Manufacturing method of water-based high-gloss high-fullness high-hardness gloss oil with mirror surface effect

Abstract

The invention relates to the field of gloss oil, in particular to a preparation method of water-based high-gloss high-fullness high-hardness gloss oil with a mirror surface effect, which is used for solving the problem that the application possibility of the existing water-based gloss oil in the high-performance field is limited due to the defects of insufficient glossiness, weaker gloss retention effect, low fullness and poor hardness of the existing water-based gloss oil. According to the manufacturing method, through reasonable formula design, the prepared gloss oil has excellent fullness, a coating looks more full and three-dimensional and has extremely high glossiness, an excellent mirror surface effect is achieved, the attractiveness of a sprayed or printed product is remarkably improved, the formed coating has high strength and high hardness, and the gloss oil is suitable for being applied to a large-scale production line. The coating can resist scratches and abrasion, prolongs the service life of a product, can effectively resist erosion of severe environments such as acid, alkali, moisture and the like, and can keep long-term high glossiness and mirror surface effect.

Description

Technical Field

[0001] The present invention relates to the field of varnishes, and specifically to a method for preparing a waterborne high-gloss, high-build, and high-hardness varnish with a mirror effect. Background Art

[0002] As a transparent protective paint, varnish shines brightly after film formation. It can not only enhance the gloss and hardness of an object but also effectively protect the object surface from damage 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 waterborne varnishes. However, current waterborne varnishes generally have disadvantages such as insufficient gloss, weak light protection effect, low build, and poor hardness, restricting their application possibilities in high-performance fields.

[0004] Therefore, it is of great significance to develop a method for preparing a waterborne high-gloss, high-build, and high-hardness varnish with a mirror effect. Summary of the Invention

[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide a method for preparing a waterborne high-gloss, high-build, and high-hardness varnish with a mirror effect, which solves the problems that existing waterborne varnishes generally have disadvantages such as insufficient gloss, weak light protection effect, low build, and poor hardness, restricting their application possibilities in high-performance fields.

[0006] The purpose of the present invention can be achieved by the following technical solutions: A method for preparing a waterborne high-gloss, high-build, and high-hardness varnish with a mirror effect, comprising the following steps: Step 1: Weigh 40 - 50 parts of organosilicon-modified emulsion, 0.3 - 1.1 parts of coated modified carbon nanotubes, 4 - 12 parts of fluorine-modified nano-aluminum oxide, 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 defoaming agent, 0.2 - 0.4 parts of antioxidant, 0.3 - 0.5 parts of thickener, 3 - 7 parts of absolute ethanol, and 20 - 22 parts of deionized water, and set aside; Step 2: Add the organosilicon-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano-aluminum oxide, wetting and dispersing agent, leveling agent, film-forming aid, defoaming agent, antioxidant, thickener, absolute ethanol, and deionized water to a mixer, and stir and mix at a temperature of 25 - 30 °C and a stirring rate of 800 - 1000 r / min for 20 - 30 min to obtain a premix; Step 3: Add the premix into a grinder, grind it for 3 - 4 h under the condition of a rotation speed of 1800 - 2000 r / min, and then pass it through a 200 - 300 mesh sieve to obtain a water - based high - gloss, high - fullness, high - hardness varnish with a mirror effect.

[0007] As a further scheme of the present invention: The wetting dispersant is BYK - 193 wetting dispersant.

[0008] As a further scheme of the present invention: The leveling agent is ZY - 130 leveling agent.

[0009] As a further scheme of the present invention: The film - forming auxiliary agent is dodecyl alcohol ester.

[0010] As a further scheme of the present invention: The defoaming agent is BYK - 024 defoaming agent.

[0011] As a further scheme of the present invention: The antioxidant is antioxidant 168.

[0012] As a further scheme of the present invention: The thickening agent is carrageenan.

[0013] As a further scheme of the present invention: The organosilicon - modified emulsion is prepared by the following steps: Step a1: Add 1,1,3,3 - tetramethyldisiloxane, allyl glycidyl ether, chloroplatinic acid and isopropanol into a three - necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen for protection, stir and react for 30 - 50 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, then raise the temperature to 85 - 90 °C and continue to stir and react 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. Step a2: Add the terminal - epoxy organosilicon, acrylic acid, tetrabutylammonium bromide, 4 - methoxyphenol and isopropanol into a three - necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen for protection, stir and react for 30 - 50 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, then raise the temperature to 80 - 85 °C and continue to stir and react for 1 - 2 h, then raise the temperature to 100 - 105 °C and continue to stir and react 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. Step a3: Add butyl acrylate, styrene, acrylic acid, terminal alkenyl silicone, sodium dodecyl sulfate, and deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then, while stirring, gradually add an ammonium persulfate solution dropwise under the condition of raising the temperature to 85 - 90 °C, control the dropping rate at 1 - 2 drops / s. After the dropping is completed, continue to stir and react for 2 - 3 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 7 - 8 with ammonia water to obtain an organosilicon-modified emulsion.

[0014] As a further scheme of the present invention: The dosage ratio of the 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.

[0015] As a further scheme of the present invention: The dosage ratio of the terminal epoxy silicone, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol, and isopropanol in step a2 is 10 mmol: 20 mmol: 0.8 - 1.0 g: 0.2 - 0.3 g: 60 - 70 mL.

[0016] As a further scheme of the present invention: The dosage ratio of the butyl acrylate, styrene, acrylic acid, terminal alkenyl silicone, 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.

[0017] As a further scheme 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%.

[0018] As a further scheme of the present invention: The coated and modified carbon nanotubes are prepared by the following steps: Add carbon nanotubes and Tris-HCl buffer solution into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react for 30 - 50 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min. Then, add dopamine hydrochloride and continue to stir and react for 1 - 2 h. Then, continue to stir and react for 4 - 5 h under the condition of raising the temperature to 40 - 45 °C. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate with absolute ethanol and distilled water 2 - 3 times successively, and then place it in a vacuum drying oven and dry it at 70 - 75 °C for 1 - 2 h to obtain the coated and modified carbon nanotubes.

[0019] As a further solution of the present invention: the dosage ratio of the carbon nanotubes, Tris-HCl buffer solution and dopamine hydrochloride is 1 g: 40-50 mL: 0.3-0.9 g.

[0020] As a further solution of the present invention: the outer diameter of the carbon nanotubes 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.

[0021] As a further solution of the present invention: the fluorine-modified nano-aluminum oxide is prepared by the following steps: Add nano-aluminum oxide, deionized water and absolute ethanol into a three-necked flask equipped with a stirrer and a thermometer, ultrasonically disperse for 20-30 min under the condition that the ultrasonic frequency is 30-40 kHz, then adjust the pH to 5-6 with acetic acid, then add 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and stir and react for 10-15 min under the conditions that the temperature is 25-30 °C and the stirring rate is 200-300 r / min, then raise the temperature to 80-85 °C and continue to stir and react for 7-8 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with absolute acetone 2-3 times, and then place it in a vacuum drying oven and dry for 2-3 h under the condition that the temperature is 60-65 °C to obtain the fluorine-modified nano-aluminum oxide.

[0022] As a further solution of the present invention: the dosage ratio of the nano-aluminum oxide, deionized water, absolute ethanol and 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane is 5 g: 8-10 mL: 80-85 mL: 3-9 g.

[0023] As a further solution of the present invention: the particle size of the nano-aluminum oxide is 20-40 nm.

[0024] The beneficial effects of the present invention: Method for preparing water-based high-gloss, high-build and high-hardness varnish with mirror effect. By adding organosilicon-modified emulsion, coated and modified carbon nanotubes, fluorine-modified nano-aluminum oxide, wetting and dispersing agent, leveling agent, film-forming auxiliary, defoaming agent, antioxidant, thickening agent, absolute ethanol and deionized water into a mixer and stirring and mixing them, a premix is obtained. Then the premix is added into a grinder for grinding and then sieved to obtain the water-based high-gloss, high-build and high-hardness varnish with mirror effect. Through reasonable formulation design, the prepared varnish has excellent fullness, making the coating look more plump and three-dimensional, and has extremely high gloss, achieving an excellent mirror effect, significantly improving the aesthetics of sprayed or printed products. Moreover, the formed coating has high strength and high hardness, enabling it to resist scratches and abrasions, extend the service life of the product, and at the same time can effectively resist the erosion of harsh environments such as acid-base and humidity, maintaining a long-lasting high gloss and mirror effect. This varnish is suitable for surface treatment of various printing and packaging materials, metal substrates and plastic products, such as paper boxes, cartons, metal containers, plastic bottles, etc. Through spraying or printing processes, it can significantly improve the aesthetics and durability of products, meeting the market demand for high-quality surface treatment.

[0025] During the process of preparing the varnish, an organosilicon-modified emulsion was first prepared. First, 1,1,3,3-tetramethyldisiloxane and allyl glycidyl ether were reacted. The Si-H on 1,1,3,3-tetramethyldisiloxane and the vinyl group on allyl glycidyl ether underwent a hydrosilylation reaction, and at the same time, an epoxy group was introduced to obtain an epoxy-terminated organosilicon. Then, the epoxy-terminated organosilicon and acrylic acid were reacted. The epoxy group on the epoxy-terminated organosilicon reacted with the carboxyl group on acrylic acid, and at the same time, a vinyl group was introduced to obtain a vinyl-terminated organosilicon. Finally, butyl acrylate, styrene, acrylic acid and vinyl-terminated organosilicon were used as polymerization monomers for polymerization to form a polymer, obtaining the organosilicon-modified emulsion. This organosilicon-modified emulsion has excellent film-forming properties. During the film-forming process of the varnish, the organosilicon chain segments will migrate to the film surface, reducing the surface energy of the film surface, forming a smooth and flat surface, reducing the scattering of light, thereby increasing the gloss and producing a strong mirror effect. At the same time, the organosilicon chain segments can enhance the ability of the coating to resist the erosion of corrosive media and prevent the coating from being damaged.

[0026] In the process of preparing the varnish, a coated modified carbon nanotube and a fluorine modified nano-aluminum oxide were also prepared. First, polydopamine hydrochloride was used as a polymerization monomer to form polyaniline on the outside of the carbon nanotube, thereby wrapping the carbon nanotube to obtain the coated modified carbon nanotube. Then, 1H,1H,2H,2H-perfluorooctyltriethoxysilane was used to treat the nano-aluminum oxide. After hydrolysis of 1H,1H,2H,2H-perfluorooctyltriethoxysilane, a large number of fluorine atoms were grafted onto the particle surface of the nano-aluminum oxide by using silanol groups to obtain the fluorine modified nano-aluminum oxide; the carbon nanotube has excellent mechanical properties and enhancement effects. Adding it to the varnish can greatly improve the hardness of the coating, and after being wrapped by polyaniline, the dispersibility of the carbon nanotube can be greatly improved, enabling it to be evenly dispersed in the coating. The nano-aluminum oxide has high whiteness and gloss. Adding it to the varnish can also enhance the hardness and wear resistance of the coating, and introducing fluorine atoms can further reduce the surface energy of the coating, further improving the gloss and mirror effect of the coating, and also improving the ability of the coating to resist scratches, wear and corrosion medium erosion, avoiding coating damage; therefore, after adding the coated modified carbon nanotube and the fluorine modified nano-aluminum oxide to the varnish at the same time, it can fill the tiny depressions and unevenness on the coating surface, making the coating look more flat and plump, making it more textured, and greatly improving the gloss, mirror effect and durability of the coating. Detailed implementation mode

[0027] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0028] Example 1: The method for making a water-based high-gloss, high-plumpness and high-hardness varnish with a mirror effect in this embodiment includes the following steps: Step S1: Add 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 into a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, and stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 200 r / min. Then, continue to stir and react for 6 h under the condition of raising the temperature to 85 °C. After the reaction is completed, cool the reaction product to room temperature, and then rotate and evaporate to remove the solvent to obtain a terminal epoxy silicone; Step S2: Add 10 mmol of terminal epoxy silicone, 20 mmol of acrylic acid, 0.8 g of tetrabutylammonium bromide, 0.2 g of 4-methoxyphenol, and 60 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, raise the temperature to 80°C and continue to stir and react for 1 h. After that, raise the temperature to 100°C and continue to stir and react for 2 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 silicone; Step S3: Add 40 g of butyl acrylate, 40 g of styrene, 3 g of acrylic acid, 1 g of terminal alkenyl silicone, 1.2 g of sodium dodecyl sulfate, and 60 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel. Stir and react for 20 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, raise the temperature to 85°C and gradually add 10 mL of a 2% ammonium persulfate solution dropwise while stirring, controlling the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 2 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 7 with 20% ammonia water to obtain an organosilicon-modified emulsion; Step S4: Add 1 g of carbon nanotubes and 40 mL of a Tris-HCl buffer solution with a molar concentration of 10 mmol / L and a pH value of 8.5 into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, add 0.3 g of dopamine hydrochloride and continue to stir and react for 1 h. After that, raise the temperature to 40°C and continue to stir and react for 4 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate with anhydrous ethanol and distilled water twice each, and then place it in a vacuum drying oven and dry it at 70°C for 1 h to obtain coated and modified carbon nanotubes; Step S6: Add 5 g of nano-aluminum oxide, 8 mL of deionized water, and 80 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 20 min under the condition of an ultrasonic frequency of 30 kHz. Then, adjust the pH to 5 with acetic acid. After that, add 3 g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir and react for 10 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, raise the temperature to 80°C and continue to stir and react for 7 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate with anhydrous acetone twice, and then place it in a vacuum drying oven and dry it at 60°C for 2 h to obtain fluorine-modified nano-aluminum oxide; Step S6: Weigh 40 parts of organosilicon-modified emulsion, 0.3 parts of coated modified carbon nanotubes, 4 parts of fluorine-modified nano-aluminum oxide, 1 part of wetting and dispersing agent, 0.2 parts of leveling agent, 1 part of film-forming aid, 0.1 part of defoaming agent, 0.2 parts of antioxidant, 0.3 parts of thickening agent, 3 parts of absolute ethanol and 20 parts of deionized water for standby; 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 defoaming agent is BYK-024 defoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S7: Add the organosilicon-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano-aluminum oxide, wetting and dispersing agent, leveling agent, film-forming aid, defoaming agent, antioxidant, thickening agent, absolute ethanol and deionized water into a mixer, and stir and mix for 20 min under the conditions of a temperature of 25 °C and a stirring rate of 800 r / min to obtain a premix; Step S8: Add the premix into a grinder, grind it for 3 h under the condition of a rotation speed of 1800 r / min, and then pass through a 200-mesh sieve to obtain a water-based high-gloss, high-fullness and high-hardness varnish with a mirror effect.

[0029] Example 2: This example is a method for preparing a water-based high-gloss, high-fullness and high-hardness varnish with a mirror effect, including the following steps: Step S1: Add 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 into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen protection, stir and react for 40 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min, then continue to stir and react for 6.5 h under the condition of heating to 88 °C. 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; Step S2: Add 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 into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen protection, stir and react for 40 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min, then continue to stir and react for 1.5 h under the condition of heating to 82 °C, and then continue to stir and react for 2.5 h under the condition of heating to 102 °C. 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; Step S3: Add 42 g of butyl acrylate, 42 g of styrene, 4 g of acrylic acid, 6 g of terminal alkenyl silicone, 1.5 g of sodium dodecyl sulfate, and 65 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant pressure dropping funnel. Stir and react for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, while stirring, gradually add 12 mL of an ammonium persulfate solution with a mass fraction of 2.5% dropwise at a temperature of 88 °C, controlling the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 7.5 with 21% ammonia water to obtain an organosilicon-modified emulsion; Step S4: Add 1 g of carbon nanotubes and 45 mL of Tris-HCl buffer solution with a molar concentration of 10 mmol / L and a pH value of 8.5 into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection and stir and react for 40 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, add 0.6 g of dopamine hydrochloride and continue to stir and react for 1.5 h. Then, continue to stir and react for 4.5 h under the condition of heating to 42 °C. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate with absolute ethanol and distilled water twice, and then place it in a vacuum drying oven and dry it for 1.5 h at a temperature of 72 °C to obtain coated and modified carbon nanotubes; Step S5: Add 5 g of nano-aluminum oxide, 9 mL of deionized water, and 82 mL of absolute ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 25 min under the condition of an ultrasonic frequency of 35 kHz, then adjust the pH to 5.5 with acetic acid, then add 6 g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir and react for 12 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 7.5 h under the condition of heating to 82 °C. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate with anhydrous acetone twice, and then place it in a vacuum drying oven and dry it for 2.5 h at a temperature of 62 °C to obtain fluorine-modified nano-aluminum oxide; Step S6: Weigh 45 parts of the organosilicon-modified emulsion, 0.7 part of the coated and modified carbon nanotubes, 8 parts of the fluorine-modified nano-aluminum oxide, 2 parts of a wetting and dispersing agent, 0.4 part of a leveling agent, 2 parts of a film-forming auxiliary agent, 0.2 part of an antifoaming agent, 0.3 part of an antioxidant, 0.4 part of a thickening agent, 5 parts of absolute ethanol, and 21 parts of deionized water according to weight, and set aside; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming auxiliary agent is dodecyl alcohol ester; the antifoaming agent is BYK-024 antifoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S7: Add silicone-modified emulsion, coated and modified carbon nanotubes, fluorine-modified nano-aluminum oxide, wetting and dispersing agent, leveling agent, film-forming aid, defoaming agent, antioxidant, thickening agent, anhydrous ethanol and deionized water into a mixer, and stir and mix for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 900 r / min to obtain a premix; Step S8: Add the premix into a grinder, grind it for 3.5 h under the condition of a rotation speed of 1900 r / min, and then pass through a 250-mesh sieve to obtain a water-based high-gloss, high-fullness and high-hardness varnish with a mirror effect.

[0030] Example 3: The present example is a method for preparing a water-based high-gloss, high-fullness and high-hardness varnish with a mirror effect, including the following steps: Step S1: Add 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 into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen for protection, stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then raise the temperature to 90 °C and continue to stir and react for 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 silicone; Step S2: Add 10 mmol of terminal epoxy silicone, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4-methoxyphenol and 70 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen for protection, stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then raise the temperature to 85 °C and continue to stir and react for 2 h, then raise the temperature to 105 °C and continue to stir and react for 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 silicone; Step S3: Add 45 g of butyl acrylate, 45 g of styrene, 5 g of acrylic acid, 11 g of terminal alkenyl silicone, 1.8 g of sodium dodecyl sulfate and 70 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then raise the temperature to 90 °C and dropwise add 15 mL of a 3% ammonium persulfate solution drop by drop while stirring, control the dropping rate at 2 drops / s, continue to stir and react for 3 h after the dropping is completed. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 8 with 22% ammonia water to obtain a silicone-modified emulsion; Step S4: Add 1 g of carbon nanotubes, 50 mL of Tris-HCl buffer solution with a molar concentration of 10 mmol / L and a pH value of 8.5 into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe. Introduce nitrogen for protection. Stir and react for 50 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then add 0.9 g of dopamine hydrochloride and continue to stir and react for 2 h. Then raise the temperature to 45 °C and continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with absolute ethanol and distilled water three times respectively, and then place it in a vacuum drying oven and dry for 2 h at a temperature of 75 °C to obtain coated and modified carbon nanotubes; Step S5: Add 5 g of nano-aluminum oxide, 10 mL of deionized water and 85 mL of absolute ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 30 min under the condition of an ultrasonic frequency of 40 kHz. Then adjust the pH to 6 with acetic acid. Then add 9 g of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and stir and react for 15 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then raise the temperature to 85 °C and continue to stir and react for 8 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with absolute acetone three times, and then place it in a vacuum drying oven and dry for 3 h at a temperature of 65 °C to obtain fluorine-modified nano-aluminum oxide; Step S6: Weigh 50 parts of organosilicon-modified emulsion, 1.1 parts of coated and modified carbon nanotubes, 12 parts of fluorine-modified nano-aluminum oxide, 3 parts of wetting and dispersing agent, 0.6 parts of leveling agent, 3 parts of film-forming aid, 0.3 parts of defoaming agent, 0.4 parts of antioxidant, 0.5 parts of thickening agent, 7 parts of absolute ethanol and 22 parts of deionized water, and set aside; 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 defoaming agent is BYK-024 defoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S7: Add the organosilicon-modified emulsion, coated and modified carbon nanotubes, fluorine-modified nano-aluminum oxide, wetting and dispersing agent, leveling agent, film-forming aid, defoaming agent, antioxidant, thickening agent, absolute ethanol and deionized water into a mixer, and stir and mix for 30 min at a temperature of 30 °C and a stirring rate of 1000 r / min to obtain a premix; Step S8: Add the premix into a grinder and grind for 4 h at a rotation speed of 2000 r / min, and then pass through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness and high-hardness varnish with a mirror effect.

[0031] Comparative Example 1: This comparative example is a method for preparing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect, which includes the following steps: Step S1: Add 45 g of butyl acrylate, 45 g of styrene, 5 g of acrylic acid, 1.8 g of sodium dodecyl sulfate, and 70 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel. Stir and react for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 15 mL of an ammonium persulfate solution with a mass fraction of 3% dropwise at a temperature of 90 °C, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 8 with 22% ammonia water to obtain a modified emulsion; Step S2: Weigh 50 parts of the modified emulsion, 3 parts of a wetting and dispersing agent, 0.6 part of a leveling agent, 3 parts of a film-forming auxiliary, 0.3 part of an antifoaming agent, 0.4 part of an antioxidant, 0.5 part of a thickening agent, 7 parts of absolute ethanol, and 22 parts of deionized water, and set aside; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming auxiliary is dodecyl alcohol ester; the antifoaming agent is BYK-024 antifoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S3: Add the modified emulsion, wetting and dispersing agent, leveling agent, film-forming auxiliary, antifoaming agent, antioxidant, thickening agent, absolute ethanol, and deionized water into a mixer, and stir and mix for 30 min at a temperature of 30 °C and a stirring rate of 1000 r / min to obtain a premix; Step S4: Add the premix into a grinder, grind for 4 h at a rotation speed of 2000 r / min, and then pass through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect.

[0032] Comparative Example 2: This comparative example is a method for preparing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect, which includes the following steps: Step S1: Add 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 into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection, and stir and react for 50 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 7 h at a temperature of 90 °C. After the reaction is completed, cool the reaction product to room temperature, and then remove the solvent by rotary evaporation to obtain a terminal epoxy organosilicon; Step S2: Add 10 mmol of terminal epoxy silicone, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4-methoxyphenol, and 70 mL of isopropanol into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection, and stir and react at a temperature of 30 °C and a stirring rate of 300 r / min for 50 min. Then, raise the temperature to 85 °C and continue stirring and reacting for 2 h. Subsequently, raise the temperature to 105 °C and continue stirring and reacting for 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 silicone; Step S3: Add 45 g of butyl acrylate, 45 g of styrene, 5 g of acrylic acid, 11 g of terminal alkenyl silicone, 1.8 g of sodium dodecyl sulfate, and 70 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel. Stir and react at a temperature of 30 °C and a stirring rate of 300 r / min for 30 min. Then, raise the temperature to 90 °C and gradually add 15 mL of a 3% ammonium persulfate solution dropwise while stirring, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue stirring and reacting for 3 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 8 with 22% ammonia water to obtain an organosilicon-modified emulsion; Step S4: Weigh 50 parts of the organosilicon-modified emulsion, 3 parts of a wetting and dispersing agent, 0.6 part of a leveling agent, 3 parts of a film-forming auxiliary agent, 0.3 part of an antifoaming agent, 0.4 part of an antioxidant, 0.5 part of a thickening agent, 7 parts of absolute ethanol, and 22 parts of deionized water, and set aside; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming auxiliary agent is dodecyl alcohol ester; the antifoaming agent is BYK-024 antifoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S6: Add the organosilicon-modified emulsion, the wetting and dispersing agent, the leveling agent, the film-forming auxiliary agent, the antifoaming agent, the antioxidant, the thickening agent, absolute ethanol, and deionized water into a mixer, and stir and mix at a temperature of 30 °C and a stirring rate of 1000 r / min for 30 min to obtain a premix; Step S6: Add the premix into a grinder and grind it at a rotational speed of 2000 r / min for 4 h, and then pass it through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror finish.

[0033] Comparative Example 3: This comparative example is a method for preparing a water-based high-gloss, high-fullness, and high-hardness varnish with a mirror finish, including the following steps: Step S1: Add 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 into a three - necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. Protect it by introducing nitrogen. Stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to 90 °C and continue to stir and react for 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 silicone; Step S2: Add 10 mmol of terminal epoxy silicone, 20 mmol of acrylic acid, 1.0 g of tetrabutylammonium bromide, 0.3 g of 4 - methoxyphenol, and 70 mL of isopropanol into a three - necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. Protect it by introducing nitrogen. Stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to 85 °C and continue to stir and react for 2 h. Then, raise the temperature to 105 °C and continue to stir and react for 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 silicone; Step S3: Add 45 g of butyl acrylate, 45 g of styrene, 5 g of acrylic acid, 11 g of terminal alkenyl silicone, 1.8 g of sodium dodecyl sulfate, and 70 mL of deionized water into a four - necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant - pressure dropping funnel. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, raise the temperature to 90 °C and gradually add 15 mL of a 3% ammonium persulfate solution drop by drop while stirring, controlling the dropping rate at 2 drops / s. After the dropping is completed, continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 8 with 22% ammonia water to obtain an organosilicon - modified emulsion; Step S4: Add 1 g of carbon nanotubes and 50 mL of a Tris - HCl buffer solution with a molar concentration of 10 mmol / L and a pH value of 8.5 into a three - necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. Protect it by introducing nitrogen. Stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, add 0.9 g of dopamine hydrochloride and continue to stir and react for 2 h. Then, raise the temperature to 45 °C and continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate with anhydrous ethanol and distilled water three times each, and then place it in a vacuum drying oven and dry it at 75 °C for 2 h to obtain coated and modified carbon nanotubes; Step S5: Weigh 50 parts of organosilicon-modified emulsion, 1.1 parts of coated modified carbon nanotubes, 3 parts of wetting and dispersing agent, 0.6 parts of leveling agent, 3 parts of film-forming aid, 0.3 parts of defoaming agent, 0.4 parts of antioxidant, 0.5 parts of thickening agent, 7 parts of absolute ethanol and 22 parts of deionized water for standby; 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 defoaming agent is BYK-024 defoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S6: Add the organosilicon-modified emulsion, coated modified carbon nanotubes, wetting and dispersing agent, leveling agent, film-forming aid, defoaming agent, antioxidant, thickening agent, absolute ethanol and deionized water into a mixer, and stir and mix for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 1000 r / min to obtain a premix; Step S7: Add the premix into a grinder, grind it for 4 h under the condition of a rotation speed of 2000 r / min, and then pass through a 300-mesh sieve to obtain a waterborne high-gloss, high-fullness and high-hardness varnish with a mirror effect.

[0034] Comparative Example 4: The production method of the waterborne high-gloss, high-fullness and high-hardness varnish with a mirror effect in this comparative example includes the following steps: Step S1: Add 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 into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen protection, and stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 7 h under the condition of heating to 90 °C. 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; Step S2: Add 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 into a three-necked flask equipped with a stirrer, a thermometer and a gas pipe, introduce nitrogen protection, and stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 2 h under the condition of heating to 85 °C, and then continue to stir and react for 3 h under the condition of heating to 105 °C. 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; Step S3: Add 45 g of butyl acrylate, 45 g of styrene, 5 g of acrylic acid, 11 g of terminal alkenyl silicone, 1.8 g of sodium dodecyl sulfate, and 70 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel. Stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 15 mL of an ammonium persulfate solution with a mass fraction of 3% dropwise under the condition of heating up to 90 °C, control the dropping rate to be 2 drops / s. After the dropping is completed, continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, and then adjust the pH to 8 with ammonia water with a mass fraction of 22% to obtain an organosilicon-modified emulsion; Step S4: Add 5 g of nano-aluminum oxide, 10 mL of deionized water, and 85 mL of absolute ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 30 min under the condition of an ultrasonic frequency of 40 kHz. Then, adjust the pH to 6 with acetic acid. Then, add 9 g of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and stir and react for 15 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 8 h under the condition of heating up to 85 °C. After the reaction is completed, cool the reaction product to room temperature, and then centrifuge. Wash the precipitate 3 times with absolute acetone, and then place it in a vacuum drying oven and dry for 3 h under the condition of a temperature of 65 °C to obtain fluorine-modified nano-aluminum oxide; Step S5: Weigh 50 parts of the organosilicon-modified emulsion, 12 parts of the fluorine-modified nano-aluminum oxide, 3 parts of a wetting and dispersing agent, 0.6 part of a leveling agent, 3 parts of a film-forming auxiliary agent, 0.3 part of an antifoaming agent, 0.4 part of an antioxidant, 0.5 part of a thickening agent, 7 parts of absolute ethanol, and 22 parts of deionized water according to weight parts for standby; the wetting and dispersing agent is BYK-193 wetting and dispersing agent; the leveling agent is ZY-130 leveling agent; the film-forming auxiliary agent is dodecyl alcohol ester; the antifoaming agent is BYK-024 antifoaming agent; the antioxidant is antioxidant 168; the thickening agent is carrageenan; Step S6: Add the organosilicon-modified emulsion, the fluorine-modified nano-aluminum oxide, the wetting and dispersing agent, the leveling agent, the film-forming auxiliary agent, the antifoaming agent, the antioxidant, the thickening agent, absolute ethanol, and deionized water into a mixer, and stir and mix for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 1000 r / min to obtain a premix; Step S7: Add the premix into a grinder and grind for 4 h under the condition of a rotation speed of 2000 r / min, and then pass through a 300-mesh sieve to obtain a water-based high-gloss, high-fullness, high-hardness varnish with a mirror effect.

[0035] According to the GB / T 1727-2021 standard, a four-sided spreader (coating thickness 50 μm) was used to evenly spread the water-based high-gloss, high-fullness, and high-hardness varnish with a mirror effect of Examples 1-3 and Comparative Examples 1-4 on the surface of tinplate. After the surface was dried, it was transferred to a high-temperature drying oven and dried at a temperature of 80 °C for 2 h to form a coating. The glossiness 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 following table:

[0036] Referring to the data in the above table, by comparing Examples 1-3 and Comparative Examples 1-4, it can be known that the water-based high-gloss, high-fullness, and high-hardness varnish of the present application has high glossiness and hardness, and can resist the erosion of corrosive media, so that it maintains a good gloss retention rate and has an excellent mirror effect.

[0037] Among them, water treatment was to immerse the sample in deionized water for 72 h; acid treatment was to immerse the sample in a hydrochloric acid solution with a molar concentration of 1 mol / L for 72 h; alkali treatment was to immerse the sample in a sodium hydroxide solution with a molar concentration of 1 mol / L for 72 h; gloss retention rate = (glossiness after treatment / glossiness before treatment) × 100%.

[0038] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0039] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the invention or exceed the scope defined by the present application, they should all belong to the protection scope of the present invention.

Claims

1. A method for preparing a water-based high-gloss, high-fullness, high-hardness varnish with a mirror effect, characterized in that: The following steps are involved: Step 1: Weigh 40-50 parts of organosilicon 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 defoaming agent, 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 according to weight parts, and set aside; Step 2: Add the organosilicon-modified emulsion, coated modified carbon nanotubes, fluorine-modified nano-alumina, wetting and dispersing agent, leveling agent, film-forming aid, defoaming agent, antioxidant, thickener, anhydrous ethanol and deionized water into a mixer, stir and mix for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 800-1000 r / min to obtain a premix; Step 3: Add the premix into a grinder, grind for 3-4 hours at a rotation speed of 1800-2000 r / min, and then pass through a 200-300 mesh sieve to obtain a water-based high-gloss, high-fullness, high-hardness varnish with a mirror effect; 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; The thickener is carrageenan.

2. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 1, characterized in that: The organosilicon modified emulsion is prepared by the following steps: Step a1: stirring 1,1,3,3-tetramethyldisiloxane, allyl glycidyl ether, chloroplatinic acid and isopropanol for reaction, cooling the reaction product after the reaction is completed, and then rotary evaporating to obtain epoxy-terminated silicone; Step a2: stirring and reacting the epoxy-terminated organosilicon, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol and isopropanol, cooling the reaction product after the reaction is completed, and then rotary evaporating to obtain the olefin-terminated organosilicon; Step a3: Stir butyl acrylate, styrene, acrylic acid, terminal olefinic silicone, sodium dodecyl sulfate and deionized water for reaction, then add ammonium persulfate solution dropwise while stirring, continue stirring the reaction after the addition is complete, cool the reaction product after the reaction is complete, and then adjust the pH with ammonia water to obtain a silicone-modified emulsion.

3. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 2, characterized in that: The usage ratio of the 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.

4. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 2, characterized in that: The usage ratio of the epoxy-terminated silicone, acrylic acid, tetrabutylammonium bromide, 4-methoxyphenol and isopropanol in step a2 is 10 mmol: 20 mmol: 0.8-1.0 g: 0.2-0.3 g: 60-70 mL.

5. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 2, characterized in that: The usage ratio of the butyl acrylate, styrene, acrylic acid, terminal olefin silicone, 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.

6. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 2, characterized in that: The mass fraction of the ammonium persulfate solution in step a3 is 2-3%; the mass fraction of the ammonia water is 20-22%.

7. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 1, characterized in that: The coated modified carbon nanotubes are prepared by the following steps: The carbon nanotubes and Tris-HCl buffer solution are stirred for reaction, and then dopamine hydrochloride is added and the stirring reaction is continued. After the reaction is completed, the reaction product is cooled and then centrifuged. The precipitate is washed and dried to obtain the coated modified carbon nanotubes.

8. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 7, characterized in that: The usage ratio of the carbon nanotube, Tris-HCl buffer solution and dopamine hydrochloride is 1g:40-50mL:0.3-0.9g; the outer diameter of the carbon nanotube is 15-25nm, and the tube length is 5-15μm; the molar concentration of the Tris-HCl buffer solution is 10mmol / L, and the pH value is 8.

5.

9. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 1, characterized in that: The fluorine-modified nano-alumina is prepared by the following steps: The nano-alumina, deionized water and anhydrous ethanol are ultrasonically dispersed, and then the pH is adjusted with acetic acid, and then 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane is added for stirring reaction. After the reaction is completed, the reaction product is cooled and then centrifuged, and the precipitate is washed and dried to obtain fluorine-modified nano-alumina.

10. The method for preparing the water-based high-gloss, high-volume, high-hardness varnish with mirror effect according to claim 9, characterized in that: The dosage ratio of the nano-alumina, deionized water, anhydrous ethanol and 1H, 1H, 2H, 2H-perfluorooctyl triethoxysilane is 5g: 8-10mL: 80-85mL: 3-9g; the particle size of the nano-alumina is 20-40nm.

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