Environment-friendly antibacterial PVC material and shoes

Abstract

The invention relates to an environment-friendly antibacterial PVC (polyvinyl chloride) material and shoes, and belongs to the technical field of polyvinyl chloride materials, the environment-friendly antibacterial PVC material comprises the following raw materials in parts by weight: 40-60 parts of PVC powder, 45-50 parts of a plasticizer, 0.4-0.8 part of a calcium-zinc stabilizer, 10-20 parts of a slow-release silver ion composite material and 5-10 parts of an anti-aging auxiliary agent, the calcium-zinc stabilizer is adopted as the auxiliary agent, and the anti-aging auxiliary agent is adopted as the anti-aging agent. According to the present invention, the heat stability of the PVC material is improved, the antibacterial effect and the aging effect are improved by adsorbing and wrapping the antibacterial silver ions, the dispersibility and the aging resistance of the anti-aging auxiliary agent are improved by using the nanometer intercalation composite technology, the aging time of the PVC material is prolonged, the durability of the prepared PVC shoe is improved, and the environmental protection PVC material is prepared by using the benzene-free or low-benzene plasticizer, the environment and health risks caused by traditional phthalate plasticizers are effectively avoided, the prepared PVC material is safer and more environmentally friendly and meets the environment protection standard of PVC shoes, meanwhile, the proportion of the plasticizers is set, and the flexibility of the PVC material is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polyvinyl chloride materials and relates to an environmentally friendly antibacterial PVC material and a shoe. Background Art

[0002] Polyvinyl chloride (PVC) is a widely used thermoplastic plastic. It is widely used in construction, medical, electronics, packaging, and shoemaking due to its superior physical properties and chemical stability. PVC material has high mechanical strength, chemical corrosion resistance and good processing adaptability. Its flexibility, weather resistance and other properties can be adjusted by adding additives to meet the needs of different fields.

[0003] In the shoemaking industry, PVC is often used to make soles, insoles and upper materials due to its good wear resistance, anti-skid properties and low price. It plays an important role in sports shoes, casual shoes and rain boots. Unmodified PVC itself is a hard material, and it is necessary to add additives such as plasticizers to improve its flexibility and plasticity, so as to prepare soft PVC materials suitable for shoemaking. However, the performance of PVC materials is closely related to the additives added to them, especially the type and amount of plasticizers, which not only have an important impact on the performance of the shoe materials, but also pose a certain potential threat to the environment and human health.

[0004] Phthalate plasticizers have long been the most commonly used additives in PVC products. They have good plasticizing effects, low volatility and relatively low costs. Therefore, the global usage of this type of plasticizer is very large. However, recent studies have shown that phthalate plasticizers are potentially harmful to the environment and human health. Phthalate esters can enter the environment through migration, volatilization and degradation, causing pollution to soil, water and air, and may be enriched through the food chain, posing a threat to the ecosystem.

[0005] Especially in the field of shoemaking, shoe materials are in direct contact with human skin during wearing, and phthalate plasticizers may enter the human body through volatilization or contact migration, thus posing a health hazard. Studies have shown that phthalates are toxic, may interfere with the endocrine system, cause damage to the liver and reproductive system, and even have potential carcinogenic risks. Based on these problems, some countries have imposed strict restrictions on the use of phthalate plasticizers and issued relevant regulations to prohibit their use in areas that are in close contact with the human body, such as children's products, food contact materials, and shoe materials. With the enhancement of environmental awareness and the promotion of the concept of sustainable development, the application of phthalate plasticizers is gradually decreasing, and seeking green and environmentally friendly alternatives has become an important research direction in the global materials science and shoemaking industries. Summary of the invention

[0006] The invention relates to an environmentally friendly antibacterial PVC material and a shoe, belonging to the technical field of polyvinyl chloride materials. The material comprises the following raw materials in parts by weight: 40-60 parts by weight of PVC powder, 45-50 parts by weight of a plasticizer, 0.4-0.8 parts by weight of a calcium zinc stabilizer, 10-20 parts by weight of a slow-release silver ion composite material and 5-10 parts by weight of an anti-aging auxiliary agent. The calcium zinc stabilizer is used as an auxiliary agent to improve the thermal stability of the PVC material, the antibacterial effect and time effectiveness are increased by adsorbing and encapsulating the antibacterial silver ions, the dispersibility and anti-aging performance of the anti-aging auxiliary agent are improved by a nano-intercalation composite technology, the aging time of the PVC material is prolonged, and the durability of the prepared PVC shoes is improved. The environmentally friendly PVC material is prepared by using a benzene-free or low-benzene plasticizer, the environmental and health risks brought by a traditional phthalate plasticizer are effectively avoided, the prepared PVC material is safer and more environmentally friendly, and meets the environmental protection standard of PVC shoes. Meanwhile, the proportion of the plasticizer is set to effectively improve the flexibility of the PVC material.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] An environmentally friendly antibacterial PVC material comprises the following raw materials in parts by weight: 40-60 parts by weight of PVC powder, 45-50 parts by weight of a plasticizer, 0.4-0.8 parts by weight of a calcium zinc stabilizer, 10-20 parts by weight of a slow-release silver ion composite material and 5-10 parts by weight of an anti-aging additive.

[0009] As a preferred technical solution of the present invention, the plasticizer is one or more of DOTP, TBC, ATBC, and DOA.

[0010] As a preferred technical solution of the present invention, the preparation steps of the sustained-release silver ion composite material include:

[0011] A1. Place the porous carrier in deionized water, perform ultrasonic treatment for 10-15 minutes, further treat with 0.1M dilute hydrochloric acid solution for 1-2 hours to remove metal ions or impurities adsorbed on the surface, then rinse with deionized water until neutral, calcine at 500-600°C for 1-3 hours and set aside;

[0012] A2, adding the porous carrier to a 0.1M silver nitrate solution, stirring with ultrasound assistance for 4-6 hours, filtering and washing with deionized water to remove the unabsorbed silver ions on the surface;

[0013] A3, add to an ammonia solution, stir evenly, so that the silver ions are deposited on the surface of the porous carrier, wash and dry at 70-90°C for 10-14 hours to obtain a composite carrier loaded with silver ions;

[0014] A4. Disperse the composite carrier loaded with silver ions into the polymer solution, stir ultrasonically for 20-40 minutes to form a uniformly dispersed emulsion, treat it by spray drying to prepare microsphere particles coated with silver ions, dry it at 50-70°C for 10-14 hours to enhance the compactness of the coating layer, and prepare a slow-release silver ion composite material.

[0015] As a preferred technical solution of the present invention, the porous carrier in step A1 is zeolite powder or SiO2 nanoparticles; the mass ratio of the porous carrier to the dilute hydrochloric acid solution is 1:5-10.

[0016] As a preferred technical solution of the present invention, the mass ratio of the porous carrier to the silver nitrate solution in step A2 is 1:10-20.

[0017] As a preferred technical solution of the present invention, the concentration of the ammonia solution in step A3 is 0.1-0.5M, and the pH is adjusted to 5.0-6.0 with 0.5M dilute hydrochloric acid; the mass ratio of the porous carrier to the ammonia solution is 1:6-10.

[0018] As a preferred technical solution of the present invention, the method for preparing the polymer solution in step A4 is: preparing a 4-8wt% polyvinyl alcohol solution, heating the solution to 80-90°C, and continuously stirring for 30-60 minutes; dissolving chitosan in a 1% acetic acid solution, the concentration of the chitosan solution being 1-2wt%; adding the chitosan solution dropwise to the polyvinyl alcohol solution, using a high-speed homogenizer at 5000-8000rpm, and processing for 3-5min; the mass ratio of the composite carrier loaded with silver ions to the polymer solution is 1:5-10; the volume ratio of the chitosan solution to the polyvinyl alcohol solution is 1:1-3.

[0019] As a preferred technical solution of the present invention, the anti-aging auxiliary agent comprises the following raw materials in parts by weight: 4-6 parts by weight of montmorillonite, 50-70 parts by weight of deionized water, 0.05-0.1 parts by weight of intercalation agent, 0.5-0.8 parts by weight of antioxidant, 0.5-0.8 parts by weight of light stabilizer, and 30-40 parts by weight of anhydrous ethanol; the preparation steps are:

[0020] B1. Disperse the nanosheet montmorillonite in deionized water and perform ultrasonic treatment for 20-40 minutes to reduce the stacking of the sheets and form a stable dispersion;

[0021] B2, adding intercalation agent benzalkonium chloride or tetramethylammonium hydroxide, stirring evenly to improve lipophilicity, and preparing nanomaterial dispersion;

[0022] B3, dissolving the antioxidant Irganox 1010 and the light stabilizer Tinuvin 770 in anhydrous ethanol to form an additive solution;

[0023] B4, adding the additive solution dropwise to the nanomaterial dispersion, stirring at 50-80°C for 2-4 hours to promote the insertion of the additive molecules into the nanosheet layer;

[0024] B5. Remove the solvent by rotary evaporation or reduced pressure distillation to obtain the intercalation complex, dry it in vacuum at 50-60° C. for 7-9 hours, and then grind it into a uniform powder.

[0025] As a preferred technical solution of the present invention, the preparation method of the environmentally friendly antibacterial PVC material is as follows: adding an anti-aging agent to a plasticizer and stirring evenly, then adding calcium zinc to stabilize and mix evenly, and then adding to PVC powder, stirring at 60-80°C with a high-speed stirrer for 5-10 minutes, adding a slow-release silver ion composite material and continuing to stir for 5-10 minutes; using a twin-screw extruder for melt plasticization and granulation.

[0026] Furthermore, the environmentally friendly antibacterial PVC material is applied to the production of shoes.

[0027] Beneficial effects of the present invention:

[0028] (1) The present invention adopts a benzene-free or low-benzene plasticizer to prepare an environmentally friendly PVC material, which effectively avoids the environmental and health risks brought by traditional phthalate plasticizers, making the prepared PVC material safer and more environmentally friendly, and making the prepared PVC shoes meet environmental protection standards. At the same time, the ratio of the plasticizer is set to effectively improve the flexibility of the PVC material.

[0029] (2) The present invention increases the dispersibility of silver ions in PVC materials by adsorbing and encapsulating antibacterial silver ions, thereby improving the antibacterial effect and timeliness. Traditional silver ion antibacterial agents are released too quickly. Although they have a strong antibacterial effect in the initial stage, their antibacterial effect will gradually weaken as the silver ion concentration decreases rapidly. The sustained-release material controls the silver ions within an appropriate release range through physical adsorption, chemical modification and coating, thereby ensuring the continuity and stability of the antibacterial effect.

[0030] (3) The present invention improves the dispersibility and anti-aging performance of the anti-aging agent through nano-intercalation composite technology, prolongs the aging time of PVC materials, and improves the durability of the manufactured PVC shoes. Anti-aging agents are often easy to agglomerate in the polymer matrix, resulting in uneven dispersion, which in turn affects their functional performance. The nano-intercalation composite technology disperses the additives between the nano-sheets of the layered material to form a uniform intercalation structure, significantly improving the distribution quality of the additives in the matrix, effectively avoiding the agglomeration problem of traditional additive particles, thereby improving the efficiency of its anti-aging effect, and the nano-intercalation material montmorillonite itself has good ultraviolet shielding ability, which can synergize with the anti-aging agent to further improve the anti-ultraviolet performance of the material. DETAILED DESCRIPTION

[0031] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0032] In the following examples and comparative examples, the PVC powder was purchased from Shanghai Jinsuyu Plastic Raw Materials Co., Ltd. with the item number PVC220; the calcium zinc stabilizer was purchased from Xingzhibao New Materials Co., Ltd. with the item number CZ-60.

[0033] Example 1

[0034] An environmentally friendly antibacterial PVC material comprises the following raw materials in parts by weight: 50 parts by weight of PVC powder, 48 parts by weight of a plasticizer, 0.6 parts by weight of a calcium zinc stabilizer, 15 parts by weight of a slow-release silver ion composite material and 8 parts by weight of an anti-aging additive.

[0035] The plasticizers are DOTP and TBC in a mass ratio of 1:1.

[0036] The preparation steps of the sustained-release silver ion composite material include:

[0037] A1. Place the porous carrier in deionized water, ultrasonicate for 12 minutes, and further treat with 0.1M dilute hydrochloric acid solution for 1.5 hours to remove metal ions or impurities adsorbed on the surface, then rinse with deionized water until neutral, and calcine at 550°C for 2 hours for use;

[0038] A2, adding the porous carrier to 0.1M silver nitrate solution, stirring for 5 hours with ultrasound assistance, filtering and washing with deionized water to remove the silver ions not adsorbed on the surface;

[0039] A3, add to an ammonia solution, stir evenly, so that the silver ions are deposited on the surface of the porous carrier, wash and dry at 80°C for 12 hours to obtain a composite carrier loaded with silver ions;

[0040] A4. The composite carrier loaded with silver ions was dispersed in the polymer solution, ultrasonically stirred for 30 minutes to form a uniformly dispersed emulsion, and treated by spray drying to prepare microsphere particles coated with silver ions. The particles were dried at 60° C. for 12 hours to enhance the compactness of the coating layer, thereby preparing a sustained-release silver ion composite material.

[0041] Wherein, the porous carrier in step A1 is zeolite powder; the mass ratio of the porous carrier to the dilute hydrochloric acid solution is 1:8;

[0042] The mass ratio of the porous carrier to the silver nitrate solution in step A2 is 1:15;

[0043] The concentration of the ammonia solution in step A3 is 0.3 M, and the pH is adjusted to 5.5 with 0.5 M dilute hydrochloric acid; the mass ratio of the porous carrier to the ammonia solution is 1:8;

[0044] The preparation method of the polymer solution in step A4 is as follows: prepare a 6wt% polyvinyl alcohol solution, heat the solution to 80-90°C, and continue stirring for 30-60 minutes; dissolve chitosan in 1% acetic acid solution, and the concentration of the chitosan solution is 1.5wt%; add the chitosan solution dropwise to the polyvinyl alcohol solution, use a high-speed homogenizer at 6500rpm, and process for 4 minutes; the mass ratio of the composite carrier loaded with silver ions to the polymer solution is 1:7; the volume ratio of the chitosan solution to the polyvinyl alcohol solution is 1:2.

[0045] The anti-aging aid comprises the following raw materials in parts by weight: 5 parts by weight of montmorillonite, 60 parts by weight of deionized water, 0.08 parts by weight of an intercalant, 0.65 parts by weight of an antioxidant, 0.65 parts by weight of a light stabilizer, and 35 parts by weight of anhydrous ethanol; the preparation steps are as follows:

[0046] B1, dispersing the nanosheet montmorillonite in deionized water, and ultrasonically treating for 30 minutes to reduce the stacking of the sheets and form a stable dispersion;

[0047] B2, adding intercalation agent benzalkonium chloride, stirring evenly to improve lipophilicity, and preparing nanomaterial dispersion;

[0048] B3, dissolving the antioxidant Irganox 1010 and the light stabilizer Tinuvin 770 in anhydrous ethanol to form an additive solution;

[0049] B4, adding the additive solution dropwise to the nanomaterial dispersion and stirring at 65°C for 3 hours to promote the insertion of the additive molecules into the nanosheet layer;

[0050] B5. Remove the solvent by rotary evaporation or reduced pressure distillation to obtain the intercalation complex, dry it in vacuum at 55° C. for 8 h, and then grind it into a uniform powder.

[0051] The preparation method of the environmentally friendly antibacterial PVC material comprises the following steps: adding an anti-aging agent to a plasticizer and stirring evenly, adding calcium zinc to stabilize the mixture and stirring evenly, adding the mixture to PVC powder, stirring the mixture at 70° C. for 8 minutes with a high-speed stirrer, adding a slow-release silver ion composite material and stirring the mixture for another 8 minutes; and using a twin-screw extruder for melt plasticization and granulation.

[0052] The environmentally friendly antibacterial PVC material is applied to the production of shoes.

[0053] Example 2

[0054] An environmentally friendly antibacterial PVC material comprises the following raw materials in parts by weight: 40 parts by weight of PVC powder, 45 parts by weight of a plasticizer, 0.4 parts by weight of a calcium zinc stabilizer, 10 parts by weight of a slow-release silver ion composite material and 5 parts by weight of an anti-aging additive.

[0055] The plasticizers are TBC and ATBC in a mass ratio of 1:1.

[0056] The preparation steps of the sustained-release silver ion composite material include:

[0057] A1. Place the porous carrier in deionized water, ultrasonicate for 10 min, further treat with 0.1 M dilute hydrochloric acid solution for 1 h to remove metal ions or impurities adsorbed on the surface, then rinse with deionized water until neutral, calcine at 500 ° C for 1 h and set aside;

[0058] A2, adding the porous carrier to 0.1M silver nitrate solution, stirring for 4 hours with ultrasound assistance, filtering and washing with deionized water to remove the silver ions not adsorbed on the surface;

[0059] A3, add to an ammonia solution, stir evenly, so that silver ions are deposited on the surface of the porous carrier to form silver particles, and then dry at 70° C. for 10 hours after washing to obtain a composite carrier loaded with silver ions;

[0060] A4. The composite carrier loaded with silver ions was dispersed in the polymer solution, ultrasonically stirred for 20 minutes to form a uniformly dispersed emulsion, and treated by spray drying to prepare microsphere particles coated with silver ions. The particles were dried at 50° C. for 10 hours to enhance the compactness of the coating layer, thereby preparing a sustained-release silver ion composite material.

[0061] Wherein, the porous carrier in step A1 is zeolite powder; the mass ratio of the porous carrier to the dilute hydrochloric acid solution is 1:5;

[0062] The mass ratio of the porous carrier to the silver nitrate solution in step A2 is 1:10;

[0063] The concentration of the ammonia solution in step A3 is 0.1 M, and the pH is adjusted to 5.0 with 0.5 M dilute hydrochloric acid; the mass ratio of the porous carrier to the ammonia solution is 1:6;

[0064] The preparation method of the polymer solution in step A4 is as follows: prepare a 4wt% polyvinyl alcohol solution, heat the solution to 80°C, and continue stirring for 30 minutes; dissolve chitosan in a 1% acetic acid solution, and the concentration of the chitosan solution is 1wt%; add the chitosan solution dropwise to the polyvinyl alcohol solution, and use a high-speed homogenizer at 5000rpm for 3min; the mass ratio of the composite carrier loaded with silver ions to the polymer solution is 1:5; the volume ratio of the chitosan solution to the polyvinyl alcohol solution is 1:1.

[0065] The anti-aging aid comprises the following raw materials in parts by weight: 4 parts by weight of montmorillonite, 50 parts by weight of deionized water, 0.05 parts by weight of an intercalant, 0.5 parts by weight of an antioxidant, 0.5 parts by weight of a light stabilizer, and 30 parts by weight of anhydrous ethanol; the preparation steps are as follows:

[0066] B1, dispersing the nanosheet montmorillonite in deionized water and ultrasonically treating for 20 minutes to reduce the stacking of the sheets and form a stable dispersion;

[0067] B2, adding intercalation agent benzalkonium chloride or tetramethylammonium hydroxide, stirring evenly to improve lipophilicity, and preparing nanomaterial dispersion;

[0068] B3, dissolving the antioxidant Irganox 1010 and the light stabilizer Tinuvin 770 in anhydrous ethanol to form an additive solution;

[0069] B4, adding the additive solution dropwise to the nanomaterial dispersion and stirring at 50°C for 2 hours to promote the insertion of the additive molecules into the nanosheet layer;

[0070] B5. Remove the solvent by rotary evaporation or reduced pressure distillation to obtain the intercalation complex, dry it in vacuum at 50° C. for 7 h, and then grind it into a uniform powder.

[0071] The preparation method of the environmentally friendly antibacterial PVC material comprises the following steps: adding an anti-aging agent to a plasticizer and stirring evenly, then adding calcium zinc to stabilize and mix evenly, then adding to PVC powder, stirring at 60° C. for 5 minutes with a high-speed stirrer, adding a slow-release silver ion composite material and continuing stirring for 5 minutes; and using a twin-screw extruder for melt plasticization and granulation.

[0072] The environmentally friendly antibacterial PVC material is applied to the production of shoes.

[0073] Example 3

[0074] An environmentally friendly antibacterial PVC material comprises the following raw materials in parts by weight: 60 parts by weight of PVC powder, 50 parts by weight of a plasticizer, 0.8 parts by weight of a calcium zinc stabilizer, 20 parts by weight of a slow-release silver ion composite material and 10 parts by weight of an anti-aging additive.

[0075] The plasticizer is DOTP.

[0076] The preparation steps of the sustained-release silver ion composite material include:

[0077] A1. Place the porous carrier in deionized water, perform ultrasonic treatment for 15 min, further treat with 0.1 M dilute hydrochloric acid solution for 2 h to remove metal ions or impurities adsorbed on the surface, then rinse with deionized water until neutral, and calcine at 600 ° C for 3 h for use;

[0078] A2, adding the porous carrier to 0.1M silver nitrate solution, stirring for 6 hours with ultrasonic assistance, filtering and washing with deionized water to remove the silver ions not adsorbed on the surface;

[0079] A3, add to an ammonia solution, stir evenly, so that silver ions are deposited on the surface of the porous carrier to form silver particles, and then dry at 90° C. for 14 hours after washing to obtain a composite carrier loaded with silver ions;

[0080] A4. The composite carrier loaded with silver ions was dispersed in the polymer solution, ultrasonically stirred for 40 minutes to form a uniformly dispersed emulsion, and treated by spray drying to prepare microsphere particles coated with silver ions. The particles were dried at 70° C. for 14 hours to enhance the compactness of the coating layer, thereby preparing a sustained-release silver ion composite material.

[0081] Wherein, the porous carrier in step A1 is SiO2 nanoparticles; the mass ratio of the porous carrier to the dilute hydrochloric acid solution is 1:10;

[0082] The mass ratio of the porous carrier to the silver nitrate solution in step A2 is 1:20;

[0083] The concentration of the ammonia solution in step A3 is 0.5 M, and the pH is adjusted to 6.0 with 0.5 M dilute hydrochloric acid; the mass ratio of the porous carrier to the ammonia solution is 1:10;

[0084] The preparation method of the polymer solution in step A4 is as follows: prepare 8wt% polyvinyl alcohol solution, heat the solution to 90°C, and continue stirring for 60 minutes; dissolve chitosan in 1% acetic acid solution, and the concentration of the chitosan solution is 2wt%; add the chitosan solution dropwise to the polyvinyl alcohol solution, use a high-speed homogenizer at 8000rpm, and process for 5 minutes; the mass ratio of the composite carrier loaded with silver ions to the polymer solution is 1:10; the volume ratio of the chitosan solution to the polyvinyl alcohol solution is 1:3.

[0085] The anti-aging aid comprises the following raw materials in parts by weight: 6 parts by weight of montmorillonite, 70 parts by weight of deionized water, 0.1 parts by weight of an intercalant, 0.8 parts by weight of an antioxidant, 0.8 parts by weight of a light stabilizer, and 40 parts by weight of anhydrous ethanol; the preparation steps are as follows:

[0086] B1, dispersing the nanosheet montmorillonite in deionized water and ultrasonically treating for 40 minutes to reduce the stacking of the sheets and form a stable dispersion;

[0087] B2, adding intercalation agent benzalkonium chloride or tetramethylammonium hydroxide, stirring evenly to improve lipophilicity, and preparing nanomaterial dispersion;

[0088] B3, dissolving the antioxidant Irganox 1010 and the light stabilizer Tinuvin 770 in anhydrous ethanol to form an additive solution;

[0089] B4, adding the additive solution dropwise to the nanomaterial dispersion and stirring at 80°C for 4 hours to promote the insertion of the additive molecules into the nanosheet layer;

[0090] B5. Remove the solvent by rotary evaporation or reduced pressure distillation to obtain the intercalation complex, dry it in vacuum at 60° C. for 9 h, and then grind it into a uniform powder.

[0091] As a preferred technical solution of the present invention, the preparation method of the environmentally friendly antibacterial PVC material is as follows: adding an anti-aging agent to a plasticizer and stirring evenly, then adding calcium zinc to stabilize and mix evenly, and then adding to PVC powder, stirring at 80°C for 10 minutes with a high-speed stirrer, adding a slow-release silver ion composite material and continuing to stir for 10 minutes; using a twin-screw extruder for melt plasticization and granulation.

[0092] The environmentally friendly antibacterial PVC material is applied to the production of shoes.

[0093] Example 4

[0094] An environmentally friendly antibacterial PVC material comprises the following raw materials in parts by weight: 45 parts by weight of PVC powder, 50 parts by weight of a plasticizer, 0.5 parts by weight of a calcium zinc stabilizer, 12 parts by weight of a slow-release silver ion composite material and 6 parts by weight of an anti-aging additive.

[0095] The plasticizer is DOA.

[0096] The preparation steps of the sustained-release silver ion composite material include:

[0097] A1. Place the porous carrier in deionized water, ultrasonicate for 12 minutes, and further treat with 0.1M dilute hydrochloric acid solution for 2 hours to remove metal ions or impurities adsorbed on the surface, then rinse with deionized water until neutral, and calcine at 520°C for 1 hour for use;

[0098] A2, adding the porous carrier to 0.1M silver nitrate solution, stirring for 5 hours with ultrasound assistance, filtering and washing with deionized water to remove the silver ions not adsorbed on the surface;

[0099] A3, add to an ammonia solution, stir evenly, so that silver ions are deposited on the surface of the porous carrier to form silver particles, and then dry at 75° C. for 12 hours after washing to obtain a composite carrier loaded with silver ions;

[0100] A4. The composite carrier loaded with silver ions was dispersed in the polymer solution, ultrasonically stirred for 25 minutes to form a uniformly dispersed emulsion, and treated by spray drying to prepare microsphere particles coated with silver ions. The particles were dried at 55° C. for 13 hours to enhance the compactness of the coating layer, thereby preparing a sustained-release silver ion composite material.

[0101] The porous carrier in step A1 is SiO2 nanoparticles; the mass ratio of the porous carrier to the dilute hydrochloric acid solution is 1:6;

[0102] The mass ratio of the porous carrier to the silver nitrate solution in step A2 is 1:18;

[0103] The concentration of the ammonia solution in step A3 is 0.2 M, and the pH is adjusted to 5.2 with 0.5 M dilute hydrochloric acid; the mass ratio of the porous carrier to the ammonia solution is 1:7;

[0104] The preparation method of the polymer solution in step A4 is as follows: prepare a 5wt% polyvinyl alcohol solution, heat the solution to 84°C, and continue stirring for 35 minutes; dissolve chitosan in a 1% acetic acid solution, and the concentration of the chitosan solution is 2wt%; add the chitosan solution dropwise to the polyvinyl alcohol solution, use a high-speed homogenizer at 5000rpm, and process for 5 minutes; the mass ratio of the composite carrier loaded with silver ions to the polymer solution is 1:6; the volume ratio of the chitosan solution to the polyvinyl alcohol solution is 1:2.5.

[0105] The anti-aging aid comprises the following raw materials in parts by weight: 5 parts by weight of montmorillonite, 50 parts by weight of deionized water, 0.1 parts by weight of an intercalant, 0.5 parts by weight of an antioxidant, 0.5 parts by weight of a light stabilizer, and 40 parts by weight of anhydrous ethanol; the preparation steps are as follows:

[0106] B1, disperse the nanosheet montmorillonite in deionized water and perform ultrasonic treatment for 35 minutes to reduce the stacking of the sheets and form a stable dispersion;

[0107] B2, adding intercalation agent benzalkonium chloride or tetramethylammonium hydroxide, stirring evenly to improve lipophilicity, and preparing nanomaterial dispersion;

[0108] B3, dissolving the antioxidant Irganox 1010 and the light stabilizer Tinuvin 770 in anhydrous ethanol to form an additive solution;

[0109] B4, adding the additive solution dropwise to the nanomaterial dispersion and stirring at 60°C for 2 hours to promote the insertion of the additive molecules into the nanosheet layer;

[0110] B5. Remove the solvent by rotary evaporation or reduced pressure distillation to obtain the intercalation complex, dry it in vacuum at 60° C. for 9 h, and then grind it into a uniform powder.

[0111] The preparation method of the environmentally friendly antibacterial PVC material comprises the following steps: adding an anti-aging agent to a plasticizer and stirring evenly, adding calcium zinc to stabilize the mixture and stirring evenly, adding the mixture to PVC powder, stirring the mixture at 80° C. for 5 minutes with a high-speed stirrer, adding a slow-release silver ion composite material and stirring the mixture for 5 minutes; and using a twin-screw extruder for melt plasticization and granulation.

[0112] The environmentally friendly antibacterial PVC material is applied to the production of shoes.

[0113] Comparative Example 1

[0114] On the basis of Example 1, the silver ions were not subjected to adsorption and encapsulation treatment, and an equal amount of silver nitrate was directly added, and the rest was consistent with Example 1.

[0115] Comparative Example 2

[0116] On the basis of Example 1, no anti-aging agent was added, and equal amounts of antioxidant Irganox 1010 and light stabilizer Tinuvin 770 were directly added, and the rest were consistent with Example 1.

[0117] Comparative Example 3

[0118] On the basis of Example 1, no anti-aging agent was added, and 8 parts by weight of antioxidant Irganox 1010 was directly added, and the rest was the same as Example 1.

[0119] Comparative Example 4

[0120] On the basis of Example 1, no anti-aging agent was added, and 8 parts by weight of light stabilizer Tinuvin 770 was directly added, and the rest was consistent with Example 1.

[0121] Comparative Example 5

[0122] On the basis of Example 1, the plasticizer was changed to dioctyl phthalate, and the rest was consistent with Example 1.

[0123] Comparative Example 6

[0124] On the basis of Example 1, the plasticizer was changed to diisodecyl phthalate, and the rest was consistent with Example 1.

[0125] Performance Test:

[0126] Antibacterial performance test: The national standard GB / T31402-2023 "Test method for antibacterial performance of plastic surface" was used for testing. The test method adopted the film method. Escherichia coli ATYCC 8739 was used for the test 5 times in parallel, and the average value was taken.

[0127] Aging resistance test: tensile strength test refers to GBT1040.1-2018 standard test; aging resistance: UV oven irradiation test (UV light intensity 1200μW / cm2, aging temperature 60℃, aging time 3 days), measuring tensile strength retention rate and elongation at break retention rate.

[0128] VOC test: Take 100g of each material of Examples 1-4 and Comparative Examples 1-6 and spread it on 1m 3The samples were placed in an environmental release chamber for 3 days (23°C, 50% humidity), benzene hydrocarbons were adsorbed using Tenax tubes, and detected using ATD-GC-MS.

[0129]

[0130] The material of Example 1 was made into rain boots and tested for decomposable harmful aromatic amines, formaldehyde, heavy metals, phthalate MN, dimethyl fumarate, short-chain chlorinated paraffin SMN, and broken needles according to the national standard GB 25038-2024:

[0131]

[0132] The test results of rain boots are as follows:

[0133]

[0134]

[0135] From the test results, it can be seen that the present invention adopts benzene-free or low-benzene plasticizer to prepare environmentally friendly PVC materials, increases the antibacterial effect and timeliness by adsorbing and encapsulating antibacterial silver ions, improves the anti-aging performance of anti-aging additives by nano-intercalation composite technology, and significantly improves the anti-aging ability of PVC materials. The rain boots made from them meet the requirements of various standards when submitted for inspection.

[0136] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any indirect modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. An environmentally friendly antibacterial PVC material, characterized by: The invention comprises the following raw materials in parts by weight: 40-60 parts by weight of PVC powder, 45-50 parts by weight of plasticizer, 0.4-0.8 parts by weight of calcium zinc stabilizer, 10-20 parts by weight of slow-release silver ion composite material and 5-10 parts by weight of anti-aging auxiliary agent.

2. The environmentally friendly antibacterial PVC material according to claim 1, characterized in that: The plasticizer is one or more of DOTP, TBC, ATBC and DOA.

3. The environmentally friendly antibacterial PVC material according to claim 1, characterized in that: The preparation steps of the sustained-release silver ion composite material include: A1. Place the porous carrier in deionized water, perform ultrasonic treatment for 10-15 minutes, further treat with 0.1M dilute hydrochloric acid solution for 1-2 hours to remove metal ions or impurities adsorbed on the surface, then rinse with deionized water until neutral, calcine at 500-600°C for 1-3 hours and set aside; A2, adding the porous carrier to a 0.1M silver nitrate solution, stirring with ultrasound assistance for 4-6 hours, filtering and washing with deionized water to remove the unabsorbed silver ions on the surface; A3, add to an ammonia solution, stir evenly, so that the silver ions are deposited on the surface of the porous carrier, wash and dry at 70-90°C for 10-14 hours to obtain a composite carrier loaded with silver ions; A4. Disperse the composite carrier loaded with silver ions into the polymer solution, stir ultrasonically for 20-40 minutes to form a uniformly dispersed emulsion, treat it by spray drying to prepare microsphere particles coated with silver ions, dry it at 50-70°C for 10-14 hours to enhance the compactness of the coating layer, and prepare a slow-release silver ion composite material.

4. The environmentally friendly antibacterial PVC material according to claim 3, characterized in that: In step A1, the porous carrier is zeolite powder or SiO2 nanoparticles; the mass ratio of the porous carrier to the dilute hydrochloric acid solution is 1:5-10.

5. The environmentally friendly antibacterial PVC material according to claim 3, characterized in that: The mass ratio of the porous carrier to the silver nitrate solution in step A2 is 1:10-20.

6. The environmentally friendly antibacterial PVC material according to claim 3, characterized in that: In step A3, the concentration of the aqueous ammonia solution is 0.1-0.5 M, and the pH is adjusted to 5.0-6.0 with 0.5 M dilute hydrochloric acid; the mass ratio of the porous carrier to the aqueous ammonia solution is 1:6-10.

7. The environmentally friendly antibacterial PVC material according to claim 3, characterized in that: The preparation method of the polymer solution in step A4 is as follows: prepare 4-8wt% polyvinyl alcohol solution, heat the solution to 80-90°C, and continue stirring for 30-60 minutes; dissolve chitosan in 1% acetic acid solution, and the concentration of the chitosan solution is 1-2wt%; add the chitosan solution dropwise to the polyvinyl alcohol solution, and use a high-speed homogenizer at 5000-8000rpm for 3-5min; the mass ratio of the composite carrier loaded with silver ions to the polymer solution is 1:5-10; the volume ratio of the chitosan solution to the polyvinyl alcohol solution is 1:1-3.

8. The environmentally friendly antibacterial PVC material according to claim 1, characterized in that: The anti-aging aid comprises the following raw materials in parts by weight: 4-6 parts by weight of montmorillonite, 50-70 parts by weight of deionized water, 0.05-0.1 parts by weight of an intercalant, 0.5-0.8 parts by weight of an antioxidant, 0.5-0.8 parts by weight of a light stabilizer, and 30-40 parts by weight of anhydrous ethanol; The preparation steps are: B1. Disperse the nanosheet montmorillonite in deionized water and perform ultrasonic treatment for 20-40 minutes to reduce the stacking of the sheets and form a stable dispersion; B2, adding intercalation agent benzalkonium chloride or tetramethylammonium hydroxide, stirring evenly to improve lipophilicity, and preparing nanomaterial dispersion; B3, dissolving the antioxidant Irganox 1010 and the light stabilizer Tinuvin 770 in anhydrous ethanol to form an additive solution; B4, adding the additive solution dropwise to the nanomaterial dispersion, stirring at 50-80°C for 2-4 hours to promote the insertion of the additive molecules into the nanosheet layer; B5. Remove the solvent by rotary evaporation or reduced pressure distillation to obtain the intercalation complex, dry it in vacuum at 50-60° C. for 7-9 hours, and then grind it into a uniform powder.

9. The environmentally friendly antibacterial PVC material according to claim 1, characterized in that: The preparation method of the environmentally friendly antibacterial PVC material comprises the following steps: adding an anti-aging agent to a plasticizer, stirring evenly, adding calcium and zinc to stably mix evenly, adding the mixture to PVC powder, stirring at 60-80° C. for 5-10 minutes with a high-speed stirrer, adding a slow-release silver ion composite material and continuing stirring for 5-10 minutes; and using a twin-screw extruder for melt plasticization and granulation.

10. An application of the environmentally friendly antibacterial PVC material according to any one of claims 1 to 9, characterized in that: The environmentally friendly antibacterial PVC material is applied to the production of shoes.

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