Two-component polyurethane road marking paint and preparation method and application thereof

Abstract

The present invention provides a two-component polyurethane road marking paint and a preparation method and application thereof, wherein the road marking paint comprises a component A and a component B, wherein the component A comprises a vegetable oil polyol, internally mixed glass beads, a filler and a catalyst; and the component B comprises an isocyanate having an NCO functionality equal to or greater than 2. Thus, the road marking paint can significantly improve the durable and high-brightness reflective performance of traffic road markings.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular, relates to a two-component polyurethane road marking coating and a preparation method and application thereof. Background Art

[0002] In terms of the reflective performance of road traffic markings, the entire road traffic marking industry has the following unresolved problems: According to the national standard "Quality Requirements and Testing Methods for Road Traffic Markings" (GB / T 16311-2024), the retro-reflective brightness coefficient of newly painted white markings during the handover stage must reach the standard of no less than 150mcd•m -2 •lx -1 However, during the normal use period after completion and operation and maintenance, or even after a few months of use, it is difficult to reach the standard requirement of not less than 80mcd•m -2 •lx -1 There are serious hidden dangers to driving safety and legal disputes over traffic accidents.

[0003] Therefore, existing road traffic marking paint needs to be improved. Summary of the invention

[0004] The present invention aims to solve at least one of the above technical problems to a certain extent. To this end, one object of the present invention is to provide a two-component polyurethane road marking paint and a preparation method and application thereof, which can significantly improve the long-lasting high-brightness reflective performance of traffic road markings.

[0005] In a first aspect of the present invention, the present invention provides a two-component polyurethane road marking paint, comprising component A and component B.

[0006] in,

[0007] The component A comprises vegetable oil polyol, internally mixed glass beads, filler and catalyst;

[0008] The component B comprises an isocyanate having an NCO functionality of 2 or more.

[0009] Therefore, the use of the road marking paint of the present invention can significantly improve the long-lasting high-brightness reflective performance of traffic road markings.

[0010] In some embodiments, the component A includes 15 to 30 parts by weight of the vegetable oil polyol, 30 to 45 parts by weight of the internally mixed glass beads, 1 to 25 parts by weight of the filler, and 0.01 to 0.15 parts by weight of the catalyst. Thus, the durable and high-brightness reflective performance of the traffic road marking can be further improved.

[0011] In some embodiments, the component A includes 20 to 25 parts by weight of the vegetable oil polyol, 35 to 40 parts by weight of the internally mixed glass beads, 2 to 15 parts by weight of the filler, and 0.08 to 0.09 parts by weight of the catalyst. Thus, the durable and high-brightness reflective performance of the traffic road marking can be further improved.

[0012] In some embodiments, the vegetable oil polyol has a hydroxyl value of 150 mgKOH / g to 450 mgKOH / g.

[0013] In some embodiments, the hydroxyl functionality of the vegetable oil polyol is equal to or greater than 3.

[0014] In some embodiments, the vegetable oil polyol includes one or more of castor oil polyol, lesquerella oil polyol, soybean oil polyol, sunflower oil polyol, palm oil polyol, linseed oil polyol, rapeseed oil polyol, tung oil polyol, cashew oil polyol, and neem oil polyol.

[0015] In some embodiments, the internally mixed glass beads meet one or more of the following conditions: the refractive index is 1.6-2.4, the circularity is greater than or equal to 90%; the particle size distribution conforms to the provisions of No. 2 internally mixed glass beads in "Glass Beads for Road Marking" (GB / T 24722-2020); the internally mixed glass beads are pre-hydroxylated; the surface of the internally mixed glass beads has hydroxyl groups; the surface hydroxyl content of the internally mixed glass beads is 500ppm-600ppm. In this way, the durable and high-brightness reflective performance of traffic road markings can be further improved.

[0016] In some embodiments, the Dv50 of the filler is 20 mesh to 1250 mesh, thereby further improving the durable and high-brightness reflective performance of the traffic road marking.

[0017] In some embodiments, the filler includes one or more of heavy calcium carbonate, light calcium carbonate, calcined kaolin, and talc.

[0018] In some embodiments, the catalyst includes one or more of a Lewis acidic organometallic catalyst and an organic amine catalyst.

[0019] In some embodiments, the isocyanate includes one or more of aliphatic isocyanate, alicyclic isocyanate and derivatives thereof.

[0020] In some embodiments, the isocyanate includes one or more of HDI, HDI dimer, HDI trimer, HDI biuret, IPDI, IPDI trimer, HMDI, NDI, PPDI, CHDI, XDI, HXDI, TMHDI, NBDI, TODI, and HTDI.

[0021] In some embodiments, the road marking paint includes 85 parts by weight of the component A and 15 parts by weight to 20 parts by weight of the component B. Thus, the durable and high-brightness reflective performance of the traffic road marking can be further improved.

[0022] In some embodiments, the component A further comprises 10 to 25 parts by weight of anti-skid aggregate, thereby improving the anti-skid performance of the traffic road marking.

[0023] In some embodiments, the Dv50 of the anti-skid aggregate is 0.075 mm to 2.36 mm, thereby improving the anti-skid performance of traffic road markings.

[0024] In some embodiments, the anti-slip aggregate includes one or more of white corundum, white ceramic, glass sand, and quartz sand.

[0025] In some embodiments, the component A further comprises 5 to 15 parts by weight of titanium dioxide, thereby improving the durable reflective performance and service life of the traffic road marking.

[0026] In some embodiments, the component A further comprises 8 to 10 parts by weight of titanium dioxide. Thus, the stain resistance and service life of the traffic road marking can be improved.

[0027] In some embodiments, the titanium dioxide comprises rutile titanium dioxide with a Dv50 of 15 nm-0.4 μm. Thus, the stain resistance and service life of the traffic road marking can be improved.

[0028] In some embodiments, the component A further comprises an auxiliary agent, wherein the auxiliary agent comprises one or more of an antioxidant, a dispersant, a leveling agent, a thickener and a defoaming agent.

[0029] In some embodiments, the A component includes 0.1-0.5 parts by weight of an antioxidant, 0.3-0.8 parts by weight of a dispersant, 0.2-0.6 parts by weight of a leveling agent, 0.1-0.9 parts by weight of a thickener, and 0.2-0.5 parts by weight of a defoamer.

[0030] In some embodiments, the A component includes 0.2-0.4 parts by weight of an antioxidant, 0.5-0.6 parts by weight of a dispersant, 0.3-0.4 parts by weight of a leveling agent, 0.5-0.6 parts by weight of a thickener, and 0.3-0.4 parts by weight of a defoamer.

[0031] In some embodiments, the antioxidant includes an aromatic amine antioxidant and / or a hindered phenol antioxidant, thereby improving the stain resistance and service life of the traffic road marking.

[0032] In the second aspect of the present invention, the present invention provides a method for preparing the two-component polyurethane road marking paint according to the first invention of the present invention, comprising: mixing component A including vegetable oil polyol, internally mixed glass beads, filler and catalyst and component B including isocyanate with NCO functionality equal to or greater than 2. Thus, the above-mentioned marking paint can be prepared, thereby significantly improving the durable and high-brightness reflective performance of traffic road markings.

[0033] In the third aspect of the present invention, the present invention proposes the use of the two-component polyurethane road marking paint described in the first aspect of the present invention on road traffic markings.

[0034] Additional aspects and advantages of the present invention will be given in part in the following description and in part will be obvious from the following description, or will be learned through practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0036] Figure 1 The present invention is a schematic diagram of a two-component polyurethane road marking paint process according to an embodiment of the present invention. DETAILED DESCRIPTION

[0037] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0038] In the present invention, the following definitions and methods are provided to better define the present invention and guide those skilled in the art in the practice of the present invention. Unless otherwise specified, terms are understood according to the conventional usage of those skilled in the relevant art.

[0039] As used herein, the terms "include" and "comprising" should be interpreted as inclusive and open-ended, rather than exclusive. Specifically, when used in the specification and claims, the terms "include" and "comprising" and their variations mean including the specified features, steps, or components. These terms should not be interpreted to exclude the presence of other features, steps, or components.

[0040] The terms "optional", "optionally", "optionally" or "optionally" as used herein mean that the subsequently described event or circumstance can, but does not have to, occur, and the description includes instances where the event or circumstance occurs and instances where it does not occur.

[0041] In the description of the present invention, “plurality” means at least two, for example, two, three, etc., unless otherwise clearly and specifically defined.

[0042] "Scope" disclosed in the present invention is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a particular parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3,4 and 5 are listed, the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present invention, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0043] If not otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form a new technical solution.

[0044] Unless otherwise specified, all technical features and optional technical features of the present invention can be combined with each other to form a new technical solution.

[0045] In the first aspect of the present invention, the present invention provides a two-component polyurethane road marking paint, comprising component A and component B, wherein component A comprises vegetable oil polyol, internally mixed glass beads, filler and catalyst, and the internally mixed glass beads have hydroxyl groups on the surface; component B comprises isocyanate having an NCO functionality equal to or greater than 2.

[0046] Therefore, when using the road marking paint, the components A and B are mixed, and the vegetable oil polyol in the component A is mixed with the isocyanate in the component B, and then a polycondensation reaction is rapidly carried out under the action of a catalyst to form a polymer / inorganic composite material to achieve curing. During the curing process, the NCO group reacts with the OH group to form a carbamate bond. At the same time, the glass beads mixed in the component A have high-brightness reflective properties, and the filler can improve the wear resistance and scratch resistance of the paint. Therefore, the road marking paint of the present invention can significantly improve the long-lasting high-brightness reflective performance of traffic road markings.

[0047] In some embodiments of the present invention, the A component includes 15 to 30 parts by weight of the vegetable oil polyol, 30 to 45 parts by weight of the internally mixed glass beads, 1 to 25 parts by weight of the filler, and 0.01 to 0.15 parts by weight of the catalyst. For example, the vegetable oil polyol is 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 27 parts by weight, or 30 parts by weight, or a range consisting of any two values; the internally mixed glass beads are 30 parts by weight, 33 parts by weight, 35 parts by weight, or 40 parts by weight. The filler is 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 22 parts by weight or 25 parts by weight or any two parts by weight; the catalyst is 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.12 parts by weight or 0.15 parts by weight or any two parts by weight. Thus, the present invention adopts the component A of this composition to significantly improve the durable and high-brightness reflective performance of traffic road markings. In other embodiments of the present invention, the component A includes 20 parts by weight to 25 parts by weight of the vegetable oil polyol, 35 parts by weight to 40 parts by weight of the internally mixed glass beads, 2 parts by weight to 15 parts by weight of the filler and 0.08 parts by weight to 0.09 parts by weight of the catalyst.

[0048] In some embodiments of the present invention, the hydroxyl value of the vegetable oil polyol is 150 mgKOH / g-450 mgKOH / g, for example, 150 mgKOH / g, 160 mgKOH / g, 170 mgKOH / g, 180 mgKOH / g, 190 mgKOH / g, 200 mgKOH / g, 210 mgKOH / g, 220 mgKOH / g, 230 mgKOH / g, 240 mgKOH / g, 250 mgKOH / g, 270 mgKOH / g, 300 mgKOH / g, 320 mgKOH / g, 350 mgKOH / g, 370 mgKOH / g, 400 mgKOH / g, 420 mgKOH / g or 450 mgKOH / g, or a range consisting of any two values.

[0049] In some embodiments of the present invention, the hydroxyl functionality of the vegetable oil polyol is equal to or greater than 3, and the present invention has no particular restrictions on the specific composition of the vegetable oil polyol, for example, the vegetable oil polyol includes but is not limited to castor oil polyol, lesquerella oil polyol, soybean oil polyol, sunflower oil polyol, palm oil polyol, linseed oil polyol, rapeseed oil polyol, tung oil polyol, cashew oil polyol, neem oil polyol, one or more thereof. In other embodiments of the present invention, the vegetable oil polyol includes castor oil polyol and / or soybean oil polyol.

[0050] In some embodiments of the present invention, the refractive index of the internally mixed glass beads is 1.6-2.4, such as 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3 or 2.4, or a range consisting of any two values. Thus, the use of internally mixed glass beads meeting this refractive index can further improve the durable and high-brightness reflective performance of traffic road markings.

[0051] In some embodiments of the present invention, the roundness of the internally mixed glass beads is greater than or equal to 90%. Therefore, using internally mixed glass beads that meet this roundness will effectively improve the long-lasting reflective performance of the marking during normal use.

[0052] Specifically, the roundness test of the internally mixed glass beads in the present invention is carried out according to the method specified in GB / T 24722-2020.

[0053] In some embodiments of the present invention, the particle size distribution of the internally mixed glass beads complies with the requirements for No. 2 internally mixed glass beads in "Glass Beads for Road Marking" (GB / T 24722-2020).

[0054] In some embodiments of the present invention, the internally mixed glass beads are pre-hydroxylated, for example, the preparation steps of the Pirahan solution method are as follows: Step 1, cleaning the surface of the glass beads: using acetone, anhydrous ethanol, and deionized water as cleaning solutions in turn, cleaning the glass beads in an ultrasonic cleaning machine, and the cleaning time of each cleaning solution is not less than 30 minutes. The cleaned glass beads are placed in an oven for drying, and the drying temperature is 40°C-60°C, and the drying time is 8h-12h. Step 2, Pirahan solution preparation: Measure 700ml of 15wt%-30wt% H2O2 and pour it into a clean beaker, place the beaker in an ice bath environment, measure 300ml of 95wt%-98wt% H2SO4, slowly add it to the H2O2 solution, and continue to stir slowly and evenly with a glass rod. Step 3: Surface hydroxylation of glass beads: immerse the glass beads dried in the first step in the pre-prepared Pirahan solution, treat them in a water bath at 75℃-85℃ for 30min-60min, take out the glass beads, wash them thoroughly with deionized water, and dry them with high-purity nitrogen to obtain surface hydroxylated glass beads. It should be noted that the surface hydroxyl content of the internally mixed glass beads can be adjusted accordingly by adjusting the Pirahan solution and the hydroxylation treatment time.

[0055] The inner-mixed glass beads are pre-treated with hydroxylation to form hydroxyl groups on their surfaces, which can react with NCO groups in polyurethane, thereby improving the adhesion, compatibility and uniform dispersion of the inner-mixed glass beads and the polyurethane material. In the reaction process of the organic / inorganic hybrid material, the "cutting" and "assembly" of the inner-mixed glass bead material can be achieved. During the full life cycle of the road marking paint of the present invention, the hydroxyl groups on the surface of the inner-mixed glass microbeads participate in the chemical reaction, so the dispersion is uniform, the adhesion is super strong, and the paint is not easy to fall off.

[0056] In some embodiments of the present invention, the surface hydroxyl content of the internally mixed glass beads is 500ppm-600ppm, such as 500ppm, 510ppm, 520ppm, 530ppm, 540ppm, 550ppm, 560ppm, 570ppm, 580ppm, 590ppm or 600ppm, or a range consisting of any two values. Thus, by using the internally mixed glass beads with the hydroxyl value content, the connection sites between the internally mixed glass beads and the polyurethane material can be increased, thereby further improving the adhesion, compatibility and uniformity of dispersion of the internally mixed glass beads and the polyurethane material. At the same time, the internally mixed glass beads are evenly dispersed in the coating, have super strong adhesion, and are not easy to fall off.

[0057] In some embodiments of the present invention, the Dv50 of the filler is 20-1250 mesh, for example, 20 mesh, 50 mesh, 100 mesh, 200 mesh, 300 mesh, 400 mesh, 500 mesh, 600 mesh, 700 mesh, 800 mesh, 900 mesh, 1000 mesh, 1100 mesh, 1200 mesh or 1250 mesh, or a range consisting of any two values. Thus, by using a filler with such a particle size, the filler can be evenly dispersed in the coating, thereby improving the wear resistance and scratch resistance of the coating.

[0058] In some embodiments of the present invention, the filler includes but is not limited to one or more of heavy calcium carbonate, light calcium carbonate, calcined kaolin, and talc. Preferably, the present invention uses light calcium carbonate with a specification of 1250 mesh.

[0059] In some embodiments of the present invention, the catalyst includes one or more of a Lewis acidic organic metal catalyst and an organic amine catalyst. For example, the Lewis acidic metal catalyst includes dibutyltin dilaurate, stannous octoate, dibutyltin (dodecylsulfide), dibutyltin diacetate, dioctyltin dilaurate, dialkyltin dimaleate, dialkyltin dithiol, potassium isooctanoate, potassium acetate, potassium oleate, lead isooctanoate, phenylmercuric acetate, zinc isooctanoate, bismuth isooctanoate, bismuth neodecanoate, bismuth cyclopentaneate, bismuth laurate, tetrabutyl titanate, tetraisopropyl titanate, and tetraisopropyl titanate. esters; the organic amine catalyst includes triethylenediamine, bis (dimethylaminoethyl) ether, bis (dimethylaminoethyl) glycol ether, dimethylcyclohexylamine, N-methyldicyclohexylamine, pentamethyldiethyltriamine, pentamethyldipropylenetriamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexanediamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,3,5-tris (dimethylaminopropyl) hexahydrotriazine, tris (dimethylaminopropyl) amine, N,N-dimethylbenzylamine, N,N-dimethyl (hexadecyl) amine, dimethylethyl Alcoholamine, dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine, trimethylhydroxyethylpropylenediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N,N,N'-trimethyl-N'-hydroxyethylbisaminoethyl ether, N-(dimethylaminopropyl)diisopropanolamine, tetramethyldipropylenetriamine, bis(dimethylamino)-2-propanol, diethylethanolamine, N,N',N'-tri(2-hydroxypropyl)ethylenediamine, 1,4-dimethylpiperazine, 1-dimethylaminoethyl-4-methylpiperazine, N-methyl-N'-hydroxyethylpiperazine, N,N-dimethyl( One or more of 4-methyl-1-piperazinyl)ethylamine, N-methylmorpholine, N-ethylmorpholine, dimorpholinyl diethyl ether, N-cocomorpholine, dimorpholine triethyl ether, N-(dimethylaminoethyl)morpholine, 4-(2-methoxyethyl)morpholine, dimorpholine polyoxyethylene ether, 4-butylmorpholine, 1-(4-morpholinyl)-2-propylamine, N-methylimidazole, 1,2-dimethylimidazole, N-2-(hydroxypropyl)imidazole, N-2-(hydroxyethyl)imidazole, N-2-(aminopropyl)imidazole, 1,8-diazacycloundecene, and triethylamine. Preferably, the catalyst of the present invention adopts dioctyltin dilaurate.

[0060] In some embodiments of the present invention, the isocyanate includes one or more of aliphatic isocyanate, alicyclic isocyanate and derivatives thereof, for example, the isocyanate includes one or more of HDI, HDI dimer, HDI trimer, HDI biuret, IPDI, IPDI trimer, HMDI, NDI, PPDI, CHDI, XDI, HXDI, TMHDI, NBDI, TODI and HTDI, preferably XDI.

[0061] In some embodiments of the present invention, the road marking paint comprises 85 parts by weight of the component A and 15 to 20 parts by weight of the component B, for example, the component B comprises 15 parts by weight, 15.5 parts by weight, 16 parts by weight, 16.7 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight or 20 parts by weight, or a range consisting of any two values, etc. Thus, the components A and B in the road marking paint are mixed in this ratio, and the vegetable oil polyol in the component A and the isocyanate in the component B are mixed and then rapidly undergo a polycondensation reaction under the action of a catalyst to form a polymer / inorganic composite material to achieve curing, and at the same time, the sufficient internally mixed glass beads in the component A not only have high-brightness reflective properties, but also have hydroxyl groups on their surfaces, which can react with NCO groups in polyurethane, thereby further improving the adhesion, compatibility and dispersion uniformity of the internally mixed glass beads and the polyurethane material, and further improving the durable high-brightness reflective performance of the traffic road marking.

[0062] In some embodiments of the present invention, the A component further comprises 10-25 parts by weight of anti-skid aggregate, for example, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, 20 parts by weight, 22 parts by weight or 25 parts by weight, or a range consisting of any two values. Specifically, adding the anti-skid aggregate of this composition to the marking paint can achieve a long-lasting high anti-skid performance throughout the life cycle of the marking. In other embodiments of the present invention, the A component comprises 15-20 parts by weight of anti-skid aggregate.

[0063] In some embodiments of the present invention, the Dv50 of the anti-skid aggregate is 0.075mm-2.36mm, such as 0.075mm, 0.1mm, 0.3mm, 0.5mm, 0.7mm, 1mm, 1.2mm, 1.5mm, 1.7mm, 2mm, 2.1mm, 2.2mm, 2.3mm or 2.36mm, or a range consisting of any two values. Further, the anti-skid aggregate includes one or more of white corundum, white ceramic, glass sand and quartz sand. Specifically, this type of anti-skid aggregate has a very high Mohs hardness and rich surface texture and angularity. When the road marking paint is applied to the road surface, the anti-skid aggregate matches the excellent mechanics of the polyurethane polymer material, such as compressive strength, elasticity, elongation at break, etc., combining softness and hardness, and the anti-skid aggregate and the internally mixed glass beads are evenly distributed in all directions in the road marking coating. When the vehicle tires roll over the marking surface, the different material hardness and different particle size gradation combination of the anti-skid aggregate, filler, internally mixed glass beads and other inorganic materials in the marking work synergistically with the elasticity of the polyurethane polymer material to form a good surface groove depth (not less than 0.50mm), thereby further improving the long-lasting high anti-skid performance of the marking throughout its life cycle.

[0064] In some embodiments of the present invention, the A component further comprises 5-15 parts by weight of titanium dioxide, for example, the titanium dioxide is 5 parts by weight, 7 parts by weight, 10 parts by weight, 12 parts by weight or 15 parts by weight, or a range consisting of any two values. In other embodiments of the present invention, the A component comprises 8-10 parts by weight of titanium dioxide and 0.2-0.4 parts by weight of an antioxidant.

[0065] In some embodiments of the present invention, the titanium dioxide includes rutile titanium dioxide with a Dv50 of 15nm-0.4μm. Rutile nano titanium dioxide is added to the road marking paint of the present invention, and rutile nano titanium dioxide has significant advantages in absorbing ultraviolet rays. The ultraviolet shielding mechanism of rutile titanium dioxide is related to the particle size. When the particle size is large, the blocking of ultraviolet rays is mainly reflection and scattering, and it is effective for ultraviolet rays in the medium-wave region and long-wave region. As the particle size decreases, the absorption of nano titanium dioxide to ultraviolet rays in the medium-wave region is significantly enhanced, mainly absorbing ultraviolet rays in the medium-wave region, while the blocking of ultraviolet rays in the long-wave region is mainly scattering. This mechanism of absorbing ultraviolet rays makes the application of rutile nano titanium dioxide in ultraviolet shielding more effective. The rutile nano dioxide in the particle size range of this application can significantly improve the anti-powdering ability, durability, and weather resistance of the coating. In addition, the application adds the above-mentioned content and particle size of rutile nano titanium dioxide, which can not only significantly improve the overall hardness of the marking coating, increase the wear resistance of the coating, and extend the service life of the coating under the same traffic volume; but also form a dense protective layer on the surface of the coating after the coating is formed, thereby greatly improving the surface density and smoothness of the marking coating and reducing the surface tension of the paint film. When the vehicle tires roll over the markings and dirt such as dust and oil are attached, it is difficult to combine with the surface of the markings. Under the scouring of rain, the surface of the markings can still remain clean, which greatly improves the stain resistance of the marking coating surface and maintains the long-lasting high-brightness reflective performance of the markings throughout their life cycle.

[0066] In the road marking paint of the present invention, the component A further comprises an auxiliary agent, and the auxiliary agent comprises one or more of an antioxidant, a dispersant, a leveling agent, a thickener and a defoaming agent.

[0067] Antioxidants can not only effectively absorb and scatter ultraviolet rays, but also inhibit and delay the oxidative degradation of polyurethane materials in coatings, protect polyurethane materials from the effects of oxidation, and increase the service life of markings.

[0068] In some embodiments of the present invention, the antioxidant includes an aromatic amine antioxidant and / or a hindered phenol antioxidant, for example, the antioxidant includes one or more of Irganox 1010, Irganox 1076, Irganox 1098, Irganox 245, Irganox B900, Irganox 3114, and Irganox PS800. Such antioxidants can effectively prevent the oxidation of polyurethane materials by oxygen by acting as terminators of free radicals or growth chains of polyurethane polymers. They can decompose the products produced by oxidative degradation of polyurethane materials into non-free radical stable compounds, thereby protecting polyurethane two-component coatings from damage by oxidative stress, thereby further improving the service life of the marking. Preferably, the antioxidant is Irganox B900.

[0069] The dispersant, leveling agent, thickener and defoamer added in the present invention are all conventional components frequently used in coatings, and the present invention has no particular limitation on them.

[0070] For example, the dispersant may include various commercially available wetting and dispersing additives, including but not limited to one or more of BYK-107, BYK-108, BYK-110, BYK-161, BYK-163, BYK-164, BYK-168, BYK-190, BYK-2050, BYK-220S, BYK-2015, BYK-P104S, BYK-P104, and BYK-250. Preferably, the present invention uses dispersant BYK-P168.

[0071] The leveling agent may include various commercially available organic silicon leveling agents, including but not limited to one or more of BYK-300, BYK-306, BYK-310, BYK-323, BYK-333, BYK-307, BYK-331, BYK-325, BYK-337, BYK-344, BYK-346, BYK-347, and BYK-378. Preferably, the present invention uses the leveling agent BYK-310.

[0072] The thickener may include one or more of various commercially available organic additives BYK-410, BYK-420, BYK-425, BYK-7420 ES, BYK-R 605, BYK-R 606, BYK-R 607, CLAYTONE-40, GARAMITE-1958, LAPONITE RD, and LAPONITE RDS. Preferably, the present invention uses the leveling agent BYK-420.

[0073] The defoamer may include various commercially available organosilicon defoaming agents, including but not limited to one or more of BYK-024, BYK-028, BYK-065, BYK-066, and BYK-141. Preferably, the defoamer BYK-066 is used in the present invention.

[0074] In some embodiments of the present invention, the A component includes 0.1-0.5 parts by weight of an antioxidant, 0.3-0.8 parts by weight of a dispersant, 0.2-0.6 parts by weight of a leveling agent, 0.1-0.9 parts by weight of a thickener, and 0.2-0.5 parts by weight of a defoamer, for example, the antioxidant is 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, or 0.5 parts by weight, or any two parts thereof; the dispersant is 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, or any two parts thereof; The amount of the leveling agent is 0.2 parts by mass, 0.3 parts by mass, 0.4 parts by mass, 0.5 parts by mass or 0.6 parts by mass or the like, or a range consisting of any two values; the amount of the thickener is 0.1 parts by mass, 0.2 parts by mass, 0.3 parts by mass, 0.4 parts by mass, 0.5 parts by mass, 0.6 parts by mass, 0.7 parts by mass, 0.8 parts by mass or 0.9 parts by mass or the like, or a range consisting of any two values; the amount of the defoamer is 0.2 parts by mass, 0.3 parts by mass, 0.4 parts by mass or 0.5 parts by mass or the like, or a range consisting of any two values. In some other embodiments of the present invention, the component A includes 0.2-0.4 parts by weight of an antioxidant, 0.5-0.6 parts by weight of a dispersant, 0.3-0.4 parts by weight of a leveling agent, 0.5-0.6 parts by weight of a thickener and 0.3-0.4 parts by weight of a defoamer.

[0075] Specifically, the component A and the component B in the road marking paint of the present invention are packaged independently, and the component A is mixed with the component B before use during construction.

[0076] In some embodiments of the present invention, the road marking paint of the present invention can improve the long-lasting anti-skid, reflective, stain-resistant, weather-resistant, durable and wear-resistant properties of road traffic markings, improve the quality of road traffic markings throughout the life cycle, and make them have the same lifespan as the road surface; and have the advantages of no odor during the construction process, human health and environmental friendliness.

[0077] In the second aspect of the present invention, the present invention proposes a method for preparing the above-mentioned road marking paint, comprising: mixing component A including vegetable oil polyol, internally mixed glass beads, filler and catalyst and component B including isocyanate with NCO functionality equal to or greater than 2.

[0078] Specifically, the present invention divides the raw materials in component A into two categories, powder and liquid, according to their phase states, and adds them into a powder-liquid homogenizing mixer with a double feed port respectively. Under high shear force, the components are circulated and homogenized and dispersed to obtain component A, thereby ensuring that the components have overall sameness, homogeneity or uniformity in terms of state and quality. Meanwhile, no solvent is used in the preparation process of the vegetable oil polyol and the isocyanate curing agent in component A, and the solid content of the raw materials is nearly 100%. No solvent is added in the preparation of the coating, so compared with the traditional two-component acrylic road marking coating, the coating of the present invention is odorless and more environmentally friendly.

[0079] In some embodiments of the present invention, component A may also contain the above-mentioned anti-slip aggregate, titanium dioxide, additives, and the like.

[0080] It should be noted that the above-mentioned features and advantages of the road marking paint are also applicable to the method for preparing the road marking paint, and will not be described in detail here.

[0081] In a third aspect of the present invention, the present invention proposes the application of a marking paint on a road traffic marking. In some embodiments of the present invention, the marking paint of the present invention can be applied to road traffic markings, especially to road traffic markings that require long-lasting anti-skid, reflective and stain-resistant properties and have the same lifespan as the road surface.

[0082] The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Where specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in the art or the product specifications are used. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be obtained commercially.

[0083] The method for preparing the road marking paint of Example 1-Example 28 and Comparative Examples 1-2 comprises:

[0084] refer to Figure 1 First, add the vegetable oil polyol into the liquid phase feed port of the double-feed-port powder-liquid homogenizing mixer and disperse it under high shear force at a speed of 400 rpm / min for 2 minutes. Then add the dispersant, defoamer, antioxidant, and catalyst in turn, and mix and disperse them thoroughly for 3 minutes.

[0085] Slowly increase the speed to 500 rpm, first add internally mixed glass beads from the powder feed port (the particle size distribution conforms to the provisions of No. 2 internally mixed glass beads in "Glass Beads for Road Marking" (GB / T 24722-2020), the internally mixed glass beads used in component A of the marking paint of Example 1-27 are hydroxylated, and the internally mixed glass beads used in component A of the marking paint of Example 28 are not hydroxylated), then add anti-slip aggregate, mix and disperse for 5 minutes, then add titanium dioxide, fully mix and disperse for about 10 minutes, add filler after the nano titanium dioxide is homogeneously mixed and dispersed to a single particle nano state, and then fully mix and disperse for 10 minutes.

[0086] Then add leveling agent, thickener, water, etc. in sequence and disperse for about 5 minutes to ensure that component A is homogeneously mixed and dispersed, and the viscosity (about 100KU), no stratification and precipitation meet the control standards. The dispersed component A is isolated from the air and quickly packaged, and the preparation of component A is completed.

[0087] The marking paint is obtained by packaging component A and component B (isocyanate) respectively according to the mass ratio.

[0088] The compositions of component A and component B in the road marking paints of Examples 1-28 and Comparative Examples 1-2 are shown in Table 1-6.

[0089] Table 1

[0090]

[0091]

[0092]

[0093] Table 2

[0094]

[0095]

[0096] Table 3

[0097]

[0098]

[0099]

[0100] Table 4

[0101]

[0102]

[0103] Table 5

[0104]

[0105]

[0106]

[0107] Table 6

[0108]

[0109]

[0110] Comparative Example 2 is a two-component acrylic high-gloss road marking paint produced by Nanjing Bell Transportation Technology Co., Ltd.

[0111] The above-mentioned coatings are applied by scraping or throwing with a vehicle-mounted marking machine. During the construction, component A and component B are fully mixed and evenly applied. The mixed coatings are applied to the road surface within 25 minutes. During the construction, the marking line also needs to be sprinkled with anti-skid glass beads, and the non-stick drying time of the coating is controlled within 60 minutes.

[0112] The following technical indicators of coatings and markings are tested, and the test methods of each technical indicator are as follows:

[0113] State of prepared component A in the container: tested according to the method specified in JT / T 280-2022;

[0114] Content of mixed glass beads in the prepared road marking paint (wt%): tested according to the method specified in JT / T 280-2022;

[0115] Appearance of road marking coating: tested according to the method specified in JT / T 280-2022;

[0116] Brightness factor of road marking coating: tested according to the method specified in JT / T 280-2022;

[0117] Water resistance of road marking coating: tested according to the method specified in GB / T 1733-1993;

[0118] Alkali resistance of road marking coating: tested according to the method specified in GB / T 9265-2009;

[0119] Artificial accelerated weathering resistance of road marking coating: tested according to the method specified in GB / T 1865-2009;

[0120] Drying time of non-stick tire for road marking coating (min): tested according to the method specified in JT / T 280-2022;

[0121] Marking coating coverage (%): tested according to the method specified in JT / T 280-2022;

[0122] Abrasion resistance of marking coating (mg) (weight loss after 200 turns / 1000g): tested according to the method specified in JT / T 280-2022;

[0123] Low temperature crack resistance of road marking coating: tested according to the method specified in JT / T 280-2022;

[0124] Reflective performance after 800,000 times of wear test on a road marking material wear simulator turntable: After 800,000 times of wear test on a road marking material wear simulator turntable that meets the requirements of BS EN 13197:2011+A1:2014, the excess anti-skid glass beads on the marking surface were removed and tested according to the method specified in GB / T 16311-2009;

[0125] Anti-skid performance after 800,000 times of wear test on a road marking material wear simulator turntable: After 800,000 times of wear test on a road marking material wear simulator turntable that meets the requirements of BS EN 13197:2011+A1:2014, the excess anti-skid glass beads on the marking surface are removed and tested according to the method specified in T0964 or T 0969 in JTG 3450-2019;

[0126] Reflective performance of test marking dividing lines for demonstration projects: tested according to the method specified in GB / T 16311-2009;

[0127] Anti-skid performance of test marking dividing lines for demonstration projects: tested according to the method specified in T0964 or T 0969 in JTG 3450-2019;

[0128] Anti-fouling performance of road marking dividing lines for demonstration projects: visual inspection and photography.

[0129] The technical indicators of the coatings and markings tested in the embodiments and comparative examples are shown in Tables 7-10.

[0130] Table 7

[0131]

[0132]

[0133]

[0134] Table 8

[0135]

[0136]

[0137]

[0138] Table 9

[0139]

[0140]

[0141]

[0142] Table 10

[0143]

[0144]

[0145]

[0146]

[0147] Conclusion: As shown in Table 1-10, the road marking paints in Examples 1-28 all use internally mixed glass beads, while the road marking paint in Comparative Example 1 does not use internally mixed glass beads. Obviously, the initial reflective performance of the demonstration project road test marking boundary line of the road marking paint in Comparative Example 1, the reflective performance after 800,000 times of road marking material wear simulator turntable test, and the reflective performance of the demonstration project road test marking boundary line after 12 months are all worse than those of the road marking paint in Examples 1-28. At the same time, the reflective performance of the marking lines of the road marking paint in Examples 1-28 is significantly better than that of the marking lines of the commercially available two-component acrylic high-gloss road marking paint produced by Nanjing Bell Traffic Technology Co., Ltd. in Comparative Example 2. At the same time, the marking lines of the road marking paint in Examples 1-28 have excellent water resistance, alkali resistance, weather resistance, low-temperature crack resistance, skid resistance and stain resistance, thereby indicating that the road marking paint composed of the present application is applied to road traffic markings, which can meet the requirements of durable skid resistance, reflection and stain resistance.

[0148] The present invention has been described in detail above with general descriptions and specific embodiments, but it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention and any combination can be made as required. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A two-component polyurethane road marking paint, characterized in that: The composition comprises 85 parts by weight of component A and 15 to 20 parts by weight of component B. in, The component A comprises 20 to 27 parts by weight of vegetable oil polyol, 30 to 45 parts by weight of internally mixed glass beads, 1 to 25 parts by weight of filler, 0.01 to 0.15 parts by weight of catalyst, 10 to 25 parts by weight of anti-slip aggregate, and 8 to 12 parts by weight of titanium dioxide. The particle size distribution of the internally mixed glass beads complies with the provisions of No. 2 glass beads in "Glass Beads for Road Marking" GB / T 24722-2020; The Dv50 of the filler is 20 mesh to 1250 mesh; The Dv50 of the anti-slip aggregate is 1mm-2.36mm; The titanium dioxide comprises rutile titanium dioxide with a Dv50 of 15nm-300nm; The component B comprises an isocyanate having an NCO functionality of 2 or more.

2. The road marking paint according to claim 1, characterized in that: The component A includes 20 to 25 parts by weight of the vegetable oil polyol, 35 to 40 parts by weight of the internally mixed glass beads, 2 to 15 parts by weight of the filler, 0.08 to 0.09 parts by weight of the catalyst, 10 to 25 parts by weight of the anti-slip aggregate, and 8 to 12 parts by weight of titanium dioxide.

3. The road marking paint according to claim 1 or 2, characterized in that: The vegetable oil polyol meets one or more of the following conditions: The hydroxyl value of the vegetable oil polyol is 150 mgKOH / g-450 mgKOH / g; The vegetable oil polyol includes one or more of castor oil polyol, lesquerella oil polyol, soybean oil polyol, sunflower oil polyol, palm oil polyol, linseed oil polyol, rapeseed oil polyol, tung oil polyol, cashew oil polyol and neem oil polyol.

4. The road marking paint according to claim 1 or 2, characterized in that: The internally mixed glass beads meet one or more of the following conditions: The refractive index of the internally mixed glass beads is 1.9-2.4, and the roundness of the internally mixed glass beads is greater than or equal to 90%; The internally mixed glass beads have hydroxyl groups on their surfaces.

5. The road marking paint according to claim 4, characterized in that: The surface hydroxyl content of the internally mixed glass beads is 500ppm-600ppm.

6. The road marking paint according to claim 1, characterized in that: The filler includes one or more of heavy calcium carbonate, light calcium carbonate, calcined kaolin and talc.

7. The road marking paint according to claim 1 or 2, characterized in that: The catalyst includes one or more of a Lewis acidic organic metal catalyst and an organic amine catalyst.

8. The road marking paint according to claim 1 or 2, characterized in that: The isocyanate includes one or more of aliphatic isocyanate, alicyclic isocyanate and derivatives thereof; or The isocyanate includes one or more of HDI, HDI dimer, HDI trimer, HDI biuret, IPDI, IPDI trimer, HMDI, NDI, PPDI, CHDI, XDI, HXDI, TMHDI, NBDI, TODI, and HTDI.

9. The road marking paint according to claim 1 or 2, characterized in that: The anti-slip aggregate includes one or more of white corundum, white ceramic, glass sand and quartz sand.

10. The road marking paint according to claim 1 or 2, characterized in that: The component A further comprises an auxiliary agent, and the auxiliary agent comprises one or more of an antioxidant, a dispersant, a leveling agent, a thickener and a defoaming agent.

11. The road marking paint according to claim 10, characterized in that: The component A comprises 0.1 to 0.5 parts by weight of an antioxidant, 0.3 to 0.8 parts by weight of a dispersant, 0.2 to 0.6 parts by weight of a leveling agent, 0.1 to 0.9 parts by weight of a thickener, and 0.2 to 0.5 parts by weight of a defoamer; or The component A comprises 0.2-0.4 parts by weight of an antioxidant, 0.5-0.6 parts by weight of a dispersant, 0.3-0.4 parts by weight of a leveling agent, 0.5-0.6 parts by weight of a thickener and 0.3-0.4 parts by weight of a defoamer.

12. A method for preparing the two-component polyurethane road marking paint according to any one of claims 1 to 11, characterized in that: include: The A component including vegetable oil polyol, internally mixed glass beads, filler and catalyst and the B component including isocyanate with NCO functionality equal to or greater than 2 are mixed.

13. Use of the marking paint according to any one of claims 1 to 11 on road traffic markings.

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