Wear resistant photocured polyurethane coating and method of use thereof

Abstract

The application provides a polyurethane coating, which is a two-component polyurethane coating, and the two-component polyurethane coating comprises component A and component B, wherein the component A is composed of the following components in parts by weight: 120-180 parts of water-based polyurethane acrylate, 40-60 parts of water-based polyurethane / boron nitride compound, 2-5 parts of photoinitiator, 0.5-3 parts of auxiliary agent, and 40-70 parts of water; and the component B is composed of the following components in important parts: 5-10 parts of porous titanium dioxide loaded with copper ions or zinc ions, and 90-100 parts of ethanol. The application provides a wear-resistant photocuring polyurethane coating, which is coated on the surface of a substrate in steps and layers to obtain a wear-resistant polyurethane coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional coatings, specifically to a wear-resistant light-cured polyurethane coating and its application method. BACKGROUND

[0002] Wood is a traditional and widely used building and decorative material, playing an irreplaceable role in furniture manufacturing, interior decoration, building facade decoration, etc. Due to the porous nature and relatively soft texture of wood, it is susceptible to wear, scratches, and environmental factors such as UV light and humidity changes, which can affect its aesthetic appearance and service life. Light-curing technology is an efficient and environmentally friendly curing technology. Compared with traditional thermal curing technology, light-curing has the advantages of fast curing speed, low energy consumption, and low volatile organic compound (VOC) emissions during the curing process. In the field of coatings, light-curing technology can quickly convert liquid coatings into solid coatings, greatly improving production efficiency. Polyurethane coatings have excellent wear resistance, flexibility, chemical resistance, and other properties. Combining polyurethane coatings with light-curing technology can leverage the strengths of both, providing high-performance protective coatings for wood. This wear-resistant light-cured polyurethane coating for wood can form a tough, wear-resistant, and aesthetically pleasing protective film on the surface of wood, improving the quality and durability of wood products.

[0003] Although existing wear-resistant light-cured polyurethane coatings for wood have some wear resistance, they still need to be further improved in terms of wear resistance in some high-wear scenarios, such as public wood floors, frequently used wooden furniture, etc. Although current methods can enhance the wear resistance of the coating by optimizing the molecular structure of polyurethane, introducing more wear-resistant functional groups, or adding nano-sized wear-resistant fillers (such as nano-silicon dioxide, nano-aluminum oxide, etc.), the wear resistance of the coating still needs to be further improved. SUMMARY

[0004] The technical problem to be solved is to provide a wear-resistant light-cured polyurethane coating that can be applied in steps and layers on the surface of a substrate to achieve a wear-resistant polyurethane coating.

[0005] Technical solution: A wear-resistant light-cured polyurethane coating, the polyurethane coating is a two-component polyurethane coating, the two-component polyurethane coating includes component A and component B, wherein component A is composed of the following components by weight:

[0006] Waterborne polyurethane acrylate 120-180 parts

[0007] Waterborne polyurethane / boron nitride composite 40-60 parts

[0008] Photoinitiator 2-5 parts

[0009] Auxiliary agent 0.5-3 parts

[0010] Sodium lignosulfonate 10-20 parts

[0011] Water 40-70 parts;

[0012] The component B is composed of the following important parts:

[0013] Porous titanium dioxide loaded with copper ions or zinc ions 5-10 parts

[0014] Ethanol 90-100 parts;

[0015] The water-based polyurethane acrylate is any one or both of a polyether type water-based polyurethane acrylate and a polyester type water-based polyurethane acrylate;

[0016] The photoinitiator is any one or a mixture of more than one of 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl propiophenone and 2-hydroxy-2-methyl-1-phenyl-1-propanone;

[0017] The auxiliary agent includes any one or a mixture of more than one of an antifoaming agent, a formaldehyde removal additive, an antibacterial additive, an anti-settling agent, a matting agent, a handle wax, and a dispersing agent.

[0018] The preparation method of the water-based polyurethane / boron nitride composite is as follows:

[0019] S11. Boric acid and urea are mixed in a mass ratio of 1:10-14 and added to water, and a BN precursor is obtained by heating and stirring in a water bath at 85-90℃. The BN precursor is reacted at high temperature to obtain flaky boron nitride;

[0020] S12. The flaky boron nitride, urea, and water are mixed and ball milled at a speed of 500-800r / min for 15-20h. The mixed solution after ball milling is diluted and ultrasonically treated for 1-2h, filtered and dried to obtain amino-modified boron nitride;

[0021] S13. The amino-modified boron nitride is dispersed in acetone and ultrasonically dispersed uniformly to obtain a boron nitride dispersion;

[0022] S14. Polytetrahydrofuran ether diol and isophorone diisocyanate are mixed and reacted at a temperature of 90-95℃ for 1.5-2.5h. After cooling to 80℃, dimethylolpropionic acid and 1,4-butanediol are added and reacted for 2h. After cooling to 70℃ again, dibutyltin dilaurate is added dropwise and reacted for 3h to obtain a polyurethane prepolymer. Then, the boron nitride dispersion is added, and after reacting for 1-1.5h, the temperature is lowered to room temperature to obtain a water-based polyurethane / boron nitride composite material.

[0023] The preparation method of the porous titanium dioxide loaded with copper ions or zinc ions comprises the following steps:

[0024] S21. Tetrabutyl titanate is added to ethanol, stirred and uniformly dispersed, then water is added, stirring is continued until tetrabutyl titanate is completely hydrolyzed, then ammonium bicarbonate is added to the hydrolysis solution, the mass-volume ratio of tetrabutyl titanate, ethanol, water and sodium bicarbonate is 2-4 mL: 10-20 mL: 50-100 mL: 1-2 g, reaction is carried out at 170-190 °C for 40-50 h, and finally, nano-porous titanium dioxide powder is obtained by washing and drying;

[0025] S22. Copper sulfate or zinc sulfate is added to a hydroxypropyl methyl cellulose aqueous solution with a concentration of 0.5-1 wt%, stirring and uniformly dispersing to obtain a mixed solution, the concentration of copper sulfate or zinc sulfate in the mixed solution is 1-3 wt%;

[0026] S23. Nano-porous titanium dioxide is added to the mixed solution in step S22, ultrasonic dispersion is carried out, and then porous titanium dioxide loaded with copper ions or zinc ions is obtained by filtering and drying.

[0027] The application method of the above wear-resistant photocurable polyurethane coating comprises the following steps:

[0028] S1. The water-based polyurethane acrylate in component A is added to water according to the weight parts, then the water-based polyurethane / boron nitride composite, the photoinitiator and the auxiliary agent are sequentially added, mixing and stirring are uniformly carried out, and coating X is obtained;

[0029] S2. The sodium lignosulfonate in component A is added to water according to the weight parts, stirring and mixing are uniformly carried out, then the water-based polyurethane acrylate, the water-based polyurethane / boron nitride composite, the photoinitiator and the auxiliary agent are sequentially added, mixing and stirring are uniformly carried out, and coating Y is obtained;

[0030] S3. The porous titanium dioxide loaded with copper ions or zinc ions is added to ethanol, ultrasonic dispersion is uniformly carried out, and coating Z is obtained;

[0031] S4. Coating X is coated on the substrate, the coating amount is 45-125 g / m 2 , after ultraviolet irradiation curing, coating Y is coated on the substrate, the coating amount is 35-85 g / m 2 , finally, coating Z is coated, and again ultraviolet irradiation curing is carried out to obtain a wear-resistant coating. Preferably, the substrate comprises: a wooden board, a stone-plastic composite floor;

[0032] The wooden board comprises: a: solid wood floor; b: any other core material, substrate but the surface is taken as a surface layer of solid wood floor product; the stone-plastic composite floor is: a solid base layer with high density and high fiber network structure formed by stone powder, and a wear-resistant polyurethane coating is covered on the surface.

[0033] Preferably, the parameters of the high-temperature reaction in step S11 are as follows: heating at a rate of 3℃ / min to 500-550℃ and holding for 3h.

[0034] Preferably, the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol, dimethylol propionic acid and 1,4-butanediol in step S14 is 5-10:1-2:1-2:2.6-5.5.

[0035] Preferably, the content of boron nitride in the polyurethane prepolymer in step S14 is 12-16wt%.

[0036] Beneficial effects: The coating of the present application has the following advantages:

[0037] 1. The abrasion-resistant light-cured polyurethane coating in the present application comprises two components A and B. When coating the substrate, a low-content water-based polyurethane / boron nitride composite coating is coated on the bottom layer of the substrate, and the low-content filler coating has good adhesion to the substrate. A high-content water-based polyurethane / boron nitride composite coating is coated on the outside of the low-content water-based polyurethane / boron nitride composite coating. Through the design of the gradient structure coating, the abrasion resistance of the coating can be improved.

[0038] 2. In the present application, component B is coated on the outside of component A coating, and component B contains porous titanium dioxide loaded with copper ions or zinc ions. The copper ions or zinc ions of the porous titanium dioxide loaded with copper ions or zinc ions can complex with the sodium lignosulfonate contained in component A, thereby improving the adhesion and abrasion resistance of the overall coating. By introducing various types of fillers into the coating, the advantages of various fillers can be utilized to further improve the overall performance of the coating. DETAILED DESCRIPTION

[0039] The present application will be further described below in conjunction with examples. The following examples are an explanation of the present application and the present application is not limited to the following examples:

[0040] Example 1

[0041] The preparation method of the water-based polyurethane / boron nitride composite is as follows:

[0042] S11. Boric acid and urea were mixed in water at a mass ratio of 1:10, heated in a water bath at 85℃ and stirred to obtain a BN precursor. The BN precursor was heated at a rate of 3℃ / min to 550℃ and held for 3h to obtain flaky boron nitride.

[0043] S12. The flaky boron nitride, urea and water were mixed and ball milled at a speed of 500r / min for 20h. The mixed solution after ball milling was diluted and ultrasonically treated for 1h, filtered and dried to obtain amino-modified boron nitride.

[0044] S13. The amino-modified boron nitride is dispersed in acetone, and uniformly dispersed by ultrasonic dispersion to obtain a boron nitride dispersion liquid;

[0045] S14. Polytetrahydrofuran ether glycol and isophorone diisocyanate are mixed and reacted, the reaction temperature is 95°C, the reaction time is 1.5h, after cooling to 80°C, dimethylol propionic acid and 1,4-butanediol are added and reacted for 2h, again cooling to 70°C, dibutyl tin dilaurate is added dropwise and reacted for 3h to obtain a polyurethane prepolymer, then the boron nitride dispersion liquid is added, reacted for 1h, and then cooled to room temperature to obtain a water-based polyurethane / boron nitride composite material, wherein the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol, dimethylol propionic acid and 1,4-butanediol is 5:1:1:2.6, and the content of boron nitride in the polyurethane prepolymer is 12wt%.

[0046] Example 2

[0047] The preparation method of the water-based polyurethane / boron nitride composite is as follows:

[0048] S11. Boric acid and urea are mixed according to a mass ratio of 1:14 and added to water, heated in a water bath at 90°C and stirred to obtain a BN precursor, the BN precursor is heated to 500°C at a rate of 3°C / min and kept for 3h to obtain flaky boron nitride;

[0049] S12. The flaky boron nitride, urea and water are mixed and ball milled at a speed of 800r / min for 15h, the mixed solution after ball milling is diluted and ultrasonically treated for 2h, filtered and dried to obtain amino-modified boron nitride;

[0050] S13. The amino-modified boron nitride is dispersed in acetone, and uniformly dispersed by ultrasonic dispersion to obtain a boron nitride dispersion liquid;

[0051] S14. Polytetrahydrofuran ether glycol and isophorone diisocyanate are mixed and reacted, the reaction temperature is 90°C, the reaction time is 2.5h, after cooling to 80°C, dimethylol propionic acid and 1,4-butanediol are added and reacted for 2h, again cooling to 70°C, dibutyl tin dilaurate is added dropwise and reacted for 3h to obtain a polyurethane prepolymer, then the boron nitride dispersion liquid is added, reacted for 1.5h, and then cooled to room temperature to obtain a water-based polyurethane / boron nitride composite material, wherein the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol, dimethylol propionic acid and 1,4-butanediol is 10:2:2:5.5, and the content of boron nitride in the polyurethane prepolymer is 16wt%.

[0052] Example 3

[0053] The preparation method of the water-based polyurethane / boron nitride composite is as follows:

[0054] S11. Boric acid and urea are mixed in water in a mass ratio of 1:12, heated in a water bath at 90°C and stirred to obtain a BN precursor, the BN precursor is heated at a rate of 3°C / min to 530°C and kept for 3h to obtain flaky boron nitride;

[0055] S12. The flaky boron nitride, urea and water are mixed and ball milled at a speed of 600r / min for 16h, the mixed solution after ball milling is diluted and ultrasonically treated for 2h, filtered and dried to obtain amino-modified boron nitride;

[0056] S13. The amino-modified boron nitride is dispersed in acetone and ultrasonically dispersed to obtain a boron nitride dispersion;

[0057] S14. Polytetrahydrofuran ether glycol and isophorone diisocyanate are mixed and reacted at a temperature of 95°C for 2h, then cooled to 80°C, dimethylol propionic acid and 1,4-butanediol are added and reacted for 2h, then cooled to 70°C, dibutyltin dilaurate is added dropwise and reacted for 3h to obtain a polyurethane prepolymer, then the boron nitride dispersion is added, reacted for 1.2h, and then cooled to room temperature to obtain a water-based polyurethane / boron nitride composite material, wherein the molar ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol, dimethylol propionic acid and 1,4-butanediol is 8:1.6:1.6:4.5, and the content of boron nitride in the polyurethane prepolymer is 15wt%.

[0058] Example 4

[0059] The preparation method of the porous titanium dioxide loaded with copper ions or zinc ions comprises the following steps:

[0060] S21. Tetrabutyl titanate is added to ethanol, stirred and dispersed uniformly, then water is added, stirring is continued until the tetrabutyl titanate is completely hydrolyzed, then ammonium bicarbonate is added to the hydrolysis solution, the mass / volume ratio of tetrabutyl titanate, ethanol, water and sodium bicarbonate is 3mL:10mL:50mL:1g, reaction is carried out at 190°C for 40h, and finally the nano-porous titanium dioxide powder is obtained by washing and drying;

[0061] S22. Copper sulfate or zinc sulfate is added to a hydroxypropyl methyl cellulose aqueous solution with a concentration of 0.5wt%, stirring and dispersing uniformly to obtain a mixed solution, the concentration of copper sulfate or zinc sulfate in the mixed solution is 3wt%;

[0062] S23. Nano-porous titanium dioxide is added to the mixed solution in step S22, ultrasonically dispersed, then filtered and dried to obtain porous titanium dioxide loaded with copper ions or zinc ions.

[0063] Example 5

[0064] A method for preparing a porous titanium dioxide loaded with copper ions or zinc ions comprises the following steps:

[0065] S21. Tetrabutyl titanate is added to ethanol, and after stirring and uniformly dispersing, water is added. Stirring is continued until the tetrabutyl titanate is completely hydrolyzed. Then, ammonium bicarbonate is added to the hydrolysis solution. The mass-volume ratio of the tetrabutyl titanate, ethanol, water, and sodium bicarbonate is 2 mL: 20 mL: 100 mL: 1.8 g. Reaction is carried out at 170°C for 50 h. Finally, the porous titanium dioxide nanopowder is obtained after washing and drying;

[0066] S22. Copper sulfate or zinc sulfate is added to a hydroxypropyl methyl cellulose aqueous solution with a concentration of 1 wt%. After stirring and uniformly dispersing, a mixed solution is obtained. The concentration of the copper sulfate or zinc sulfate in the mixed solution is 1.5 wt%.

[0067] S23. The porous titanium dioxide nanopowder is added to the mixed solution in step S22. After ultrasonic dispersion, the porous titanium dioxide loaded with copper ions or zinc ions is obtained after filtration and drying.

[0068] Example 6

[0069] A method for preparing a porous titanium dioxide loaded with copper ions or zinc ions comprises the following steps:

[0070] S21. Tetrabutyl titanate is added to ethanol, and after stirring and uniformly dispersing, water is added. Stirring is continued until the tetrabutyl titanate is completely hydrolyzed. Then, ammonium bicarbonate is added to the hydrolysis solution. The mass-volume ratio of the tetrabutyl titanate, ethanol, water, and sodium bicarbonate is 3 mL: 16 mL: 70 mL: 1.5 g. Reaction is carried out at 180°C for 45 h. Finally, the porous titanium dioxide nanopowder is obtained after washing and drying;

[0071] S22. Copper sulfate or zinc sulfate is added to a hydroxypropyl methyl cellulose aqueous solution with a concentration of 0.7 wt%. After stirring and uniformly dispersing, a mixed solution is obtained. The concentration of the copper sulfate or zinc sulfate in the mixed solution is 2.2 wt%.

[0072] S23. The porous titanium dioxide nanopowder is added to the mixed solution in step S22. After ultrasonic dispersion, the porous titanium dioxide loaded with copper ions or zinc ions is obtained after filtration and drying.

[0073] Example 7

[0074] A wear-resistant light-cured polyurethane coating, the polyurethane coating is a two-component polyurethane coating, the two-component polyurethane coating comprises component A and component B, wherein component A is composed of: water-based polyurethane acrylate, water-based polyurethane / boron nitride composite prepared in Example 1, photoinitiator, silicone defoamer, dispersant DIS-900, sodium lignosulfonate, water; the component B is composed of: porous titanium dioxide loaded with copper ions or zinc ions prepared in Example 4 and ethanol;

[0075] The preparation method of the water-based polyurethane acrylate is: after melting the polyester diol, adding isophorone diisocyanate for reaction, then adding dimethylol propionic acid and hydroxyethyl acrylate in turn, finally adding N, N-dimethyl ethanolamine for neutralization and salt reaction, and finally adding water for hydration reaction to obtain a water-based polyurethane acrylate prepolymer, wherein the ratio of n(-NCO) to n(-OH) is 1.6;

[0076] The application method of the above-mentioned wear-resistant light-cured polyurethane coating comprises the following steps:

[0077] S1. The water-based polyurethane acrylate in component A is added to water according to the following weight parts, and then the water-based polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzoin, silicone defoamer and dispersant DIS-900 are added in turn, mixed and stirred uniformly to obtain a coating X,

[0078] In the component A: the water-based polyurethane acrylate is 120 parts, the water-based polyurethane / boron nitride composite is 40 parts, the 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzoin is 2 parts, the silicone defoamer is 0.3 parts, the dispersant DIS-900 is 0.2 parts, and the water is 40 parts;

[0079] S2. The sodium lignosulfonate in component A is added to water according to the weight parts, and then the water-based polyurethane acrylate, the water-based polyurethane / boron nitride composite, the 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzoin, the silicone defoamer and the dispersant DIS-900 are added in turn after stirring and mixing uniformly to obtain a coating Y;

[0080] In the component A: the water-based polyurethane acrylate is 120 parts, the water-based polyurethane / boron nitride composite is 60 parts, the 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzoin is 2 parts, the silicone defoamer is 0.3 parts, the dispersant DIS-900 is 0.2 parts, the sodium lignosulfonate is 10 parts, and the water is 40 parts;

[0081] S3. The copper ion-loaded or zinc ion-loaded porous titanium dioxide is added to ethanol and uniformly dispersed by ultrasonic, to obtain a coating Z, wherein the copper ion-loaded or zinc ion-loaded porous titanium dioxide is 5 parts, and the ethanol is 90 parts;

[0082] S4. The coating X is coated on a substrate, with a coating amount of 80 g / m 2 After ultraviolet irradiation and curing, the coating Y is coated on the substrate, with a coating amount of 55 g / m 2 Finally, the coating Z is coated, with a coating amount of 20 g / m 2 After ultraviolet irradiation and curing again, a wear-resistant coating is obtained.

[0083] Example 8

[0084] A wear-resistant photocuring polyurethane coating, which is a two-component polyurethane coating, comprising component A and component B, wherein the component A is composed of: water-based polyurethane acrylate, water-based polyurethane / boron nitride composite prepared in Example 2, photoinitiator, silicone defoaming agent, dispersant DIS-900, sodium lignosulfonate, and water; and the component B is composed of: copper ion-loaded or zinc ion-loaded porous titanium dioxide prepared in Example 5 and ethanol;

[0085] The preparation method of the water-based polyurethane acrylate is: after melting the polyester diol, adding isophorone diisocyanate for reaction, then adding dimethylol propionic acid and hydroxyethyl acrylate in sequence, finally adding N, N-dimethyl ethanolamine for neutralization and salt reaction, and finally adding water for hydration reaction, to obtain a water-based polyurethane acrylate prepolymer, wherein the ratio of n(-NCO) and n(-OH) is 1.55;

[0086] The application method of the above wear-resistant photocuring polyurethane coating, comprising the following steps:

[0087] S1. The water-based polyurethane acrylate in component A is added to water according to the following weight parts, and then the water-based polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzoin, silicone defoaming agent, and dispersant DIS-900 are added in sequence, mixed and stirred uniformly, to obtain a coating X,

[0088] In the component A: the water-based polyurethane acrylate is 180 parts, the water-based polyurethane / boron nitride composite is 40 parts, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzoin is 5 parts, silicone defoaming agent is 1.5 parts, dispersant DIS-900 is 1.5 parts, and water is 70 parts;

[0089] S2. Add sodium lignosulfonate from component A to water according to the weight parts, stir and mix evenly, then add waterborne polyurethane acrylate, waterborne polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methylphenylacetone, organosilicon defoamer and dispersant DIS-900 in sequence, mix and stir evenly to obtain coating Y;

[0090] Component A comprises: 180 parts of waterborne polyurethane acrylate, 60 parts of waterborne polyurethane / boron nitride composite, 5 parts of 2-hydroxy-4'(2-hydroxyethoxy)-2-methylphenylacetone, 1.5 parts of silicone defoamer, 1.5 parts of dispersant DIS-900, 20 parts of sodium lignosulfonate, and 70 parts of water.

[0091] S3. Add porous titanium dioxide loaded with copper ions or zinc ions to ethanol and ultrasonically disperse it evenly to obtain coating Z, wherein the porous titanium dioxide loaded with copper ions or zinc ions is 10 parts and the ethanol is 100 parts.

[0092] S4. Apply coating X to the substrate at a coating weight of 65 g / m². 2 After UV curing, coating Y is then applied to the substrate at a coating weight of 70 g / m². 2 Finally, apply paint Z at a rate of 20g / m². 2 After being cured by ultraviolet irradiation again, a wear-resistant coating is obtained.

[0093] Example 9

[0094] A wear-resistant, light-curable polyurethane coating, wherein the polyurethane coating is a two-component polyurethane coating comprising component A and component B, wherein component A is composed of the following components: waterborne polyurethane acrylate, waterborne polyurethane / boron nitride composite prepared in Example 3, photoinitiator, silicone defoamer, dispersant DIS-900, sodium lignosulfonate, and water; and component B is composed of the following components: porous titanium dioxide loaded with copper ions or zinc ions prepared in Example 6 and ethanol.

[0095] The method for preparing the waterborne polyurethane acrylate is as follows: after melting the polyester diol, isophorone diisocyanate is added and reacted, then dimethylolpropionic acid and hydroxyethyl acrylate are added sequentially, and finally N,N-dimethylethanolamine is added to neutralize and form a salt. Finally, water is added for hydration to obtain the waterborne polyurethane acrylate prepolymer, wherein the ratio of n(-NCO) to n(-OH) is 1.5.

[0096] The application method of the above-mentioned wear-resistant UV-cured polyurethane coating includes the following steps:

[0097] S1. The waterborne polyurethane acrylate in component A is added to water according to the following weight parts, and then the waterborne polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone, silicone antifoaming agent and dispersant DIS-900 are sequentially added, mixed and stirred uniformly to obtain coating X,

[0098] In the component A: the waterborne polyurethane acrylate is 140 parts, the waterborne polyurethane / boron nitride composite is 45 parts, 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone is 3 parts, silicone antifoaming agent is 0.5 parts, dispersant DIS-900 is 0.5 parts, and water is 50 parts;

[0099] S2. The sodium lignosulfonate in component A is added to water according to the weight parts, and after stirring and mixing uniformly, the waterborne polyurethane acrylate, the waterborne polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone, silicone antifoaming agent and dispersant DIS-900 are sequentially added, mixed and stirred uniformly to obtain coating Y;

[0100] In the component A: the waterborne polyurethane acrylate is 140 parts, the waterborne polyurethane / boron nitride composite is 55 parts, 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone is 3 parts, silicone antifoaming agent is 0.5 parts, dispersant DIS-900 is 0.5 parts, sodium lignosulfonate is 10 parts, and water is 50 parts;

[0101] S3. The porous titanium dioxide loaded with copper ions or zinc ions is added to ethanol and ultrasonically dispersed uniformly to obtain coating Z, wherein the porous titanium dioxide loaded with copper ions or zinc ions is 8 parts and ethanol is 90 parts;

[0102] S4. Coating X is coated on the substrate at a coating amount of 70 g / m 2 , and after ultraviolet irradiation curing, coating Y is coated on the substrate at a coating amount of 65 g / m 2 , and finally coating Z is coated, at a coating amount of 20 g / m 2 , and after ultraviolet irradiation curing again, a wear-resistant coating is obtained.

[0103] Example 10

[0104] A wear-resistant photocuring polyurethane coating, which is a two-component polyurethane coating, comprising component A and component B, wherein component A is composed of: waterborne polyurethane acrylate, waterborne polyurethane / boron nitride composite prepared in Example 3, photoinitiator, silicone antifoaming agent, dispersant DIS-900, sodium lignosulfonate, and water; and component B is composed of: porous titanium dioxide loaded with copper ions or zinc ions prepared in Example 6 and ethanol;

[0105] The preparation method of the water-based polyurethane acrylate is: after melting the polyester diol, adding isophorone diisocyanate for reaction, then adding dimethylol propionic acid and hydroxyethyl acrylate in turn, finally adding N, N-dimethyl ethanolamine for neutralization and salt reaction, and finally adding water for hydration reaction to obtain the water-based polyurethane acrylate prepolymer, wherein the ratio of n(-NCO) to n(-OH) is 1.5;

[0106] The application method of the above wear-resistant photocurable polyurethane coating comprises the following steps:

[0107] S1. The water-based polyurethane acrylate in component A is added to water in the following weight parts, and then the water-based polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzophenone, silicone defoaming agent and dispersant DIS-900 are added in turn, mixed and stirred uniformly to obtain a coating X,

[0108] In the component A: the water-based polyurethane acrylate is 160 parts, the water-based polyurethane / boron nitride composite is 45 parts, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzophenone is 4 parts, silicone defoaming agent is 1.2 parts, dispersant DIS-900 is 1.2 parts, and water is 60 parts;

[0109] S2. The sodium lignosulfonate in component A is added to water according to the weight parts, and after stirring and mixing uniformly, the water-based polyurethane acrylate, the water-based polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzophenone, silicone defoaming agent and dispersant DIS-900 are added in turn, mixed and stirred uniformly to obtain a coating Y;

[0110] In the component A: the water-based polyurethane acrylate is 160 parts, the water-based polyurethane / boron nitride composite is 55 parts, 2-hydroxy-4'(2-hydroxyethoxy)-2-methyl benzophenone is 4 parts, silicone defoaming agent is 1.2 parts, dispersant DIS-900 is 1.2 parts, sodium lignosulfonate is 20 parts, and water is 60 parts;

[0111] S3. The porous titanium dioxide loaded with copper ions or zinc ions is added to ethanol for ultrasonic dispersion to obtain a coating Z, wherein the porous titanium dioxide loaded with copper ions or zinc ions is 10 parts and ethanol is 100 parts;

[0112] S4. The coating X is coated on the substrate with a coating amount of 75 g / m 2 , and after ultraviolet irradiation curing, the coating Y is coated on the substrate with a coating amount of 60 g / m 2 , and finally the coating Z is coated, with a coating amount of 20 g / m 2 , and after ultraviolet irradiation curing again, a wear-resistant coating is obtained.

[0113] Comparative Example 1

[0114] The difference between Comparative Example 1 and Example 10 is that the content of waterborne polyurethane / boron nitride in step S1 is higher than that in step S2, specifically:

[0115] The application method of the abrasion-resistant photocurable polyurethane coating includes the following steps:

[0116] S1. The waterborne polyurethane acrylate in component A is added to water according to the following weight parts, and then the waterborne polyurethane / boron nitride composite, 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone, silicone defoaming agent and dispersant DIS-900 are added in sequence, mixed and stirred uniformly to obtain a coating X,

[0117] In the component A: the waterborne polyurethane acrylate is 160 parts, the waterborne polyurethane / boron nitride composite is 60 parts, the 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone is 4 parts, the silicone defoaming agent is 1.2 parts, the dispersant DIS-900 is 1.2 parts, and the water is 60 parts;

[0118] S2. The sodium lignosulfonate in component A is added to water according to the weight parts, and after stirring and mixing uniformly, the waterborne polyurethane acrylate, the waterborne polyurethane / boron nitride composite, the 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone, the silicone defoaming agent and the dispersant DIS-900 are added in sequence, mixed and stirred uniformly to obtain a coating Y;

[0119] In the component A: the waterborne polyurethane acrylate is 160 parts, the waterborne polyurethane / boron nitride composite is 30 parts, the 2-hydroxy-4'(2-hydroxyethoxy)-2-methylbenzophenone is 4 parts, the silicone defoaming agent is 1.2 parts, the dispersant DIS-900 is 1.2 parts, the sodium lignosulfonate is 20 parts, and the water is 60 parts;

[0120] S3. The porous titanium dioxide loaded with copper ions or zinc ions is added to ethanol and ultrasonically dispersed uniformly to obtain a coating Z, wherein the porous titanium dioxide loaded with copper ions or zinc ions is 10 parts and the ethanol is 100 parts;

[0121] S4. The coating X is coated on the substrate at a coating amount of 75 g / m 2 , and after ultraviolet irradiation and curing, the coating Y is coated on the substrate at a coating amount of 60 g / m 2 , and finally the coating Z is coated, at a coating amount of 20 g / m 2 , and then ultraviolet irradiation and curing are performed again to obtain an abrasion-resistant coating.

[0122] Comparative Example 2

[0123] Comparative Example 2 differs from Example 10 in that no sodium lignosulfonate is added in step S2.

[0124] Comparative Example 3

[0125] Comparative Example 3 differs from Example 10 in that no coating Z is applied.

[0126] Comparative Example 4

[0127] Comparative Example 4 differs from Example 10 in that coatings Y and Z are applied, and no coating X is applied.

[0128] Comparative Example 5

[0129] Comparative Example 5 differs from Example 10 in that no flaky BN is used, and spherical boron nitride is used.

[0130] According to the above examples and comparative examples, and in combination with the application method, the abrasion-resistant photocured polyurethane coating is obtained, and the conventional performance (substrate adhesion (crosshatch), coating film hardness), abrasion resistance, and Vickers hardness tests are performed.

[0131] The conventional performance of the coating is tested using conventional coating detection methods;

[0132] The Vickers hardness of the coating is tested using a hardness tester, with an applied load of 0.0981 N, and the hardness value (Hv) is measured;

[0133] The abrasion resistance of the coating is tested using a plane abrasion tester, with the following experimental conditions: an applied load of 294 N, 600# abrasive paper is used, 4800 times of plane abrasion, with an abrasion mark of 30 mm x 12 mm, and the wear rate is calculated.

[0134] Substrate adhesion (Gardner) Vickers hardness Hv (MPa) Wear rate (%) Example 7 5B 122.1 0.52 Example 8 5B 118.9 0.48 Example 9 5B 116.7 0.55 Example 10 5B 121.5 0.45 Comparative Example 1 4B 119.2 0.57 Comparative Example 2 4B 120.3 1.54 Comparative Example 3 5B 108.4 1.48 Comparative Example 4 4B 112.7 0.71 Comparative Example 5 5B 118.8 0.89

[0135] Obviously, the above examples are merely examples for the purpose of clarity, and are not limitations on the embodiments. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. All embodiments do not need to be exhaustively listed here. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A method of applying a wear resistant photocured polyurethane coating, characterized in that, Includes the following steps: S1. Add the waterborne polyurethane acrylate from component A to water according to the weight parts, then add the waterborne polyurethane / boron nitride composite, photoinitiator and additives in sequence, mix and stir evenly to obtain coating X; S2. Add sodium lignosulfonate from component A to water according to the weight parts, stir and mix evenly, then add waterborne polyurethane acrylate, waterborne polyurethane / boron nitride composite, photoinitiator and additives in sequence, mix and stir evenly to obtain coating Y; S3. Porous titanium dioxide loaded with copper ions or zinc ions is added to ethanol and ultrasonically dispersed evenly to obtain coating Z; S4. A low content waterborne polyurethane / boron nitride composite coating is applied to the primer layer of the substrate, the low content filler coating has good adhesion to the substrate, a high content waterborne polyurethane / boron nitride composite coating is applied to the outer side of the low content waterborne polyurethane / boron nitride composite coating, through the design of the gradient structure coating, coating X is applied to the substrate, the coating amount is 45-125 g / m 2 , after ultraviolet irradiation curing, coating Y is applied to the substrate, the coating amount is 35-85 g / m 2 , and finally coating Z is applied, and the abrasion-resistant coating is obtained after ultraviolet irradiation curing again; The method for preparing the aqueous polyurethane / boron nitride composite is as follows: S11. Boric acid and urea are mixed in water at a mass ratio of 1:10-14, and heated and stirred in a water bath at 85-90℃ to obtain a BN precursor. The BN precursor is then reacted at high temperature to obtain plate-like boron nitride. S12. Mix flake boron nitride, urea and water, and ball mill at a speed of 500-800 r / min for 15-20 h. Dilute the ball-milled mixture and sonicate it for 1-2 h. Filter and dry to obtain amino-modified boron nitride. S13. Disperse amino-modified boron nitride in acetone and ultrasonically disperse until uniform to obtain a boron nitride dispersion; S14. Polytetrahydrofuran ether diol and isophorone diisocyanate were mixed and reacted at a temperature of 90-95℃ for 1.5-2.5h. After cooling to 80℃, dimethylolpropionic acid and 1,4-butanediol were added and reacted for 2h. After cooling to 70℃ again, dibutyltin dilaurate was added dropwise and reacted for 3h to obtain a polyurethane prepolymer. Then, boron nitride dispersion was added and reacted for 1-1.5h. After cooling to room temperature, an aqueous polyurethane / boron nitride composite material was obtained.

2. The method of applying a wear resistant photocured polyurethane coating according to claim 1, characterized in that: The method for preparing porous titanium dioxide loaded with copper ions or zinc ions includes the following steps: S21. Add tetrabutyl titanate to ethanol, stir to disperse evenly, then add water and continue stirring until tetrabutyl titanate is completely hydrolyzed. Then add ammonium bicarbonate to the hydrolysis solution. The mass-volume ratio of tetrabutyl titanate, ethanol, water and ammonium bicarbonate is 2-4 mL: 10-20 mL: 50-100 mL: 1-2 g. React at 170-190℃ for 40-50 h. Finally, wash and dry to obtain nanoporous titanium dioxide powder. S22. Add copper sulfate or zinc sulfate to a 0.5-1 wt% aqueous solution of hydroxypropyl methylcellulose, stir and disperse evenly to obtain a mixed solution, wherein the concentration of copper sulfate or zinc sulfate in the mixed solution is 1-3 wt%. S23. Add nanoporous titanium dioxide to the mixed solution in step S22, disperse it by ultrasonication, filter and dry to obtain porous titanium dioxide loaded with copper ions or zinc ions.

3. The method of applying a wear resistant photocured polyurethane coating according to claim 1, characterized in that: The substrate includes: wood panels and stone-plastic composite flooring; Wherein, the wood board includes: a: solid wood floor; b: any other core material, base material but the surface with solid wood floor as the surface layer product; stone plastic composite floor is: the use of stone powder constitutes a high density, high fiber network structure of solid base, surface covered with wear-resistant polyurethane coating.

4. The method of applying a wear resistant photocured polyurethane coating according to claim 1, characterized in that: The parameters of the high-temperature reaction in the step S11 are: increasing the temperature to 500-550 DEG C at 3 DEG C / min and keeping for 3h.

5. The method of applying a wear resistant photocured polyurethane coating according to claim 1, characterized in that: The molar ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol, dimethylol propionic acid and 1,4-butanediol in the step S14 is 5-10:1-2:1-2:2.6-5.

5.

6. The method of applying a wear resistant photocured polyurethane coating according to claim 1, characterized in that: The content of boron nitride in the polyurethane prepolymer in the step S14 is 12-16wt%. The parameters of the high-temperature reaction in the step S11 are: increasing the temperature to 500-550 DEG C at 3 DEG C / min and keeping for 3h.