Water-based aerosol spray paint for repairing wooden furniture and preparation method of water-based aerosol spray paint

Abstract

The invention discloses water-based aerosol spray paint for repairing wooden furniture and a preparation method of the water-based aerosol spray paint, and relates to the technical field of aerosol spray paint. Comprising the following raw materials in parts by mass: 200-240 parts of modified waterborne polyurethane emulsion, 2-4 parts of mildew preventive, 3-5 parts of synergistic particles, 1-3 parts of pigment and 0.3-0.5 part of defoaming agent. By introducing the modified waterborne polyurethane emulsion prepared from components such as polytetramethylene ether glycol, pretreated tung oil and isophorone diisocyanate, the adhesive force and the self-repairing capability of the waterborne aerosol spray paint are effectively improved; due to the introduction of the mildew preventive, the synergistic particles and other components, the flame retardant capacity, the self-repairing capacity and the mildew-proof capacity of the water-based aerosol spray paint are further improved. Therefore, the water-based aerosol spray paint for repairing the wooden furniture, which is prepared by the invention, has a wider application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a water-based aerosol spray paint for repairing wooden furniture and a preparation method thereof. Background Art

[0002] Wooden furniture is prone to surface damage during use. To avoid the repaired surface from interfering with the original surface and to achieve optimal repair results, existing repair methods typically involve localized repairs using aerosol sprays, which are typically composed of resins, pigments, additives, and solvents. Water-based paints, primarily based on water or ethanol, are non-toxic, environmentally friendly, free of harmful solvents like benzene, and safe and convenient to use. Among them, water-based polyurethane resin coatings are environmentally friendly coatings that use polyurethane resin as the primary film-forming substance and water as the dispersion medium. They combine the high performance of solvent-based polyurethane coatings (such as high wear resistance, flexibility, and chemical resistance) with the low volatile organic compound emissions and safety and environmental benefits of water-based coatings.

[0003] However, in practical applications, waterborne polyurethane coatings still suffer from poor mildew resistance, making them susceptible to mold growth in humid environments; as well as poor flame retardancy, making them unable to improve the fire resistance of wooden furniture after film formation. Therefore, the mildew resistance and flame retardancy of existing waterborne polyurethane resin coatings still need to be improved. Summary of the Invention

[0004] The purpose of the present invention is to provide a water-based aerosol spray paint for repairing wooden furniture and a preparation method thereof, so as to solve the following technical problems: Existing water-based polyurethane coatings still have the problem of relatively poor mildew resistance and flame retardancy.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A water-based aerosol spray paint for repairing wooden furniture comprises the following raw materials in parts by mass: 200-240 parts of modified water-based polyurethane emulsion, 2-4 parts of mildew inhibitor, 3-5 parts of synergistic particles, 1-3 parts of pigment, and 0.3-0.5 parts of defoaming agent.

[0006] Preferably, the preparation method of the modified aqueous polyurethane emulsion is: A1: Under a nitrogen atmosphere, dehydrate tung oil at 94-96°C for 30-40 minutes. After the temperature drops to 58-62°C, add diethanolamine and sodium methoxide solution and stir for 7-8 hours. After the temperature drops to 20-30°C, add dichloromethane and centrifuge for 10-15 minutes. Then, wash the organic phase with saturated sodium chloride solution 5-7 times and dry it over anhydrous magnesium sulfate. After filtering, the filtrate is rotary evaporated at 25-30°C and -0.09 MPa to a temperature of 109-145 g. Finally, vacuum dry it at 63-65°C and -0.1 MPa for 12-15 hours to obtain pretreated tung oil. A2: Add 3-aminophenylboronic acid to tetrahydrofuran and stir for 60-90 minutes to obtain a 3-aminophenylboronic acid solution; A3: After dehydrating polytetramethylene ether glycol at 93-95°C and -0.1MPa for 12-15h, pretreated tung oil was added and stirred at 68-70°C for 30-50min. Then, isophorone diisocyanate and dibutyltin dilaurate were slowly added dropwise in sequence and prepolymerized for 3-4h. Then, 2,2-dihydroxymethylpropionic acid was added and reacted for 3-4h. Then, 3-aminophenylboronic acid solution was slowly added dropwise and reacted at 73-75°C for 15-20h. After cooling to 30-40°C, triethylamine was added and neutralized for 30-40min. Finally, deionized water at 1-5°C was added and stirred at 5000-10000r / min for 1-1.5h. After rotary evaporation to 318-530g, a modified waterborne polyurethane emulsion was obtained.

[0007] Preferably, the usage ratio of tung oil, diethanolamine, sodium methoxide solution, dichloromethane, and anhydrous magnesium sulfate in A1 is 66-88.5 g: 40.2-53.6 g: 0.9-1.1 mL: 262.5-350 mL: 4-5 g; The mass fraction of the sodium methoxide solution described in A1 is 30%.

[0008] Preferably, the ratio of tetrahydrofuran to 3-aminophenylboronic acid in A2 is 30-50 mL: 2.3-3.8 g; The usage ratio of polytetramethylene ether glycol, pretreated tung oil, isophorone diisocyanate, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 3-aminophenylboric acid solution, triethylamine, and deionized water in A3 is 45.9-76.5 g: 8.4-14 g: 19.2-32 g: 0.3-0.6 g: 3.6-6 g: 30-50 mL: 2.8-4.6 g: 240-400 g.

[0009] Preferably, the preparation method of the mildew inhibitor is as follows: Ammonium polyphosphate is added to deionized water at 70-75° C. and stirred for 30-60 minutes. Then, carboxymethyl chitosan is added and stirred for 1.5-2.5 hours. Then, halloysite nanotubes are added and ultrasonically dispersed for 30-50 minutes. After stirring for 4-5 hours, a mildew inhibitor is obtained.

[0010] Preferably, the usage ratio of the deionized water, ammonium polyphosphate, carboxymethyl chitosan and halloysite nanotubes is 60-100 mL: 1.8-3 g: 0.9-1.5 g: 0.3-0.5 g.

[0011] Preferably, the preparation method of the synergistic granules is as follows: B1: Add deionized water, basic copper carbonate, and aminotrimethylenephosphonic acid to formamide and stir for 40-60 minutes to obtain a mixed solution; B2: Tetrabutyl titanate and Tween-80 are added to formamide and stirred for 20-30 minutes. Then, the mixture is added dropwise at 1-3 mL / min at 45-50° C. and stirred for 6-7 hours. Then, ammonium fluoride is added and stirred at 83-85° C. for 24-26 hours. Finally, the mixture is centrifuged at 8000-10000 rpm for 10-20 minutes. The precipitate is then washed with deionized water 3-5 times and vacuum dried for 13-15 hours to obtain a phosphorus-containing composition. B3: Add the phosphorus-containing composition and tris(hydroxymethyl)aminomethane to deionized water and stir for 2-3 hours. Then, adjust the pH to 9 with sodium hydroxide solution. Then, add dopamine and perform ultrasonic treatment for 6-8 hours. Finally, centrifuge at 8000-10000 rpm for 10-20 minutes. Then, wash the precipitate with deionized water 3-5 times and vacuum dry for 13-15 hours to obtain a modified phosphorus-containing composition. B4: Add sodium dodecylbenzenesulfonate and the modified phosphorus-containing composition to deionized water and stir at 80-85°C for 0.5-1h, then add cetyl alcohol and stir at 85-87°C for 0.5-1h, then add methyl methacrylate, aminotrimethylenephosphonic acid, ethylene glycol methacrylate, and ammonium persulfate and react for 4-6h, finally centrifuge at 8000-10000 r / min for 10-20min, wash the precipitate with deionized water 5-7 times, and vacuum dry at 30-35°C and -0.1MPa for 13-15h to obtain synergistic particles.

[0012] Preferably, the ratio of formamide, deionized water, basic copper carbonate, and aminotrimethylenephosphonic acid in B1 is 50-60 mL: 2-2.4 g: 1-1.2 g: 3-3.6 g; The dosage ratio of formamide, tetrabutyl titanate, Tween-80, mixed solution, and ammonium fluoride in B2 is 100-120 mL: 10-12 g: 1-1.2 g: 50-60 mL: 2-2.4 g; The usage ratio of the deionized water, the phosphorus-containing composition, tris(hydroxymethyl)aminomethane, and dopamine in B3 is 100-120 mL: 5-6 g: 0.3-0.36 g: 2-2.4 g; The usage ratio of deionized water, sodium dodecylbenzenesulfonate, modified phosphorus-containing composition, cetyl alcohol, methyl methacrylate, aminotrimethylenephosphonic acid, ethylene glycol methacrylate, and ammonium persulfate in B4 is 200-300 mL: 2-3 g: 2-3 g: 40-60 g: 50-75 mL: 1-1.5 g: 5-7.5 g: 0.3-0.5 g.

[0013] Preferably, the pigment is any one of titanium dioxide, carbon black, iron oxide red, iron oxide yellow, phthalocyanine blue, phthalocyanine green and matte powder.

[0014] A method for preparing a water-based aerosol spray paint for repairing wooden furniture comprises the following steps: A mildew preventer, synergistic particles, pigment and defoamer are added to the modified waterborne polyurethane emulsion and ultrasonically dispersed for 20-30 minutes. Finally, the emulsion is sheared at 12000-13000 r / min for 15-20 minutes to obtain a waterborne aerosol spray paint for repairing wooden furniture.

[0015] Beneficial effects of the present invention: The present invention provides a water-based aerosol spray paint for repairing wooden furniture and a preparation method thereof. The present invention effectively improves the flame retardancy and mildew resistance of the water-based polyurethane paint through the following method.

[0016] (1) The multiple hydroxyl groups contained in the molecular chain of the pretreated tung oil of the present invention will undergo an addition reaction with the isocyanate group of isophorone diisocyanate to form an urethane bond, which becomes part of the hard segment of the polyurethane. After pretreatment, the unsaturated fatty acid chain of the tung oil is not completely reacted, and some double bonds are retained. During the film formation process, a three-dimensional network can be further formed through oxidative crosslinking. The tung oil side chains and borate groups in the polymer network form multiple dynamic bonding units, which endow the polymer chain segments at the wound of the coating with efficient dissociation and reconstruction at room temperature, thereby achieving self-repair efficiency. The dopamine-modified phosphorus-containing composition can form strong adhesion with the polyurethane matrix through its catechol group. At the same time, the oxidative self-polymerization property of dopamine may form secondary crosslinking points at the damaged area, promoting repair. After amination, the tung oil contains amino groups and hydroxyl groups, which can form hydrogen bonds with the hydroxyl and carbonyl groups on the wood surface, thereby improving the adhesion of the paint film. The low molecular weight precursor of the tung oil can also penetrate into the pores of the wood, forming an "anchoring" effect, further enhancing the adhesion of the paint film. The double bonds of tung oil can be grafted onto the functional groups in the mildew inhibitor, or copolymerized with the methacrylate groups in the synergistic particles to enhance mildew resistance and flame retardancy.

[0017] (2) The ammonium polyphosphate in the mildew inhibitor of the present invention contains a phosphorus-nitrogen synergistic flame retardant system, which decomposes at high temperatures to produce phosphoric acid, polymetaphosphoric acid and ammonia, forming a glassy coating on the surface of the paint film, isolating oxygen and inhibiting the release of combustible gases and diluting the combustible gases, reducing the combustion rate, and promoting the carbonization of the paint film. The carboxymethyl chitosan in the mildew inhibitor contains amino and carboxyl groups, which can destroy the mold cell membrane and cause the leakage of intracellular substances through electrostatic adsorption. At the same time, it can also chelate metal ions necessary for mold growth, inhibiting its metabolic enzyme activity and spore germination. The halloysite nanotubes in the mildew inhibitor can load carboxymethyl chitosan and delay its release, extending the retention time of carboxymethyl chitosan on the paint film surface and improving the long-term mildew prevention effect; its nanoscale tubular structure can adsorb smoke particles generated by combustion and reduce the amount of smoke released; it can entangle with polyurethane molecular chains, transfer stress through "bridging" action, and improve the tensile strength and elongation at break of the paint film; at the same time, it can also fill the internal defects of the paint film, reduce porosity, and increase hardness. When halloysite nanotubes are evenly distributed, they form a "maze structure", which extends the permeation path of ethanol molecules and reduces the diffusion rate; the hydroxyl groups on the surface of halloysite nanotubes can form hydrogen bonds or physical entanglements with polar groups in the polyurethane matrix, enhancing the density of the coating and inhibiting solvent swelling.

[0018] (3) The basic copper carbonate in the synergistic particles of the present invention has a broad-spectrum antimicrobial activity, which can inhibit the growth of mold and bacteria in wood substrates and enhance the anti-corrosion ability of spray paint; it can catalyze carbonization during combustion, reduce smoke release and inhibit flame propagation, and form a synergistic flame retardant effect with phosphorus-containing components; its copper ions can also synergize with carboxymethyl chitosan and halloysite nanotubes in the antifungal agent to significantly enhance the mold inhibition effect on wood substrates. The phosphorus element in aminotrimethylenephosphonic acid can inhibit combustion through condensed phase flame retardant mechanisms and gas phase flame retardant mechanisms, thereby improving the fire resistance of the coating; it can be combined with elements such as copper and titanium to form a "phosphorus-copper-titanium" composite flame retardant system, enhancing the smoke suppression effect. The hydrolysis product of tetrabutyl titanate can be used as a filler to improve the hardness, wear resistance and impact resistance of the coating, and improve the mechanical properties of the repaired wood surface. Dopamine forms a polydopamine layer through oxidative self-polymerization. Its polyphenol structure can form hydrogen bonds or covalent bonds with the amino and hydroxyl groups in waterborne polyurethane, strengthening the interfacial bonding between the particles and the substrate and improving the coating's adhesion. The polydopamine layer can also adsorb metal ions or functional molecules, further expanding the particles' load capacity. Methyl methacrylate and ethylene glycol esters form a polymer shell through emulsion polymerization, enhancing the hydrophilicity of the particles and maintaining long-term stable dispersion in aqueous systems, preventing sedimentation. Ethylene glycol methacrylate, as a crosslinker, can adjust the shell's crosslinking density, imparting both rigidity and flexibility to the particles and improving the coating's crack resistance. Functional groups, such as ester groups, can also be introduced into the polymer shell to enhance the coating's hydrophobicity, water resistance, and ease of cleaning.

[0019] Therefore, the water-based aerosol spray paint for repairing wooden furniture prepared by the present invention has excellent adhesion, hardness, solvent resistance, self-repairing ability, flame retardancy and mildew resistance, as well as broader application prospects. DETAILED DESCRIPTION

[0020] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0021] Unless otherwise specified, some of the raw materials used in the following examples and comparative examples of the present invention are as follows: Tung oil was purchased from Hubei Xinhongli Chemical Co., Ltd., item number: XHL0297; polytetramethylene ether glycol was purchased from Shanghai Saikurui Biotechnology Co., Ltd., item number: SCPP-80406; defoaming agent was purchased from Kunshan Qiancai Chemical Co., Ltd., model: BYK-024.

[0022] Example 1: A method for preparing a water-based aerosol spray paint for repairing wooden furniture comprises the following steps: S1: Under a nitrogen atmosphere, 66 g of tung oil was dehydrated at 94 ° C for 30 min. After cooling to 58 ° C, 40.2 g of diethanolamine and 0.9 mL of a 30% sodium methoxide aqueous solution were added and stirred at 300 r / min for 7 h. After cooling to 20 ° C, 262.5 mL of dichloromethane was added and centrifuged for 10 min. The organic phase was then washed with saturated sodium chloride solution 5 times and then dried with 4 g of anhydrous magnesium sulfate. After filtration, the filtrate was rotary evaporated at 25 ° C and -0.09 MPa to 109 g. Finally, it was vacuum dried at 63 ° C and -0.1 MPa for 12 h to obtain pretreated tung oil; S2: Add 2.3 g of 3-aminophenylboronic acid to 30 mL of tetrahydrofuran and stir for 60 min to obtain a 3-aminophenylboronic acid solution; S3: After dehydrating 45.9 g of polytetramethylene ether glycol at 93 ° C and -0.1 MPa for 12 h, 8.4 g of pretreated tung oil was added and stirred at 68 ° C for 30 min. Then, 19.2 g of isophorone diisocyanate and 0.3 g of dibutyltin dilaurate were slowly added dropwise and prepolymerized for 3 h. Then, 3.6 g of 2,2-dihydroxymethylpropionic acid was added and reacted for 3 h. Then, 30 mL of 3-aminophenylboronic acid solution was slowly added dropwise and reacted at 73 ° C for 15 h. After cooling to 30 ° C, 2.8 g of triethylamine was added and neutralized for 30 min. Finally, 240 g of deionized water at 1 ° C was added and stirred at 5000 r / min for 1 h. After rotary evaporation to 318 g, a modified waterborne polyurethane emulsion was obtained; S4: 1.8 g of ammonium polyphosphate was added to 60 mL of deionized water at 70° C. and stirred for 30 min, followed by the addition of 0.9 g of carboxymethyl chitosan and stirring for 1.5 h, and then 0.3 g of halloysite nanotubes was added and ultrasonically dispersed at a power of 250 W and a frequency of 20 kHz for 30 min, and stirred for 4 h to obtain a mildew inhibitor; S5: Add 2 g of deionized water, 1 g of basic copper carbonate, and 3 g of aminotrimethylenephosphonic acid to 50 mL of formamide and stir for 40 min to obtain a mixed solution; S6: 10 g of tetrabutyl titanate and 1 g of Tween-80 were added to 100 mL of formamide and stirred for 20 min. Then, 50 mL of the mixture was added dropwise at 1 mL / min at 45° C. and stirred at 800 rpm for 6 h. Then, 2 g of ammonium fluoride was added and stirred at 80 rpm at 83° C. for 24 h. Finally, the mixture was centrifuged at 8000 rpm for 10 min. The precipitate was washed three times with deionized water and vacuum dried at 30° C. and −0.1 MPa for 13 h to obtain a phosphorus-containing composition. S7: 5 g of the phosphorus-containing composition and 0.3 g of tris(hydroxymethyl)aminomethane) were added to 100 mL of deionized water and stirred at 400 rpm for 2 h. The pH was then adjusted to 9 with a 1 mol / L sodium hydroxide solution. 2 g of dopamine was then added and ultrasonic treatment was performed at a power of 200 W and a frequency of 20 kHz for 6 h. Finally, the mixture was centrifuged at 8000 rpm for 10 min. The precipitate was washed three times with deionized water and vacuum dried at 30° C. and −0.1 MPa for 13 h to obtain a modified phosphorus-containing composition. S8: Add 2 g of sodium dodecylbenzenesulfonate and 2 g of the modified phosphorus-containing composition to 200 mL of deionized water and stir at 80° C. and 1500 r / min for 0.5 h, then add 40 g of cetyl alcohol and stir at 85° C. and 1500 r / min for 0.5 h, then add 50 mL of methyl methacrylate, 1 g of aminotrimethylenephosphonic acid, 5 g of ethylene glycol methacrylate, and 0.3 g of ammonium persulfate and react for 4 h, finally centrifuge at 8000 r / min for 10 min, wash the precipitate with deionized water 5 times, and vacuum dry at 30° C. and -0.1 MPa for 13 h to obtain synergistic particles; S9: Add 2g of mildew inhibitor, 3g of synergistic particles, 1g of phthalocyanine blue, and 0.3g of defoaming agent to 200g of modified water-based polyurethane emulsion and perform ultrasonic dispersion at a power of 350W and a frequency of 20kHz for 20min. Finally, shear at 12000r / min for 15min to obtain water-based aerosol spray paint for repairing wooden furniture.

[0023] Example 2: A method for preparing a water-based aerosol spray paint for repairing wooden furniture comprises the following steps: S1: Under a nitrogen atmosphere, 775 g of tung oil was dehydrated at 95 ° C for 35 min. After cooling to 60 ° C, 46.9 g of diethanolamine and 1 mL of 30% sodium methoxide solution were added and stirred at 330 r / min for 7.5 h. After cooling to 25 ° C, 306.25 mL of dichloromethane was added and centrifuged for 13 min. The organic phase was then washed 6 times with saturated sodium chloride solution and then dried with 4.5 g of anhydrous magnesium sulfate. After filtration, the filtrate was rotary evaporated at 28 ° C and -0.09 MPa to 127 g. Finally, it was vacuum dried at 64 ° C and -0.1 MPa for 13 h to obtain pretreated tung oil; S2: Add 2.5 g of 3-aminophenylboronic acid to 40 mL of tetrahydrofuran and stir for 80 min to obtain a 3-aminophenylboronic acid solution; S3: After dehydrating 61.2 g of polytetramethylene ether glycol at 94 ° C and -0.1 MPa for 13 h, 11.2 g of pretreated tung oil was added and stirred at 69 ° C for 40 min. Then, 25.6 g of isophorone diisocyanate and 0.4 g of dibutyltin dilaurate were slowly added dropwise and prepolymerized for 3.5 h. Then, 4.8 g of 2,2-dimethylolpropionic acid was added and reacted for 3.5 h. Then, 40 mL of 3-aminophenylboric acid solution was slowly added dropwise and reacted at 74 ° C for 18 h. After cooling to 35 ° C, 3.7 g of triethylamine was added and neutralized for 35 min. Finally, 320 g of deionized water at 3 ° C was added and stirred at 8000 r / min for 1.2 h. After rotary evaporation to 424 g, a modified waterborne polyurethane emulsion was obtained; S4: 2.4 g of ammonium polyphosphate was added to 80 mL of deionized water at 73° C. and stirred for 45 min. 1.2 g of carboxymethyl chitosan was then added and stirred for 2 h. 0.4 g of halloysite nanotubes was then added and ultrasonically dispersed at a power of 280 W and a frequency of 23 kHz for 40 min. The mixture was stirred for 4.5 h to obtain a mildew inhibitor. S5: Add 2.2 g of deionized water, 1.1 g of basic copper carbonate, and 3.3 g of aminotrimethylenephosphonic acid to 55 mL of formamide and stir for 50 min to obtain a mixed solution; S6: 11 g of tetrabutyl titanate and 1.1 g of Tween-80 were added to 110 mL of formamide and stirred for 25 minutes. Then, 55 mL of the mixture was added dropwise at 2 mL / min at 48° C. and stirred at 900 rpm for 6.5 hours. Then, 2.2 g of ammonium fluoride was added and stirred at 90 rpm at 84° C. for 25 hours. Finally, the mixture was centrifuged at 9000 rpm for 15 minutes. The precipitate was washed with deionized water four times and vacuum dried at 33° C. and −0.1 MPa for 14 hours to obtain a phosphorus-containing composition. S7: 5.5 g of the phosphorus-containing composition and 0.33 g of tris(hydroxymethyl)aminomethane were added to 110 mL of deionized water and stirred at 450 rpm for 2.5 h. The pH was then adjusted to 9 with a 1 mol / L sodium hydroxide solution. 2.2 g of dopamine was then added and ultrasonicated at a power of 230 W and a frequency of 23 kHz for 7 h. The mixture was then centrifuged at 9000 rpm for 15 min. The precipitate was then washed four times with deionized water and vacuum dried at 33° C. and −0.1 MPa for 14 h to obtain a modified phosphorus-containing composition. S8: 2.5 g of sodium dodecylbenzenesulfonate and 2.5 g of the modified phosphorus-containing composition were added to 250 mL of deionized water and stirred at 1600 r / min at 83° C. for 0.8 h, followed by adding 50 g of cetyl alcohol and stirring at 1600 r / min at 86° C. for 0.8 h, followed by adding 62.5 mL of methyl methacrylate, 1.3 g of aminotrimethylenephosphonic acid, 6.2 g of ethylene glycol methacrylate, and 0.4 g of ammonium persulfate and reacting for 5 h, and finally centrifuging at 9000 r / min for 15 min, washing the precipitate with deionized water 6 times, and vacuum drying at 33° C. and -0.1 MPa for 14 h to obtain synergistic particles; S9: Add 3g of mildew inhibitor, 4g of synergistic particles, 2g of phthalocyanine green, and 0.4g of defoaming agent to 220g of modified water-based polyurethane emulsion and perform ultrasonic dispersion at a power of 380W and a frequency of 23kHz for 25min. Finally, shear at 12500r / min for 18min to obtain water-based aerosol spray paint for repairing wooden furniture.

[0024] Example 3: A method for preparing a water-based aerosol spray paint for repairing wooden furniture comprises the following steps: S1: Under a nitrogen atmosphere, 88.5 g of tung oil was dehydrated at 96 ° C for 40 min. After cooling to 62 ° C, 53.6 g of diethanolamine and 1.1 mL of 30% sodium methoxide solution were added and stirred at 350 r / min for 8 h. After cooling to 30 ° C, 350 mL of dichloromethane was added and centrifuged for 15 min. The organic phase was then washed 7 times with saturated sodium chloride solution and then dried with 5 g of anhydrous magnesium sulfate. After filtration, the filtrate was rotary evaporated at 30 ° C and -0.09 MPa to 145 g. Finally, it was vacuum dried at 65 ° C and -0.1 MPa for 15 h to obtain pretreated tung oil; S2: Add 3.8 g of 3-aminophenylboronic acid to 50 mL of tetrahydrofuran and stir for 90 min to obtain a 3-aminophenylboronic acid solution; S3: After dehydrating 76.5 g of polytetramethylene ether glycol at 95° C. and -0.1 MPa for 15 h, 14 g of pretreated tung oil was added and stirred at 70° C. for 50 min. Subsequently, 32 g of isophorone diisocyanate and 0.6 g of dibutyltin dilaurate were slowly added dropwise and prepolymerized for 4 h. Then, 6 g of 2,2-dimethylolpropionic acid was added and reacted for 4 h. Then, 50 mL of 3-aminophenylboronic acid solution was slowly added dropwise and reacted at 75° C. for 20 h. After cooling to 40° C., 4.6 g of triethylamine was added and neutralized for 40 min. Finally, 400 g of deionized water at 5° C. was added and stirred at 10,000 r / min for 1.5 h. After rotary evaporation to 530 g, a modified waterborne polyurethane emulsion was obtained. S4: 3 g of ammonium polyphosphate was added to 100 mL of deionized water at 75° C. and stirred for 60 min. 1.5 g of carboxymethyl chitosan was then added and stirred for 2.5 h. 0.5 g of halloysite nanotubes was then added and ultrasonically dispersed at a power of 300 W and a frequency of 25 kHz for 50 min. The mixture was stirred for 5 h to obtain a mildew inhibitor. S5: Add 2.4 g of deionized water, 1.2 g of basic copper carbonate, and 3.6 g of aminotrimethylenephosphonic acid to 60 mL of formamide and stir for 60 min to obtain a mixed solution; S6: 12 g of tetrabutyl titanate and 1.2 g of Tween-80 were added to 120 mL of formamide and stirred for 30 min. Then, 60 mL of the mixture was added dropwise at 3 mL / min at 50° C. and stirred at 1000 rpm for 7 h. Then, 2.4 g of ammonium fluoride was added and stirred at 100 rpm at 85° C. for 26 h. Finally, the mixture was centrifuged at 10,000 rpm for 20 min. The precipitate was washed with deionized water five times and vacuum dried at 35° C. and −0.1 MPa for 15 h to obtain a phosphorus-containing composition. S7: 6 g of the phosphorus-containing composition and 0.36 g of tris(hydroxymethyl)aminomethane) were added to 120 mL of deionized water and stirred at 500 rpm for 3 h. The pH was then adjusted to 9 with a 1 mol / L sodium hydroxide solution. 2.4 g of dopamine was then added and ultrasonic treatment was performed at a power of 250 W and a frequency of 25 kHz for 8 h. Finally, the mixture was centrifuged at 10,000 rpm for 20 min. The precipitate was washed five times with deionized water and vacuum dried at 35° C. and −0.1 MPa for 15 h to obtain a modified phosphorus-containing composition. S8: 3 g of sodium dodecylbenzenesulfonate and 3 g of the modified phosphorus-containing composition were added to 300 mL of deionized water and stirred at 85° C. and 1700 r / min for 1 h. Subsequently, 60 g of cetyl alcohol was added and stirred at 87° C. and 1700 r / min for 1 h. Subsequently, 75 mL of methyl methacrylate, 1.5 g of aminotrimethylenephosphonic acid, 7.5 g of ethylene glycol methacrylate, and 0.5 g of ammonium persulfate were added and reacted for 6 h. Finally, the mixture was centrifuged at 10,000 r / min for 20 min, the precipitate was washed with deionized water 7 times, and vacuum dried at 35° C. and -0.1 MPa for 15 h to obtain synergistic particles. S9: Add 4g of mildew inhibitor, 5g of synergistic particles, 3g of titanium dioxide, and 0.5g of defoaming agent to 240g of modified water-based polyurethane emulsion and perform ultrasonic dispersion at a power of 400W and a frequency of 25kHz for 30min. Finally, shear at 13000r / min for 20min to obtain water-based aerosol spray paint for repairing wooden furniture.

[0025] Comparative Example 1: Compared with Example 1, this comparative example only does not add "pretreated tung oil" during the preparation of S3. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0026] Comparative Example 2: Compared with Example 1, this comparative example only does not add "ammonium polyphosphate" during the preparation of S4. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0027] Comparative Example 3: Compared with Example 1, this comparative example only does not add "carboxymethyl chitosan" during the preparation of S4. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0028] Comparative Example 4: Compared with Example 1, this comparative example only does not add "halloysite nanotubes" during the preparation of S4. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0029] Comparative Example 5: Compared with Example 1, this comparative example only does not add "basic copper carbonate and aminotrimethylenephosphonic acid" during the preparation of S5. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0030] Comparative Example 6: Compared with Example 1, this comparative example only replaces the "synergistic particles" added in the preparation process of S9 with "phosphorus-containing composition", and the remaining steps and parameters are the same. This comparative example will not be repeated, and finally a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0031] Comparative Example 7: Compared with Example 1, this comparative example only replaces the "synergistic particles" added in the preparation process of S9 with the "modified phosphorus-containing composition". The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0032] Comparative Example 8: Compared with Example 1, this comparative example only does not add "synergistic particles" during the preparation of S9. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0033] Comparative Example 9: Compared with Example 1, this comparative example only does not add the "mildew inhibitor" during the preparation of S9. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, a water-based aerosol spray paint for repairing wooden furniture is obtained.

[0034] Performance testing: The water-based aerosol spray paint for repairing wooden furniture prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 9 was evenly sprayed on a smooth, dry and clean maple board (dry density 0.7 g / cm 3 , moisture content 16.5%, specifications 15cm×2.5cm×0.3cm), and after curing at 50℃ for 75h, a test specimen with a coating thickness of 0.2mm was obtained.

[0035] Determination of adhesion: With reference to the standard GB / T 9286-2021 "Scratch Test for Paints and Varnishes", the coating adhesion (grade) of the water-based aerosol spray paints for repairing wooden furniture prepared in Examples 1 to 3 and Comparative Examples 1 to 9 was measured. The test results are shown in Table 1.

[0036] Determination of hardness: With reference to GB / T 6739-2022 "Determination of Film Hardness of Paints and Varnishes by Pencil Method", the coating hardness (grade) of the water-based aerosol spray paints for repairing wooden furniture prepared in Examples 1 to 3 and Comparative Examples 1 to 9 of the present invention was measured. The measurement results are shown in Table 1. Determination of solvent resistance: With reference to GB / T 23989-2009 "Determination of Solvent Resistance of Coatings," a manual rubbing method (Method A) was used, ethanol was selected as the organic solvent, and the number of solvent rubs on the coating was recorded. The solvent resistance (times) of the water-based aerosol spray paints for restoring wooden furniture prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 9 was measured according to the above method. The measurement results are shown in Table 1. Determination of self-repair ability: The coatings were cut into standard dumbbell-shaped specimens (25mm × 2.05mm × 0.2mm, length × width × thickness) and randomly divided into two groups. One group underwent a direct tensile test at a loading speed of 50mm / min to determine the original fracture strain. The other group was placed on a glass slide, and two cross-cut scratches were made on the coating surface with a scalpel. After aligning the scratches, the healed samples were placed at 25°C for 24 hours. The tensile properties of the healed samples were then tested again to determine the post-treatment fracture strain. The repair efficiency was then calculated (100% × post-treatment fracture strain / original fracture strain). The self-repair capacity (%) of the water-based aerosol spray paints for repairing wooden furniture prepared in Examples 1-3 and Comparative Examples 1-9 was determined using the above method. The test results are shown in Table 1. Determination of fire resistance: With reference to GB 12441-2018 "Fire-retardant coating for surface finishes", the test panels prepared by the water-based aerosol spray paint for repairing wooden furniture prepared in Examples 1 to 3 and Comparative Examples 1 to 9 were measured using the large plate combustion method (the test panels were specially made according to the requirements of the large plate combustion method; the substrate was a 5 mm thick first-level three-layer plywood with a size of 900 mm × 900 mm and a wet coating ratio of 500 g / m 2 ) The time required for the back-fire surface temperature to reach 220°C or for penetration to occur (min) is used to reflect the fire resistance of the water-based aerosol spray paint for repairing wooden furniture (min). The test results are shown in Table 1. Determination of anti-mildew ability: Referring to the standard GB / T 1741-2020 "Determination of Mold Resistance of Paint Films," 10 mL of a suspension of Aspergillus niger ATCC 16404 at a concentration of 5 × 10 5 spores / mL was evenly applied to the paint film surface of the test sample. After incubation at a temperature of 37°C and a relative humidity of 95% for 28 days, the mold growth area percentage (%) was measured to reflect the mold resistance. The smaller the mold growth area percentage, the stronger the mold resistance. According to this method, the mold resistance (%) of the test sample coatings made with the water-based aerosol spray paints for repairing wooden furniture prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 9 was determined. The test results are shown in Table 1.

[0037] Table 1: Performance test results of Examples 1-3 and Comparative Examples 1-9

[0038] Data Analysis: As can be seen from Table 1, the water-based aerosol spray paint for repairing wooden furniture prepared in the embodiment of the present invention has excellent adhesion, hardness, solvent resistance, self-repairing ability, flame retardancy and mildew resistance.

[0039] The above is a detailed description of an embodiment of the present invention. However, the content described is only a preferred embodiment of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A water-based aerosol spray paint for repairing wooden furniture, characterized in that: The invention comprises the following raw materials in parts by weight: 200-240 parts of modified waterborne polyurethane emulsion, 2-4 parts of mildew inhibitor, 3-5 parts of synergistic particles, 1-3 parts of pigment and 0.3-0.5 parts of defoaming agent.

2. The water-based aerosol spray paint for repairing wooden furniture according to claim 1, characterized in that: The preparation method of the modified aqueous polyurethane emulsion is: A1: Dehydrate tung oil under a nitrogen atmosphere. After the temperature drops to 58-62°C, add diethanolamine and sodium methoxide solution and stir for 7-8 hours. After the temperature drops to 20-30°C, add dichloromethane and centrifuge for 10-15 minutes. Wash the organic phase 5-7 times, dry it with anhydrous magnesium sulfate, filter it, and then rotary evaporate and vacuum dry the filtrate to obtain pretreated tung oil. A2: Add 3-aminophenylboronic acid to tetrahydrofuran and stir for 60-90 minutes to obtain a 3-aminophenylboronic acid solution; A3: After dehydration of polytetramethylene ether glycol, pretreated tung oil is added and stirred at 68-70°C for 30-50 minutes. Then, isophorone diisocyanate and dibutyltin dilaurate are added dropwise in sequence and prepolymerized for 3-4 hours. Then, 2,2-dihydroxymethylpropionic acid is added and reacted for 3-4 hours. Then, 3-aminophenylboric acid solution is added dropwise and reacted at 73-75°C for 15-20 hours. After cooling to 30-40°C, triethylamine is added and neutralized for 30-40 minutes. Finally, deionized water is added and stirred at 5000-10000 r / min for 1-1.5 hours. After rotary evaporation, a modified waterborne polyurethane emulsion is obtained.

3. The water-based aerosol spray paint for repairing wooden furniture according to claim 2, characterized in that: The usage ratio of tung oil, diethanolamine, sodium methoxide solution, dichloromethane, and anhydrous magnesium sulfate in step A1 is 66-88.5 g: 40.2-53.6 g: 0.9-1.1 mL: 262.5-350 mL: 4-5 g; The mass fraction of the sodium methoxide solution in step A1 is 30%.

4. The water-based aerosol spray paint for repairing wooden furniture according to claim 2, characterized in that: The ratio of tetrahydrofuran to 3-aminophenylboronic acid in step A2 is 30-50 mL: 2.3-3.8 g; The usage ratio of polytetramethylene ether glycol, pretreated tung oil, isophorone diisocyanate, dibutyltin dilaurate, 2,2-dihydroxymethylpropionic acid, 3-aminophenylboric acid solution, triethylamine, and deionized water in step A3 is 45.9-76.5 g: 8.4-14 g: 19.2-32 g: 0.3-0.6 g: 3.6-6 g: 30-50 mL: 2.8-4.6 g: 240-400 g.

5. The water-based aerosol spray paint for repairing wooden furniture according to claim 1, characterized in that: The preparation method of the mildew inhibitor is as follows: Ammonium polyphosphate is added to deionized water at 70-75° C. and stirred for 30-60 minutes. Then, carboxymethyl chitosan is added and stirred for 1.5-2.5 hours. Then, halloysite nanotubes are added and ultrasonically dispersed for 30-50 minutes. After stirring for 4-5 hours, a mildew inhibitor is obtained.

6. The water-based aerosol spray paint for repairing wooden furniture according to claim 5, characterized in that: The usage ratio of the deionized water, ammonium polyphosphate, carboxymethyl chitosan and halloysite nanotubes is 60-100 mL: 1.8-3 g: 0.9-1.5 g: 0.3-0.5 g.

7. The water-based aerosol spray paint for repairing wooden furniture according to claim 1, characterized in that: The preparation method of the synergistic granules comprises the following steps: B1: Add deionized water, basic copper carbonate, and aminotrimethylenephosphonic acid to formamide and stir for 40-60 minutes to obtain a mixed solution; B2: Tetrabutyl titanate and Tween-80 are added to formamide and stirred for 20-30 minutes. Then, the mixture is added dropwise at 45-50°C and stirred for 6-7 hours. Then, ammonium fluoride is added and stirred at 83-85°C for 24-26 hours. Finally, the mixture is centrifuged, the precipitate is washed, and vacuum dried to obtain a phosphorus-containing composition. B3: Adding the phosphorus-containing composition and tris(hydroxymethyl)aminomethane to deionized water and stirring for 2-3 hours, then adjusting the pH to 8.8-9.2, then adding dopamine and ultrasonically treating for 6-8 hours, finally centrifuging, washing the precipitate, and vacuum drying to obtain a modified phosphorus-containing composition; B4: Sodium dodecylbenzenesulfonate and the modified phosphorus-containing composition are added to deionized water and stirred at 80-85°C for 0.5-1h. Then, cetyl alcohol is added and stirred at 85-87°C for 0.5-1h. Then, methyl methacrylate, aminotrimethylenephosphonic acid, ethylene glycol methacrylate, and ammonium persulfate are added and reacted for 4-6h. Finally, the mixture is centrifuged, precipitated, and vacuum dried to obtain synergistic particles.

8. The water-based aerosol spray paint for repairing wooden furniture according to claim 7, characterized in that: The ratio of formamide, deionized water, basic copper carbonate, and aminotrimethylenephosphonic acid in step B1 is 50-60 mL: 2-2.4 g: 1-1.2 g: 3-3.6 g; The dosage ratio of formamide, tetrabutyl titanate, Tween-80, mixed solution, and ammonium fluoride in step B2 is 100-120 mL: 10-12 g: 1-1.2 g: 50-60 mL: 2-2.4 g; In step B3, the ratio of deionized water, phosphorus-containing composition, tris(hydroxymethyl)aminomethane, and dopamine is 100-120 mL: 5-6 g: 0.3-0.36 g: 2-2.4 g; The usage ratio of deionized water, sodium dodecylbenzenesulfonate, modified phosphorus-containing composition, cetyl alcohol, methyl methacrylate, aminotrimethylenephosphonic acid, ethylene glycol methacrylate, and ammonium persulfate in step B4 is 200-300 mL: 2-3 g: 2-3 g: 40-60 g: 50-75 mL: 1-1.5 g: 5-7.5 g: 0.3-0.5 g.

9. The water-based aerosol spray paint for repairing wooden furniture according to claim 1, characterized in that: The pigment is any one of titanium dioxide, carbon black, iron red, iron yellow, phthalocyanine blue, phthalocyanine green and matte powder.

10. A method for preparing a water-based aerosol spray paint for repairing wooden furniture according to any one of claims 1 to 9, characterized in that: The following steps are involved: A mildew preventer, synergistic particles, pigment and defoamer are added to the modified waterborne polyurethane emulsion and ultrasonically dispersed for 20-30 minutes, and finally sheared for 15-20 minutes to obtain a waterborne aerosol spray paint for repairing wooden furniture.

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