based road marking material.

[0089] In order to further illustrate the scheme of the present invention, the following preferred embodiments (Examples 4-6) of the preparation of the water-based road marking material of the present invention are given as examples for illustration. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0090] Example 4 (Preparation of water-based road marking material)

[0091] This embodiment provides a water-based road marking material, and the preparation method is as follows:

[0092] S1. Weigh the following raw material components in parts by weight according to the mass ratio: 12.97% aqueous acrylic emulsion, 12.97% organosilicon-modified acrylic emulsion prepared in Example 1, 7.23% self-crosslinking resin liquid, 6.69% nano titanium dioxide, 9.39% deionized water, 2.82% dispersant (BYK-191), 1.41% leveling agent (SN612), 34.91% filler (including 325 mesh silicon micropowder: 800 mesh heavy calcium powder = 50:50), 9.39% pigment (rutile titanium dioxide), 1.41% film-forming agent (alcohol ester twelve), and 0.81% defoaming agent (BYK019).

[0093] S2. Add nano-titanium dioxide particles to part of the deionized water and half of the dispersant at the same time, and use ultrasonic dispersion for 30 minutes to ensure that the nano-titanium dioxide particles are evenly dispersed to obtain a stable nano-titanium dioxide dispersion. During the ultrasonic dispersion process, the equipment temperature needs to be controlled below 50°C to avoid agglomeration of nano-particles.

[0094] S3. Add the aqueous acrylic emulsion, the silicone-modified acrylic emulsion, the self-crosslinking resin liquid and the remaining deionized water and the dispersant into a container with a sealing device, and stir at a speed of 500 rpm for 10 minutes to ensure that the components in the emulsion are evenly mixed to obtain a pre-emulsified emulsion.

[0095] S4, after stirring, slowly add the titanium dioxide dispersion of S2 to the pre-emulsified emulsion of S3 and continue stirring for 7 minutes, then slowly add pigments and fillers several times, increase the stirrer speed to 1200 rpm, until there are no obvious particles in the solution, add leveling agent, film-forming aid and defoamer in turn, and continue stirring at 1000 rpm for 15 minutes. Finally, use an appropriate amount of ammonia water to adjust the pH value to 9, filter with an 80-mesh filter, transfer to a sealed light-proof container for storage, and obtain a water-based road marking material.

[0096] Example 5 (Preparation of water-based road marking material)

[0097] This embodiment provides a water-based road marking material, and the preparation method is as follows:

[0098] S1. Weigh the following raw material components in parts by weight according to the mass ratio: 13.68% of aqueous acrylic emulsion, 13.68% of the organosilicon-modified acrylic emulsion prepared in Example 2, 8.02% of self-crosslinking resin liquid, 8.5% of nano titanium dioxide, 9.08% of deionized water, 2.36% of dispersant (SN5040), 1.70% of leveling agent (SN612), 30.52% of filler (including 325 mesh silicon micropowder: 800 mesh heavy calcium powder = 35:65), 8.83% of pigment (rutile titanium dioxide), 1.50% of film-forming agent (alcohol ester twelve), and 1.13% of defoaming agent (BYK028).

[0099] S2. Add nano titanium dioxide particles to part of the deionized water and half of the dispersant at the same time, and use ultrasonic dispersion for 35 minutes to ensure that the nano titanium dioxide particles are evenly dispersed to obtain a stable nano titanium dioxide dispersion. During the ultrasonic dispersion process, the equipment temperature needs to be controlled below 50°C to avoid agglomeration of nanoparticles.

[0100] S3. Add the aqueous acrylic emulsion, the silicone-modified acrylic emulsion, the self-crosslinking resin liquid and the remaining deionized water and the dispersant into a container with a sealing device, and stir at a speed of 500 rpm for 10 minutes to ensure that the components in the emulsion are evenly mixed to obtain a pre-emulsified emulsion.

[0101] S4, after stirring, slowly add the titanium dioxide dispersion of S2 to the pre-emulsified emulsion of S3 and continue stirring for 7 minutes, then slowly add pigments and fillers several times, increase the stirrer speed to 1200 rpm, until there are no obvious particles in the solution, add leveling agent, film-forming aid and defoamer in turn, and continue stirring at 1000 rpm for 15 minutes. Finally, use an appropriate amount of ammonia water to adjust the pH value to 10, filter with an 80-mesh filter, transfer to a sealed light-proof container for storage, and obtain a water-based road marking material.

[0102] Example 6 (Preparation of water-based road marking material)

[0103] This embodiment provides a water-based road marking material, and the preparation method is as follows:

[0104] S1. Weigh the following raw material components in parts by weight according to the mass ratio: 9.31% of aqueous acrylic emulsion, 9.31% of organosilicon-modified acrylic emulsion prepared in Example 3, 8.16% of self-crosslinking resin liquid, 5.57% of nano titanium dioxide, 8.83% of deionized water, 2.86% of dispersant (SN5040), 1.59% of leveling agent (SN612), 42.41% of filler (including 325 mesh silicon micropowder: 800 mesh heavy calcium powder = 35:65), 9.74% of pigment (rutile titanium dioxide), 1.27% of film-forming agent (alcohol ester twelve), and 0.95% of defoaming agent (BYK028).

[0105] S2. Add nano-titanium dioxide particles to part of the deionized water and half of the dispersant at the same time, and use ultrasonic dispersion for 30 minutes to ensure that the nano-titanium dioxide particles are evenly dispersed to obtain a stable nano-titanium dioxide dispersion. During the ultrasonic dispersion process, the equipment temperature needs to be controlled below 50°C to avoid agglomeration of nano-particles.

[0106] S3. Add the aqueous acrylic emulsion, the silicone-modified acrylic emulsion, the self-crosslinking resin liquid and the remaining deionized water and the dispersant into a container with a sealing device, and stir at a speed of 500 rpm for 10 minutes to ensure that the components in the emulsion are evenly mixed to obtain a pre-emulsified emulsion.

[0107] S4, after stirring, slowly add the titanium dioxide dispersion of S2 to the pre-emulsified emulsion of S3 and continue stirring for 8 minutes, then slowly add pigments and fillers several times, increase the stirrer speed to 1500 rpm, until there are no obvious particles in the solution, add leveling agent, film-forming aid and defoamer in turn, and continue stirring at 1000 rpm for 15 minutes. Finally, use an appropriate amount of ammonia water to adjust the pH value to 9, filter with an 80-mesh filter, transfer to a sealed light-proof container for storage, and obtain a water-based road marking material.

[0108] Comparative Example 1

[0109] The present embodiment provides a water-based road marking material, which is different from the embodiment 4 in that a pure water-based acrylic emulsion is used instead of a silicone-modified acrylic emulsion, and the remaining components are the same as those in the embodiment 4, specifically as follows: 25.94% water-based acrylic emulsion, 7.23% self-crosslinking resin liquid, 9.39% deionized water, 2.82% dispersant (BYK-191), 1.41% leveling agent (SN612), 34.91% filler (including 325 mesh silicon micropowder: 800 mesh heavy calcium powder = 50:50), 16.08% pigment (rutile titanium dioxide), 1.41% film-forming agent (alcohol ester twelve), and 0.81% defoaming agent (BYK019).

[0110] The preparation method is as follows: first, add water-based acrylic emulsion, self-crosslinking resin liquid, dispersant and deionized water into a container with a sealing device, stir at a speed of 500 rpm for 10 minutes to ensure that the components in the emulsion are evenly mixed to obtain a pre-emulsified emulsion, slowly add pigments and fillers several times after stirring, increase the stirrer speed to 1000 rpm, add leveling agent, film-forming aid and defoamer until there are no obvious particles in the solution, and continue stirring for 15 minutes. Finally, use an appropriate amount of ammonia water to adjust the pH value to 9, filter with an 80-mesh filter, transfer to a sealed light-proof container for storage, and obtain a water-based road marking material.

[0111] Comparative Example 2

[0112] The present embodiment provides a water-based road marking material, which uses the organosilicon-modified acrylic emulsion prepared in Example 1, but does not use the self-crosslinking resin liquid. Instead, pure water-based acrylic emulsion and organosilicon-modified acrylic emulsion are used. The mass ratios of the remaining components are the same as those in Example 4, specifically as follows: 16.59% water-based acrylic emulsion, 16.59% organosilicon-modified acrylic emulsion prepared in Example 1, 6.69% nano titanium dioxide, 9.39% deionized water, 2.81% dispersant (BYK-191), 1.41% leveling agent (SN612), 34.91% filler (including 325 mesh silicon micropowder: 800 mesh heavy calcium powder = 50:50), 9.39% pigment (rutile titanium dioxide), 1.41% film-forming agent (alcohol ester twelve), and 0.81% defoaming agent (BYK019).

[0113] The preparation method is as follows: add nano titanium dioxide to deionized water, add half of the dispersant at the same time, use ultrasonic dispersion for 30 minutes to ensure that the nano titanium dioxide particles are evenly dispersed to obtain a stable nano titanium dioxide dispersion. During the ultrasonic dispersion process, the equipment temperature needs to be controlled below 50°C to avoid agglomeration of nanoparticles. Then add the aqueous acrylic emulsion, silicone-modified acrylic emulsion and the remaining dispersant to a container with a sealing device, stir at a speed of 500 rpm for 10 minutes to ensure that the components in the emulsion are evenly mixed to obtain a pre-emulsified emulsion. After stirring, slowly add the titanium dioxide dispersion to the pre-emulsified emulsion and continue stirring for 5 minutes, then slowly add pigments and fillers several times, increase the stirrer speed to 1000 rpm, add leveling agent, film-forming aid and defoamer until there are no obvious particles in the solution, and continue stirring for 15 minutes. Finally, use an appropriate amount of ammonia water to adjust the pH value to 9, filter with an 80-mesh filter, transfer to a sealed light-proof container for storage, and obtain a water-based road marking material.

[0114] In order to verify the feasibility and effectiveness of the present invention, the performance of each water-based road marking material prepared in the above embodiments and comparative examples was tested. Referring to the specification JT / T 280-2022 "Road Marking Paint", the basic performance and water contact angle of the marking paint were tested, and the results are shown in Table 1.

[0115] Table 1 Performance test results of the road marking paints according to the present invention and comparative examples

[0116] project Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Wear resistance(mg) 38 42 55 43 51 Chroma 0.88 0.92 0.89 0.88 0.89 Coverage rate (%) 95.68 97.41 93.29 93.19 95.13 Water contact angle (°) 121.9 128.7 112 91.15 107 Viscosity(KU) 89.5 91.4 98.4 87.7 102.1 Water resistance qualified qualified qualified qualified qualified Alkali resistance qualified qualified qualified qualified qualified

[0117] By comparing the data of the road marking paint provided by the embodiments and comparative examples in Table 1 above, it can be seen that: Comparative Example 1 uses pure water-based acrylic emulsion to replace the organosilicon-modified acrylic emulsion of the present invention, and the rest is the same as Example 4. The results show that the mass loss after abrasion under this formula without using the organosilicon-modified acrylic emulsion is also significantly increased compared with Example 4, indicating that the addition of organosilicon-modified acrylic emulsion can improve the wear resistance of the road marking. Comparative Example 2 does not use self-crosslinking resin liquid, and the rest is the same as Example 4. The results show that under this formula without using the self-crosslinking resin liquid, the mass loss after abrasion is significantly increased compared with Example 4, indicating that the addition of the self-crosslinking resin liquid can also significantly improve the wear resistance of the road marking. In addition, compared with the comparative example, the coating of the present invention also has a more obvious performance improvement in hydrophobicity and hiding power.

[0118] In summary, the water-based road marking material provided by the present invention has better properties such as abrasion resistance, hydrophobicity and hiding power than ordinary water-based acrylic paint.

[0119] The above descriptions are only some preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A hydrophobic and wear-resistant water-based road marking paint, characterized in that: It is mainly prepared from the following raw materials in percentage by mass: Water-based acrylic emulsion 15% to 45%; Silicone modified water-based acrylic emulsion 10% to 30%; Self-crosslinking resin liquid 5% to 23%; Filler 20%~55%; Pigment 5% to 35%; Nano titanium dioxide particles 2% to 18%; Dispersant 1% to 3%; Leveling agent 0.5%~2%; Film-forming aid 0.5% to 1.5%; Defoaming agent 0.2%~1.5%; The balance was deionized water.

2. The hydrophobic and wear-resistant water-based road marking paint according to claim 1, characterized in that: The organosilicon-modified water-based acrylic emulsion is prepared by polymerization of a composite emulsifier, EHA, a silane coupling agent, St and an initiator.

3. The hydrophobic and wear-resistant water-based road marking paint according to claim 2, characterized in that: The preparation process of the organosilicon-modified acrylic emulsion specifically includes the following steps: (1) dissolving the composite emulsifier in deionized water and stirring thoroughly to dissolve, adding the polymer monomer silane coupling agent, EHA, and St, and ultrasonically dispersing for 10 to 13 minutes to prepare a pre-emulsion; (2) Then, the pre-emulsion is partially transferred to a container with nitrogen protection and condensation reflux device, and a part of the initiator solution is slowly added dropwise until blue fluorescence appears, and then the remaining pre-emulsion and initiator solution are slowly added dropwise within a preset time, while the temperature is controlled at 75-80° C. After the addition is completed, the heat preservation reaction is continued for 1-2.5 hours; after the polymerization is completed, when the emulsion temperature inside the container drops below 50-55° C., a pH adjuster is added to adjust the pH value to 8-8.5 to obtain a silicone-modified acrylic emulsion.

4. The hydrophobic and wear-resistant water-based road marking paint according to claim 2 or 3, characterized in that: The composite emulsifier accounts for 2.5% to 3% of the total weight of the organosilicon-modified water-based acrylic emulsion, and the composite emulsifier consists of polyoxyethylene octylphenol ether and sodium dodecyl sulfate; the mass ratio of polyoxyethylene octylphenol ether to sodium dodecyl sulfate is 6:

4.

5. The hydrophobic and wear-resistant water-based road marking paint according to claim 2 or 3, characterized in that: The silane coupling agent is KH570 or KH550.

6. The hydrophobic and wear-resistant water-based road marking paint according to claim 5, characterized in that: The silane coupling agent is KH570, and the mass ratio of EHA, St and KH570 monomers is (65-75): (20-25): (3-7); The initiator is potassium persulfate, which accounts for 0.34% to 1% of the total amount of all polymer monomers.

7. The hydrophobic and wear-resistant water-based road marking paint according to claim 1, characterized in that: The main component of the aqueous acrylic emulsion is a polymer of 2-ethylhexyl acrylate and styrene; The self-crosslinking resin liquid is mainly composed of a polymer of 2-methyl-2-methyl acrylate, 2-butyl acrylate, vinylbenzene and 2-acrylic acid.

8. The hydrophobic and wear-resistant water-based road marking paint according to claim 1, characterized in that: The pigment is rutile titanium dioxide with a particle size of 1 to 8 μm; The particle size of nano titanium dioxide is 0.05-0.1 μm; The filler is a mixture of 325-mesh silicon micropowder and 800-mesh heavy calcium powder; the mass ratio of silicon micropowder to heavy calcium powder is (35-55): (45-65).

9. The hydrophobic and wear-resistant water-based road marking paint according to claim 1, characterized in that: The leveling agent includes one or two or more of H421, RM2020 and SN612; The dispersant includes one or two or more of BYK180, BYK190, BYK191, SN5040, and SN5027; The defoaming agent includes one or two or more of BYK019, BYK024 and BYK028; The film-forming aid includes one or two or more of DPNB, DPM, alcohol lipid twelve and alcohol lipid sixteen.

10. A method for preparing the hydrophobic and wear-resistant water-based road marking paint according to any one of claims 1 to 9, characterized in that: The main steps are as follows: S1, weighing the raw material components of corresponding weight parts for standby use; S2, adding nano titanium dioxide particles to part of deionized water, adding part of dispersant at the same time, and ultrasonically dispersing for 30 to 40 minutes at an ultrasonic frequency of 20 to 25 kHz to obtain a nano titanium dioxide dispersion; controlling the temperature below 50° C. during the ultrasonic dispersion process; S3, placing the aqueous acrylic emulsion, the silicone-modified acrylic emulsion, the self-crosslinking resin liquid, the remaining deionized water, and the dispersant in a container, stirring and mixing at a speed of 300 to 500 rpm for 10 to 15 minutes to obtain a pre-emulsified emulsion; S4. Add the nano titanium dioxide dispersion prepared in S2 to the pre-emulsified emulsion of S3, then slowly add pigments and fillers for multiple times, and then add leveling agent, film-forming aid and defoaming agent in sequence after there are no obvious particles in the solution; stir and mix at a speed of 800-1000 rpm for 15-18 minutes, then adjust the pH value to 9-10, then filter through an 80-mesh filter, and transfer to a sealed light-proof container to obtain a water-based road marking material.

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