Polyurethane coating for road marking and method for preparing the same

Abstract

The present application relates to a kind of polyurethane paint for road marking, the polyurethane marking paint is using different construction method to be constructed on road surface with polyurethane paint, then glass bead is scattered, and it plays the role of guiding and controlling traffic, the material has the advantages such as the wide range of substrate selection, adjustable open time, high strength, good toughness, superior freeze-thaw resistance, low energy consumption, good stain resistance, no odor, human health and environment friendly.

Description

Technical Field

[0001] This invention relates to the field of road marking, and more specifically to a two-component polyurethane coating for road marking and its preparation method. Background Technology

[0002] Road markings are a type of safety signage. Traffic management departments use them to guide and instruct traffic, thereby improving traffic safety, reducing traffic accidents, and further enhancing road transport capacity.

[0003] In the field of road marking, the most commonly used materials are hot-melt coatings and two-component MMA coatings. Hot-melt coatings are solid at room temperature and require heating for application, resulting in high operational risks and energy consumption. They are also brittle, have poor low-temperature resistance, are easily damaged, and have a very short service life. While two-component MMA coatings have a longer service life compared to hot-melt coatings, they suffer from drawbacks such as long winter open time, poor health effects, poor environmental friendliness, and highly flammable curing agents. Currently used polyurethane marking coatings are mainly water-based polyurethane coatings and hydroxyl acrylate polyurethane coatings. Both still have significant shortcomings. For example, the former cannot be used to prepare structural markings and has a long winter open time, while the latter contains a large amount of solvents and other volatile substances, posing a significant threat to human health and the environment, thus limiting the application of polyurethane marking coatings in the field of road marking coatings.

[0004] Due to its excellent mechanical, optical, and long-lasting properties, polyurethane has begun to be used in road marking. Among these, patents CN116948516A and CN113372806A use polyurethane-modified acrylate materials to improve the toughness and strength of the material; however, the main component is still acrylate, resulting in relatively poor toughness, mechanical strength, and safety. Patent CN114525073A uses hydroxyacrylate and HDI biuret to prepare two-component polyurethane road markings. While this achieves better mechanical properties and a longer lifespan, hydroxyacrylate contains a large amount of volatile organic solvents (such as toluene), which is detrimental to the molding of thicker markings and poses significant health and environmental hazards. Patent CN116102970A uses water-based polyurethane acrylate to prepare road markings via photocuring; however, as a water-based material, it is difficult to prepare structural markings of a certain thickness, limiting its practical application. Furthermore, it contains a large amount of acrylate monomers, which pose certain health risks to the environment and human health.

[0005] Therefore, it is essential to obtain a polyurethane material for road markings that has a wide range of optional substrates, a wide range of construction thicknesses that does not affect the opening time, an adjustable opening time, high strength, good toughness, excellent freeze-thaw resistance, low energy consumption, good stain resistance, no odor, and is both healthy and environmentally friendly. Summary of the Invention

[0006] This invention provides a polyurethane material for road marking paint and its preparation method. When applied to road markings, this material offers advantages such as a wide range of substrate options, adjustable open time, high strength, good toughness, excellent freeze-thaw resistance, low energy consumption, good stain resistance, odorless properties, and environmental friendliness. Furthermore, as a bio-based material, it complies with national laws and regulations.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] A polyurethane coating for road markings includes component A and component B, wherein the mass ratio of component A to component B is 100:4-18, preferably 100:7-14.

[0009] Component A comprises the following raw materials in parts by mass:

[0010]

[0011]

[0012] In this invention, component B is selected from one or more of aliphatic isocyanates, alicyclic isocyanates and their derivatives with an NCO functionality ≥ 2.

[0013] In this invention, the modified vegetable oil polyol is a vegetable oil polyol whose molecular chain includes aromatic rings, alicyclic rings and / or heterocyclic rings, and has a hydroxyl value of 120-20 mgKOH / g.

[0014] In this invention, the monomers for preparing the modified vegetable oil polyol include a vegetable oil polyol and a cyclic monocarboxylic acid. The modified vegetable oil polyol is prepared by reacting the vegetable oil polyol and the cyclic monocarboxylic acid, wherein the mass ratio of the vegetable oil polyol to the cyclic monocarboxylic acid is 100:0.1-10.0, the reaction temperature is 60-250℃, and the reaction time is 1-24 h.

[0015] In this invention, the plant oil polyol is selected from plant oil polyols with a hydroxyl functionality of ≥3, preferably one or more of castor oil, Resclero oil, soybean oil polyol, sunflower seed oil polyol, palm oil polyol, linseed oil polyol, rapeseed oil polyol, tung oil polyol, cashew oil polyol, and neem oil polyol, with a hydroxyl value of 150-250 mgKOH / g, more preferably castor oil and / or soybean oil polyol.

[0016] In this invention, the cyclic monocarboxylic acid is a monocarboxylic acid containing an aromatic ring, an alicyclic ring, and / or a heterocyclic ring, with a molecular weight of 50-300 g / mol. Preferably, it contains a carboxylic acid with the following structure, where the carboxyl group can be directly attached to the ring or attached to the ring in the form of HOOC-(CH2)-, etc., and n = 1-30:

[0017]

[0018] In this invention, the water-reducing agent is one or more of chemical water-reducing agents and / or physical water-reducing agents. Preferably, the chemical water-reducing agent is one or more of p-toluenesulfonyl isocyanate, triethyl orthoformate, and oxazolidine water-reducing agents, and / or the physical water-reducing agent is one or more of anhydrous calcium chloride, barium oxide, calcium oxide, magnesium sulfate, calcium sulfate, calcium hydride, and molecular sieve activated powder, more preferably molecular sieve activated powder.

[0019] In this invention, the catalyst is one or more of Lewis acidic organometallic catalysts and organic amine catalysts. Preferably, the organic amine catalyst is selected from triethylenediamine, bis(dimethylaminoethyl) ether, bis(dimethylaminoethyl) ethylene 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-dimethyl... Benzylamine, N,N-dimethyl(hexadecyl)amine, dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethyl ethylenediamine, trimethylhydroxyethyl propanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N,N,N'-trimethyl-N'-hydroxyethyl diaminoethyl ether, N-(dimethylaminopropyl)diisopropanolamine, tetramethyldipropylenetriamine, bis(dimethylamino)-2-propanol, diethylethanolamine, N,N',N'-tris(2-hydroxypropyl)ethylenediamine, 1,4-dimethylpiperazine, 1-dimethylaminoethyl-4-methylpiperazine, N-methyl-N'-hydroxyethyl Piperazine, N,N-dimethyl(4-methyl-1-piperazinyl)ethylamine, N-methylmorpholine, N-ethylmorpholine, bismorpholino diethyl ether, N-cocomorpholine, dimorpholino triethyl ether, N-(dimethylaminoethyl)morpholine, 4-(2-methoxyethyl)morpholine, dimorpholino polyethylene oxide ether, 4-butylmorpholine, 1-(4-morpholinyl)-2-propylamine, N-methylimidazolium, 1,2-dimethylimidazolium, N-2-(hydroxypropyl)imidazolium, N-2-(hydroxyethyl)imidazolium, N-2-(aminopropyl)imidazolium, 1,8-diazacycloundecene, triethylamine, or one of the following: Multiple; and / or, the organometallic catalyst is selected from one or more of organotin compounds, organopotassium compounds, organolead compounds, organobismuth compounds, organomercuric compounds, and titanates, more preferably dibutyltin dilaurate, stannous octanoate, di(dodecyl sulfide)dibutyltin, dibutyltin diacetate, dioctylenetin dilaurate, dialkyltin dimaleate, dithiol dialkyltin, potassium isooctanoate, potassium acetate, potassium oleate, lead isooctanoate, phenylmercuric acetate, zinc isooctanoate, bismuth isooctanoate, bismuth neodecanoate, bismuth naphthenate, bismuth laurate, tetrabutyl titanate, and tetraisopropyl titanate.

[0020] In this invention, the pigments and fillers are selected from inorganic and / or organic powders with a particle size of 1 nm-2 mm. Preferably, the inorganic powders are one or more of glass beads, calcium carbonate, talc, quartz powder, mineral powder, titanium dioxide, aluminum hydroxide, molecular sieve activated powder, bentonite, glass fiber, kaolin, silica powder, and fumed silica, and / or the organic powders are one or more of plastic powder, rubber powder, organic starch, cellulose, and chitin, preferably calcium carbonate, titanium dioxide, and glass beads.

[0021] In this invention, component B is a curing agent component and is 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.

[0022] This invention also provides a method for preparing the polyurethane coating for road markings, comprising the following steps:

[0023] S1: Component A is obtained by mixing modified vegetable oil polyol, water-reducing agent, catalyst, pigments and fillers;

[0024] S2: After mechanically mixing component A and curing agent component B, apply the mixture to the substrate using scraping, extrusion, swiping, or spraying methods. The total dosage of components A and B is 1-8 kg / m². 2 Preferred weight: 2-6 kg / m 2 .

[0025] Preferably, in S2, the substrate is inorganic cementitious concrete and / or organic cementitious concrete, more preferably gypsum concrete, cement concrete, asphalt concrete and / or resin concrete.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] (1) Solvent-free coatings and bio-based materials are friendly to human health and the environment.

[0028] (2) The construction temperature range is wide, and the opening time can be adjusted at any time by adjusting the catalyst, which solves the problem of long opening time in winter.

[0029] (3) Modified vegetable oil polyols have outstanding weather resistance, water resistance and freeze-thaw resistance, while the hydrophobicity and anti-fouling properties of the material are enhanced, which greatly increases the service life of the material.

[0030] (4) Modified vegetable oil polyols introduce rigid rings in the molecular chain, which have strong resistance to deformation and wear resistance. They also have strong shear resistance, compressive strength and adhesive strength. Combined with the vegetable oil molecular chain, the material exhibits high strength and high toughness. It still exhibits the same performance in winter and is suitable for different regional environments.

[0031] (5) The material contains both non-polar and polar segments, making it suitable for road surface materials of different materials.

[0032] (6) The two-component polyurethane marking paint has higher whiteness and brightness compared to the current two-component MMA paint. Detailed Implementation

[0033] The present invention will be further described below with reference to relevant embodiments. These embodiments are only for illustration and do not limit the scope of the present invention.

[0034] The main raw materials used in the embodiments of this invention are as follows; unless otherwise specified, all other raw materials are common commercially available materials:

[0035] Vegetable oil polyols: castor oil, hydroxyl value 163 mg KOH / g; soybean oil polyol, brand name HM-13200, purchased from Haierma, hydroxyl value 200±20 mg KOH / g; cashew nut shell oil polyol, purchased from Guangzhou Haoyi New Material Technology Co., Ltd., brand name FX-9001LV, hydroxyl value 175 mg KOH / g.

[0036] Modified vegetable oil polyols: Polyols-1, Polyols-2, Polyols-3, Polyols-4, Polyols-5, Polyols-6, Polyols-7, and Polyols-8 (self-made).

[0037] Water-reducing agent: Molecular sieve activated powder, purchased from Shanghai Yilan.

[0038] Catalysts: Potassium isooctanoate K-15, Zinc neodecanoate ZN-1910.

[0039] Two-component MMA coating: scraper type, purchased from Zhejiang Brothers Road Signs.

[0040] Isocyanates: IPP-270, HT-100, purchased from Wanhua Chemical.

[0041] Modified vegetable oil polyol-1

[0042] Esterification reaction: castor oil and benzoic acid were mixed at a mass ratio of 100:1 and heated to 235℃ for 1 hour to prepare Polyols-1 with a hydroxyl value of 160±20mgKOH / g.

[0043] Modified vegetable oil polyol-2

[0044] Esterification reaction: castor oil and cyclopentalic acid were mixed at a mass ratio of 100:1 and heated to 60℃ for 24 h to prepare Polyols-2 with a hydroxyl value of 155±20 mgKOH / g.

[0045] Modified vegetable oil polyol-3

[0046] Esterification reaction: Soybean oil polyols and phenylacetic acid were mixed at a mass ratio of 100:2 and reacted at 235℃ for 1 h to prepare Polyols-3 with a hydroxyl value of 190±20 mgKOH / g.

[0047] Modified vegetable oil polyol-4

[0048] Esterification reaction: Cashew nut shell oil polyol and phenylpropionic acid were mixed at a mass ratio of 100:9 and reacted at 235℃ for 1 hour to prepare Polyols-4 with a hydroxyl value of 130±20mgKOH / g.

[0049] Modified vegetable oil polyol-5

[0050] Esterification reaction: castor oil and 1-naphthoic acid were mixed at a mass ratio of 100:5 and heated to 235℃ for 24 h to prepare Polyols-5 with a hydroxyl value of 140±20 mgKOH / g.

[0051] Modified vegetable oil polyol-6

[0052] Esterification reaction: castor oil and cyclohexanecarboxylic acid were mixed at a mass ratio of 100:4 and heated to 200℃ for 24 h to prepare Polyols-6 with a hydroxyl value of 140±20 mgKOH / g.

[0053] Modified vegetable oil polyol-7

[0054] Esterification reaction: castor oil and epoxypropionic acid were mixed at a mass ratio of 100:2.5 and heated to 60℃ for 24 h to prepare Polyols-7 with a hydroxyl value of 140±20 mgKOH / g.

[0055] Modified vegetable oil polyol-8

[0056] Esterification reaction: castor oil and 4-pyridineacetic acid were mixed at a mass ratio of 100:4 and heated to 235℃ for 24 h to prepare Polyol s-8 with a hydroxyl value of 140±20 mgKOH / g.

[0057] The performance testing method used in this embodiment of the invention is as follows:

[0058] Tensile strength and elongation at break: tested in accordance with GB / T 1040-2018.

[0059] Pull-out strength: Tested in accordance with JG / T 24-2018.

[0060] Contact angle: Tested in accordance with GB / T 30693-2014.

[0061] Abrasion resistance: Tested according to T0752 in JTG E20-2011.

[0062] Aging resistance: Tested according to GB / T 16777-2008.

[0063] Stain resistance: Tested according to GB / T 9780-2013.

[0064] Examples 1-11

[0065] Two-component polyurethane road marking paint: Prepared according to the raw materials and dosages in Table 1 below.

[0066] The two-component polyurethane marking paints of Examples 1-11 were prepared according to the following method:

[0067] (1) Modified vegetable oil polyol, water-reducing agent, catalyst, pigments and fillers were mixed using a disperser (1000 RPM × 2 min) to obtain component A;

[0068] (2) After mechanically mixing component A and curing agent component B (1000 RPM × 2 min), apply the mixture to the substrate using a scraper, at a rate of 2 kg / m². 2 The substrates were selected from steel plates, cement concrete, and asphalt concrete, resulting in the two-component polyurethane marking paints described in Examples 1-11.

[0069] Table 1 shows the types and amounts (g) of raw materials used in the examples.

[0070]

[0071]

[0072] Comparative Example

[0073] The comparative example was prepared by directly using the same amount of two-component MMA coating.

[0074] The various embodiments and comparative examples were subjected to tests for odor, tensile strength and elongation, pull-out strength, strength and elongation after aging, contact angle, etc. The results are shown in Table 2.

[0075] Table 2 Adhesive Performance Test Data

[0076]

[0077] The adhesive test data in Table 2 show that the use of modified vegetable oil polyols in two-component polyurethane marking paints gives them advantages such as a wide range of substrate options, adjustable open time, high strength, good toughness, excellent freeze-thaw resistance, low energy consumption, good stain resistance, no odor, human health benefits, and environmental friendliness, which can meet the requirements of road marking applications.

[0078] The above description is only a preferred embodiment of the present invention. It should be noted that any other improvements or additions made by those skilled in the art without departing from the present invention should be within the scope of protection of the present invention.

Claims

1. A polyurethane coating for road marking, characterized in that, comprising component A and component B, wherein the mass ratio of component A and component B is 100:4-18; said component A comprises each raw material in the following mass fraction: said component B is selected from one or more of aliphatic isocyanate, alicyclic isocyanate and derivatives thereof with NCO functionality ≥2; said modified vegetable oil polyol is a vegetable oil polyol comprising aromatic ring, alicyclic ring and / or heterocyclic ring in the molecular chain, and the preparation monomer of the modified vegetable oil polyol comprises vegetable oil polyol and ring-containing monocarboxylic acid.

2. The polyurethane coating according to claim 1, characterized in that, The mass ratio of component A and component B is 100:7-14; said component A comprises each raw material in the following mass fraction:

3. The polyurethane coating according to claim 1, characterized in that, said modified vegetable oil polyol has a hydroxyl value of 120-240 mgKOH / g.

4. The polyurethane coating of claim 1, wherein, said vegetable oil polyol is selected from vegetable oil polyol with hydroxyl functionality ≥3.

5. The polyurethane coating according to claim 4, characterized in that said vegetable oil polyol is selected from one or more of castor oil, lesquerella oil, soybean oil polyol, sunflower oil polyol, palm oil polyol, flaxseed oil polyol, rapeseed oil polyol, tung oil polyol, cashew oil polyol, and / or neem oil polyol, with a hydroxyl value of 150-250 mgKOH / g.

6. The polyurethane coating according to claim 5, characterized in that said vegetable oil polyol is selected from castor oil and / or soybean oil polyol.

7. The polyurethane coating according to any one of claims 1 to 6, characterized in that, said ring-containing monocarboxylic acid is a monocarboxylic acid containing aromatic ring, alicyclic ring and / or heterocyclic ring, with a molecular weight of 50-300 g / mol.

8. The polyurethane coating according to claim 7, characterized in that said ring-containing monocarboxylic acid is a carboxylic acid containing the following structure:

9. The polyurethane coating according to any one of claims 1 to 6, characterized in that, The mass ratio of the vegetable oil polyol to the ring-containing monocarboxylic acid is 100:0.1-10.0, and the reaction temperature of the vegetable oil polyol and the ring-containing monocarboxylic acid is 60-250°C, and the reaction time is 1-24 h.

10. The polyurethane coating according to any one of claims 1 to 6, characterized in that, The water reducing agent is one or more of chemical type water reducing agent and / or physical type water reducing agent.

11. The polyurethane coating according to claim 10, characterized in that said chemical type water reducing agent is one or more of p-toluenesulfonyl isocyanate, triethyl orthoformate, and oxazolidine water reducing agent, and / or, said physical type water reducing agent is one or more of anhydrous calcium chloride, barium oxide, calcium oxide, magnesium sulfate, calcium sulfate, calcium hydride, and molecular sieve activated powder.

12. The polyurethane coating according to claim 11, characterized in that The water reducing agent is molecular sieve activated powder.

13. The polyurethane coating according to any one of claims 1 to 6, characterized in that, said catalyst is one or more of Lewis acid organic metal catalyst and organic amine catalyst.

14. The polyurethane coating according to claim 13, characterized in that The organic amine catalyst is selected from one or more of triethylenediamine, bis(dimethylaminoethyl) ether, bis(dimethylaminoethyl) glycol ether, dimethylcyclohexylamine, N-methyldicyclohexylamine, pentamethyldiethyltriamine, pentamethyldipropylene triamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, tris(dimethylaminopropyl)amine, N,N-dimethylbenzylamine, N,N-dimethyl(hexadecyl)amine, dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethyl ethylenediamine, trimethylhydroxyethyl propylenediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N,N,N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether, N-(dimethylaminopropyl)diisopropanolamine, tetramethyldipropylene triamine, bis(dimethylamino)-2-propanol, diethylethanolamine, N,N',N'-tris(2-hydroxypropyl)ethylenediamine, 1,4-dimethylpiperazine, 1-dimethylaminoethyl-4-methylpiperazine, N-methyl-N'-hydroxyethylpiperazine, N,N-dimethyl(4-methyl-1-piperazinyl)ethylamine, N-methylmorpholine, N-ethylmorpholine, bis(morpholinyl)diethyl ether, N-coco morpholine, dimorpholino triethyl ether, N-(dimethylaminoethyl)morpholine, 4-(2-methoxyethyl)morpholine, dimorpholino polyethylene oxide ether, 4-butylmorpholine, 1-(4-morpholinyl)-2-propanamine, N-methylimidazole, 1,2-dimethylimidazole, N-2-(hydroxypropyl)imidazole, N-2-(hydroxyethyl)imidazole, N-2-(aminopropyl)imidazole, 1,8-diazabicycloundecene, triethylamine; and / or, the Lewis acidic organometallic catalyst is selected from one or more of an organotin compound, an organopotassium compound, an organolead compound, an organobismuth compound, an organomercury compound, a titanate.

15. The polyurethane coating according to claim 14, characterized in that The Lewis acidic organometallic catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, dibutyltin bis(dodecylthioate), dibutyltin diacetate, dioctyltin dilaurate, dialkyltin dimaleate, dialkyltin dithiolate, potassium isooctoate, potassium acetate, potassium oleate, lead isooctoate, phenylmercury acetate, bismuth isooctoate, bismuth neodecanoate, bismuth naphthenate, bismuth laurate, tetrabutyl titanate, tetraisopropyl titanate.

16. The polyurethane coating of any one of claims 1-6, wherein, The color filler is selected from inorganic and / or organic powder having a particle size of 1 nm to 2 mm.

17. The polyurethane coating of claim 16, wherein, The inorganic powder is one or more of glass bead, calcium carbonate, talc, quartz powder, mineral powder, titanium dioxide, aluminum hydroxide, molecular sieve activated powder, bentonite, glass fiber, kaolin, silica powder, fumed silica, and / or the organic powder is one or more of plastic powder, rubber powder, organic starch, cellulose, chitin.

18. The polyurethane coating of any one of claims 1-6, wherein, The component B is one or more of HDI, HDI dimer, HDI trimer, HDI biuret, IPDI, IPDI trimer, HMDI, NDI, PPDI, CHDI, XDI, HXDI, TMHDI, NBDI, TODI, HTDI.

19. Process for the production of polyurethane coatings according to any of claims 1 to 18, characterized in that, The method comprises the following steps: (1) mixing modified vegetable oil polyol, water reducing agent, catalyst and pigment filler to obtain component A; (2) After mechanical mixing of component A and component B, the total amount of component A and component B is 1-8 kg / m 2 .

20. The method of claim 19, wherein, The total amount of component A and component B is 2-6 kg / m 2 .

21. The method of claim 19, wherein, In step (2), the substrate is inorganic cementitious material concrete and / or organic binder concrete.

22. The method of claim 21, wherein, The substrate is gypsum concrete, cement concrete, asphalt concrete and / or resin concrete.

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