A rubber touch paint and a preparation method thereof

Abstract

This invention relates to the field of coating technology and discloses a rubber-feel coating and its preparation method. The invention introduces a fluorinated guanidine quaternary phosphonium salt chain extender and glycerol monomethacrylate into the polyurethane backbone to prepare a fluorinated guanidine quaternary phosphonium salt modified polyurethane. Using this modified polyurethane as a film-forming material, it is combined with phosphocholine-modified organosilicon micropowder, polyethylene wax powder, photoinitiator 184, isobornyl acrylate, butyl acetate diluent, and Tween 80. After dispersion, grinding, and mixing, a rubber-feel coating is obtained. In this coating, glycerol monomethacrylate acts as a chain extender containing carbon-carbon double bonds, which is incorporated into the polyurethane backbone. Under the action of the photoinitiator, free radical polymerization is initiated by UV irradiation, enabling the photocuring of the coating. The coating prepared by this invention possesses both excellent smooth feel and highly efficient and long-lasting antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a rubber-feel coating and its preparation method. Background Technology

[0002] Rubber-feel coatings, also known as elastic paints or rubber paints, are special functional coatings that, when applied to the surface of an object, create a rubber-like feel. They are widely used on the surfaces of products such as mobile phone casings, mice, automotive interior parts, and home appliances. These coatings typically use polyurethane resin as the main film-forming agent, combined with matting agents, feel additives, and curing agents. Their core value lies in providing a soft, smooth, and delicate tactile experience, enhancing user comfort and perceived quality. However, existing rubber-feel coatings still have the following technical shortcomings: First, it is difficult to balance feel and antibacterial properties. Current technologies mainly improve the smoothness and smoothness of the coating by adding physical additives such as organosilicon micropowder and wax powder. However, these additives only provide a single tactile adjustment function and do not possess antibacterial activity. Currently, commercially available antibacterial coatings often achieve antibacterial functions by directly adding nano-silver or organic antibacterial agents. However, these antibacterial agents lack synergistic design with feel additives, often sacrificing the smoothness of the coating while introducing antibacterial function, leading to a deterioration in feel. Second, the antibacterial durability is insufficient. In existing technologies, antibacterial agents are mostly added to coatings in a physically dispersed manner, lacking chemical bonding with the resin matrix. During use, they are easily migrated and lost from the coating due to factors such as friction and washing, resulting in a significant decrease in antibacterial performance and making it difficult to achieve long-lasting antibacterial effects. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention provides a rubber-feel coating and its preparation method. The coating prepared by this invention possesses both excellent antibacterial properties and a smooth, slippery feel.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a rubber-feel coating comprising the following weight components: 95-105 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 3-5 parts by weight of choline phosphate modified organosilicon micro powder, 1-3 parts by weight of polyethylene wax powder, 5-10 parts by weight of isobornyl acrylate, 3-4 parts by weight of photoinitiator 184, 10-20 parts by weight of butyl acetate diluent, and 0.2-0.5 parts by weight of Tween 80.

[0005] Preferably, the fluorinated guanidine quaternary phosphonium salt modified polyurethane is prepared by the following steps: (1) Add 8-10 mL of deionized water and 30-40 mL of anhydrous ethanol to the reaction flask as solvents, add 8-10 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH value with triethylamine, purge with nitrogen for protection, heat to 60-68℃, add 1.7-2.13 g of a mixed solution of 1,2-epoxychlorobutane and 10-15 mL of anhydrous ethanol dropwise over a period of 25-35 min, and after the addition is complete, react for 6.5-8.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1-1.4 g of guanidine salt intermediate and 0.01-0.03 g of potassium iodide catalyst to 10-20 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen gas for protection, heat to 65-70℃, and dropwise add 1.3-1.82 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 8-12 mL of anhydrous acetonitrile solution, the dropwise addition time is 20-30 min, after the dropwise addition is completed, react for 18-20 h, after the reaction is completed, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain fluorinated guanidine quaternary phosphonium salt chain extender; (3) Add 4-6g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 110-120℃ and dehydrate under vacuum for 40-50min, cool to 58-62℃, release the vacuum, add 0.16-0.24g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.2-0.3g of glycerol monomethacrylate, 0.04-0.06g of 1,4-butanediol, and 2.5-3.5mL of butyl acetate diluent, stir and mix, add 0.63-0.95g of hexamethylene diisocyanate and 0.002-0.003g of dibutyltin dilaurate catalyst, heat to 75-80℃ and react for 4-6h, after the reaction is completed, add 1-2mL of butyl acetate diluent, stir for 20-30min to obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane.

[0006] Preferably, the pH value in step (1) is 8-9.

[0007] Preferably, the choline-modified organosilicon micropowder is prepared by the following steps: S1. Add 2-4 mL of deionized water and 18-22 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2-2.4 g of phosphocholine, stir to dissolve, add 2.09-2.51 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.0-5.5 with hydrochloric acid solution, purge with nitrogen for protection, add 2.22-2.66 g of a mixed solution of 3-aminopropyltriethoxysilane and 10-15 mL of anhydrous ethanol dropwise over 20-25 min, after which react at 24-30℃ for 14-16 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; S2. Add 0.15-0.25g of sodium dodecyl sulfate surfactant, 6.8-9.6g of dimethyldiethoxysilane, 0.8-1.2g of methyltrimethoxysilane, and 0.8-1.2g of phosphocholine-modified silane coupling agent to 40-60mL of deionized water solvent. Stir and emulsify for 10-20min, heat to 50-60℃, adjust the pH to 9-10 with ammonia water, and react for 8-10h. After the reaction is complete, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine-modified organosilicon micropowder.

[0008] Preferably, the mass fraction of the hydrochloric acid solution in S1 is 0.3%-0.5%.

[0009] Preferably, the mass fraction of ammonia in S2 is 25%-28%.

[0010] Preferably, the preparation method of the rubber-feel coating includes the following steps: adding fluorinated guanidine quaternary phosphonium salt modified polyurethane, Tween 80, phosphocholine modified organosilicon micro powder, and polyethylene wax powder to a dispersion vessel, stirring at 500-800 rpm for 10-15 min to obtain a pre-dispersed slurry, putting the pre-dispersed slurry into a sand mill, using zirconia beads as the grinding media, grinding at 1500-2000 rpm for 20-30 min, and then transferring it to a paint mixing vessel, adding isobornyl acrylate, photoinitiator 184, and butyl acetate diluent, stirring at 400-600 rpm for 5-10 min to obtain the rubber-feel coating.

[0011] In summary, this application includes at least one of the following beneficial technical effects: This invention introduces a fluorinated guanidine quaternary phosphonium salt chain extender and glycerol monomethacrylate into the polyurethane backbone to prepare a fluorinated guanidine quaternary phosphonium salt modified polyurethane. Using the fluorinated guanidine quaternary phosphonium salt modified polyurethane as a film-forming material, it is combined with phosphocholine-modified organosilicon micropowder, polyethylene wax powder, photoinitiator and other components. After dispersion, grinding and paint preparation, a rubber-feel coating is obtained. In this coating, glycerol monomethacrylate acts as a chain extender containing carbon-carbon double bonds and is incorporated into the polyurethane backbone. Under the action of the photoinitiator, free radical polymerization is initiated by UV irradiation, which can realize the photocuring of the coating.

[0012] This invention uses photocurable polyurethane resin as the film-forming material, combined with choline phosphate modified organosilicon micro powder and polyethylene wax powder, to prepare a rubber-feel coating that has both antibacterial and smooth feel.

[0013] Fluorinated guanidine quaternary phosphonium salt chain extenders are chemically bonded to the polyurethane backbone. The perfluorodecyl segments in their molecular structure have extremely low surface energy. During coating curing, these perfluoro segments spontaneously migrate and accumulate on the coating surface, forming a dense, low-surface-energy lubricating layer. This reduces the coefficient of friction, decreasing resistance when fingers glide across the surface and producing a smooth feel. The guanidine salt group is a cationic polymer; the positive charge on its molecular chain can adsorb the negatively charged bacterial cell membrane, inhibiting bacterial division and rendering them infertile. Simultaneously, the guanidine salt polymer can form a thin film on the bacterial surface, blocking the respiratory channels of microorganisms and causing them to rapidly suffocate and die. The quaternary phosphonium salt group also carries a positive charge and can bind to negatively charged sites on the bacterial cell membrane, inserting into and disrupting the cell membrane's integrity, leading to leakage of intracellular substances. Kills bacteria; both guanidine salt and quaternary phosphonium salt antibacterial groups exist simultaneously in the same chain extender molecule, synergistically inhibiting bacteria through their respective mechanisms of action, thus improving the antibacterial performance of the coating; phosphocholine-modified organosilicon microparticles are uniformly distributed on the coating surface. When a finger slides across the surface, the microparticles generate a rolling effect similar to "micro-balls," converting sliding friction into rolling friction, reducing frictional resistance between the finger and the coating, and improving the smoothness of the coating; phosphocholine contains both quaternary ammonium and phosphate groups, exhibiting an amphoteric structure. This structure mimics the structure of the extracellular membrane, giving the material surface excellent biocompatibility, enabling it to interact with bacterial cell membranes, interfering with the integrity and normal function of bacterial cell membranes, and inhibiting bacterial growth and reproduction. By copolymerizing phosphocholine groups onto the surface of organosilicon microparticles, the antibacterial durability is further improved. Attached Figure Description

[0014] Figure 1 It is the synthetic reaction formula for fluorinated guanidine quaternary phosphonium salt chain extenders.

[0015] Figure 2 It is the synthetic reaction formula for phosphoric acid choline-modified silane coupling agents. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] To better understand the above technical solutions, the following will provide a detailed description of the technical solutions in conjunction with the accompanying drawings and specific embodiments.

[0018] Example 1 (1) Add 8 mL of deionized water and 30 mL of anhydrous ethanol to the reaction flask as solvents, add 8 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH to 8 with triethylamine, purge with nitrogen for protection, heat to 60 °C, add 1.7 g of a mixed solution of 1,2-epoxychlorobutane and 10 mL of anhydrous ethanol dropwise over a period of 25 min, and after the addition is complete, react for 6.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1 g of guanidine salt intermediate and 0.01 g of potassium iodide catalyst to 10 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen for protection, heat to 65 °C, and add dropwise a mixed solution of 1.3 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 8 mL of anhydrous acetonitrile over a period of 20 min. After the addition is complete, react for 18 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water, and freeze dry to obtain a fluorinated guanidine quaternary phosphonium salt chain extender; the synthesis reaction formula is as follows. Figure 1 As shown; (3) Add 4g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 110℃ and dehydrate under vacuum for 40min, cool to 58℃, release the vacuum, add 0.16g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.2g of glycerol monomethacrylate, 0.04g of 1,4-butanediol, and 2.5mL of butyl acetate diluent, stir and mix, add 0.63g of hexamethylene diisocyanate and 0.002g of dibutyltin dilaurate catalyst, heat to 75℃ and react for 4h, after the reaction is completed, add 1mL of butyl acetate diluent, stir for 20min, and obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane; (4) Add 2 mL of deionized water and 18 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2 g of phosphocholine, stir to dissolve, add 2.09 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.0 with 0.3% hydrochloric acid solution, purge with nitrogen for protection, add 2.22 g of a mixed solution of 3-aminopropyltriethoxysilane and 10 mL of anhydrous ethanol dropwise over 20 min, and after the addition is complete, react at 24 °C for 14 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; the synthesis reaction formula is as follows. Figure 2 As shown; (5) Add 0.15g of sodium dodecyl sulfate surfactant, 6.8g of dimethyldiethoxysilane, 0.8g of methyltrimethoxysilane, and 0.8g of phosphocholine modified silane coupling agent to 40mL of deionized water solvent, stir and emulsify for 10min, heat to 50℃, adjust the pH to 9 with 25% ammonia water, react for 8h, after the reaction is completed, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine modified organosilicon micro powder; (6) Add 95 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 0.2 parts by weight of Tween 80, 3 parts by weight of phosphocholine modified organosilicon micro powder, and 1 part by weight of polyethylene wax powder to the dispersion vessel. Stir at 500 rpm for 10 min to obtain a pre-dispersed slurry. Put the pre-dispersed slurry into a sand mill with zirconia beads as the grinding medium. Grind at 1500 rpm for 20 min and then transfer it to a paint mixing vessel. Add 5 parts by weight of isoborneol acrylate, 3 parts by weight of photoinitiator 184, and 10 parts by weight of butyl acetate diluent. Stir at 400 rpm for 5 min to obtain a rubber-feel coating.

[0019] Example 2 (1) Add 10 mL of deionized water and 40 mL of anhydrous ethanol to the reaction flask as solvents, add 10 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH to 9 with triethylamine, purge with nitrogen for protection, heat to 68 °C, add 2.13 g of a mixed solution of 1,2-epoxychlorobutane and 15 mL of anhydrous ethanol dropwise over a period of 35 min, and after the addition is complete, react for 8.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1.4 g of guanidine salt intermediate and 0.03 g of potassium iodide catalyst to 20 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen gas for protection, heat to 70 °C, and add dropwise a mixed solution of 1.82 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 12 mL of anhydrous acetonitrile over a period of 30 min. After the addition is complete, react for 20 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water, and freeze dry to obtain a fluorinated guanidine quaternary phosphonium salt chain extender; the synthesis reaction formula is as follows. Figure 1 As shown; (3) Add 6g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 120℃ and dehydrate under vacuum for 50min, cool to 62℃, release the vacuum, add 0.24g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.3g of glycerol monomethacrylate, 0.06g of 1,4-butanediol, and 3.5mL of butyl acetate diluent, stir and mix, add 0.95g of hexamethylene diisocyanate and 0.003g of dibutyltin dilaurate catalyst, heat to 80℃ and react for 6h, after the reaction is completed, add 2mL of butyl acetate diluent, stir for 30min, and obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane; (4) Add 4 mL of deionized water and 22 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2.4 g of phosphocholine, stir to dissolve, add 2.51 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.5 with 0.5% hydrochloric acid solution, purge with nitrogen for protection, add 2.66 g of a mixed solution of 3-aminopropyltriethoxysilane and 15 mL of anhydrous ethanol dropwise over 25 min, and after the addition is complete, react at 30 °C for 16 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; the synthesis reaction formula is as follows. Figure 2 As shown; (5) Add 0.25g of sodium dodecyl sulfate surfactant, 9.6g of dimethyldiethoxysilane, 1.2g of methyltrimethoxysilane, and 1.2g of phosphocholine modified silane coupling agent to 60mL of deionized water solvent, stir and emulsify for 20min, heat to 60℃, adjust the pH to 10 with 28% ammonia water, react for 10h, after the reaction is completed, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine modified organosilicon micro powder; (6) Add 105 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 0.5 parts by weight of Tween 80, 5 parts by weight of phosphocholine modified organosilicon micro powder, and 3 parts by weight of polyethylene wax powder to the dispersion vessel. Stir at 800 rpm for 15 min to obtain a pre-dispersed slurry. Put the pre-dispersed slurry into a sand mill with zirconia beads as the grinding medium. Grind at 2000 rpm for 30 min and then transfer it to a paint mixing vessel. Add 10 parts by weight of isoborneol acrylate, 4 parts by weight of photoinitiator 184, and 20 parts by weight of butyl acetate diluent. Stir at 600 rpm for 10 min to obtain a rubber-feel coating.

[0020] Example 3 (1) Add 9 mL of deionized water and 35 mL of anhydrous ethanol to the reaction flask as solvents, add 9 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH to 8.5 with triethylamine, purge with nitrogen for protection, heat to 64 °C, add 1.92 g of a mixed solution of 1,2-epoxychlorobutane and 12 mL of anhydrous ethanol dropwise over 30 min, and after the addition is complete, react for 7.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1.2 g of guanidine salt intermediate and 0.02 g of potassium iodide catalyst to 15 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen for protection, heat to 68 °C, and add dropwise a mixed solution of 1.56 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 10 mL of anhydrous acetonitrile over a period of 25 min. After the addition is complete, react for 19 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water, and freeze dry to obtain a fluorinated guanidine quaternary phosphonium salt chain extender; the synthesis reaction formula is as follows. Figure 1 As shown; (3) Add 5g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 115℃ and dehydrate under vacuum for 45min, cool to 60℃, release the vacuum, add 0.2g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.25g of glycerol monomethacrylate, 0.05g of 1,4-butanediol, and 3mL of butyl acetate diluent, stir and mix, add 0.79g of hexamethylene diisocyanate and 0.0025g of dibutyltin dilaurate catalyst, heat to 78℃ and react for 5h, after the reaction is completed, add 1.5mL of butyl acetate diluent, stir for 25min to obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane; (4) Add 3 mL of deionized water and 20 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2.2 g of phosphocholine, stir to dissolve, add 2.3 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.2 with 0.4% hydrochloric acid solution, purge with nitrogen for protection, add 2.44 g of a mixed solution of 3-aminopropyltriethoxysilane and 12 mL of anhydrous ethanol dropwise over 22 min, and after the addition is complete, react at 27 °C for 15 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; the synthesis reaction formula is as follows. Figure 2 As shown; (5) Add 0.2g of sodium dodecyl sulfate surfactant, 8.2g of dimethyldiethoxysilane, 1g of methyltrimethoxysilane, and 1g of phosphocholine modified silane coupling agent to 50mL of deionized water solvent, stir and emulsify for 15min, heat to 55℃, adjust the pH to 9.5 with 26.5% ammonia water, react for 9h, after the reaction is completed, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine modified organosilicon micro powder; (6) Add 100 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 0.35 parts by weight of Tween 80, 4 parts by weight of phosphocholine modified organosilicon micro powder, and 2 parts by weight of polyethylene wax powder to the dispersion vessel. Stir at 650 rpm for 12 min to obtain a pre-dispersed slurry. Put the pre-dispersed slurry into a sand mill with zirconia beads as the grinding medium. Grind at 1750 rpm for 25 min and then transfer it to a paint mixing vessel. Add 7.5 parts by weight of isobornyl acrylate, 3.5 parts by weight of photoinitiator 184, and 15 parts by weight of butyl acetate diluent. Stir at 500 rpm for 8 min to obtain a rubber-feel coating.

[0021] Example 4 (1) Add 9 mL of deionized water and 35 mL of anhydrous ethanol to the reaction flask as solvents, add 9 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH to 8.5 with triethylamine, purge with nitrogen for protection, heat to 64 °C, add 1.92 g of a mixed solution of 1,2-epoxychlorobutane and 12 mL of anhydrous ethanol dropwise over 30 min, and after the addition is complete, react for 7.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1.2 g of guanidine salt intermediate and 0.02 g of potassium iodide catalyst to 15 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen for protection, heat to 68 °C, and add dropwise a mixed solution of 1.56 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 10 mL of anhydrous acetonitrile over a period of 25 min. After the addition is complete, react for 19 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water, and freeze dry to obtain a fluorinated guanidine quaternary phosphonium salt chain extender; the synthesis reaction formula is as follows. Figure 1 As shown; (3) Add 4g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 110℃ and dehydrate under vacuum for 40min, cool to 58℃, release the vacuum, add 0.16g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.2g of glycerol monomethacrylate, 0.04g of 1,4-butanediol, and 2.5mL of butyl acetate diluent, stir and mix, add 0.63g of hexamethylene diisocyanate and 0.002g of dibutyltin dilaurate catalyst, heat to 75℃ and react for 4h, after the reaction is completed, add 1mL of butyl acetate diluent, stir for 20min, and obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane; (4) Add 2 mL of deionized water and 18 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2 g of phosphocholine, stir to dissolve, add 2.09 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.0 with 0.3% hydrochloric acid solution, purge with nitrogen for protection, add 2.22 g of a mixed solution of 3-aminopropyltriethoxysilane and 10 mL of anhydrous ethanol dropwise over 20 min, and after the addition is complete, react at 24 °C for 14 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; the synthesis reaction formula is as follows. Figure 2 As shown; (5) Add 0.25g of sodium dodecyl sulfate surfactant, 9.6g of dimethyldiethoxysilane, 1.2g of methyltrimethoxysilane, and 1.2g of phosphocholine modified silane coupling agent to 60mL of deionized water solvent, stir and emulsify for 20min, heat to 60℃, adjust the pH to 10 with 28% ammonia water, react for 10h, after the reaction is completed, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine modified organosilicon micro powder; (6) Add 105 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 0.5 parts by weight of Tween 80, 5 parts by weight of phosphocholine modified organosilicon micro powder, and 3 parts by weight of polyethylene wax powder to the dispersion vessel. Stir at 800 rpm for 15 min to obtain a pre-dispersed slurry. Put the pre-dispersed slurry into a sand mill with zirconia beads as the grinding medium. Grind at 2000 rpm for 30 min and then transfer it to a paint mixing vessel. Add 10 parts by weight of isoborneol acrylate, 4 parts by weight of photoinitiator 184, and 20 parts by weight of butyl acetate diluent. Stir at 600 rpm for 10 min to obtain a rubber-feel coating.

[0022] Example 5 (1) Add 8 mL of deionized water and 30 mL of anhydrous ethanol to the reaction flask as solvents, add 8 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH to 8 with triethylamine, purge with nitrogen for protection, heat to 60 °C, add 1.7 g of a mixed solution of 1,2-epoxychlorobutane and 10 mL of anhydrous ethanol dropwise over a period of 25 min, and after the addition is complete, react for 6.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1 g of guanidine salt intermediate and 0.01 g of potassium iodide catalyst to 10 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen for protection, heat to 65 °C, and add dropwise a mixed solution of 1.3 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 8 mL of anhydrous acetonitrile over a period of 20 min. After the addition is complete, react for 18 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water, and freeze dry to obtain a fluorinated guanidine quaternary phosphonium salt chain extender; the synthesis reaction formula is as follows. Figure 1 As shown; (3) Add 6g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 120℃ and dehydrate under vacuum for 50min, cool to 62℃, release the vacuum, add 0.24g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.3g of glycerol monomethacrylate, 0.06g of 1,4-butanediol, and 3.5mL of butyl acetate diluent, stir and mix, add 0.95g of hexamethylene diisocyanate and 0.003g of dibutyltin dilaurate catalyst, heat to 80℃ and react for 6h, after the reaction is completed, add 2mL of butyl acetate diluent, stir for 30min, and obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane; (4) Add 4 mL of deionized water and 22 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2.4 g of phosphocholine, stir to dissolve, add 2.51 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.5 with 0.5% hydrochloric acid solution, purge with nitrogen for protection, add 2.66 g of a mixed solution of 3-aminopropyltriethoxysilane and 15 mL of anhydrous ethanol dropwise over 25 min, and after the addition is complete, react at 30 °C for 16 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; the synthesis reaction formula is as follows. Figure 2 As shown; (5) Add 0.2g of sodium dodecyl sulfate surfactant, 8.2g of dimethyldiethoxysilane, 1g of methyltrimethoxysilane, and 1g of phosphocholine modified silane coupling agent to 50mL of deionized water solvent, stir and emulsify for 15min, heat to 55℃, adjust the pH to 9.5 with 26.5% ammonia water, react for 9h, after the reaction is completed, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine modified organosilicon micro powder; (6) Add 100 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 0.35 parts by weight of Tween 80, 4 parts by weight of phosphocholine modified organosilicon micro powder, and 2 parts by weight of polyethylene wax powder to the dispersion vessel. Stir at 650 rpm for 12 min to obtain a pre-dispersed slurry. Put the pre-dispersed slurry into a sand mill with zirconia beads as the grinding medium. Grind at 1750 rpm for 25 min and then transfer it to a paint mixing vessel. Add 7.5 parts by weight of isobornyl acrylate, 3.5 parts by weight of photoinitiator 184, and 15 parts by weight of butyl acetate diluent. Stir at 500 rpm for 8 min to obtain a rubber-feel coating.

[0023] Comparative Example 1 Compared with Example 5, this comparative example does not include steps (1) and (2), and does not contain fluorinated guanidine quaternary phosphonium salt chain extender in step (3) to obtain unmodified polyurethane. In step (6), unmodified polyurethane is used instead of fluorinated guanidine quaternary phosphonium salt modified polyurethane.

[0024] Comparative Example 2 The difference between this comparative example and Example 5 is that it does not include steps (4) and (5), and step (6) does not contain phosphocholine-modified organosilicon micropowder.

[0025] The coatings from Examples 1-5 and Comparative Examples 1-2 were applied to the ABS substrate at a uniform speed along the horizontal direction using a scraper. The wet film thickness was 80 μm. The coated substrate was placed horizontally in an oven at 80°C for 2-3 minutes for pre-baking, and then cured under ultraviolet light. After curing, the substrate was placed in an environment at 25°C and 50% relative humidity for 24 hours to obtain the coating sample.

[0026] The coefficient of friction of the coated samples was tested according to ASTM D1894. The test results are shown in Table 1.

[0027] Table 1: Friction coefficient test.

[0028]

[0029] According to GB / T 31402-2023, Escherichia coli and Staphylococcus aureus were used as test bacteria to test the antibacterial properties of the coating samples. The test results are shown in Table 2.

[0030] Table 2: Antibacterial performance test.

[0031]

[0032] As shown in Tables 1 and 2, the coatings in Examples 1-5 of the present invention have lower static and dynamic friction coefficients compared to the coatings in Comparative Examples 1-2, indicating that they have a better smooth feel; at the same time, they have a higher antibacterial rate, and the antibacterial rate remains above 99% after 50 washes, indicating that their antibacterial performance is highly efficient and long-lasting.

[0033] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0034] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0035] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A rubber-feel coating, characterized in that, It includes the following components by weight: 95-105 parts by weight of fluorinated guanidine quaternary phosphonium salt modified polyurethane, 3-5 parts by weight of choline phosphate modified organosilicon micro powder, 1-3 parts by weight of polyethylene wax powder, 5-10 parts by weight of isobornyl acrylate, 3-4 parts by weight of photoinitiator 184, 10-20 parts by weight of butyl acetate diluent, and 0.2-0.5 parts by weight of Tween 80.

2. The rubber-feel coating according to claim 1, characterized in that, The fluorinated guanidine quaternary phosphonium salt modified polyurethane is prepared by the following steps: (1) Add 8-10 mL of deionized water and 30-40 mL of anhydrous ethanol to the reaction flask as solvents, add 8-10 g of polyhexamethylene guanidine, stir to dissolve, adjust the pH value with triethylamine, purge with nitrogen for protection, heat to 60-68℃, add 1.7-2.13 g of a mixed solution of 1,2-epoxychlorobutane and 10-15 mL of anhydrous ethanol dropwise over a period of 25-35 min, and after the addition is complete, react for 6.5-8.5 h. After the reaction is complete, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain the guanidine salt intermediate; (2) Add 1-1.4 g of guanidine salt intermediate and 0.01-0.03 g of potassium iodide catalyst to 10-20 mL of anhydrous acetonitrile solvent, stir and mix, purge with nitrogen gas for protection, heat to 65-70℃, and dropwise add 1.3-1.82 g of biphenyl [4-(1H,1H,2H,2H-perfluorodecyl)phenyl]phosphine and 8-12 mL of anhydrous acetonitrile solution, the dropwise addition time is 20-30 min, after the dropwise addition is completed, react for 18-20 h, after the reaction is completed, remove the solvent by rotary evaporation, dialyze in deionized water and freeze dry to obtain fluorinated guanidine quaternary phosphonium salt chain extender; (3) Add 4-6g of polycaprolactone diol to the reaction flask, purge with nitrogen for protection, heat to 110-120℃ and dehydrate under vacuum for 40-50min, cool to 58-62℃, release the vacuum, add 0.16-0.24g of fluorinated guanidine quaternary phosphonium salt chain extender, 0.2-0.3g of glycerol monomethacrylate, 0.04-0.06g of 1,4-butanediol, and 2.5-3.5mL of butyl acetate diluent, stir and mix, add 0.63-0.95g of hexamethylene diisocyanate and 0.002-0.003g of dibutyltin dilaurate catalyst, heat to 75-80℃ and react for 4-6h, after the reaction is completed, add 1-2mL of butyl acetate diluent, stir for 20-30min to obtain fluorinated guanidine quaternary phosphonium salt modified polyurethane.

3. The rubber-feel coating according to claim 2, characterized in that, The pH value in step (1) is 8-9.

4. The rubber-feel coating according to claim 1, characterized in that, The choline-modified organosilicon micropowder is prepared through the following steps: S1. Add 2-4 mL of deionized water and 18-22 mL of anhydrous ethanol to the reaction flask as a mixed solvent, add 2-2.4 g of phosphocholine, stir to dissolve, add 2.09-2.51 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride condensing agent, adjust the pH to 5.0-5.5 with hydrochloric acid solution, purge with nitrogen for protection, add 2.22-2.66 g of a mixed solution of 3-aminopropyltriethoxysilane and 10-15 mL of anhydrous ethanol dropwise over 20-25 min, after which react at 24-30℃ for 14-16 h. After the reaction is complete, remove the solvent by rotary evaporation, wash and vacuum dry to obtain phosphocholine-modified silane coupling agent; S2. Add 0.15-0.25g of sodium dodecyl sulfate surfactant, 6.8-9.6g of dimethyldiethoxysilane, 0.8-1.2g of methyltrimethoxysilane, and 0.8-1.2g of phosphocholine-modified silane coupling agent to 40-60mL of deionized water solvent. Stir and emulsify for 10-20min, heat to 50-60℃, adjust the pH to 9-10 with ammonia water, and react for 8-10h. After the reaction is complete, centrifuge to collect the precipitate, wash the precipitate with water and alcohol, and vacuum dry to obtain phosphocholine-modified organosilicon micropowder.

5. The rubber-feel coating according to claim 4, characterized in that, The mass fraction of hydrochloric acid solution in S1 is 0.3%-0.5%.

6. The rubber-feel coating according to claim 4, characterized in that, The mass fraction of ammonia in S2 is 25%-28%.

7. A method for preparing a rubber-feel coating as described in any one of claims 1-6, characterized in that, Includes the following steps: Add fluorinated guanidine quaternary phosphonium salt modified polyurethane, Tween 80, phosphocholine modified organosilicon micro powder, and polyethylene wax powder to a dispersion vessel. Stir at 500-800 rpm for 10-15 min to obtain a pre-dispersed slurry. Put the pre-dispersed slurry into a sand mill with zirconia beads as the grinding media. Grind at 1500-2000 rpm for 20-30 min and then transfer it to a paint mixing vessel. Add isoborneol acrylate, photoinitiator 184, and butyl acetate diluent. Stir at 400-600 rpm for 5-10 min to obtain a rubber-feel coating.

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