Method for making water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect

Abstract

This invention relates to the field of varnishes, specifically to a method for producing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect. This method addresses the shortcomings of existing water-based varnishes, such as insufficient gloss, weak gloss retention, low fullness, and poor hardness, which limit their application in high-performance fields. Through a rational formulation design, this method produces a varnish with excellent fullness, making the coating appear fuller and more three-dimensional, and possessing extremely high gloss, achieving a superior mirror-like effect. This significantly improves the aesthetics of sprayed or printed products. Furthermore, the resulting coating has high strength and high hardness, enabling it to resist scratches and abrasion, extending the product's lifespan. It also effectively resists corrosion from harsh environments such as acids, alkalis, and humidity, maintaining its high gloss and mirror-like effect for a long time.

Description

Technical Field

[0001] This invention relates to the field of varnishes, and more specifically to a method for producing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect. Background Technology

[0002] As a transparent protective varnish, varnish produces a glossy film after it forms, which not only enhances the gloss and hardness of objects, but also effectively protects the surface of objects from damage caused by the external environment.

[0003] Traditional solvent-based varnishes can significantly improve the aesthetics of products, but they contain a large amount of volatile organic compounds, which are harmful to human health, and are gradually being replaced by water-based varnishes. However, current water-based varnishes generally have shortcomings such as insufficient gloss, weak gloss retention, low fullness, and poor hardness, which limit their application potential in high-performance fields.

[0004] Therefore, it is of great significance to develop a method for producing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect. Summary of the Invention

[0005] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide a method for manufacturing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect. This method solves the problems that existing water-based varnishes usually have shortcomings such as insufficient gloss, weak gloss retention, low fullness, and poor hardness, which limit their application potential in high-performance fields.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] The method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect includes the following steps:

[0008] Step 1: Weigh out the following components by weight: 40-50 parts of silicone-modified emulsion, 0.3-1.1 parts of coated modified carbon nanotubes, 4-12 parts of fluorine-modified nano-alumina, 1-3 parts of wetting and dispersing agent, 0.2-0.6 parts of leveling agent, 1-3 parts of film-forming aid, 0.1-0.3 parts of defoamer, 0.2-0.4 parts of antioxidant, 0.3-0.5 parts of thickener, 3-7 parts of anhydrous ethanol, and 20-22 parts of deionized water. Set aside for later use.

[0009] Step 2: Add the silicone-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano alumina, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol, and deionized water to a mixer and mix for 20-30 minutes at a temperature of 25-30℃ and a stirring speed of 800-1000 r / min to obtain a premix.

[0010] Step 3: Add the premixed material to the grinder and grind it for 3-4 hours at a speed of 1800-2000 r / min. Then pass it through a 200-300 mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0011] As a further aspect of the present invention: the wetting and dispersing agent is BYK-193 wetting and dispersing agent.

[0012] As a further aspect of the present invention: the leveling agent is ZY-130 leveling agent.

[0013] As a further aspect of the present invention, the film-forming aid is a dodecyl alcohol ester.

[0014] As a further aspect of the present invention: the defoamer is BYK-024 defoamer.

[0015] As a further aspect of the present invention: the antioxidant is antioxidant 168.

[0016] As a further aspect of the present invention: the thickener is carrageenan.

[0017] As a further aspect of the present invention: the organosilicon-modified emulsion is prepared by the following steps:

[0018] Step a1: Add 1,1,3,3-tetramethyldisiloxane, allyl glycidyl ether, chloroplatinic acid and isopropanol to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection and stir at 25-30℃ and 200-300 r / min for 30-50 min. Then raise the temperature to 85-90℃ and continue stirring for 6-7 h. After the reaction is completed, cool the reaction product to room temperature and then remove the solvent by rotary evaporation to obtain terminal epoxy organosilicon.

[0019] Step a2: Add terminal epoxy organosilicon, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol and isopropanol to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Purge with nitrogen for protection. Stir and react for 30-50 min at a temperature of 25-30℃ and a stirring rate of 200-300 r / min. Then raise the temperature to 80-85℃ and continue stirring and reacting for 1-2 h. Then raise the temperature to 100-105℃ and continue stirring and reacting for 2-3 h. After the reaction is completed, cool the reaction product to room temperature and then remove the solvent by rotary evaporation to obtain terminal alkenyl organosilicon.

[0020] Step a3: Add butyl acrylate, styrene, acrylic acid, terminal alkenyl organosilicon, sodium dodecyl sulfate, and deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and constant pressure dropping funnel. Stir the reaction at 25-30℃ and a stirring rate of 200-300 r / min for 20-30 min. Then, raise the temperature to 85-90℃ and add ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 1-2 drops / s. After the addition is complete, continue stirring the reaction for 2-3 h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 7-8 with ammonia water to obtain the organosilicon modified emulsion.

[0021] As a further aspect of the present invention: the ratio of 1,1,3,3-tetramethyldisiloxane, allyl glycidyl ether, chloroplatinic acid and isopropanol in step a1 is 10 mmol: 20 mmol: 0.03-0.05 g: 40-50 mL.

[0022] As a further embodiment of the present invention: the ratio of the amount of terminal epoxy organosilicon, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol and isopropanol in step a2 is 10mmol:20mmol:0.8-1.0g:0.2-0.3g:60-70mL.

[0023] As a further aspect of the present invention: the ratio of the amounts of butyl acrylate, styrene, acrylic acid, terminal alkenyl organosilicon, sodium dodecyl sulfate, deionized water and ammonium persulfate solution in step a3 is 40-45g: 40-45g: 3-5g: 1-11g: 1.2-1.8g: 60-70mL: 10-15mL.

[0024] As a further aspect of the present invention: the mass fraction of the ammonium persulfate solution in step a3 is 2-3%; the mass fraction of the ammonia water is 20-22%.

[0025] As a further aspect of the present invention: the coated and modified carbon nanotubes are prepared by the following steps:

[0026] Carbon nanotubes and Tris-HCl buffer solution were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 25-30℃ and 200-300 r / min for 30-50 min. Dopamine hydrochloride was then added, and the mixture was stirred for another 1-2 h. The temperature was then raised to 40-45℃, and the mixture was stirred for another 4-5 h. After the reaction was completed, the product was cooled to room temperature and centrifuged. The precipitate was washed 2-3 times with anhydrous ethanol and distilled water, and then placed in a vacuum drying oven and dried at 70-75℃ for 1-2 h to obtain the coated modified carbon nanotubes.

[0027] As a further aspect of the present invention, the ratio of the carbon nanotubes, Tris-HCl buffer solution and dopamine hydrochloride is 1g:40-50mL:0.3-0.9g.

[0028] As a further aspect of the present invention: the outer diameter of the carbon nanotube is 15-25 nm and the tube length is 5-15 μm; the molar concentration of the Tris-HCl buffer solution is 10 mmol / L and the pH value is 8.5.

[0029] As a further aspect of the present invention: the fluorine-modified nano-alumina is prepared by the following steps:

[0030] Nano-alumina, deionized water, and anhydrous ethanol were added to a three-necked flask equipped with a stirrer and a thermometer. The mixture was ultrasonically dispersed at a frequency of 30-40 kHz for 20-30 min. The pH was then adjusted to 5-6 with acetic acid. 1H,1H,2H,2H-perfluorooctyltriethoxysilane was added, and the mixture was stirred at 25-30℃ and a stirring rate of 200-300 r / min for 10-15 min. The temperature was then raised to 80-85℃, and the reaction was continued with stirring for 7-8 h. After the reaction was completed, the product was cooled to room temperature, centrifuged, and the precipitate was washed 2-3 times with anhydrous acetone. The precipitate was then placed in a vacuum drying oven and dried at 60-65℃ for 2-3 h to obtain fluorine-modified nano-alumina.

[0031] As a further aspect of the present invention: the ratio of the amount of nano-alumina, deionized water, anhydrous ethanol and 1H,1H,2H,2H-perfluorooctyltriethoxysilane is 5g:8-10mL:80-85mL:3-9g.

[0032] As a further aspect of the present invention, the particle size of the nano-alumina is 20-40 nm.

[0033] The beneficial effects of this invention are:

[0034] The present invention discloses a method for preparing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect. This involves adding an organosilicon-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano-alumina, a wetting and dispersing agent, a leveling agent, a film-forming aid, a defoamer, an antioxidant, a thickener, anhydrous ethanol, and deionized water to a mixer and stirring to obtain a premix. The premix is ​​then ground in a grinder and sieved to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect. This method, through a rational formulation design, results in a varnish with excellent fullness, making the coating appear fuller and more three-dimensional. It boasts extremely high gloss, achieving an excellent mirror-like effect and significantly enhancing the aesthetics of sprayed or printed products. Furthermore, the resulting coating possesses high strength and hardness, resisting scratches and abrasions, extending product lifespan. It also effectively resists corrosion from harsh environments such as acids, alkalis, and humidity, maintaining its long-lasting high gloss and mirror-like finish. This varnish is suitable for surface treatment of various printed packaging materials, metal substrates, and plastic products, such as paper boxes, cartons, metal containers, and plastic bottles. Through spraying or printing processes, it can significantly improve the aesthetics and durability of products, meeting market demands for high-quality surface treatment.

[0035] In the preparation of the varnish, a silicone-modified emulsion was first prepared. Firstly, 1,1,3,3-tetramethyldisiloxane and allyl glycidyl ether were reacted. The Si-H group on 1,1,3,3-tetramethyldisiloxane and the alkenyl group on allyl glycidyl ether underwent a hydrosilylation reaction, simultaneously introducing epoxy groups to obtain terminal epoxy silicone. Then, the terminal epoxy silicone was reacted with acrylic acid. The epoxy groups on the terminal epoxy silicone reacted with the carboxyl groups on the acrylic acid, simultaneously introducing alkenyl groups to obtain terminal alkenyl silicone. Finally, butyl acrylate, styrene, acrylic acid, and the terminal alkenyl silicone were used as monomers for polymerization to form a polymer, resulting in the silicone-modified emulsion. This silicone-modified emulsion exhibits excellent film-forming properties. During the film-forming process, silicone segments migrate to the film surface, reducing the surface energy and forming a smooth, flat surface, reducing light scattering, thereby improving gloss and producing a strong mirror effect. Simultaneously, the silicone segments can enhance the coating's resistance to corrosive media, preventing coating damage.

[0036] In the preparation of the varnish, a coated modified carbon nanotube and a fluorine-modified nano-alumina were also prepared. First, dopamine hydrochloride was used as a polymer monomer to form polyaniline on the outside of the carbon nanotubes, thus encapsulating the carbon nanotubes and obtaining coated modified carbon nanotubes. Then, the nano-alumina was treated with 1H,1H,2H,2H-perfluorooctyltriethoxysilane. After hydrolysis of 1H,1H,2H,2H-perfluorooctyltriethoxysilane, a large number of fluorine atoms were grafted onto the surface of the nano-alumina particles using silanol groups, resulting in fluorine-modified nano-alumina. Carbon nanotubes possess excellent mechanical properties and reinforcing effects; adding them to the varnish significantly improves the hardness of the coating, and the polyaniline encapsulation further enhances their properties. The addition of fluorine-modified carbon nanotubes significantly improves the dispersibility of carbon nanotubes, allowing them to be uniformly dispersed in the coating. Nano-alumina has high whiteness and gloss, and its addition to the varnish can enhance the hardness and wear resistance of the coating. Furthermore, the introduction of fluorine atoms can further reduce the surface energy of the coating, further enhancing its gloss and mirror effect. It can also improve the coating's resistance to scratches, wear, and corrosive media, preventing coating damage. Therefore, when coated modified carbon nanotubes and fluorine-modified nano-alumina are added to the varnish at the same time, they can fill the tiny depressions and unevenness on the coating surface, making the coating look smoother and fuller, giving it a more textured appearance, and significantly improving the coating's gloss, mirror effect, and durability. Detailed Implementation

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0038] Example 1:

[0039] This embodiment describes a method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0040] Step S1: 10 mmol of 1,1,3,3-tetramethyldisiloxane, 20 mmol of allyl glycidyl ether, 0.03 g of chloroplatinic acid and 40 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 200 r / min for 30 min. Then the temperature was raised to 85 °C and the mixture was stirred for 6 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal epoxy organosilicon.

[0041] Step S2: 10 mmol of terminal epoxy organosilicon, 20 mmol of acrylic acid, 0.8 g of tetrabutylammonium bromide, 0.2 g of 4-methoxyphenol and 60 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 25 °C and 200 r / min for 30 min. Then the temperature was raised to 80 °C and the mixture was stirred for 1 h. After that, the temperature was raised to 100 °C and the mixture was stirred for 2 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal alkenyl organosilicon.

[0042] Step S3: Add 40g butyl acrylate, 40g styrene, 3g acrylic acid, 1g terminal alkenyl organosilicon, 1.2g sodium dodecyl sulfate and 60mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Stir the reaction at 25℃ and 200r / min for 20min. Then, raise the temperature to 85℃ and add 10mL of 2% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 1 drop / s. After the addition is complete, continue stirring for 2h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 7 with 20% ammonia water to obtain organosilicon modified emulsion.

[0043] Step S4: Add 1g of carbon nanotubes and 40mL of Tris-HCl buffer solution with a molar concentration of 10mmol / L and a pH of 8.5 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 25℃ and a stirring rate of 200r / min for 30min. Then add 0.3g of dopamine hydrochloride and continue stirring for 1h. Then raise the temperature to 40℃ and continue stirring for 4h. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate twice with anhydrous ethanol and distilled water, and then place it in a vacuum drying oven and dry at 70℃ for 1h to obtain coated modified carbon nanotubes.

[0044] Step S5: Add 5g of nano-alumina, 8mL of deionized water and 80mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and a thermometer. Disperse the mixture ultrasonically at a frequency of 30kHz for 20min. Then adjust the pH to 5 with acetic acid. Add 3g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir at 25℃ and a stirring rate of 200r / min for 10min. Then raise the temperature to 80℃ and continue stirring for 7h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate twice with anhydrous acetone, and then place it in a vacuum drying oven and dry at 60℃ for 2h to obtain fluorine-modified nano-alumina.

[0045] Step S6: Weigh out 40 parts by weight of silicone-modified emulsion, 0.3 parts by weight of coated modified carbon nanotubes, 4 parts by weight of fluorine-modified nano-alumina, 1 part by weight of wetting and dispersing agent, 0.2 parts by weight of leveling agent, 1 part by weight of film-forming aid, 0.1 parts by weight of defoamer, 0.2 parts by weight of antioxidant, 0.3 parts by weight of thickener, 3 parts by weight of anhydrous ethanol, and 20 parts by weight of deionized water, and set aside for later use; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024 defoamer; the antioxidant is antioxidant 168; and the thickener is carrageenan;

[0046] Step S7: Add the silicone-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano alumina, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and stir and mix for 20 minutes at a temperature of 25°C and a stirring speed of 800 r / min to obtain a premix.

[0047] Step S8: Add the premixed material to the grinder and grind it for 3 hours at a speed of 1800 r / min. Then pass it through a 200-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0048] Example 2:

[0049] This embodiment describes a method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0050] Step S1: 10 mmol of 1,1,3,3-tetramethyldisiloxane, 20 mmol of allyl glycidyl ether, 0.04 g of chloroplatinic acid and 45 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 28 °C and 250 r / min for 40 min. Then the temperature was raised to 88 °C and the mixture was stirred for 6.5 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal epoxy organosilicon.

[0051] Step S2: 10 mmol of terminal epoxy organosilicon, 20 mmol of acrylic acid, 0.9 g of tetrabutylammonium bromide, 0.25 g of 4-methoxyphenol, and 65 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the reaction was stirred at 28 °C and 250 r / min for 40 min. Then, the temperature was raised to 82 °C and the reaction was stirred for 1.5 h. After that, the temperature was raised to 102 °C and the reaction was stirred for 2.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain terminal alkenyl organosilicon.

[0052] Step S3: Add 42g butyl acrylate, 42g styrene, 4g acrylic acid, 6g terminal alkenyl organosilicon, 1.5g sodium dodecyl sulfate, and 65mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and constant pressure dropping funnel. Stir the mixture at 28℃ and a stirring rate of 250r / min for 25min. Then, while stirring, add 12mL of 2.5% ammonium persulfate solution dropwise to 88℃, controlling the dropping rate to 1 drop / s. After the addition is complete, continue stirring for 2.5h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 7.5 with 21% ammonia water to obtain the organosilicon modified emulsion.

[0053] Step S4: 1 g of carbon nanotubes and 45 mL of Tris-HCl buffer solution with a molar concentration of 10 mmol / L and a pH of 8.5 were added to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Nitrogen gas was introduced for protection, and the mixture was stirred at 28 °C and a stirring rate of 250 r / min for 40 min. Then, 0.6 g of dopamine hydrochloride was added and the mixture was stirred for another 1.5 h. The mixture was then heated to 42 °C and stirred for another 4.5 h. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed twice with anhydrous ethanol and distilled water, and then placed in a vacuum drying oven and dried at 72 °C for 1.5 h to obtain the coated modified carbon nanotubes.

[0054] Step S5: Add 5g of nano-alumina, 9mL of deionized water, and 82mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and a thermometer. Disperse the mixture ultrasonically at a frequency of 35kHz for 25min. Then adjust the pH to 5.5 with acetic acid. Add 6g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir at 28℃ and a stirring rate of 250r / min for 12min. Then raise the temperature to 82℃ and continue stirring for 7.5h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate twice with anhydrous acetone, and then place it in a vacuum drying oven and dry at 62℃ for 2.5h to obtain fluorine-modified nano-alumina.

[0055] Step S6: Weigh out 45 parts by weight of silicone-modified emulsion, 0.7 parts by weight of coated modified carbon nanotubes, 8 parts by weight of fluorine-modified nano-alumina, 2 parts by weight of wetting and dispersing agent, 0.4 parts by weight of leveling agent, 2 parts by weight of film-forming aid, 0.2 parts by weight of defoamer, 0.3 parts by weight of antioxidant, 0.4 parts by weight of thickener, 5 parts by weight of anhydrous ethanol, and 21 parts by weight of deionized water for later use; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024 defoamer; the antioxidant is antioxidant 168; and the thickener is carrageenan;

[0056] Step S7: Add the silicone-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano alumina, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and stir and mix for 25 minutes at a temperature of 28°C and a stirring rate of 900 r / min to obtain a premix.

[0057] Step S8: Add the premixed material to the grinder and grind it for 3.5 hours at a speed of 1900 r / min. Then pass it through a 250 mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0058] Example 3:

[0059] This embodiment describes a method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0060] Step S1: 10 mmol of 1,1,3,3-tetramethyldisiloxane, 20 mmol of allyl glycidyl ether, 0.05 g of chloroplatinic acid and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 90 °C and the mixture was stirred for 7 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal epoxy organosilicon.

[0061] Step S2: 10 mmol of terminal epoxy organosilicon, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4-methoxyphenol and 70 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 85 °C and the mixture was stirred for 2 h. After that, the temperature was raised to 105 °C and the mixture was stirred for 3 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal alkenyl organosilicon.

[0062] Step S3: Add 45g butyl acrylate, 45g styrene, 5g acrylic acid, 11g terminal alkenyl organosilicon, 1.8g sodium dodecyl sulfate and 70mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Stir the reaction at 30℃ and 300r / min for 30min. Then, raise the temperature to 90℃ and add 15mL of 3% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 2 drops / s. After the addition is complete, continue stirring for 3h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 8 with 22% ammonia water to obtain organosilicon modified emulsion.

[0063] Step S4: Add 1g of carbon nanotubes and 50mL of Tris-HCl buffer solution with a molar concentration of 10mmol / L and a pH of 8.5 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and a stirring rate of 300r / min for 50min. Then add 0.9g of dopamine hydrochloride and continue stirring for 2h. Then raise the temperature to 45℃ and continue stirring for 5h. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate three times with anhydrous ethanol and distilled water, and then place it in a vacuum drying oven and dry at 75℃ for 2h to obtain coated modified carbon nanotubes.

[0064] Step S5: Add 5g of nano-alumina, 10mL of deionized water and 85mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and a thermometer. Disperse the mixture ultrasonically at a frequency of 40kHz for 30min. Then adjust the pH to 6 with acetic acid. Add 9g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir at 30℃ for 15min. Then raise the temperature to 85℃ and continue stirring for 8h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate three times with anhydrous acetone, and then place it in a vacuum drying oven and dry at 65℃ for 3h to obtain fluorine-modified nano-alumina.

[0065] Step S6: Weigh out 50 parts by weight of silicone-modified emulsion, 1.1 parts by weight of coated modified carbon nanotubes, 12 parts by weight of fluorine-modified nano-alumina, 3 parts by weight of wetting and dispersing agent, 0.6 parts by weight of leveling agent, 3 parts by weight of film-forming aid, 0.3 parts by weight of defoamer, 0.4 parts by weight of antioxidant, 0.5 parts by weight of thickener, 7 parts by weight of anhydrous ethanol, and 22 parts by weight of deionized water, and set aside for later use; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024 defoamer; the antioxidant is antioxidant 168; and the thickener is carrageenan;

[0066] Step S7: Add the silicone-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano alumina, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and stir and mix for 30 minutes at a temperature of 30℃ and a stirring speed of 1000r / min to obtain a premix.

[0067] Step S8: Add the premixed material to the grinder and grind it for 4 hours at a speed of 2000 r / min. Then pass it through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0068] Comparative Example 1:

[0069] This comparative example demonstrates the method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0070] Step S1: Add 45g butyl acrylate, 45g styrene, 5g acrylic acid, 1.8g sodium dodecyl sulfate and 70mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Stir the reaction at 30℃ and 300r / min for 30min. Then, while stirring at 90℃, add 15mL of 3% ammonium persulfate solution dropwise, controlling the dropping rate to 2 drops / s. After the addition is complete, continue stirring for 3h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 8 with 22% ammonia water to obtain the modified emulsion.

[0071] Step S2: Weigh out 50 parts by weight of the modified emulsion, 3 parts by weight of the wetting and dispersing agent, 0.6 parts by weight of the leveling agent, 3 parts by weight of the film-forming aid, 0.3 parts by weight of the defoamer, 0.4 parts by weight of the antioxidant, 0.5 parts by weight of the thickener, 7 parts by weight of the anhydrous ethanol, and 22 parts by weight of the deionized water, and set aside for later use; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024 defoamer; the antioxidant is antioxidant 168; and the thickener is carrageenan;

[0072] Step S3: Add the modified emulsion, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and mix for 30 minutes at a temperature of 30°C and a stirring speed of 1000 r / min to obtain a premix.

[0073] Step S4: Add the premixed material to the grinder and grind it for 4 hours at a speed of 2000 r / min. Then pass it through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0074] Comparative Example 2:

[0075] This comparative example demonstrates the method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0076] Step S1: 10 mmol of 1,1,3,3-tetramethyldisiloxane, 20 mmol of allyl glycidyl ether, 0.05 g of chloroplatinic acid and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 90 °C and the mixture was stirred for 7 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal epoxy organosilicon.

[0077] Step S2: 10 mmol of terminal epoxy organosilicon, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4-methoxyphenol and 70 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 85 °C and the mixture was stirred for 2 h. After that, the temperature was raised to 105 °C and the mixture was stirred for 3 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal alkenyl organosilicon.

[0078] Step S3: Add 45g butyl acrylate, 45g styrene, 5g acrylic acid, 11g terminal alkenyl organosilicon, 1.8g sodium dodecyl sulfate and 70mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Stir the reaction at 30℃ and 300r / min for 30min. Then, raise the temperature to 90℃ and add 15mL of 3% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 2 drops / s. After the addition is complete, continue stirring for 3h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 8 with 22% ammonia water to obtain organosilicon modified emulsion.

[0079] Step S4: Weigh out 50 parts by weight of the silicone-modified emulsion, 3 parts by weight of the wetting and dispersing agent, 0.6 parts by weight of the leveling agent, 3 parts by weight of the film-forming aid, 0.3 parts by weight of the defoamer, 0.4 parts by weight of the antioxidant, 0.5 parts by weight of the thickener, 7 parts by weight of the anhydrous ethanol, and 22 parts by weight of the deionized water. The wetting and dispersing agent is BYK-193; the leveling agent is ZY-130; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024; the antioxidant is antioxidant 168; and the thickener is carrageenan.

[0080] Step S5: Add the silicone-modified emulsion, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and mix for 30 minutes at a temperature of 30°C and a stirring speed of 1000 r / min to obtain a premix.

[0081] Step S6: Add the premixed material to the grinder and grind it for 4 hours at a speed of 2000 r / min. Then pass it through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0082] Comparative Example 3:

[0083] This comparative example demonstrates the method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0084] Step S1: 10 mmol of 1,1,3,3-tetramethyldisiloxane, 20 mmol of allyl glycidyl ether, 0.05 g of chloroplatinic acid and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 90 °C and the mixture was stirred for 7 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal epoxy organosilicon.

[0085] Step S2: 10 mmol of terminal epoxy organosilicon, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4-methoxyphenol and 70 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 85 °C and the mixture was stirred for 2 h. After that, the temperature was raised to 105 °C and the mixture was stirred for 3 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal alkenyl organosilicon.

[0086] Step S3: Add 45g butyl acrylate, 45g styrene, 5g acrylic acid, 11g terminal alkenyl organosilicon, 1.8g sodium dodecyl sulfate and 70mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Stir the reaction at 30℃ and 300r / min for 30min. Then, raise the temperature to 90℃ and add 15mL of 3% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 2 drops / s. After the addition is complete, continue stirring for 3h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 8 with 22% ammonia water to obtain organosilicon modified emulsion.

[0087] Step S4: Add 1g of carbon nanotubes and 50mL of Tris-HCl buffer solution with a molar concentration of 10mmol / L and a pH of 8.5 to a three-necked flask equipped with a stirrer, thermometer, and gas delivery tube. Purge with nitrogen for protection and stir at 30℃ and a stirring rate of 300r / min for 50min. Then add 0.9g of dopamine hydrochloride and continue stirring for 2h. Then raise the temperature to 45℃ and continue stirring for 5h. After the reaction is complete, cool the reaction product to room temperature and centrifuge. Wash the precipitate three times with anhydrous ethanol and distilled water, and then place it in a vacuum drying oven and dry at 75℃ for 2h to obtain coated modified carbon nanotubes.

[0088] Step S5: Weigh out 50 parts by weight of silicone-modified emulsion, 1.1 parts by weight of coated modified carbon nanotubes, 3 parts by weight of wetting and dispersing agent, 0.6 parts by weight of leveling agent, 3 parts by weight of film-forming aid, 0.3 parts by weight of defoamer, 0.4 parts by weight of antioxidant, 0.5 parts by weight of thickener, 7 parts by weight of anhydrous ethanol, and 22 parts by weight of deionized water for later use; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024 defoamer; the antioxidant is antioxidant 168; and the thickener is carrageenan.

[0089] Step S6: Add the silicone-modified emulsion, coated modified carbon nanotubes, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and stir and mix for 30 minutes at a temperature of 30°C and a stirring speed of 1000 r / min to obtain a premix.

[0090] Step S7: Add the premixed material to the grinder and grind it for 4 hours at a speed of 2000 r / min. Then pass it through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0091] Comparative Example 4:

[0092] This comparative example demonstrates the method for creating a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror-like effect, including the following steps:

[0093] Step S1: 10 mmol of 1,1,3,3-tetramethyldisiloxane, 20 mmol of allyl glycidyl ether, 0.05 g of chloroplatinic acid and 50 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 90 °C and the mixture was stirred for 7 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal epoxy organosilicon.

[0094] Step S2: 10 mmol of terminal epoxy organosilicon, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4-methoxyphenol and 70 mL of isopropanol were added to a three-necked flask equipped with a stirrer, thermometer and gas delivery tube. Nitrogen gas was introduced for protection. The mixture was stirred at 30 °C and 300 r / min for 50 min. Then the temperature was raised to 85 °C and the mixture was stirred for 2 h. After that, the temperature was raised to 105 °C and the mixture was stirred for 3 h. After the reaction was completed, the reaction product was cooled to room temperature and the solvent was removed by rotary evaporation to obtain terminal alkenyl organosilicon.

[0095] Step S3: Add 45g butyl acrylate, 45g styrene, 5g acrylic acid, 11g terminal alkenyl organosilicon, 1.8g sodium dodecyl sulfate and 70mL deionized water to a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel. Stir the reaction at 30℃ and 300r / min for 30min. Then, raise the temperature to 90℃ and add 15mL of 3% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 2 drops / s. After the addition is complete, continue stirring for 3h. After the reaction is complete, cool the reaction product to room temperature and then adjust the pH to 8 with 22% ammonia water to obtain organosilicon modified emulsion.

[0096] Step S4: Add 5g of nano-alumina, 10mL of deionized water and 85mL of anhydrous ethanol to a three-necked flask equipped with a stirrer and a thermometer. Disperse the mixture ultrasonically at a frequency of 40kHz for 30min. Then adjust the pH to 6 with acetic acid. Add 9g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir at 30℃ and a stirring rate of 300r / min for 15min. Then raise the temperature to 85℃ and continue stirring for 8h. After the reaction is complete, cool the reaction product to room temperature, centrifuge, wash the precipitate three times with anhydrous acetone, and then place it in a vacuum drying oven and dry at 65℃ for 3h to obtain fluorine-modified nano-alumina.

[0097] Step S5: Weigh out 50 parts by weight of silicone-modified emulsion, 12 parts by weight of fluorine-modified nano-alumina, 3 parts by weight of wetting and dispersing agent, 0.6 parts by weight of leveling agent, 3 parts by weight of film-forming aid, 0.3 parts by weight of defoamer, 0.4 parts by weight of antioxidant, 0.5 parts by weight of thickener, 7 parts by weight of anhydrous ethanol, and 22 parts by weight of deionized water for later use; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming aid is dodecyl alcohol ester; the defoamer is BYK-024 defoamer; the antioxidant is antioxidant 168; and the thickener is carrageenan.

[0098] Step S6: Add the silicone-modified emulsion, fluorine-modified nano-alumina, wetting and dispersing agent, leveling agent, film-forming aid, defoamer, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, and stir and mix for 30 minutes at a temperature of 30℃ and a stirring speed of 1000r / min to obtain a premix.

[0099] Step S7: Add the premixed material to the grinder and grind it for 4 hours at a speed of 2000 r / min. Then pass it through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0100] According to GB / T 1727-2021 standard, using a four-sided preparation apparatus (coating thickness 50 μm), the water-based high-gloss, high-fullness, and high-hardness varnishes with a mirror effect from Examples 1-3 and Comparative Examples 1-4 were evenly spread on the tinplate surface. After the surface dried, they were transferred to a high-temperature drying oven and dried at 80°C for 2 hours to form a coating. The gloss of the coating at a 60° angle was tested according to GB / T 9754-2007, and the pencil hardness of the coating was tested according to GB / T 6739-2022. The performance test results are shown in the table below:

[0101]

[0102] Referring to the data in the table above, and based on the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the water-based high-gloss, high-fullness, and high-hardness varnish of this application has high gloss and hardness, and can resist the erosion of corrosive media, thus maintaining good gloss retention and having excellent mirror effect.

[0103] Among them, water treatment involved immersing the sample in deionized water for 72 hours; acid treatment involved immersing the sample in a hydrochloric acid solution with a molar concentration of 1 mol / L for 72 hours; alkali treatment involved immersing the sample in a sodium hydroxide solution with a molar concentration of 1 mol / L for 72 hours; gloss retention rate = (gloss after treatment / gloss before treatment) × 100%.

[0104] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0105] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A method for producing a water-based high-gloss, high- shine, high-hardness gloss oil having a mirror effect, characterized by, It comprises the following steps: Step one: according to the weight part, the silicone modified emulsion 40-50 parts, the coated modified carbon nanotube 0.3-1.1 parts, the fluorine modified nano alumina 4-12 parts, the wet dispersing agent 1-3 parts, the leveling agent 0.2-0.6 parts, the film forming aid 1-3 parts, the defoaming agent 0.1-0.3 parts, the antioxidant 0.2-0.4 parts, the thickening agent 0.3-0.5 parts, the anhydrous ethanol 3-7 parts and the deionized water 20-22 parts are weighed, and are prepared for use; Step two: the silicone modified emulsion, the coated modified carbon nanotube, the fluorine modified nano alumina, the wet dispersing agent, the leveling agent, the film forming aid, the defoaming agent, the antioxidant, the thickening agent, the anhydrous ethanol and the deionized water are added to the mixing machine, and are stirred and mixed under the condition that the temperature is 25-30 DEG C and the stirring rate is 800-1000 r / min for 20-30 min, to obtain the premix; Step three: the premix is added to the grinder, and is ground under the condition that the rotating speed is 1800-2000 r / min for 3-4 h, and then is screened through the 200-300 mesh sieve, to obtain the water-based high light high fullness high hardness gloss oil with mirror effect; The wet dispersing agent is BYK-193 wet dispersing agent; The leveling agent is ZY-130 leveling agent; The film forming aid is dodecanol ester; The defoaming agent is BYK-024 defoaming agent; The antioxidant is antioxidant 168; The thickening agent is carrageenan; The silicone modified emulsion is prepared by the following steps: Step a1: 1, 1, 3, 3-tetramethyldisiloxane, allyl glycidyl ether, chloroplatinic acid and isopropyl alcohol are stirred and reacted, the reaction product is cooled after the reaction is completed, and then is rotary evaporated, to obtain the terminal epoxy silicone; Step a2: the terminal epoxy silicone, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol and isopropyl alcohol are stirred and reacted, the reaction product is cooled after the reaction is completed, and then is rotary evaporated, to obtain the terminal alkenyl silicone; Step a3: butyl acrylate, styrene, acrylic acid, terminal alkenyl silicone, sodium dodecyl sulfate and deionized water are stirred and reacted, then ammonium persulfate solution is added dropwise while stirring, and then the reaction is continued after the dropwise addition is completed, the reaction product is cooled after the reaction is completed, and then the pH is adjusted with ammonia water, to obtain the silicone modified emulsion; The coated modified carbon nanotube is prepared by the following steps: The carbon nanotube and Tris-HCl buffer solution are stirred and reacted, then hydrochloric acid dopamine is added and the reaction is continued, the reaction product is cooled after the reaction is completed, and then is centrifuged, and the precipitate is washed and dried, to obtain the coated modified carbon nanotube; The fluorine modified nano alumina is prepared by the following steps: The nano alumina, deionized water and anhydrous ethanol are ultrasonically dispersed, then the pH is adjusted with acetic acid, then 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane is added and stirred and reacted, the reaction product is cooled after the reaction is completed, and then is centrifuged, and the precipitate is washed and dried, to obtain the fluorine modified nano alumina.

2. The method for producing the water-based high-gloss, high-highlight, high-fullness, and high-hardness gloss oil having a mirror effect according to claim 1, characterized by, The amount ratio of the 1,1,3,3-tetramethyldisiloxane, allyl glycidyl ether, chloroplatinic acid and isopropyl alcohol in step a1 is 10 mmol:20 mmol:0.03-0.05 g:40-50 mL.

3. The method for producing the water-based high-gloss, high-highlight, high-fullness, and high-hardness gloss oil having a mirror effect according to claim 1, characterized by, The amount ratio of the terminal epoxy organosilicon, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol and isopropyl alcohol in step a2 is 10 mmol:20 mmol:0.8-1.0 g:0.2-0.3 g:60-70 mL.

4. The method for producing the water-based high-gloss, high-highlight, high-fullness, and high-hardness gloss oil having a mirror effect according to claim 1, characterized by, The amount ratio of the butyl acrylate, styrene, acrylic acid, terminal alkenyl organosilicon, sodium dodecyl sulfate, deionized water and ammonium persulfate solution in step a3 is 40-45 g:40-45 g:3-5 g:1-11 g:1.2-1.8 g:60-70 mL:10-15 mL.

5. The method for producing the water-based high-gloss, high-highlight, high-fullness, and high-hardness gloss oil having a mirror effect according to claim 1, characterized by, The mass fraction of the ammonium persulfate solution in step a3 is 2-3%; the mass fraction of the ammonia water is 20-22%.

6. The method of claim 1, wherein the water-based high-gloss, high- brilliance, high-hardness gloss oil having a mirror effect is characterized by, The amount ratio of the carbon nanotube, Tris-HCl buffer solution and dopamine hydrochloride is 1 g:40-50 mL:0.3-0.9 g; the outer diameter of the carbon nanotube is 15-25 nm, and the tube length is 5-15 μm; the molar concentration of the Tris-HCl buffer solution is 10 mmol / L, and the pH value is 8.

5.

7. The method of claim 1, wherein the water-based high-gloss, high- brilliance, high-hardness gloss oil having a mirror effect is characterized by, The amount ratio of the nano-alumina, deionized water, anhydrous ethanol and 1H,1H,2H,2H-perfluorooctyltriethoxysilane is 5 g:8-10 mL:80-85 mL:3-9 g; the particle size of the nano-alumina is 20-40 nm.

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