High-strength antibacterial durable ABS plastic clothes hanger and preparation method thereof

Abstract

The invention relates to the field of plastic products, and particularly discloses a high-strength antibacterial durable ABS plastic clothes hanger as well as a preparation method and application thereof. The invention discloses a high-strength antibacterial durable ABS plastic clothes hanger. Comprising the following raw materials in parts by weight: 50-100 parts of ABS resin, 25-35 parts of polystyrene resin, 10-15 parts of LDPE, 5-10 parts of a polystyrene-butadiene copolymer, 5-10 parts of a silver-loaded antibacterial agent, 6-12 parts of chitosan short fibers, 3-7 parts of lignin porous microspheres, 2-6 parts of an organic antibacterial agent, 0.1-2 parts of a light stabilizer, 0.1-2 parts of an antioxidant, 0.1-1.5 parts of a lubricant, 1-2 parts of a flexibilizer and 0.5-1 part of an antistatic agent. The silver-loaded antibacterial agent is silver-loaded polystyrene / cellulose acetate fiber. The plastic clothes hanger has the advantages of being high in antibacterial capacity, lasting in antibacterial property, excellent in weather resistance and high in mechanical property.

Description

Technical Field

[0001] The present application relates to the technical field of plastic products, and more specifically, to a high-strength, antibacterial and durable ABS plastic hanger and a preparation method thereof. Background Art

[0002] Hangers are essential in our daily lives. Solid wood hangers and plastic hangers are the two most common types on the market. Solid wood hangers are often made from virgin wood, which takes a long time to prepare and consumes a large amount of natural wood. Plastic hangers are primarily made from PP, PS, and ABS, supplemented with non-slip soft adhesives like PVC, EVA, and silicone. They are fast to produce, lightweight, and come in a variety of colors.

[0003] ABS resin is an acrylonitrile-butadiene-styrene terpolymer with excellent properties such as good gloss, good impact resistance, high surface hardness, dimensional stability, chemical resistance and good electrical properties, and easy molding and machining. However, when used in hangers, it is very easy to produce bacteria and mold due to long-term contact with damp clothes, causing the hangers to mold.

[0004] The antimicrobial agents used in ABS resin are mainly divided into three categories: inorganic, organic and natural antimicrobial agents. Organic antimicrobial agents use thiazole, quaternary ammonium salts, etc., which have strong antimicrobial ability, but they are easy to overflow from plastic products, resulting in the gradual weakening of antimicrobial ability. Although natural antimicrobial agents have high antimicrobial efficiency, safety and non-toxicity, they have poor heat resistance and short antibacterial time. Inorganic antimicrobial agents are popular due to their industrialization, good temperature resistance and broad antimicrobial spectrum.

[0005] In the prior art, inorganic antimicrobial agents are mainly loaded gold, silver, copper or zinc, with silver-loaded antimicrobial agents being the most commonly used. The main carriers are apatite, titanium oxide, zirconium phosphate, glass, silica gel, aluminum oxide and zeolite. However, loaded antimicrobial agents still have problems such as uneven distribution of antimicrobial metal ions on the carrier surface, weak binding force, easy detachment of antimicrobial metal ions, low antimicrobial efficiency and short antimicrobial life. In addition, the loaded antimicrobial agents have a small particle size, a small specific surface area in contact with bacteria, etc., and are prone to aggregation, resulting in stress concentration in the ABS material, thereby affecting the tensile strength and impact strength of the ABS material. Summary of the Invention

[0006] In order to provide an ABS clothes hanger with good antibacterial effect, long service life and good mechanical properties, the present application provides a high-strength, antibacterial and durable ABS plastic clothes hanger and a preparation method thereof.

[0007] In a first aspect, the present application provides a high-strength, antibacterial, and durable ABS plastic hanger, which adopts the following technical solutions: A high-strength, antibacterial, and durable ABS plastic hanger comprises the following raw materials in parts by weight: 50-100 parts of ABS resin, 25-35 parts of polystyrene resin, 10-15 parts of LDPE, 5-10 parts of polystyrene-butadiene copolymer, 5-10 parts of a silver-loaded antibacterial agent, 6-12 parts of chitosan short fibers, 3-7 parts of lignin porous microspheres, 2-6 parts of an organic antibacterial agent, 0.1-2 parts of a light stabilizer, 0.1-2 parts of an antioxidant, 0.1-1.5 parts of a lubricant, 1-2 parts of a toughening agent, and 0.5-1 part of an antistatic agent. The silver-loaded antibacterial agent is silver-loaded polystyrene / cellulose acetate fiber, the mass ratio of polystyrene to cellulose acetate is 8-9:1-2, and the amount of nanosilver is 2-3.25wt% of the total amount of polystyrene and cellulose acetate.

[0008] By adopting the above technical solution, ABS resin is used as the main material, and polystyrene, LDPE and other raw materials are mixed in. Among them, LDPE itself has certain flexibility and impact strength, which can be partially transferred to ABS through blending, thereby improving the impact strength and low-temperature brittleness resistance of ABS. Polystyrene-butadiene copolymer is styrene-butadiene rubber, which is famous for its high elasticity and toughness. It can improve the impact resistance and toughness of ABS resin, resist external impact and collision, and extend the service life of the hanger. It also has a high heat deformation temperature and glass transition temperature, which can improve the heat resistance, wear resistance, chemical corrosion resistance and weather resistance of the hanger. Lignin porous microspheres Because its molecular structure contains a large number of acidic groups such as carboxyl and phenolic hydroxyl groups, it can generate strong negative charges, which can destroy the bacterial membrane system, affect its metabolic activity, and achieve a bactericidal effect. Moreover, the negative charges generated by it can attract each other with the positive charges generated by the organic antistatic agent, so that the organic antimicrobial agent can be tightly attached to the surface of the lignin porous microspheres, increasing the chance and area of ​​contact between the antimicrobial agent and bacteria, and reducing the escape of the organic antimicrobial agent, thereby achieving a synergistic antimicrobial effect and further improving the antibacterial ability. Moreover, the lignin porous microspheres contain rich chemical bonds such as aromatic, phenolic hydroxyl, and ketone groups, which can absorb ultraviolet light and have natural anti-UV properties, which can improve the weather resistance of the hanger.

[0009] Polystyrene is synthesized from styrene monomers through free radical addition polymerization, and has the advantages of easy molding and processing, low price, etc. Adding polystyrene fibers to ABS hangers can enhance the overall rigidity, increase toughness and impact resistance; adding cellulose acetate to polystyrene fibers and spinning them to obtain fibers, cellulose acetate itself is stable to light, has good stability and compatibility, can enhance the stability of polystyrene fibers, making them more resistant to environmental factors such as light and temperature; and cellulose acetate can also play a role in lubrication and dispersion during the spinning process, improve the spinning performance, make spinning smoother, and make the fiber quality more uniform; in addition, the addition of cellulose acetate will also increase The mechanical strength of polystyrene fibers, such as tensile strength and toughness, is enhanced. Nanosilver is loaded onto polystyrene / cellulose acetate fibers through spinning, which increases the load fastness between the nanosilver and the carrier, making it less likely for the nanosilver to fall off and improving its long-lasting antibacterial properties. Furthermore, the nanosilver is added in the form of polystyrene / cellulose acetate fibers, avoiding the incorporation of the silver-loaded antimicrobial agent in a smaller particle size, which results in a smaller surface area for contact with bacteria and weaker antibacterial ability. Furthermore, the silver-loaded antimicrobial agent in fiber form is less likely to agglomerate, which does not lead to stress concentration. The fibers can overlap with each other in the ABS hanger, forming an antibacterial network, improving the antibacterial effect while also increasing the overall mechanical strength of the hanger. Chitosan fibers have inherent antibacterial properties, disrupting the integrity of bacterial cell walls, thereby improving the antibacterial ability of ABS. Furthermore, chitosan fibers possess a certain strength and modulus, which can enhance the mechanical properties of ABS hangers. Furthermore, the hydroxyl and amino groups in the chitosan molecules can interact with functional groups in the ABS molecules, such as hydrogen bonds, to improve the cohesion and mechanical strength of the composite material.

[0010] Optionally, the silver-loaded antibacterial agent further contains graphite-phase carbon nitride treated with cold plasma, and the amount of graphite-phase carbon nitride treated with cold plasma is 1-1.5 wt % of the total amount of polystyrene and cellulose acetate.

[0011] By adopting the above technical solution, graphene carbon nitride has photocatalytic antibacterial properties under visible light, and the active oxygen species generated by its photocatalysis can synergistically cooperate with nanosilver for antibacterial purposes, achieving high-efficiency and long-lasting antibacterial properties at a low silver loading. Moreover, after dispersion, the nanosilver particles can be reduced from agglomerating, making their loading in the fiber more uniform. At the same time, nanosilver has a unique SPR effect, which can improve the visible light absorption capacity, enhance the light absorption of graphene carbon nitride and reduce its band gap, thereby improving the photocatalytic antibacterial activity of graphene carbon nitride. Therefore, nanosilver and graphene carbon nitride can act synergistically, enhance the photocatalytic activity, and improve the photocatalytic antibacterial ability of the material. Cold plasma treatment is conducive to its full combination with polystyrene and cellulose acetate, exerting its photocatalytic and antibacterial effects, and cold plasma treatment can enhance the bactericidal ability of graphene carbon nitride against Gram-negative bacteria, such as Escherichia coli.

[0012] Optionally, the silver-loaded polystyrene / cellulose acetate fiber is pretreated as follows: The silver-loaded polystyrene / cellulose acetate fiber was immersed in a dopamine hydrochloride solution, the pH was adjusted to 8.5, and curcumin-loaded mesoporous titanium dioxide was added. The mixture was stirred evenly, filtered, washed, and dried, and then added to anhydrous ethanol. After ultrasonic oscillation, n-dodecanethiol was added, and the mixture was stirred evenly, filtered, washed, and dried.

[0013] By adopting the above technical scheme, the dopamine solution with adhesive properties, under an alkaline environment, has its surface catechol groups and amino functional groups in situ synthesized on the surface of the silver-loaded polystyrene / cellulose acetate fiber, and a polydopamine layer with extremely strong adhesiveness is synthesized. This not only improves its loading effect on the surface of the silver-loaded polystyrene / cellulose acetate fiber, but also increases the loading fastness of the curcumin-loaded mesoporous titanium dioxide on the surface of the silver-loaded polystyrene / cellulose acetate fiber. The curcumin-loaded mesoporous titanium dioxide has a sustained-release effect and can continuously release curcumin, which cooperates with nano-silver to achieve an antibacterial effect. At the same time, titanium dioxide has a strong ultraviolet absorption capacity, which can enhance the anti-ultraviolet aging ability of the ABS hanger, reduce photodegradation, and extend the service life of the hanger. It can also increase the heat oxidation resistance of the hanger, reduce the thermal degradation of the hanger caused by light, and enhance the overall quality and service life of the hanger.

[0014] The coating of polydopamine enables the silver-loaded polystyrene / cellulose acetate fiber to graft more n-dodecyl mercaptan, because polydopamine and n-dodecyl mercaptan can undergo Michael addition reaction, which increases the grafting rate of n-dodecyl mercaptan through the action of chemical bonds. n-Dodecyl mercaptan is composed of dodecyl chain segments and thiol groups, wherein the dodecyl chain segments are hydrophobic groups with surface energy, which can enable the silver-loaded polystyrene / cellulose acetate fiber to form a hydrophilic repulsive layer with strong hydrophobicity. Moreover, the sulfur atom tail in the n-dodecyl mercaptan molecule is also hydrophobic, which further enhances the hydrophobicity of the entire molecule, thereby reducing the surface energy of the silver-loaded polystyrene / cellulose acetate fiber, improving its dispersibility and compatibility in BA, and improving the mechanical strength of the ABS hanger. In addition, the hydrophobically modified silver-loaded polystyrene / cellulose acetate fiber can effectively enhance the moisture-proof effect of the hanger, and has no significant effect on the mechanical strength of the hanger after long-term use.

[0015] Optionally, the chitosan short fibers are pretreated as follows: Chitosan-grafted silica microspheres are ultrasonically dispersed in anhydrous ethanol to obtain a dispersion with a mass fraction of 2.5-3wt%. A polyurethane solution with a concentration of 1-1.5wt% and the dispersion are alternately sprayed on the surface of chitosan short fibers and dried. The mass ratio of polyurethane to chitosan-grafted silica microspheres is 1:1-1.5.

[0016] By adopting the above technical solution, the silica surface has a large number of hydroxyl groups. These surface hydroxyl groups are utilized to graft the hydroxyl and amide groups contained in chitosan with an additive to obtain silica with antibacterial effects, thereby further improving the antibacterial ability of chitosan. Chitosan-grafted silica microspheres and polyurethane solution are alternately sprayed onto chitosan fibers to form a coating on the chitosan fibers. The surface of the chitosan-grafted silica microspheres is uneven, forming many small pores and a micro / nano rough structure, which has good hydrophobicity. In addition, the polyurethane contains urethane groups (-NHCOO) and isocyanate groups (NCO), which have strong chemical activity and good adhesion to chitosan fibers. It can also reduce the surface energy of the chitosan fibers, increase the dispersibility and compatibility of the chitosan fibers with ABS resin, and reduce the effect of agglomeration on mechanical strength. In addition, the low surface energy makes the chitosan fibers more hydrophobic, which can prevent moisture penetration and reduce the effect of humid environments on the mechanical strength of the hanger.

[0017] Optionally, the silica microspheres are mesoporous silica microspheres loaded with ultraviolet absorbers.

[0018] By adopting the above technical solution and loading the ultraviolet absorber in the mesoporous silica microspheres, the weather resistance of the mesoporous silica microspheres can be improved, thereby increasing the service life of the hanger.

[0019] Optionally, the ultraviolet absorber is selected from at least one of ultraviolet absorber UV-531, ultraviolet absorber UV-327, ultraviolet absorber UV-328, and ultraviolet absorber UV-1084.

[0020] By adopting the above technical solution, the above ultraviolet absorber can be dissolved in acetone, which is convenient for adsorption and loading of mesoporous silica microspheres.

[0021] Optionally, the polystyrene resin includes GPPS and HIPS in a mass ratio of 1:0.5-1.

[0022] By adopting the above technical solution, GPPS is general-purpose polystyrene and HIPS is high-impact polystyrene. The two work together to have good toughness and impact resistance, significantly improve the overall toughness of the material, and improve processing fluidity, making it easier to injection mold when preparing hangers.

[0023] Optionally, the lignin porous microspheres are zinc oxide / lignin composite porous microspheres.

[0024] By adopting the above technical solution, zinc oxide not only helps to improve the antibacterial properties, but also enhances the strength of lignin-based microspheres. Lignin has a complex three-dimensional network structure and a long molecular chain, which makes the formed zinc oxide crystal nuclei highly dispersed, inhibits the growth of zinc oxide crystal nuclei, and makes the zinc oxide particle size micron-level, which is conducive to constructing nanoscale rough structures, reducing the actual contact area between water droplets and lignin-based microspheres, and promoting the improvement of the superhydrophobicity of the hanger.

[0025] Optionally, the organic antimicrobial agent is a mixture of one or both of a quaternary ammonium salt antimicrobial agent and a guanidine antimicrobial agent.

[0026] By adopting the above technical solution, the quaternary ammonium antibacterial agent and the guanidine antibacterial agent can generate positive charges in the ABS hanger, thereby producing a synergistic antibacterial effect with the lignin porous microspheres.

[0027] Optionally, the antioxidant is a mixture of one or two of 2,6-di-tert-butyl-p-cresol and 2,2'-di-tert-butyl-4,4'-methyl ether diphenol; The light stabilizer is a mixture of one or two of the following: light stabilizer 770, ultraviolet absorber UV-234, and light stabilizer UV-3346; The lubricant is selected from at least one of polyethylene wax, white oil, and paraffin wax; The antistatic agent is selected from at least one of alkyl sulfonates, quaternary ammonium salts, stearamide, fatty acid polyethylene glycol esters, polysorbates and titanates; The toughening agent is selected from at least one of acrylonitrile-styrene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, SBS and high rubber powder.

[0028] In a second aspect, the present application provides a method for preparing a high-strength, antibacterial, and durable ABS plastic hanger, using the following technical solutions: A method for preparing a high-strength, antibacterial and durable ABS plastic hanger comprises the following steps: ABS resin, polystyrene resin, LDPE and polystyrene-butadiene copolymer, light stabilizer, antioxidant, lubricant, toughening agent and antistatic agent are mixed uniformly to prepare a premix; The premix is ​​added from the main feeding port, and the organic antimicrobial agent, the silver-loaded antimicrobial agent, the chitosan fiber and the lignin porous microspheres are mixed evenly and then added from the side feeding port, and melt extrusion granulation is performed to obtain a granular material; The granular material is hot-melted and injected into a mold, cooled, and demolded to produce an ABS plastic hanger.

[0029] By adopting the above technical solution, organic antibacterial agents, silver-loaded antibacterial agents, chitosan fibers and lignin porous microspheres are added from the side feeding port for extrusion granulation, which can avoid excessive heating or shearing of these raw materials during the basic process, thereby affecting their antibacterial properties.

[0030] In summary, this application has the following beneficial effects: 1. Since this application uses ABS as the main material and adds raw materials such as LDPE, polystyrene and SBR, it can effectively improve the impact resistance and toughness of the hanger. In addition, the use of organic antibacterial agents and silver-loaded antibacterial agents can enhance the antibacterial ability of the hanger. The organic antibacterial agent is used in conjunction with the lignin porous microspheres to improve the antibacterial property and enhance the antibacterial durability. The silver-loaded antibacterial agent is silver-loaded polystyrene / cellulose acetate fiber, which can increase the contact area between nanosilver and bacteria, while increasing the loading fastness of nanosilver, improving the antibacterial property and antibacterial durability, and can also enhance the overall mechanical strength of the hanger.

[0031] 2. In this application, polydopamine, curcumin-loaded mesoporous silica and n-dodecyl mercaptan are preferably used to pretreat the silver-loaded polystyrene / cellulose acetate fiber. Polydopamine can make the curcumin-loaded mesoporous silica firmly loaded on the silver-loaded polystyrene / cellulose acetate fiber, thereby improving the antibacterial durability and aging resistance. n-dodecyl mercaptan makes the silver-loaded polystyrene / cellulose acetate fiber more hydrophobic, thereby improving its dispersibility and compatibility in ABS, reducing stress concentration, and enhancing mechanical strength and resistance to moisture aging.

[0032] 3. In this application, it is preferred to spray a polyurethane solution and a dispersion containing chitosan grafted silica microspheres on the surface of the chitosan staple fiber in sequence, so that the antibacterial ability of the chitosan staple fiber is enhanced, the surface hydrophobicity is enhanced, the dispersibility in ABS is improved, and the mechanical properties and anti-humidity aging effect of the hanger are improved. DETAILED DESCRIPTION

[0033] The following examples further illustrate the present application in detail.

[0034] Preparation Examples 1-4 of Silver-Loaded Polystyrene / Cellulose Acetate Fiber In Preparation Example 1, polystyrene was selected from Shanghai Saike, model 123P, cellulose acetate was selected from Shenzhen Zike Biotechnology, product number zk4156, nanosilver was selected from Shanghai Naio Nanotechnology, product number NO-M-004-1, and graphite phase carbon nitride was selected from Sichuan Kenye Technology, model KYG-C3N4X.

[0035] Preparation Example 1: (1) 8 g of polystyrene and cellulose acetate were added to N,N-dimethylformamide at a mass ratio of 8:2, and stirred and dissolved at 40° C. to prepare a spinning solution with a concentration of 24 wt%; (2) Adding nanosilver particles and graphite phase carbon nitride treated with cold plasma to the spinning solution, the masses of the nanosilver particles and the graphite phase carbon nitride treated with cold plasma are 3.25wt% and 1.5wt% of the total mass of polystyrene and cellulose acetate, respectively. After mixing and stirring evenly, centrifugal spinning is performed at a centrifugal speed of 10,000 rpm and a receiving rod distance of 10 cm. The collected fibers are vacuum dried at 25°C for 8 h to obtain silver-loaded polystyrene / cellulose acetate fibers. The cold plasma treatment method of the graphite phase carbon nitride is to irradiate the graphene carbon nitride under the protection of a flowing nitrogen atmosphere at a power of 500 W for 1 min.

[0036] Preparation Example 2: (1) 8 g of polystyrene and cellulose acetate were added to N,N-dimethylformamide at a mass ratio of 9:1, and stirred and dissolved at 40° C. to prepare a spinning solution with a concentration of 24 wt%; (2) Adding nanosilver particles and graphite phase carbon nitride treated with cold plasma to the spinning solution, the mass of the nanosilver particles and the graphite phase carbon nitride treated with cold plasma is 2wt% and 1wt% of the total mass of polystyrene and cellulose acetate, respectively. After mixing and stirring evenly, centrifugal spinning is performed at a centrifugal speed of 10,000 rpm and a receiving rod distance of 10 cm. The collected fibers are vacuum dried at 25°C for 8 h to obtain silver-loaded polystyrene / cellulose acetate fibers. The cold plasma treatment method of the graphite phase carbon nitride is to irradiate the graphene carbon nitride under the protection of a flowing nitrogen atmosphere at a power of 500 W for 1 min.

[0037] Preparation Example 3: Compared with Preparation Example 1, the graphene carbon nitride is not treated with cold plasma.

[0038] Preparation Example 5 of Lignin Porous Microspheres Preparation Example 5: 18 g of sodium lignin sulfonate was dissolved in 1 mol / L sodium hydroxide solution to prepare 30 g of a 60 wt% sodium lignin sulfonate solution; 30 g of the sodium lignin sulfonate solution, 5.94 g of polyetheramine 230, 1.8 g of epichlorohydrin, and 1 mL of anhydrous ethanol were mixed, 1.08 g of Span-60 and 90 g of liquid paraffin were added, and the mixture was stirred at 250 rpm and heated from 40° C. to 90° C., and 20 μL of a 50 wt% sodium hydroxide solution was added every 5 min (a total of 1000 μL was added). After reacting for 2 h, the mixture was allowed to stand for stratification, the upper oil phase was removed, and the mixture was washed with petroleum ether three times and with deionized water. The mixture was freeze-dried at −10° C. for 48 h to obtain porous lignin microspheres.

[0039] Preparation Example 6 of ZnO / Lignin Composite Porous Microspheres Preparation Example 6: Dissolve 3.5 g of zinc nitrate hexahydrate in 100 mL of deionized water to obtain solution A, dissolve 1.5 g of hexamethylenetetramine in 100 mL of deionized water to obtain solution B, mix solution A and solution B to obtain a zinc oxide precursor solution; take 20 ml of the precursor solution and mix it with 240 mL of lignin porous microsphere suspension, hydroheat it at 120 ° C for 4 hours, cool it, and freeze-dry it in a vacuum environment of -50 ° C and 1 Pa for 72 hours to obtain zinc oxide / lignin composite porous microspheres. The concentration of the lignin porous microsphere suspension is 5 mg / mL, which is made by mixing the lignin porous microspheres prepared in Preparation Example 5 and deionized water.

[0040] Preparation Example 7 of Curcumin-loaded Mesoporous Titanium Dioxide Preparation Example 7: Curcumin was added to dimethyl sulfoxide to prepare a solution with a concentration of 50 mg / mL, mesoporous titanium dioxide was added, and after ultrasonic dispersion for 10 minutes, the solvent was removed by rotary evaporation to prepare curcumin-loaded mesoporous titanium dioxide. The mass ratio of curcumin to mesoporous titanium dioxide was 0.1:1. The mesoporous titanium dioxide was selected from Xi'an Qiyue Biological, and the product number was Q-0314151.

[0041] Preparation Examples 8-9 of Chitosan Grafted Silica Microspheres Preparation Example 8: Add 0.1 g of silica microspheres to 20 mL of ethanol, ultrasonically disperse for 30 minutes, add acetic acid to adjust the pH to 4, quickly inject 1.5 mL of silane coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane into the above dispersion, stir at 400 rpm at 65 ° C for 3 hours, add 1.5 mL of 2% chitosan acetic acid solution, react at 65 ° C for 12 hours, and centrifuge to obtain chitosan grafted silica microspheres. The silica microspheres are mesoporous silica microspheres selected from Beijing Zhongke Keyou Technology, with the product number zkky-SIO2-70025.

[0042] Preparation Example 9: The difference from Preparation Example 8 is that the silica microspheres are mesoporous silica microspheres loaded with a UV absorber. The preparation method of the mesoporous silica microspheres loaded with a UV absorber is as follows: The ultraviolet absorber was added to the acetone solution and stirred to obtain a 100 mg / ml solution. Mesoporous silica microspheres were added and stirred at room temperature for 2 h. The solution was vacuumed for 30 min and opened to the atmosphere for 15 min. The vacuuming and opening to the atmosphere were repeated 3 times. The solution was filtered and dried. The ultraviolet absorber was UV-531 and the mesoporous silica microspheres were selected from Beijing Zhongke Keyou Technology with the product number zkky-SIO2-70025. Example

[0043] Example 1: A high-strength, antibacterial and durable ABS plastic hanger, the raw material usage is shown in Table 1, wherein the ABS resin is selected from Taiwan Chimei of China, with a brand name of PC-345 and a product number of 4C37X126, the polystyrene includes GPPS and HIPS with a mass ratio of 1:1, the GPPS is selected from Yuyao Maiduo Plastics Thailand Petrochemical, with a model number of GP150, the HIPS is selected from Dongguan Changping Shengxin Plastics, Yangtze BASF, with a product number of 476L, the LDPE is selected from Japan JPC, with a model number of DL0500, the polystyrene-butadiene copolymer is selected from Jilin Petrochemical, with a model number of SBR1502, the silver-loaded antibacterial The agent is silver-loaded polystyrene / cellulose acetate fiber, and is made by Preparation Example 1, the chitosan staple fiber is made by cutting chitosan fiber with a length of 38 mm into 5 parts on average, the chitosan fiber is selected from Qingdao Hailan Biological Products, and the product number is 38DD, the lignin porous microspheres are made by Preparation Example 5, the organic antibacterial agent is dioctyldimethylammonium bromide, the light stabilizer is light stabilizer 770, the antioxidant is 2,6-di-tert-butyl-p-cresol, the lubricant is polyethylene wax, selected from Yixing Shoucheng Plastic Products, model CH110, the toughening agent is ethylene-octene copolymer, selected from Dow of the United States, model 58750, and the antistatic agent is stearamide.

[0044] The method for preparing the above-mentioned high-strength, antibacterial and durable ABS plastic hanger comprises the following steps: ABS resin, polystyrene resin, LDPE and polystyrene-butadiene copolymer, light stabilizer, antioxidant, lubricant, toughening agent and antistatic agent are mixed uniformly to prepare a premix; The premix is ​​added from the main feeding port, and the organic antimicrobial agent, the silver-loaded antimicrobial agent, the chitosan fiber and the lignin porous microspheres are mixed evenly and then added from the side feeding port, and melt extrusion granulation is performed to obtain a granular material. The temperature of each zone during melt extrusion is: 220° C. for zone 1, 225° C. for zone 2, 220° C. for zone 3, 225° C. for zone 4, 225° C. for zone 5, 230° C. for zone 6, 230° C. for zone 7, and 230° C. for the die head; The granular material is hot-melted and then injected into a mold, cooled, and demolded to produce an ABS plastic hanger. The injection molding temperature is: 190°C in zone 1, 210°C in zone 2, 230°C in zone 3, 230°C in zone 4, and 230°C in zone 5.

[0045] Table 1 Raw material dosage of ABS plastic hangers in Examples 1-5 Example 2: A high-strength, antibacterial and durable ABS plastic hanger, the raw material dosage of which is shown in Table 1, wherein the ABS resin is selected from Taiwan Chimei of China, with a brand name of PC-345 and a product number of 4C37X126, the polystyrene includes GPPS and HIPS with a mass ratio of 1:0.5, the GPPS is selected from Yuyao Maiduo Plastics Thailand Petrochemical, with a model number of GP150, the HIPS is selected from Dongguan Changping Shengxin Plastic, Yangtze BASF, with a product number of 476L, the LDPE is selected from Japan JPC, with a model number of DL0500, the polystyrene-butadiene copolymer is selected from Jilin Petrochemical, with a model number of SBR1502, and the silver-loaded antibacterial agent is silver-loaded Polystyrene / cellulose acetate fiber is made by Preparation Example 2, chitosan staple fiber is made by cutting chitosan fiber with a length of 38 mm into 5 parts on average, chitosan fiber is selected from Qingdao Hailan Biological Products, item number 38DD, lignin porous microspheres are made by Preparation Example 5, the organic antibacterial agent is polyhexamethylene biguanide hydrochloride, the light stabilizer is light stabilizer UV-3346, the antioxidant is 2'-di-tert-butyl-4,4'-methyl ether diphenol, the lubricant is paraffin, the toughening agent is ethylene-vinyl acetate copolymer, selected from DuPont of the United States, model 3861, and the antistatic agent is polysorbate, selected from Shandong Xinbaihe Chemical, model TW06.

[0046] The method for preparing the above-mentioned high-strength, antibacterial and durable ABS plastic hanger comprises the following steps: ABS resin, polystyrene resin, LDPE and polystyrene-butadiene copolymer, light stabilizer, antioxidant, lubricant, toughening agent and antistatic agent are mixed uniformly to prepare a premix; The premix is ​​added from the main feeding port, and the organic antimicrobial agent, the silver-loaded antimicrobial agent, the chitosan fiber and the lignin porous microspheres are mixed evenly and then added from the side feeding port, and melt extrusion granulation is performed to obtain a granular material. The temperature of each zone during melt extrusion is: 220° C. for zone 1, 225° C. for zone 2, 220° C. for zone 3, 225° C. for zone 4, 225° C. for zone 5, 230° C. for zone 6, 230° C. for zone 7, and 230° C. for the die head; The granular material is hot-melted and then injected into a mold, cooled, and demolded to produce an ABS plastic hanger. The injection molding temperature is: 190°C in zone 1, 210°C in zone 2, 230°C in zone 3, 230°C in zone 4, and 230°C in zone 5.

[0047] Example 3-5: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 1 is that the amounts of raw materials used are as shown in Table 1.

[0048] Example 6: A high-strength, antibacterial and durable ABS plastic hanger, which differs from Example 1 in that the silver-loaded polystyrene / cellulose acetate fiber is made from Preparation Example 3.

[0049] Example 7: A high-strength, antibacterial and durable ABS plastic clothes hanger. The difference from Example 1 is that the lignin porous microspheres are zinc oxide / lignin composite porous microspheres, which are prepared according to Preparation Example 6.

[0050] Example 8: A high-strength, antibacterial and durable ABS plastic hanger. The difference from Example 7 is that the silver-loaded polystyrene / cellulose acetate fiber is pretreated by the following method before being fed into the side feed port: 12 g of silver-loaded polystyrene / cellulose acetate is immersed in a 1 g / L dopamine hydrochloride solution, the pH is adjusted to 8.5 with ammonia water, 1.2 g of curcumin-loaded mesoporous titanium dioxide is added, and the mixture is stirred at 60°C for 8 h. After filtration, washing and drying, a composite is obtained. 10 g of the composite is added to 200 mL of anhydrous ethanol, ultrasonically vibrated for 2 h, 2 ml of n-dodecanethiol is added, stirred evenly, filtered, washed and dried. The curcumin-loaded mesoporous titanium dioxide is prepared according to Preparation Example 7.

[0051] Example 9: A high-strength, antibacterial and durable ABS plastic hanger, which differs from Example 8 in that curcumin-loaded mesoporous titanium dioxide is not added.

[0052] Example 10: A high-strength, antibacterial and durable ABS plastic hanger, which differs from Example 8 in that curcumin is not loaded in the mesoporous titanium dioxide.

[0053] Example 11: A high-strength, antibacterial and durable ABS plastic hanger, which differs from Example 8 in that n-dodecyl mercaptan is not added.

[0054] Example 12: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 8 is that 12 g of silver-loaded polystyrene / cellulose acetate is immersed in a mixture of 200 mL of anhydrous ethanol and 2 mL of n-dodecyl mercaptan, filtered, washed, and dried.

[0055] Example 13: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 8 is that the chitosan fibers are pretreated by the following method before being fed into the side feed port: 3 g of chitosan-grafted silica microspheres were ultrasonically dispersed in anhydrous ethanol to obtain a dispersion with a mass fraction of 3 wt %. The chitosan-grafted silica microspheres were prepared according to Preparation Example 8. A polyurethane solution and a dispersion with a concentration of 1.5wt% were alternately sprayed on the surface of the chitosan staple fiber and dried. The mass ratio of polyurethane to chitosan grafted silica microspheres was 1:1.5, and the mass ratio of the spraying amount of polyurethane solution, the spraying amount of dispersion and the chitosan staple fiber was 0.2:0.2:1.

[0056] Example 14: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 8 is that the chitosan fibers are pretreated by the following method before being fed into the side feed port: 2.5 g of chitosan-grafted silica microspheres were ultrasonically dispersed in anhydrous ethanol to obtain a dispersion with a mass fraction of 2.5 wt %. The chitosan-grafted silica microspheres were prepared according to Preparation Example 8. A polyurethane solution and a dispersion with a concentration of 1wt% were alternately sprayed on the surface of the chitosan staple fiber and dried. The mass ratio of polyurethane to chitosan grafted silica microspheres was 1:1, and the mass ratio of the spraying amount of polyurethane solution, the spraying amount of dispersion and the chitosan staple fiber was 0.1:0.1:1.

[0057] Example 15: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 13 is that only the chitosan short fibers are pretreated with a polyurethane solution. The method is as follows: A polyurethane solution with a concentration of 1 wt% was sprayed on the surface of the chitosan short fibers and dried. The mass ratio of the sprayed amount of the polyurethane solution to the chitosan short fibers was 0.2:1.

[0058] Example 16: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 13 is that only the chitosan short fibers are pretreated with a dispersion of chitosan-grafted silica microspheres. The method is as follows: 2.5 g of chitosan-grafted silica microspheres were ultrasonically dispersed in anhydrous ethanol to obtain a dispersion with a mass fraction of 2.5 wt %. The chitosan-grafted silica microspheres were prepared according to Preparation Example 8. The dispersion was sprayed on the surface of the chitosan short fibers and dried. The mass ratio of the sprayed dispersion to the chitosan short fibers was 0.2:1.

[0059] Example 17: A high-strength, antibacterial and durable ABS plastic hanger. The difference from Example 13 is that chitosan is not grafted onto the silica microspheres, and the silica microspheres are mesoporous silica microspheres.

[0060] Example 18: A high-strength, antibacterial and durable ABS plastic hanger, which is different from Example 13 in that the chitosan-grafted silica microspheres are made from Preparation Example 9.

[0061] Comparative Example Comparative Example 1: A high-strength, antibacterial and durable ABS plastic hanger, which differs from Example 1 in that no lignin porous microspheres are added.

[0062] Comparative Example 2: A high-strength, antibacterial and durable ABS plastic hanger, which differs from Example 1 in that chitosan short fibers are not added.

[0063] Comparative Example 3: A high-strength, antibacterial, and durable ABS plastic hanger. The difference from Example 1 is that an equal amount of silver-loaded zirconium phosphate is used to replace the silver-loaded polystyrene / cellulose acetate fiber. The silver-loaded zirconium phosphate is selected from Changzhou Konada New Materials, model KND-YA30.

[0064] Performance testing ABS plastic hangers were prepared according to the methods in the examples and comparative examples, and performance tests were performed according to the following methods. The test results are recorded in Table 2.

[0065] 1. Antibacterial rate: The test was conducted in accordance with GB / T31402-2023 "Determination of antibacterial activity on the surface of plastics and other non-porous materials". The test items were Escherichia coli and Staphylococcus aureus. The test results were repeated 3 times and the average value was taken.

[0066] 2. Tensile strength: Tested according to GB / T1040.3-2006 "Determination of tensile properties of plastics Part 3: Test conditions for thin plastics and sheets".

[0067] 3. Impact strength: Tested according to GB / T1843-2008 "Determination of cantilever beam impact strength of plastics".

[0068] 4. Contact angle: Use a contact angle meter to test the contact angle of the hanger. Test each hanger 5 times and take the average value.

[0069] 6. Humidity aging: Place the specimens at a temperature of 75°C and a humidity of 95% RH for 1800 hours. Then place them at a temperature of 22°C and a humidity of 50% RH for 24 hours, and then test the notched impact strength retention of the specimens.

[0070] 7. Xenon lamp aging: According to the method of ISO 4892.2 "Plastics laboratory light source exposure method. Part 2: Xenon arc lamp", the notched impact strength retention rate and antibacterial rate of the test specimens are tested for 1000 hours.

[0071] Table 2 Performance test results of high-strength, antibacterial and durable ABS plastic hangers Combining Examples 1-5 and the data in Table 1, it can be seen that in Examples 1-5, silver-loaded polystyrene / cellulose acetate fiber is used as a silver-loaded antibacterial agent, and is combined with lignin porous microspheres, an organic antibacterial agent, and chitosan short fibers to produce hangers with strong antibacterial ability, excellent tensile strength, and excellent notched impact strength. At the same time, after aging under a xenon lamp, the impact strength and antibacterial rate retention rate are high, and the hangers have good antibacterial durability and weather resistance.

[0072] In Example 6, compared with Example 1, the silver-loaded polystyrene / cellulose acetate fiber was prepared by Preparation Example 3, in which the graphene carbon nitride was not plasma treated. It can be seen that its antibacterial rate against Escherichia coli was significantly reduced, and the antibacterial rate against Staphylococcus aureus also decreased, while the other properties did not change much.

[0073] Compared with Example 1, Example 7 is a porous lignin microsphere loaded with zinc oxide, and the zinc oxide / lignin composite porous microspheres are prepared by Preparation Example 6. The data in Table 2 show that the antibacterial rate of the plastic hanger prepared in Example 7 against Escherichia coli and Staphylococcus aureus is increased, and the impact resistance and tensile strength of the hanger are slightly increased, the hydrophobicity is improved, and the decrease in impact strength in a humid environment is reduced. In addition, the weather resistance of the hanger is enhanced and the antibacterial ability is more lasting.

[0074] Compared with Example 7, Example 8 also uses dopamine solution, curcumin-loaded mesoporous titanium dioxide and n-dodecanethiol to pretreat the silver-loaded polystyrene / cellulose acetate fiber. It can be seen that the initial antibacterial ability of the hanger in Table 2 is slightly greater. After aging with a hernia lamp, the retention rate of the antibacterial rate increases, the antibacterial durability is improved, and the mechanical strength is increased, and the anti-moisture effect is enhanced.

[0075] Compared with Example 8, Example 9 does not add curcumin-loaded mesoporous titanium dioxide. It can be seen that after irradiation with a xenon lamp, the impact strength retention rate of the hanger material decreases significantly, the UV aging resistance decreases, and the initial antibacterial ability weakens. However, in Example 10, curcumin is not loaded in the mesoporous titanium dioxide. The hanger prepared in Example 10 has a decreased initial antibacterial rate and still has good UV aging resistance, but the antibacterial persistence is weakened.

[0076] In Example 11, no n-dodecyl mercaptan was added. Compared with Example 8, the initial antibacterial ability of the hanger did not change much, the tensile strength and impact strength decreased, and the hydrophobicity weakened. The notched impact strength decreased significantly in a humid environment, but the aging resistance and antibacterial durability did not change significantly.

[0077] In Example 12, compared with Example 8, only n-dodecyl mercaptan solution was used to pretreat the silver-loaded polystyrene / cellulose acetate fiber. It can be seen that the tensile strength and notched impact strength of the hanger were slightly reduced, the contact angle was reduced, the aging resistance was weakened, and the antibacterial durability was deteriorated.

[0078] Compared with Example 8, Example 13 and Example 14 further used a dispersion of chitosan-grafted silica microspheres and a polyurethane solution to pretreat the chitosan staple fibers. The data in Table 2 show that the hangers prepared in Example 13 and Example 14 have improved antibacterial ability, enhanced surface hydrophobicity, improved moisture resistance, and improved weather resistance.

[0079] In Example 15, only the polyurethane solution was used to spray the chitosan staple fibers, and in Example 16, only the dispersion of chitosan grafted silica microspheres was used to spray the chitosan staple fibers. It can be seen that the hydrophobicity of the surfaces of the hangers prepared in Example 15 and Example 16 is quite different. The contact angle in Example 16 decreases more obviously, and the anti-moisture effect decreases significantly, but the antibacterial ability and antibacterial durability in Example 16 are better.

[0080] In Example 17, chitosan was not grafted onto the silica microspheres. Compared with Example 13, the initial antibacterial property of the hanger decreased, the antibacterial persistence was correspondingly weakened, and the other properties did not change much.

[0081] In Example 18, the chitosan-grafted silica microspheres prepared in Preparation Example 9 were used. Compared with Example 13, an ultraviolet absorber was loaded in the silica microspheres. It can be seen that the impact strength retention rate of the hanger under the irradiation of the xenon lamp was significantly increased, and the hanger had better weather resistance.

[0082] In Comparative Example 1, no lignin porous microspheres were added. Compared with Example 1, the initial antibacterial ability of the hanger was weakened, the antibacterial durability decreased, and the changes in tensile strength and other aspects were not obvious. However, after aging under a xenon lamp, the impact strength retention rate decreased, indicating that the lignin porous microspheres can not only increase the antibacterial ability of the hanger, but also improve the weather resistance of the hanger.

[0083] Comparative Example 2 compared with Example 1, without adding chitosan short fibers, it can be seen that the initial antibacterial ability of the hanger material is slightly reduced, the mechanical strength such as tensile strength is deteriorated, the hydrophobicity and the like do not change much, and the antibacterial durability is slightly weakened.

[0084] In Comparative Example 3, silver-loaded zirconium phosphate was used instead of silver-loaded polystyrene / cellulose acetate fiber. It can be seen that the initial antibacterial ability of the hanger was good, but after aging, the antibacterial ability was significantly weakened.

[0085] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high-strength, antibacterial and durable ABS plastic hanger, characterized by: The invention comprises the following raw materials in parts by weight: 50-100 parts of ABS resin, 25-35 parts of polystyrene resin, 10-15 parts of LDPE, 5-10 parts of polystyrene-butadiene copolymer, 5-10 parts of silver-loaded antibacterial agent, 6-12 parts of chitosan short fibers, 3-7 parts of lignin porous microspheres, 2-6 parts of organic antibacterial agent, 0.1-2 parts of light stabilizer, 0.1-2 parts of antioxidant, 0.1-1.5 parts of lubricant, 1-2 parts of toughening agent, and 0.5-1 parts of antistatic agent. The silver-loaded antibacterial agent is silver-loaded polystyrene / cellulose acetate fiber, the mass ratio of polystyrene to cellulose acetate is 8-9:1-2, and the amount of nanosilver is 2-3.25wt% of the total amount of polystyrene and cellulose acetate.

2. The high-strength, antibacterial and durable ABS plastic hanger according to claim 1, characterized in that: The silver-loaded antibacterial agent further comprises graphite-phase carbon nitride treated by cold plasma, wherein the amount of graphite-phase carbon nitride treated by cold plasma is 1-1.5 wt % of the total amount of polystyrene and cellulose acetate.

3. The high-strength, antibacterial and durable ABS plastic hanger according to claim 2, characterized in that: The silver-loaded polystyrene / cellulose acetate fiber is pretreated as follows: The silver-loaded polystyrene / cellulose acetate fiber was immersed in a dopamine hydrochloride solution, the pH was adjusted to 8.5, and curcumin-loaded mesoporous titanium dioxide was added. The mixture was stirred evenly, filtered, washed, and dried, and then added to anhydrous ethanol. After ultrasonic oscillation, n-dodecanethiol was added, and the mixture was stirred evenly, filtered, washed, and dried.

4. The high-strength, antibacterial and durable ABS plastic hanger according to claim 1, characterized in that: The chitosan short fibers are pretreated as follows: Ultrasonic dispersion of chitosan-grafted silica microspheres in anhydrous ethanol to obtain a dispersion with a mass fraction of 2.5-3 wt%; A polyurethane solution with a concentration of 1-1.5 wt% and the dispersion are alternately sprayed on the surface of the chitosan short fibers and dried. The mass ratio of the polyurethane to the chitosan grafted silica microspheres is 1:1-1.

5.

5. The high-strength, antibacterial and durable ABS plastic hanger according to claim 4, characterized in that: The silica microspheres are mesoporous silica microspheres loaded with ultraviolet absorbers.

6. The high-strength, antibacterial and durable ABS plastic hanger according to claim 1, characterized in that: The polystyrene resin includes GPPS and HIPS in a mass ratio of 1:0.5-1.

7. The high-strength, antibacterial and durable ABS plastic hanger according to claim 1, characterized in that: The lignin porous microspheres are zinc oxide / lignin composite porous microspheres.

8. The high-strength, antibacterial and durable ABS plastic hanger according to claim 1, characterized in that: The organic antibacterial agent is one or a mixture of two of a quaternary ammonium salt antibacterial agent and a guanidine antibacterial agent.

9. The high-strength, antibacterial and durable ABS plastic hanger according to claim 1, characterized in that: The antioxidant is a mixture of one or two of 2,6-di-tert-butyl-p-cresol and 2,2'-di-tert-butyl-4,4'-methyl ether diphenol; The light stabilizer is a mixture of one or two of the following: light stabilizer 770, ultraviolet absorber UV-234, and light stabilizer UV-3346; The lubricant is selected from at least one of polyethylene wax, white oil, and paraffin wax; The antistatic agent is selected from at least one of alkyl sulfonates, quaternary ammonium salts, stearamide, fatty acid polyethylene glycol esters, polysorbates and titanates; The toughening agent is selected from at least one of acrylonitrile-styrene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, SBS and high rubber powder.

10. The method for preparing the high-strength, antibacterial and durable ABS plastic hanger according to any one of claims 1 to 9, characterized in that: The following steps are involved: ABS resin, polystyrene resin, LDPE and polystyrene-butadiene copolymer, light stabilizer, antioxidant, lubricant, toughening agent and antistatic agent are mixed uniformly to prepare a premix; The premix is ​​added from the main feeding port, and the organic antimicrobial agent, the silver-loaded antimicrobial agent, the chitosan fiber and the lignin porous microspheres are mixed evenly and then added from the side feeding port, and melt extrusion granulation is performed to obtain a granular material; The granular material is hot-melted and injected into a mold, cooled, and demolded to produce an ABS plastic hanger.

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