An acrylic resin coating and its preparation process and application

Abstract

The present invention provides an acrylic resin coating, its preparation process and application, belonging to the technical field of coatings. The acrylic resin coating comprises the following raw materials: 50 - 80 parts by weight of an aqueous acrylic resin emulsion, 10 - 20 parts by weight of an inorganic filler, 1 - 3 parts by weight of a dispersant, 1 - 2 parts by weight of an antifoaming agent, 1 - 2 parts by weight of a leveling agent, and 10 - 30 parts by weight of water; wherein, the aqueous acrylic resin emulsion is prepared by reacting ethylene glycol monoethyl ether, 3 - perfluorobutyl propanol, a water-resistant modified SiO2 / ZrO2 composite material, an acrylic monomer and water; the inorganic filler is one or a mixture of two or more of titanium dioxide, calcium carbonate, talc powder, kaolin, and mica powder. The acrylic resin coating prepared by the present invention is green and environmentally friendly, has strong adhesion, and has good water resistance, weather resistance and wear resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and particularly relates to an acrylic resin coating, its preparation process and application. Background Art

[0002] As an important material in modern industry, coatings have evolved from early natural vegetable oil and resin-based coatings to today's high-performance coatings centered on synthetic polymer materials, with their development accompanied by humanity's continuous pursuit of environmental protection, performance, and functionality. Among various types of coatings, acrylic resin coatings stand out due to their good comprehensive properties. They use acrylate and styrene as the main raw materials, obtain acrylic resin through copolymerization reaction, and then process it into corresponding coating products. Acrylic resin coatings have the characteristics of good color retention, excellent decorative effect, low toxicity and environmental protection, and are widely used in fields such as construction, furniture decoration, and automobile manufacturing. Especially after the rise of waterborne coating technology, acrylic resin coatings have become one of the representatives of environmentally friendly coatings. Compared with traditional solvent-based coatings, waterborne acrylic resin coatings not only have a lower price but also have advantages such as safe use, resource and energy savings, and reduced environmental pollution.

[0003] Currently, the preparation of acrylic resin coatings mainly includes processes such as solution polymerization and emulsion polymerization. Among them, solution polymerization dissolves monomers in organic solvents and conducts polymerization reactions under the action of initiators to finally form a uniform resin solution. This method is simple to operate and suitable for preparing high molecular weight acrylic resins, but the volatilization of solvents will cause environmental pollution and resource waste. Emulsion polymerization disperses monomers in water and completes polymerization under the action of emulsifiers and initiators to generate stable emulsion coatings. Coatings produced by this method have the advantages of high solid content, fast drying speed, and low cost, but there are also problems of insufficient water resistance and weather resistance. Especially when exposed to a humid environment for a long time, the performance of the coating is prone to decline.

[0004] To overcome the defects of existing acrylic resin coatings, researchers have also proposed various improvement strategies. For example, by introducing nano-inorganic fillers such as nano-titanium dioxide, the thermal stability and mechanical strength of the coating can be significantly improved; by compounding with other functional resins such as epoxy resin or polyurethane resin, the water resistance and wear resistance of the coating can be improved; in addition, adjusting the monomer ratio and polymerization process parameters are also important means to optimize the coating performance. However, these improvement measures still face many challenges. On the one hand, the addition of nano-inorganic fillers may increase production costs and may cause a decrease in the transparency and gloss of the coating; on the other hand, the compatibility problem between different components during the compound modification process has not been completely solved, which will affect the overall performance of the coating. Therefore, there is an urgent need to provide a new acrylic resin coating and its preparation method that can comprehensively improve the comprehensive properties such as water resistance, wear resistance, and weather resistance of the coating on the premise of ensuring environmental protection and simple process. Summary of the Invention

[0005] The object of the present invention is to provide an acrylic resin coating. By using a self-made aqueous acrylic resin emulsion and combining it with specific inorganic fillers, the coating is not only green and environmentally friendly, has strong adhesion, but also has good water resistance, weather resistance and wear resistance.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides an acrylic resin coating, which comprises the following raw materials in parts by weight:

[0008] 50 - 80 parts by weight of aqueous acrylic resin emulsion, 10 - 20 parts by weight of inorganic filler, 1 - 3 parts by weight of dispersant, 1 - 2 parts by weight of defoamer, 1 - 2 parts by weight of leveling agent, 10 - 30 parts by weight of water.

[0009] Preferably, the preparation method of the aqueous acrylic resin emulsion comprises the following steps:

[0010] Add the ethanol solution of tetraethyl orthosilicate and the n-butanol solution of tetrabutyl zirconate to ammonia water in sequence for reaction, filter, dry, calcine to obtain SiO2 / ZrO2 composite material; add the SiO2 / ZrO2 composite material to an ethanol aqueous solution for ultrasonic treatment, then add acrylamidopropyltrimethoxysilane and citric acid aqueous solution in sequence and continue ultrasonic treatment, filter, dry to obtain surface-treated SiO2 / ZrO2 composite material; mix 4,4′-diisocyanatodicyclohexylmethane and 1-hexadecanol, heat and stir, then add the surface-treated SiO2 / ZrO2 composite material and dibutyltin dilaurate and continue stirring, filter, dry to obtain water-resistant modified SiO2 / ZrO2 composite material;

[0011] Mix ethylene glycol monoethyl ether, 3-perfluorobutylpropanol and the water-resistant modified SiO2 / ZrO2 composite material, heat and stir, then add ethyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, methacrylamide, acrylic acid and azobisisobutyronitrile and continue stirring. After completion, cool down, then add dimethylethanolamine and water and stir, and cool to obtain an aqueous acrylic resin emulsion.

[0012] The aqueous acrylic resin emulsion prepared by the present invention by adopting the above method is not only green and environmentally friendly, has strong adhesion, but also can significantly improve the water resistance, wear resistance and weather resistance of the coating.

[0013] In the present invention, the preparation method of the aqueous acrylic resin emulsion significantly improves the water resistance, abrasion resistance and weather resistance of the coating through multi-step chemical modification and the introduction of composite materials. First, tetraethyl orthosilicate and tetrabutyl zirconate are reacted in an ammonia environment to generate a SiO2 / ZrO2 composite material, which has high mechanical strength and stability and can enhance the water resistance and abrasion resistance of the coating. Secondly, 3-(trimethoxysilyl)propyl acrylamide is used to modify the surface of the SiO2 / ZrO2 composite material, introducing active functional groups and improving its compatibility and dispersibility with organic polymers. Then, by reacting 4,4'-dicyclohexylmethane diisocyanate with 1-hexadecanol, a long-chain alkyl structure is introduced onto the surface of the composite material, further enhancing the hydrophobicity and reducing the contact area of water molecules, thereby improving the water resistance performance. At the same time, the addition of 3-perfluorobutylpropanol provides a perfluorocarbon chain with extremely low surface energy in the system, effectively inhibiting the penetration of water molecules and preventing the erosion of other substances, strengthening the weather resistance of the coating. Finally, during the polymerization process, monomers such as ethyl methacrylate, butyl acrylate, etc. react together with the above-mentioned modified composite materials to form a dense cross-linked network structure, making the coating have both flexibility and hardness, and significantly improving the abrasion resistance performance.

[0014] Preferably, the weight ratio of the ethanol solution of tetraethyl orthosilicate to the n-butanol solution of tetrabutyl zirconate is 40-60:30-50;

[0015] The weight ratio of the SiO2 / ZrO2 composite material to 3-(trimethoxysilyl)propyl acrylamide is 2-8:1.5-2;

[0016] The weight ratio of 4,4'-dicyclohexylmethane diisocyanate, 1-hexadecanol, and the surface-treated SiO2 / ZrO2 composite material is (3-7):(1-3.5):(2-4);

[0017] The weight ratio of 3-perfluorobutylpropanol to the water-resistant modified SiO2 / ZrO2 composite material is 1-3:2-6;

[0018] The weight ratio of ethyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, methacrylamide, and acrylic acid is (5-10):(2-4):(2-4):(2-4):(1-3).

[0019] Furthermore, the preparation method of the aqueous acrylic resin emulsion includes the following steps:

[0020] Under the stirring conditions of 35 - 40 °C and 200 - 300 r / min, add the ethanol solution of 40 - 60 parts by weight of tetraethyl orthosilicate and the n-butanol solution of 30 - 50 parts by weight of tetrabutyl zirconate to 100 - 200 parts by weight of ammonia water in sequence and react for 7 - 15 h, filter, dry, and then calcine for 1 - 3 h to obtain the SiO2 / ZrO2 composite material; add 2 - 8 parts by weight of the SiO2 / ZrO2 composite material to 40 - 60 parts by weight of an ethanol aqueous solution and ultrasonicate for 40 - 50 min, then add 1.5 - 2 parts by weight of acrylamidopropyltrimethoxysilane and 1 - 1.5 parts by weight of a citric acid aqueous solution in sequence and continue to ultrasonicate for 50 - 60 min, filter, dry to obtain the surface-treated SiO2 / ZrO2 composite material; mix 3 - 7 parts by weight of 4,4'-diisocyanatodicyclohexylmethane and 1 - 3.5 parts by weight of 1-hexadecanol, stir at 80 - 85 °C and 100 - 200 r / min for 30 - 50 min, then add 2 - 4 parts by weight of the surface-treated SiO2 / ZrO2 composite material and 0.05 - 0.1 part by weight of dibutyltin dilaurate and continue to stir for 10 - 20 h, filter, dry to obtain the water-resistant modified SiO2 / ZrO2 composite material;

[0021] Mix 1 - 5 parts by weight of ethylene glycol monoethyl ether, 1 - 3 parts by weight of 3-perfluorobutylpropanol and 2 - 6 parts by weight of the water-resistant modified SiO2 / ZrO2 composite material, stir at 100 - 150 °C and 100 - 300 r / min for 1 - 3 h, then add 5 - 10 parts by weight of ethyl methacrylate, 2 - 4 parts by weight of butyl acrylate, 2 - 4 parts by weight of 2-hydroxyethyl acrylate, 1 - 3 parts by weight of methacrylamide, 1 - 3 parts by weight of acrylic acid and 0.5 - 1.5 parts by weight of azobisisobutyronitrile and continue to stir for 5 - 10 h. After completion, cool down to 80 - 90 °C, then add 0.5 - 1 part by weight of dimethylethanolamine and 10 - 30 parts of water and stir for 3 - 5 h, and cool to room temperature to obtain the aqueous acrylic resin emulsion.

[0022] Preferably, the concentration of the ethanol solution of tetraethyl orthosilicate is 20 - 25 wt%.

[0023] Preferably, the concentration of the n-butanol solution of tetrabutyl zirconate is 10 - 20 wt%.

[0024] Preferably, the concentration of the ammonia water is 12 - 18 wt%.

[0025] Preferably, the concentration of the ethanol aqueous solution is 50 - 65 wt%.

[0026] Preferably, the concentration of the citric acid aqueous solution is 8 - 12 wt%.

[0027] Preferably, the temperature of the calcination is 500 - 600 °C.

[0028] Preferably, the power of the ultrasonic wave is 100 - 200 W and the frequency is 30 - 50 kHz.

[0029] Preferably, the inorganic filler is one or a mixture of two or more of titanium dioxide, calcium carbonate, talc powder, kaolin, and mica powder.

[0030] The present invention also uses a specific combination of inorganic fillers in combination with the above - mentioned aqueous acrylic resin emulsion, further improving the abrasion resistance and water resistance of the coating. Among them, talc powder has good lubricity and dispersibility, which can improve the flexibility of the coating and reduce internal stress. Mica powder has a flaky structure and can form a dense barrier in the coating to enhance the anti - penetration ability. Under the synergistic effect of the two, talc powder improves the smoothness and construction performance of the coating, while mica powder strengthens the denseness and mechanical strength of the coating, thereby effectively preventing water penetration and reducing external friction damage, and finally further improving the abrasion resistance and water resistance.

[0031] Further, the inorganic filler is a mixture composed of titanium dioxide, talc powder, and mica powder in a weight ratio of 10:(1 - 3):(2 - 4).

[0032] Preferably, the dispersant is any one of dispersant EDAPLAN®516, dispersant EDAPLAN®492, and dispersant EDAPLAN®397 (Mingling, Germany).

[0033] Preferably, the defoamer is any one of defoamer BYK - 024, defoamer BYK - 012, and defoamer BYK - 019 (BYK, Germany).

[0034] Preferably, the leveling agent is any one of leveling agent Tego - 410, leveling agent Tego - 432, and leveling agent Tego - 450 (Degussa, Germany).

[0035] The present invention provides a preparation process for an acrylic resin coating, including the following steps:

[0036] Weigh each raw material according to the formula, mix the aqueous acrylic resin emulsion, inorganic filler, dispersant, and water, stir at 25 - 35°C and 400 - 600 r / min for 20 - 40 min, then add the defoamer and leveling agent and continue to stir for 10 - 30 min, and cool to room temperature to obtain the acrylic resin coating.

[0037] The present invention also provides the application of the above - mentioned acrylic resin coating in the construction field and the decoration field.

[0038] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0039] 1. The present invention provides an acrylic resin coating and a preparation method thereof. By using a self-made aqueous acrylic resin emulsion in the raw material formulation and combining it with specific inorganic fillers, wherein the aqueous acrylic resin emulsion is prepared by reacting ethylene glycol monoethyl ether, 3-perfluorobutylpropanol, a water-resistant modified SiO2 / ZrO2 composite material, acrylic monomers and water, the water resistance, weather resistance, abrasion resistance and adhesion of the coating are further improved, and it is green, environmentally friendly and has stable performance. The present invention also provides the preparation process of the above acrylic resin coating and its applications in the construction field and the decoration field.

[0040] 2. The aqueous acrylic resin emulsion prepared by the present invention significantly improves the water resistance, abrasion resistance and weather resistance of the coating through multi-step chemical modification and the introduction of composite materials. Among them, the SiO2 / ZrO2 composite material has high mechanical strength and stability, which can enhance the water resistance and abrasion resistance of the coating. By reacting 4,4'-diisocyanatodicyclohexylmethane with 1-hexadecanol, a long-chain alkyl structure is introduced onto the surface of the composite material, further enhancing the hydrophobicity and reducing the contact area of water molecules, thereby improving the water resistance performance. The addition of 3-perfluorobutylpropanol provides a perfluorocarbon chain with extremely low surface energy for the system, effectively inhibiting the penetration of water molecules and preventing the erosion of other substances, strengthening the weather resistance of the coating.

[0041] 3. The present invention uses a specific combination of inorganic fillers to be used together with the above aqueous acrylic resin emulsion. Among them, talcum powder has good lubricity and dispersibility, which can improve the flexibility of the coating and reduce internal stress. Mica powder can form a dense barrier in the coating, enhancing the anti-permeability ability. Under the synergistic effect of the two, talcum powder improves the smoothness and construction performance of the coating, while mica powder strengthens the denseness and mechanical strength of the coating, thereby effectively preventing water penetration and reducing external friction damage, further improving the abrasion resistance and water resistance of the coating. Specific embodiments

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0043] Example 1

[0044] This example provides an acrylic resin coating, which is composed of the following raw materials in parts by weight:

[0045] 65 parts by weight of aqueous acrylic resin emulsion, 15 parts by weight of inorganic filler, 2 parts by weight of dispersant, 1.5 parts by weight of defoamer, 1.5 parts by weight of leveling agent, 20 parts by weight of water. The dispersant is dispersant EDAPLAN® 516; the defoamer is defoamer BYK-024; the leveling agent is leveling agent Tego-410.

[0046] The inorganic filler is a mixture composed of titanium dioxide, talc powder, and mica powder in a weight ratio of 10:2:3. Among them, the average particle size of titanium dioxide is 0.5 μm, purchased from Tianjin Linyi Chemical Technology Co., Ltd.; the average particle size of talc powder is 10 μm, purchased from Hubei Tuobang Chemical Co., Ltd.; the average particle size of mica powder is 15 μm, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0047] The preparation method of the aqueous acrylic resin emulsion includes the following steps:

[0048] Under the stirring conditions of 37 °C and 250 r / min, 50 parts by weight of an ethanol solution of 24 wt% tetraethyl orthosilicate and 40 parts by weight of a n-butanol solution of 15 wt% tetrabutyl zirconate are successively added to 160 parts by weight of 15 wt% ammonia water and reacted for 10 h, filtered, dried, and then calcined at 550 °C for 2 h to obtain SiO2 / ZrO2 composite material; 5 parts by weight of SiO2 / ZrO2 composite material is added to 50 parts by weight of 60 wt% ethanol aqueous solution, ultrasonicated for 45 min under the conditions of ultrasonic power of 150 W and ultrasonic frequency of 40 kHz, and then 1.8 parts by weight of acrylamidopropyltrimethoxysilane and 1.2 parts by weight of 10 wt% citric acid aqueous solution are successively added and ultrasonicated for another 55 min, filtered, dried, to obtain surface-treated SiO2 / ZrO2 composite material; 5 parts by weight of 4,4′-diisocyanatodicyclohexylmethane and 3 parts by weight of 1-hexadecanol are mixed, stirred at 82 °C and 120 r / min for 40 min, then 3 parts by weight of surface-treated SiO2 / ZrO2 composite material and 0.06 parts by weight of dibutyltin dilaurate are added and stirred for 15 h, filtered, dried, to obtain water-resistant modified SiO2 / ZrO2 composite material;

[0049] 3 parts by weight of ethylene glycol monoethyl ether, 2 parts by weight of 3-perfluorobutylpropanol and 4 parts by weight of water-resistant modified SiO2 / ZrO2 composite material are mixed, stirred at 120 °C and 200 r / min for 2 h, then 8 parts by weight of ethyl methacrylate, 3 parts by weight of butyl acrylate, 3 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of methacrylamide, 2 parts by weight of acrylic acid and 1 part by weight of azobisisobutyronitrile are added and stirred for 6 h. After the reaction, the temperature is lowered to 85 °C, then 0.8 parts by weight of dimethylethanolamine and 20 parts of water are added and stirred for 4 h, and cooled to room temperature to obtain the aqueous acrylic resin emulsion.

[0050] This embodiment provides a preparation process of an acrylic resin coating, which includes the following steps:

[0051] Weigh each raw material according to the formula, mix the aqueous acrylic resin emulsion, inorganic filler, dispersant and water, stir at 30°C and 500 r / min for 30 min, then add the defoamer and leveling agent and continue to stir for 20 min, and cool to room temperature to obtain the acrylic resin coating.

[0052] Example 2

[0053] This embodiment provides an acrylic resin coating, which is composed of the following raw materials in parts by weight:

[0054] 50 parts by weight of aqueous acrylic resin emulsion, 10 parts by weight of inorganic filler, 1 part by weight of dispersant, 1 part by weight of defoamer, 1 part by weight of leveling agent, and 10 parts by weight of water. The dispersant is dispersant EDAPLAN®516; the defoamer is defoamer BYK-024; the leveling agent is leveling agent Tego-410.

[0055] The inorganic filler is a mixture composed of titanium dioxide, talc powder and mica powder in a weight ratio of 10:1:4. Among them, the average particle size of titanium dioxide is 0.5 μm, purchased from Tianjin Linyi Chemical Technology Co., Ltd.; the average particle size of talc powder is 10 μm, purchased from Hubei Tuobang Chemical Co., Ltd.; the average particle size of mica powder is 15 μm, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0056] The preparation method of the aqueous acrylic resin emulsion is the same as that in Example 1.

[0057] This embodiment provides a preparation process of an acrylic resin coating, which includes the following steps:

[0058] Weigh each raw material according to the formula, mix the aqueous acrylic resin emulsion, inorganic filler, dispersant and water, stir at 25°C and 400 r / min for 20 min, then add the defoamer and leveling agent and continue to stir for 30 min, and cool to room temperature to obtain the acrylic resin coating.

[0059] Example 3

[0060] This embodiment provides an acrylic resin coating, which is composed of the following raw materials in parts by weight:

[0061] 80 parts by weight of aqueous acrylic resin emulsion, 20 parts by weight of inorganic filler, 3 parts by weight of dispersant, 2 parts by weight of defoamer, 2 parts by weight of leveling agent, and 30 parts by weight of water. The dispersant is dispersant EDAPLAN®516; the defoamer is defoamer BYK-024; the leveling agent is leveling agent Tego-410.

[0062] The inorganic filler is a mixture composed of titanium dioxide, talc powder, and mica powder in a weight ratio of 10:3:2. Among them, the average particle size of titanium dioxide is 0.5 μm, purchased from Tianjin Linyi Chemical Technology Co., Ltd.; the average particle size of talc powder is 10 μm, purchased from Hubei Tuobang Chemical Co., Ltd.; the average particle size of mica powder is 15 μm, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0063] The preparation method of the waterborne acrylic resin emulsion is the same as that in Example 1.

[0064] This example provides a preparation process of an acrylic resin coating, including the following steps:

[0065] Weigh each raw material according to the formula, mix the waterborne acrylic resin emulsion, inorganic filler, dispersant, and water, stir at 35 °C and 600 r / min for 40 min, then add the defoamer and leveling agent and continue stirring for 10 min, and cool to room temperature to obtain the acrylic resin coating.

[0066] Comparative Example 1

[0067] The difference between this comparative example and Example 1 is that the preparation method of the waterborne acrylic resin emulsion is different, specifically as follows: The preparation method of the waterborne acrylic resin emulsion includes the following steps:

[0068] Under the stirring conditions of 37 °C and 250 r / min, successively add 50 parts by weight of an ethanol solution of 24 wt% tetraethyl orthosilicate and 40 parts by weight of a n-butanol solution of 15 wt% tetrabutyl zirconate to 160 parts by weight of 15 wt% ammonia water and react for 10 h, filter, dry, and then calcine at 550 °C for 2 h to obtain the SiO2 / ZrO2 composite material;

[0069] Mix 3 parts by weight of ethylene glycol monoethyl ether, 2 parts by weight of 3-perfluorobutylpropanol, and 4 parts by weight of the SiO2 / ZrO2 composite material, stir at 120 °C and 200 r / min for 2 h, then add 8 parts by weight of ethyl methacrylate, 3 parts by weight of butyl acrylate, 3 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of methacrylamide, 2 parts by weight of acrylic acid, and 1 part by weight of azobisisobutyronitrile and continue stirring for 6 h. After completion, cool to 85 °C, then add 0.8 parts by weight of dimethylethanolamine and 20 parts of water and stir for 4 h, and cool to room temperature to obtain the waterborne acrylic resin emulsion.

[0070] Comparative Example 2

[0071] The difference between this comparative example and Example 1 is that the preparation method of the waterborne acrylic resin emulsion is different, specifically as follows: The preparation method of the waterborne acrylic resin emulsion includes the following steps:

[0072] Under the stirring conditions of 37 °C and 250 r / min, 50 parts by weight of an ethanol solution of 24 wt% tetraethyl orthosilicate and 40 parts by weight of a n-butanol solution of 15 wt% tetrabutyl zirconate were successively added to 160 parts by weight of 15 wt% ammonia water and reacted for 10 h. After filtration and drying, it was then calcined at 550 °C for 2 h to obtain a SiO2 / ZrO2 composite material; 5 parts by weight of 4,4′-diisocyanatodicyclohexylmethane was mixed with 3 parts by weight of 1-hexadecanol, stirred at 82 °C and 120 r / min for 40 min, then 3 parts by weight of the SiO2 / ZrO2 composite material and 0.06 parts by weight of dibutyltin dilaurate were added and stirred for another 15 h. After filtration and drying, a water-resistant modified SiO2 / ZrO2 composite material was obtained;

[0073] 3 parts by weight of ethylene glycol monoethyl ether, 2 parts by weight of 3-perfluorobutylpropanol and 4 parts by weight of the water-resistant modified SiO2 / ZrO2 composite material were mixed and stirred at 120 °C and 200 r / min for 2 h. Then 8 parts by weight of ethyl methacrylate, 3 parts by weight of butyl acrylate, 3 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of methacrylamide, 2 parts by weight of acrylic acid and 1 part by weight of azobisisobutyronitrile were added and stirred for another 6 h. After cooling to 85 °C, 0.8 parts by weight of dimethylethanolamine and 20 parts of water were added and stirred for 4 h. After cooling to room temperature, an aqueous acrylic resin emulsion was obtained.

[0074] Comparative Example 3

[0075] The difference between this comparative example and Example 1 is that the preparation method of the aqueous acrylic resin emulsion is different, specifically as follows: The preparation method of the aqueous acrylic resin emulsion includes the following steps:

[0076] 5 parts by weight of nano-silica was added to 50 parts by weight of a 60 wt% ethanol aqueous solution, ultrasonicated at an ultrasonic power of 150 W and an ultrasonic frequency of 40 kHz for 45 min, then 1.8 parts by weight of acrylamidopropyltrimethoxysilane and 1.2 parts by weight of a 10 wt% citric acid aqueous solution were successively added and ultrasonicated for another 55 min. After filtration and drying, surface-treated nano-silica was obtained; 5 parts by weight of 4,4′-diisocyanatodicyclohexylmethane was mixed with 3 parts by weight of 1-hexadecanol, stirred at 82 °C and 120 r / min for 40 min, then 3 parts by weight of the surface-treated nano-silica and 0.06 parts by weight of dibutyltin dilaurate were added and stirred for another 15 h. After filtration and drying, water-resistant modified nano-silica was obtained; wherein, the average particle size of the nano-silica is 50 nm;

[0077] Mix 3 parts by weight of ethylene glycol monoethyl ether, 2 parts by weight of 3-perfluorobutylpropanol with 4 parts by weight of water-resistant modified nano-silica, stir at 120 °C and 200 r / min for 2 h, then add 8 parts by weight of ethyl methacrylate, 3 parts by weight of butyl acrylate, 3 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of methacrylamide, 2 parts by weight of acrylic acid and 1 part by weight of azobisisobutyronitrile and continue stirring for 6 h. After completion, cool down to 85 °C, then add 0.8 part by weight of dimethylethanolamine and 20 parts of water and stir for 4 h, and cool to room temperature to obtain an aqueous acrylic resin emulsion.

[0078] Comparative Example 4

[0079] The difference between this comparative example and Example 1 is that: the preparation method of the aqueous acrylic resin emulsion is different, specifically as follows: The preparation method of the aqueous acrylic resin emulsion includes the following steps:

[0080] Under the stirring conditions of 37 °C and 250 r / min, sequentially add 50 parts by weight of an ethanol solution of 24 wt% tetraethyl orthosilicate and 40 parts by weight of a n-butanol solution of 15 wt% tetrabutyl zirconate to 160 parts by weight of 15 wt% ammonia water and react for 10 h, filter, dry, and then calcine at 550 °C for 2 h to obtain a SiO2 / ZrO2 composite material; add 5 parts by weight of the SiO2 / ZrO2 composite material to 50 parts by weight of a 60 wt% ethanol aqueous solution, ultrasonicate at an ultrasonic power of 150 W and an ultrasonic frequency of 40 kHz for 45 min, then sequentially add 1.8 parts by weight of acrylamidopropyltrimethoxysilane and 1.2 parts by weight of a 10 wt% citric acid aqueous solution and continue ultrasonication for 55 min, filter, dry to obtain a surface-treated SiO2 / ZrO2 composite material; mix 5 parts by weight of 4,4′-diisocyanatodicyclohexylmethane with 3 parts by weight of 1-hexadecanol, stir at 82 °C and 120 r / min for 40 min, then add 3 parts by weight of the surface-treated SiO2 / ZrO2 composite material and 0.06 part by weight of dibutyltin dilaurate and continue stirring for 15 h, filter, dry to obtain a water-resistant modified SiO2 / ZrO2 composite material;

[0081] Mix 3 parts by weight of ethylene glycol monoethyl ether with 4 parts by weight of the water-resistant modified SiO2 / ZrO2 composite material, stir at 120 °C and 200 r / min for 2 h, then add 8 parts by weight of ethyl methacrylate, 3 parts by weight of butyl acrylate, 3 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of methacrylamide, 2 parts by weight of acrylic acid and 1 part by weight of azobisisobutyronitrile and continue stirring for 6 h. After completion, cool down to 85 °C, then add 0.8 part by weight of dimethylethanolamine and 20 parts of water and stir for 4 h, and cool to room temperature to obtain an aqueous acrylic resin emulsion.

[0082] Comparative Example 5

[0083] The difference between this comparative example and Example 1 is as follows: the inorganic filler is different, specifically: the inorganic filler is a mixture composed of titanium dioxide and mica powder in a weight ratio of 10:5; among them, the average particle size of titanium dioxide is 0.5 μm, and the average particle size of mica powder is 15 μm.

[0084] Comparative Example 6

[0085] The difference between this comparative example and Example 1 is as follows: the inorganic filler is different, specifically: the inorganic filler is a mixture composed of titanium dioxide and talc powder in a weight ratio of 10:5; among them, the average particle size of titanium dioxide is 0.5 μm, and the average particle size of talc powder is 10 μm.

[0086] Performance Test

[0087] The acrylic resin coatings obtained in the above Examples 1-3 and Comparative Examples 1-6 were coated on the surface of a polypropylene substrate and tested after curing (the coating film thickness was 30 μm). The adhesion was measured with reference to the national standard GB / T 9286-2021 (0-5 levels, with level 5 being the worst). The abrasion resistance was measured with reference to the national standard GB / T 1768-2006. The neutral salt spray resistance was measured with reference to the national standard GB / T 1771-2007, the acid resistance (50 g / L sulfuric acid solution, 72 h) was measured, and the alkali resistance (50 g / L sodium hydroxide solution, 72 h) was measured. The water resistance was measured with reference to the national standard GB / T 1733-1993. The above acrylic resin coating was coated on the surface of a wooden block and, after curing (the coating film thickness was 30 μm), was immersed in water at 25°C for 1 day. After taking it out, the mass change of the wooden block before and after soaking was measured to calculate the water absorption rate to evaluate the water resistance, and at the same time, whether there were wrinkles and damages on the coating film was recorded. The results are shown in Table 1.

[0088] Table 1: Performance Test Results of Acrylic Resin Coatings

[0089]

[0090] It can be seen from the above performance test results that the acrylic resin coatings prepared in Examples 1-3 have good adhesion, abrasion resistance, weather resistance and water resistance. In particular, the comprehensive performance of the acrylic resin coating prepared in Example 1 is the most prominent. This is because the present invention uses a self-made waterborne acrylic resin emulsion and is combined with a specific inorganic filler, which significantly improves the adhesion, abrasion resistance, weather resistance and water resistance of the acrylic resin coating. Compared with Examples 1-3, in Comparative Examples 1-4, a waterborne acrylic resin emulsion prepared by a specific method was not used, and in Comparative Examples 5-6, a specific combination of inorganic fillers was not used. It can be seen from the results that this leads to a significant decline in the comprehensive performance of the acrylic resin coating. The above experimental results further prove the importance of the technical solutions corresponding to Examples 1-3 of the present invention for their technical effects.

[0091] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. An acrylic resin coating, characterized in that: The raw material composition is: By weight, 50-80 parts of aqueous acrylic resin emulsion, 10-20 parts of inorganic filler, 1-3 parts of dispersant, 1-2 parts of defoamer, 1-2 parts of leveling agent, 10-30 parts of water; The preparation method of the water-based acrylic resin emulsion comprises: The ethanol solution of tetraethyl orthosilicate and the n-butanol solution of tetrabutyl zirconate are sequentially added into ammonia water for reaction, filtered, dried and calcined to obtain SiO2 / ZrO2 composite material; the SiO2 / ZrO2 composite material is added into ethanol aqueous solution for ultrasonication, and then acrylamide propyl trimethoxysilane and citric acid aqueous solution are sequentially added for continuous ultrasonication, filtered and dried to obtain surface-treated SiO2 / ZrO2 composite material; 4,4′-diisocyanate dicyclohexylmethane and 1-hexadecanol are mixed, heated and stirred, and then the surface-treated SiO2 / ZrO2 composite material and dibutyltin dilaurate are added for continuous stirring, filtered and dried to obtain water-resistant modified SiO2 / ZrO2 composite material; Ethylene glycol ether, 3-perfluorobutyl propanol and water-resistant modified SiO2 / ZrO2 composite material are mixed, heated and stirred, and then ethyl methacrylate, butyl acrylate, hydroxyethyl acrylate, methacrylamide, acrylic acid and azobisisobutyronitrile are added and stirred continuously, and after the mixture is cooled, dimethylethanolamine and water are added and stirred, and cooled to obtain a water-based acrylic resin emulsion; The inorganic filler is a mixture of titanium dioxide, talcum powder and mica powder in a weight ratio of 10:(1-3):(2-4).

2. The acrylic resin coating according to claim 1, characterized in that: The weight ratio of the ethanol solution of ethyl orthosilicate to the n-butanol solution of tetrabutyl zirconate is 40-60:30-50; The weight ratio of the SiO2 / ZrO2 composite material to acrylamidopropyltrimethoxysilane is 2-8:1.5-2; The weight ratio of the 4,4′-diisocyanate dicyclohexylmethane, 1-hexadecanol, and surface treated SiO2 / ZrO2 composite material is (3-7): (1-3.5): (2-4); The weight ratio of the 3-perfluorobutyl propanol and the water-resistant modified SiO2 / ZrO2 composite material is 1-3:2-6; The weight ratio of ethyl methacrylate, butyl acrylate, hydroxyethyl acrylate, methacrylamide and acrylic acid is (5-10): (2-4): (2-4): (2-4): (1-3).

3. The acrylic resin coating according to claim 1, characterized in that: The dispersant is any one of dispersant EDAPLAN®516, dispersant EDAPLAN®492 and dispersant EDAPLAN®397.

4. The acrylic resin coating according to claim 1, characterized in that: The defoamer is any one of defoamer BYK-024, defoamer BYK-012 and defoamer BYK-019.

5. The acrylic resin coating according to claim 1, characterized in that: The leveling agent is any one of leveling agent Tego-410, leveling agent Tego-432, and leveling agent Tego-450.

6. A process for preparing an acrylic resin coating as claimed in any one of claims 1 to 5, characterized in that: The following steps are involved: Weigh the raw materials according to the formula, mix the water-based acrylic resin emulsion, inorganic filler, dispersant and water, stir for 20-40 minutes at 25-35° C. and 400-600 r / min, then add the defoamer and leveling agent and continue stirring for 10-30 minutes, cool to room temperature, and obtain the acrylic resin coating.

7. Use of the acrylic resin coating according to any one of claims 1 to 5 in the field of construction or decoration.

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