A basalt flake scratch-resistant polyurethane coating, method of making and use thereof

Abstract

The application discloses basalt flake anti-scratch polyurethane paint, a preparation method and application thereof, the paint comprises a component A and a component B with a mass ratio of 4-6:1, the resin in the component A comprises modified hydroxyl acrylic resin and hydroxyl acrylic resin; wherein the modified hydroxyl acrylic resin is prepared from raw materials comprising the following components: wear-resistant component with double bonds 20-50%, acrylic monomer 10-20%, hydroxyl acrylic monomer 15-30%, second solvent 20-30% and dibenzoyl peroxide 0.5-3%. The component A of the paint adopts low-density modified hydroxyl acrylic resin containing hard wear-resistant particles, the resin is blended with traditional resins, and the low-density resin containing hard wear-resistant particles prepared in the paint will float on the surface of the coating during the surface drying process, so that a hard wear-resistant surface layer is formed, the hardness can reach more than 4H, and the paint not only has wear resistance, but also can well protect the paint from being scratched by sand or sharp objects.

Description

Technical Field

[0001] This invention relates to wear-resistant polyurethane coatings, specifically to a basalt flake scratch-resistant polyurethane coating, its preparation method, and its application. Background Technology

[0002] In the competition for a combination of high performance and environmental friendliness, polyurethane coatings have become one of the preferred raw material suppliers in the coatings industry. Polyurethane exhibits excellent performance in corrosion resistance, weather resistance, and scratch resistance, while also being environmentally friendly. Polyurethane coatings offer advantages such as good weather resistance, good gloss retention, good color stability, corrosion resistance, acid rain resistance, good low-temperature application, good recoating properties, easy repair, good coating flexibility, and excellent ductility, impact resistance, and vibration resistance. Its superior comprehensive performance has led to its increasing use in anti-corrosion projects, primarily in heavy-duty anti-corrosion fields such as bridges and chemical plants. Polyurethane coatings can achieve low-temperature curing, have good elasticity, and can be applied in all weather conditions, thus possessing promising development prospects.

[0003] Because polyurethane coatings have good elasticity, damping, and wear resistance, they can be used as topcoats in environments such as bridges and docks. However, these environments are often filled with dust particles and flying sand and gravel. Therefore, protective coatings need to have not only damping and wear resistance but also scratch resistance. Currently used polyurethane topcoats cannot meet this requirement. Summary of the Invention

[0004] To address the problem that current urethane topcoats do not possess excellent scratch resistance, this invention provides a basalt flake scratch-resistant polyurethane coating, its preparation method, and its application. This polyurethane coating, while possessing damping and wear resistance, also provides excellent protection against scratches from sand, gravel, or sharp objects.

[0005] To achieve the above objectives, the present invention provides a basalt flake scratch-resistant polyurethane coating, comprising component A and component B in a mass ratio of (4-6):1, wherein component B comprises an aliphatic polyisocyanate curing agent and anhydrous acetate butyrate in a mass ratio of (7-9):(1-3); and component A comprises, by mass percentage:

[0006] Modified hydroxyl acrylic resin 20-30%

[0007] Hydroxyacrylate resin 25-35%

[0008] Pigment 5-15%

[0009] 5-15% of filler

[0010] Basalt scales 10-20%

[0011] Additives 0.5%–3.5%

[0012] The first solvent is 4.5% to 14.5%;

[0013] The modified hydroxyl acrylic resin, by weight percentage, is obtained from raw materials comprising the following components:

[0014] Wear-resistant components containing double bonds: 20-50%

[0015] 10-20% acrylic monomer

[0016] Hydroxyacrylate monomer 15-30%

[0017] The second solvent is 20-30%.

[0018] Benzoyl peroxide 0.5-3%.

[0019] In the above technical solution, component A uses a low-density modified hydroxyl acrylic resin containing hard wear-resistant particles. This resin is blended with traditional resins. During the surface drying process, the low-density resin containing hard wear-resistant particles floats to the surface of the coating, forming a hard and wear-resistant surface layer with a hardness of 4H or higher. It is not only wear-resistant, but also provides good protection against scratches from sand or sharp objects.

[0020] Meanwhile, the resin crosslinks with the curing agent and traditional resin to form an elastic coating, and introduces basalt flakes into the coating system, further enhancing the coating's strength and corrosion resistance.

[0021] Compared with conventional polyurethane coatings, the basalt flake anti-scratch polyurethane coating of the present invention has good hardness, wear resistance, salt spray resistance, chemical resistance and other properties. In particular, it also has good damping and wear resistance while having good hardness.

[0022] Specifically, the wear-resistant component containing double bonds is obtained from the following raw materials by weight percentage:

[0023] Hollow microspheres 5-10%

[0024] Silica sol 15-25%

[0025] Siloxane monomers 10-25%

[0026] The third solvent is 10-35%.

[0027] 15-35% of the siloxane monomers contain double bonds.

[0028] Silica sol, siloxane monomers, and siloxane monomers containing double bonds react synergistically to form microparticles containing double bonds and hard, wear-resistant components. These microparticles interact strongly with hollow microspheres through the siloxane monomers, forming a wear-resistant microcomponent centered on the hollow microspheres. This wear-resistant component also contains double bonds. Subsequent polymerization with acrylic monomers and hydroxyacrylic monomers yields a modified hydroxyacrylic resin containing the wear-resistant microcomponent centered on hollow microspheres. When this resin is blended with traditional resins, the resulting coating exhibits a low-density resin containing hard, wear-resistant particles that floats to the surface during surface drying, forming a hard, wear-resistant surface layer with a hardness exceeding 4H. This not only provides wear resistance but also excellent protection against scratches from sand, gravel, or sharp objects. Simultaneously, this resin crosslinks with a curing agent and traditional resins to form an elastic coating, and the introduction of basalt flakes into the coating system further enhances the coating's strength and corrosion resistance.

[0029] More specifically, the hollow microspheres are selected from at least one of hollow glass microspheres and hollow ceramic microspheres, and the particle size of the hollow microspheres is 5-12 micrometers; and / or

[0030] The silica sol is selected from at least one of CR-23-MMA, CR-23-DMB, CR-23-PMA, and CR-23-IPA; and / or

[0031] The siloxane monomer is selected from at least one of methyltriethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, and tetraethyl orthosilicate; and / or

[0032] The siloxane monomer containing the double bond is selected from at least one of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldimethoxysilane.

[0033] The third solvent is preferably xylene or 100# solvent oil.

[0034] Preferably, the acrylic monomer is selected from at least one of methyl methacrylate, n-butyl methacrylate, methyl acrylate, and n-butyl acrylate; and / or

[0035] The hydroxyacrylate monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, and β-hydroxypropyl acrylate; and / or

[0036] The second solvent comprises xylene and butyl acetate in a mass ratio of (2-3):1.

[0037] The synergistic effect among the above components influences the evaporation rate at different times, reducing defects in coating formation, such as bubbles and unevenness.

[0038] Preferably, the basalt flakes have a particle size of 150-300 mesh.

[0039] The hydroxy acrylic resin is selected from at least one of SETALUX®1753 SS-70, KDD736, and Hypomer FS-4080F.

[0040] The additive is selected from at least one of BYK-ATU, Efka4063, BYK-052, BYK-053, MONORAL 8900, and MONORAL3300.

[0041] The coloring pigment is selected from at least one of titanium dioxide, iron oxide red, and iron oxide black.

[0042] The filler is selected from at least one of barium sulfate, silica powder, mica powder, and feldspar powder.

[0043] The solvent is selected from at least one of xylene, anhydrous butyl acetate, and 150# solvent oil.

[0044] A second aspect of the present invention provides a method for preparing the above-mentioned basalt flake scratch-resistant polyurethane coating, wherein the preparation method of component A is as follows:

[0045] After the modified hydroxy acrylic resin, hydroxy acrylic resin and additives are evenly dispersed, the pigment, filler and basalt flakes are added and evenly dispersed. Then, solvent is added to adjust the viscosity to 75-85 KU and control the fineness to <50 μm to obtain component A.

[0046] The preparation method of component B is as follows:

[0047] The aliphatic polyisocyanate curing agent is dispersed in an organic solvent to obtain component B.

[0048] Specifically, accurately measured amounts of modified hydroxyl acrylic resin, hydroxyl acrylic resin, and additives are added to a dispersion vessel and dispersed at high speed (1000–1500 rpm) for 20–30 minutes. Then, pigments, fillers, and basalt flakes are added, and the stirring speed is increased to 1500–2500 rpm for high-speed stirring for 60 minutes. After thorough mixing, a mixed solvent is added to adjust the viscosity to 75–85 KU, and the fineness is controlled to <50 μm to obtain component A.

[0049] Turn on the mixing tank and add the aliphatic polyisocyanate curing agent, such as anhydrous acetate butyrate, according to the formula at a speed of 500-800 rpm. Stir for 20-30 minutes to obtain component B.

[0050] Specifically, the preparation method of the modified hydroxy acrylic resin is as follows: 15-22.5% of the second solvent is added to the reactor and heated by mass percentage. 20-50% of the wear-resistant component containing double bonds, 10-20% of the acrylic monomer, 15-30% of the hydroxy acrylic monomer, and 0.4-2.4% of benzoyl peroxide are mixed evenly and transferred to the reactor system. After the reactor system is refluxed, the mixture is added dropwise over 2-3 hours. After the addition is completed, the mixture is kept at a constant temperature for 1-1.5 hours. Then, 5-7.5% of the second solvent and 0.1-0.6% of benzoyl peroxide are mixed and transferred to a dropping funnel for dropwise addition over 20-30 minutes. After the addition is completed, the mixture is kept at a constant temperature for 2-3 hours and then cooled to obtain the modified hydroxy acrylic resin.

[0051] Specifically, the preparation method of the wear-resistant component containing double bonds is as follows: by mass percentage, 5-10% hollow glass microspheres, 15-25% silica sol, 10-25% dimethyldiethoxysilane, 10-35% third solvent and 15-35% siloxane monomer containing double bonds are added to a reactor, mixed evenly, and then heated to reflux. After the reflux begins, the system is kept in reflux state for at least 5 hours, and then cooled to room temperature to obtain the wear-resistant component containing double bonds.

[0052] A third aspect of the present invention provides a basalt flake scratch-resistant polyurethane coating prepared by the above-described preparation method.

[0053] The fourth aspect of the present invention provides the application of the above-mentioned basalt flake anti-scratch polyurethane coating in the preparation of anti-scratch coatings.

[0054] Through the above technical solution, the present invention achieves the following beneficial effects:

[0055] 1. The A component of the coating of this invention uses a low-density modified hydroxyl acrylic resin containing hard, wear-resistant particles. This resin is blended with traditional resins. During the surface drying process, the low-density resin containing hard, wear-resistant particles floats to the surface of the coating, forming a hard, wear-resistant surface layer with a hardness of 4H or higher. This not only provides wear resistance but also excellent protection against scratches from sand, gravel, or sharp objects. Simultaneously, this resin crosslinks with the curing agent and traditional resins to form an elastic coating. Furthermore, the introduction of basalt flakes into the coating system further enhances the coating's strength and corrosion resistance. Compared to conventional polyurethane coatings, the basalt flake scratch-resistant polyurethane coating of this invention exhibits excellent hardness, wear resistance, salt spray resistance, and chemical resistance. In particular, it also possesses good damping and wear resistance while maintaining good hardness.

[0056] 2. In a preferred embodiment of the present invention, a wear-resistant component containing double bonds is prepared from hollow microspheres, silica sol, siloxane monomers, xylene, and siloxane monomers containing double bonds. The silica sol, siloxane monomers, and siloxane monomers containing double bonds react synergistically to form microparticles containing double bonds and hard wear-resistant components. These microparticles interact strongly with the hollow microspheres through the siloxane monomers, forming a wear-resistant micro-component centered on the hollow microspheres. This wear-resistant component also contains double bonds. Later, it is polymerized with acrylic monomers and hydroxyacrylic monomers to obtain a modified hydroxyacrylic resin containing wear-resistant micro-components centered on hollow microspheres. When this resin is blended with traditional resins, the low-density resin containing hard wear-resistant particles floats to the surface of the coating during the surface drying process, forming a hard, wear-resistant surface layer with a hardness of 4H or higher. This not only provides wear resistance but also excellent protection against scratches from sand, gravel, or sharp objects. Meanwhile, the resin crosslinks with the curing agent and traditional resin to form an elastic coating, and introduces basalt flakes into the coating system, further enhancing the coating's strength and corrosion resistance. Detailed Implementation

[0057] The specific embodiments of the present invention will be described in detail below with reference to examples. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0058] Wear-resistant components containing double bonds, namely B-1, B-2, and B-3, were prepared according to the components in Table 1.

[0059] Table 1. Composition and dosage of wear-resistant components containing double bonds (unit: wt%)

[0060]

[0061] The preparation method of the wear-resistant component containing double bonds is as follows: Hollow microspheres, silica sol, siloxane monomer, xylene, and siloxane monomer containing double bonds are weighed in sequence and added to the reactor. After stirring evenly, the system is heated to reflux. After the reflux begins, the system is kept in reflux state for at least 5 hours. The system is then cooled to room temperature for later use.

[0062] Modified hydroxyl acrylic resins A-1, A-2, and A-3 were prepared according to the components in Table 2.

[0063] Table 2. Composition and dosage of modified hydroxyl acrylic resin (unit: wt%)

[0064]

[0065] The preparation method of modified hydroxyl acrylic resin is as follows: Three-quarters of the total amount of solvent is weighed and added to the reactor and heated; the wear-resistant component containing double bonds, acrylic monomer, hydroxyl acrylic monomer, and four-fifths of the total amount of benzoyl peroxide are weighed and mixed evenly in a beaker and then transferred to the dropping funnel of the reactor system; after the reaction system is refluxed, the addition begins, and the mixture in the dropping funnel is added completely in 2-3 hours; after the addition is completed, the temperature is maintained for 1 hour, the remaining solvent and benzoyl peroxide are weighed, mixed and transferred to the dropping funnel, and the addition begins, and the mixture in the dropping funnel is added completely in 20-30 minutes; after the addition is completed, the temperature is maintained for 2 hours, and then cooled to obtain the self-made auxiliary film-forming resin.

[0066] Component A was prepared according to the ingredients listed in Table 3.

[0067] Table 3. Composition and dosage of component A (unit: wt%)

[0068]

[0069] Component B was prepared according to the ingredients listed in Table 4.

[0070] Table 4. Composition and dosage of component B (unit: wt%)

[0071]

[0072] The preparation method of component A is as follows:

[0073] In a dispersion vessel, accurately measured amounts of self-made modified hydroxy acrylic resin A, hydroxy acrylic resin, and additives were added and dispersed at high speed (1000–1500 rpm) for 20 minutes. Pigments, fillers, and basalt flakes were then added sequentially, and the stirring speed was increased to 1500–2500 rpm for 60 minutes. After thorough mixing, a mixed solvent was added to adjust the viscosity to 75–85 KU, controlling the fineness to <50 μm, to obtain component A.

[0074] Preparation method of component B:

[0075] Turn on the mixing tank, add aliphatic polyisocyanate curing agent and anhydrous acetate butyrate according to the formula at a speed of 500-8000 rpm, and stir for 20-30 minutes to obtain component B.

[0076] The coatings were prepared according to the components listed in Table 5.

[0077] Table 5. Composition and dosage of coatings (unit: g)

[0078]

[0079] The samples A and B prepared in the above embodiments and comparative examples were packaged separately and left to stand at room temperature for 1 month. After being mixed according to Table 4, they were prepared as test samples by spraying. The obtained samples were tested according to the items in Table 6, and the test results are shown in Table 7.

[0080] Table 6 Product Test Items and Test Standards

[0081]

[0082] Table 7 Performance Test Results

[0083]

[0084] As can be seen from Table 7, the coatings in the examples all exhibit excellent abrasion resistance, weather resistance, and corrosion resistance, and all meet the performance requirements of standard polyurethane coatings. Comparative Examples 1 and 2 were tested by replacing commercially available resins with those in Examples 1 and 2. It can be seen that the abrasion resistance of the comparative example coatings is much lower than that of the coatings in the examples.

[0085] The preferred embodiments of the present invention have been described in detail above with reference to the examples. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0086] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0087] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A basalt flake scratch resistant polyurethane coating, characterized in that, The component A and component B are included in a mass ratio of (4-6):1, the component B includes a fatty polyisocyanate curing agent and anhydrous butyl acetate in a mass ratio of (7-9):(1-3); the component A includes, in percentage by mass: 20-30% of modified hydroxyl acrylic resin 25-35% of hydroxyl acrylic resin 5-15% of pigment 5-15% of filler 10-20% of basalt flake 0.5-3.5% of auxiliary agent 4.5-14.5% of first solvent; The modified hydroxyl acrylic resin is prepared from raw materials including the following components, in percentage by mass: 20-50% of double-bond-containing wear-resistant component 10-20% of acrylic monomer 15-30% of hydroxyl acrylic monomer 20-30% of second solvent 0.5-3% of dibenzoyl peroxide; The double-bond-containing wear-resistant component is prepared from the following raw materials, in percentage by mass: 5-10% of hollow microsphere 15-25% of silica sol 10-25% of siloxane monomer 10-35% of third solvent 15-35% of double-bond-containing siloxane monomer; The particle size of the hollow microsphere is 5-12 microns.

2. The polyurethane coating according to claim 1, characterized in that The hollow microsphere is selected from at least one of hollow glass microsphere and hollow ceramic microsphere; and / or The silica sol is selected from at least one of CR-23-MMA, CR-23-DMB, CR-23-PMA, CR-23-IPA; and / or The siloxane monomer is selected from at least one of methyl triethoxysilane, dimethyl diethoxysilane, methyl phenyl diethoxysilane, tetraethyl orthosilicate; and / or The double-bond-containing siloxane monomer is selected from at least one of γ-methacryloyloxypropyl trimethoxysilane, γ-methacryloyloxypropyl triethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloyloxypropyl methyl diethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl methyl diethoxysilane, vinyl methyl dimethoxysilane.

3. The polyurethane coating of claim 1, wherein, The acrylic monomer is selected from at least one of methyl methacrylate, n-butyl methacrylate, methyl acrylate, n-butyl acrylate; and / or The hydroxyl acrylic monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate; and / or The second solvent includes xylene and butyl acetate in a mass ratio of (2-3):

1.

4. The polyurethane coating according to any one of claims 1 to 3, characterized in that, The basalt flake has a particle size of 150-300 mesh.

5. Process for the production of basalt flake scratch-resistant polyurethane coatings according to any one of claims 1 to 4, characterized in that, The preparation method of the component A is as follows: After the modified hydroxyl acrylic resin, the hydroxyl acrylic resin and the auxiliary agent are uniformly dispersed, the pigment, the filler and the basalt flake are added and uniformly dispersed, and then the solvent is added to adjust the viscosity to 75-85 KU and control the fineness to be less than 50 um, to obtain the component A; The preparation method of the component B is as follows: The fatty polyisocyanate curing agent is dispersed in the anhydrous butyl acetate to obtain the component B.

6. The method of claim 5, wherein the basalt flake scratch-resistant polyurethane coating is prepared by the steps of: The preparation method of the modified hydroxyl acrylic resin is as follows: 15-22.5% of a second solvent is added into a reactor for heating, 20-50% of a wear-resistant component containing double bonds, 10-20% of an acrylic monomer, 15-30% of a hydroxyl acrylic monomer, and 0.4-2.4% of dibenzoyl peroxide are uniformly mixed and then transferred into the reactor system, after the reactor system is refluxed, the mixed solution is started to be added dropwise, and the dropping is completed in 2-3 hours; after the dropping is completed, the system is kept for 1-1.5 hours, then 5-7.5% of the second solvent and 0.1-0.6% of dibenzoyl peroxide are mixed and then transferred into a dropping funnel for starting to be added dropwise, the dropping is completed in 20-30 minutes, after the dropping is completed, the system is kept for 2-3 hours, and the modified hydroxyl acrylic resin is obtained after cooling.

7. The method of claim 6, wherein the basalt flake scratch-resistant polyurethane coating is prepared by the steps of: The preparation method of the wear-resistant component containing double bonds is as follows: 5-10% of hollow glass microspheres, 15-25% of silica sol, 10-25% of dimethyldiethoxysilane, 10-35% of a third solvent, and 15-35% of a siloxane monomer containing double bonds are added into a reactor for mixing and heating until the system is refluxed, the refluxing is kept for at least 5 hours after the refluxing is started, and the system is cooled to room temperature to obtain the wear-resistant component containing double bonds.

8. The basalt flake scratch-resistant polyurethane coating prepared by the preparation method in any one of claims 5 to 7.

9. The use of the basalt flake scratch-resistant polyurethane coating in any one of claims 1 to 4 or claim 8 in the preparation of a scratch-resistant coating.

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