Antibacterial mildew-proof packaging material as well as preparation method and application thereof

Abstract

The invention discloses an antibacterial and mildew-proof packaging material as well as a preparation method and application thereof, and belongs to the field of antibacterial and mildew-proof packaging materials. The antibacterial and mildew-proof packaging material is prepared from the following components in parts by weight: 60 to 100 parts of biodegradable high polymer material and 0.3 to 2 parts of inorganic metal ion carrier, the invention relates to an antibacterial plastic which is prepared from the following components in parts by weight: 0.1-1 part of an organic antibacterial agent, 0.1-2 parts of an antifungal agent, 1-6 parts of polyethylene glycol, 0.1-5 parts of a plasticizer, 0.1-3 parts of a grafting monomer, 0.1-3 parts of an antistatic agent, 0.05-0.5 part of an antioxidant, 0.05-0.5 part of a light stabilizer, 0.1-2 parts of an anti-sticking agent and 0.1-5 parts of a coupling agent. The preparation method comprises the following steps: pretreating the raw materials, carrying out master batch on the active components, and carrying out integrated melt blending and granulation in a double-screw reaction extruder. The obtained composite particles can be used for forming antibacterial and mildew-proof films by a plastic film machine, or can be prepared into coating liquid to be coated on the surfaces of shoe boxes, clothing hangtags and clothing packaging boxes, so that long-acting antibacterial and mildew-proof effects are realized, and the composite particles are environment-friendly, efficient and flexible to process.

Description

Technical Field

[0001] This invention belongs to the field of antibacterial and antifungal packaging materials, and discloses an antibacterial and antifungal packaging material, its preparation method and its application. Background Technology

[0002] With increasingly stringent global demands for environmental protection and product quality, packaging materials must not only fulfill basic protective functions but also possess sustainability and added functionality. Traditional plastic packaging materials, such as polyethylene and polypropylene, place enormous pressure on the environment due to their non-degradability. Therefore, developing biodegradable packaging materials has become an important trend in the industry. However, when introducing functional components such as antibacterial and antifungal agents into biodegradable materials, challenges such as poor compatibility, low processing stability, and easy deactivation of active ingredients often arise.

[0003] In practical applications, many products, especially food, medical devices, and daily consumer goods such as footwear and clothing, are highly susceptible to microbial attack, including bacteria and mold, during storage and transportation. This leads to product spoilage, off-odors, and severely impacts product quality and shelf life. To address these issues, existing technologies typically employ various antibacterial and anti-mold strategies. One method is to directly add antibacterial agents to packaging materials. While simple, this method often suffers from uneven dispersion of the antibacterial agent within the material, easy decomposition and inactivation at high processing temperatures, and difficulty in controlling the release rate. Too rapid a release may result in short-lived efficacy, while too slow a release fails to achieve the desired antibacterial effect.

[0004] Another strategy is to coat the antibacterial agent onto the surface of the packaging material. This method is more compatible with heat-sensitive antibacterial agents, but the coating is prone to wear and peeling, resulting in poor antibacterial efficacy and a potential risk of antibacterial agent migration into the product. Furthermore, multilayer co-extrusion or composite technologies can be used to design multilayer composite structures that combine layers with different functions. For example, immediate-release and sustained-release antibacterial layers can be designed in different layers to achieve both immediate and long-lasting effects. However, the manufacturing process for such complex multilayer structures is complicated and costly, and compatibility issues may exist between the layers. Additionally, their application is still mainly limited to films or sheets, lacking broader processing flexibility.

[0005] Specifically, for products such as shoe boxes, clothing tags, and clothing packaging boxes, the packaging environment is often relatively sealed and prone to moisture, making them highly susceptible to mold growth and odor. Existing anti-mold measures mostly involve placing desiccants or simple anti-mold sheets. These methods are usually short-lived, have limited coverage, and are difficult to effectively inhibit microbial growth and odor generation. For example, Chinese patent [CN120307682A] discloses a production process for anti-fog, anti-mold, and antibacterial plastic food preservation film. Although this technology achieves multiple functions through multi-layer co-extrusion and plasma surface modification, its base material is still non-biodegradable polyethylene, and the process is relatively complex, failing to fundamentally solve the environmental pollution problem and the challenge of integrating multiple functions into a single material system. Another Chinese patent [CN120365734A] proposes a polymeric antifungal and antibacterial microfoamed breathable shoe material and its preparation method. Although this invention uses bio-based polymers and incorporates plant extracts to achieve antibacterial and antifungal effects, it is mainly applied to specific products such as shoe materials, and the preparation process involves a complex polyurethane foaming system. This differs from the broad-spectrum and versatility of the general-purpose biodegradable antibacterial and antifungal composite particles provided by this invention, which can be flexibly applied to packaging materials such as films or coatings.

[0006] In summary, existing technologies still have significant shortcomings in the field of antibacterial and antifungal packaging materials. These shortcomings primarily lie in the difficulty of simultaneously achieving stable encapsulation and controlled release of antibacterial agents within a single material system, balancing immediate and long-lasting effects while maintaining excellent processing performance. While multilayer composite structures attempt to address release control issues, their complexity, high cost, and limited application remain obstacles. Currently, the market lacks a versatile material that is both environmentally friendly and biodegradable, possesses highly efficient and broad-spectrum antibacterial and antifungal properties, and can be flexibly applied to film forming and surface coating. Therefore, developing a multifunctional antibacterial, antifungal, and biodegradable composite material with simplified structure, integrated functions, efficient preparation, flexible application, and effective solutions to product microbial contamination and odor problems is of great significance for enhancing product added value and promoting the development of the green packaging industry. Summary of the Invention

[0007] This invention provides a multifunctional antibacterial, antifungal, and biodegradable composite particle, its preparation method, and its application. It aims to solve the technical problems commonly encountered when introducing antibacterial and antifungal functions into existing packaging materials, such as uncontrolled antibacterial release, poor compatibility of functional components, easy deactivation of active ingredients during thermal processing, and difficulty in simultaneously achieving both immediate and long-lasting antibacterial performance in a single structure.

[0008] To achieve the purpose of this invention, the technical solution adopted is as follows: an antibacterial and antifungal packaging material, comprising, by weight, 60-100 parts of biodegradable polymer material, 0.3-2 parts of inorganic metal ion carrier, 0.1-1 parts of organic antibacterial agent, 0.1-2 parts of antifungal agent, 1-6 parts of polyethylene glycol, 0.1-5 parts of plasticizer, 0.1-3 parts of grafted monomer, 0.1-3 parts of antistatic agent, 0.05-0.5 parts of antioxidant, 0.05-0.5 parts of light stabilizer, 0.1-2 parts of anti-adhesive, and 0.1-5 parts of coupling agent; wherein the biodegradable polymer material is one or a combination of PBAT and PLA; the inorganic metal ion carrier is one or a combination of silver-loaded zeolite, silver-loaded oxide, zinc oxide, and copper oxide; and the organic antibacterial agent is benzyl dodecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, phenolic resin, or p-hydroxybenzene. The antifungal agent is one or more of the following: iodopropynyl butylcarbamate, miconazole, tea tree oil, and cinnamaldehyde; the plasticizer is one or more of the following: dioctyl adipate, sebacic acid ester, and glyceryl tartrate; the grafting monomer is one or more of the following: maleic anhydride, acrylate, and styrene; the antistatic agent is one or more of the following: fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene amine, glyceryl monostearate, alkyl phosphate, and polyether phosphate; the antioxidant is one or more of the following: phosphate ester, phosphate diester, and α,α-dimethylbenzyl; the light stabilizer is one or more of the following: benzotriazole, triazine, and benzophenone; the anti-adhesive agent is one or more of the following: micronized silica, talc, calcium carbonate, titanium dioxide, and glass microspheres; and the coupling agent is one or more of the following: methoxysilane and ethoxysilane.

[0009] According to an antibacterial and antifungal packaging material, the preparation of the antibacterial and antifungal packaging material includes the following steps: S1 involves drying biodegradable polymer materials at 70-75°C for 4-8 hours to reduce the moisture content to 1-200 ppm; drying polyethylene glycol and plasticizers at 40-60°C for 2-6 hours; and drying powdered components such as inorganic metal ion carriers, antistatic agents, antioxidants, light stabilizers, anti-adhesion agents, and coupling agents at 80-120°C for 2-6 hours. All liquid and heat-sensitive components are ensured to maintain their chemical stability during the drying process. All dried raw materials are stored in sealed containers at a relative humidity of 1-10% to prevent secondary moisture absorption. S2 involves mixing pre-dried biodegradable polymer materials with inorganic metal ion carriers at a weight ratio of 70-95:5-30, then adding the mixture to a twin-screw extruder for melt blending and masterbatch production. The extrusion temperature zone is set at 140-180℃, and the screw speed is 150-300 rpm. Volatile substances are continuously discharged through a vacuum end to ensure masterbatch quality. The discharged material is cooled at 25-40℃ and then pelletized, with the masterbatch moisture content controlled at 1-500 ppm and the particle size controlled at 2-5 mm. The resulting masterbatch is tested for active ingredient content and dispersion uniformity to ensure uniform dispersion and stable activity of the inorganic carrier. S3 precisely mixes pre-dried biodegradable polymer materials with organic antibacterial and antifungal agents at a weight ratio of 100:1~10, and then produces organic antibacterial / antifungal masterbatch in another twin-screw extruder; the extrusion temperature zone is set to 140~170℃, and the screw speed is 120~300rpm; after discharge, the material is cooled and pelletized, and dried at 40~80℃ for 2~6 hours to remove any trace volatiles that may be generated; the resulting masterbatch is used for subsequent metering, and its thermal stability and the release characteristics of antibacterial / antifungal active ingredients are tested; S4 uses pre-dried biodegradable polymer materials as the main feedstock, which are fed into the feed section of a twin-screw reactive extruder via a constant-speed feeder and preheated to 140-150°C. Grafted monomers are fed into the mixing zone of the extruder at a dosage of 0.5-3%, while an initiator is simultaneously added via a metering pump at the adjacent feed inlet. During the grafting reaction and melt blending processes, pretreated polyethylene glycol, plasticizers, antistatic agents, antioxidants, light stabilizers, anti-sticking agents, coupling agents, and inorganic additives are added. Metal ion carrier masterbatch and organic antibacterial / antifungal masterbatch are precisely added to the extruder according to the formula ratio using a high-precision loss-in-weight feeder; the screw speed is controlled at 120~300rpm, and the extruder temperature is controlled in stages: the mixing section temperature is controlled at 150~165℃, the kneading and strengthening section temperature is controlled at 160~175℃, and the discharge section temperature is controlled at 165~185℃; the average residence time is controlled at 20~90 seconds to ensure sufficient grafting reaction and uniform dispersion of each component; A degassing section is set after the S5 grafting reaction section, and unreacted monomers and low-boiling volatiles are continuously removed at a pressure of 1~10 mbar at the vacuum end to effectively reduce residues; the extrusion torque, extrusion temperature curve and degassing vacuum degree are monitored in real time, and the acid value increment is controlled to be 0.1~2.0 mg / KOH, and the residual monomer target is less than 0.1%; the qualified discharge is cooled to 25~40℃, granulated and dried to 1~500ppm and then stored in a sealed container to finally obtain multifunctional biodegradable composite particles with antibacterial and anti-mildew functions.

[0010] According to a method for preparing an antibacterial and antifungal packaging material, the initiator in S4 is one or more of tert-butyl peroxybenzoate, benzoyl peroxide, and azobisisobutyronitrile.

[0011] According to an antibacterial and antifungal packaging material for use in shoe boxes, clothing tags, and clothing packaging boxes, the application method is characterized by coating the prepared antibacterial and antifungal material onto the surface of the shoe box, clothing tag, or clothing packaging box by means of a coating method, or making the prepared antibacterial and antifungal material into an antibacterial and antifungal film and adhering the antibacterial and antifungal film onto the surface of the shoe box, clothing tag, or clothing packaging box by means of a molding machine.

[0012] According to the application of an antibacterial and antifungal packaging material in shoe boxes, clothing tags, and clothing packaging boxes, the method for coating the prepared antibacterial and antifungal material onto the surface of the shoe boxes, clothing tags, and clothing packaging boxes by means of a coating method is as follows: S1 grinds the prepared composite particles using a low-temperature pulverizer to obtain micro powder with an average particle size of 1~10 micrometers; In step S2, deionized water, waterborne polyurethane emulsion, wetting and dispersing agent, and defoamer are added to a high-speed mixer and premixed at 500-1000 rpm for 15-30 minutes. The ground composite particles are then added, and the mixing speed is increased to 1000-2000 rpm. The mixture is dispersed for 1-2 hours to ensure uniform particle dispersion without agglomeration. A thickener is added, and the mixing speed is adjusted to 800-1000 rpm. The mixture is stirred for 20-30 minutes until the viscosity of the coating liquid reaches 800-1200 mPa·s. The wetting and dispersing agent is one or more of polyether-modified polysiloxane, sodium fatty alcohol polyoxyethylene ether sulfate, and alkylphenol polyoxyethylene ether. The defoamer is one or more of polydimethylsiloxane, ethylene oxide, and propylene oxide. The thickener is one or more of hydrophobically modified ethoxylated polyurethane, water-soluble cellulose ether, and xanthan gum. S3 filters the prepared coating solution through a 100-200 mesh sieve to remove large particulate impurities and ensure a smooth coating. S4 is applied using an industrial roller coater, with a target wet weight of 8 g / m³. 2 The coating speed is 10~20m / min; After the S5 coating is applied, use a hot air circulating oven to dry it at 80~85℃ for 15~20 seconds to ensure the coating is completely dry.

[0013] According to the application of an antibacterial and antifungal packaging material in shoe boxes, clothing hang tags, and clothing packaging boxes, the method for preparing the antibacterial and antifungal material into an antibacterial and antifungal film, and then adhering the antibacterial and antifungal film to the surface of the shoe box, clothing hang tag, and clothing packaging box using a molding machine is as follows: S1. The prepared composite particles are vacuum dried at 60-70℃ for 2-4 hours to ensure a moisture content of 1-100 ppm. The dried composite particles are then uniformly fed into a single-screw blown film extruder with a diameter of 50-60 mm using a loss-in-weight feeder. The extruder temperature is set in stages: feeding section 128-130℃, compression section 140-142℃, homogenization section 150-152℃, die neck 158-160℃, and die orifice 160-162℃. The screw speed is 160-180 rpm, the melt pressure is 15-20 MPa, the melt temperature is 160-165℃, and the die orifice gap is 1-1.2 mm. After the S2 film is blown, it undergoes initial cooling and shaping through a cooling air ring at a temperature of 15~25℃. Then, it is sent to a heat setting box via a traction roller group and set at a temperature of 65~70℃ for 30~60 minutes. After the S3 film is shaped, it is sent to the winding machine and wound up evenly with a tension of 40~50N to obtain a uniform antibacterial and mildew-proof film roll. S4. The antibacterial and anti-mildew film roll obtained in step S3 is fed out through the unwinding device of the molding machine and aligned with the surface of the shoe box, clothing tag, or clothing packaging box that has been pre-placed or transported to the worktable of the molding machine. The antibacterial and anti-mildew film is heated and pressurized in the molding machine at a temperature of 80~120℃ and a pressure of 0.5~2.0 MPa to evenly and firmly adhere the antibacterial and anti-mildew film to the surface of the shoe box, clothing tag, or clothing packaging box. After adhesion, the composite packaging material is cooled, cut, and sorted to finally obtain a shoe box, clothing tag, or clothing packaging box with antibacterial and anti-mildew functions.

[0014] Compared with the prior art, the present invention has the following advantages: (1) Functional integration and structural simplification: Traditionally, achieving both immediate and long-lasting antibacterial and antifungal effects often requires complex multi-layer composite structures. This invention innovatively integrates short-acting, fast-release antibacterial components, long-lasting, load-bearing antibacterial components, and various additives into a single biodegradable composite particle. This "two-in-one" or even "multi-in-one" design greatly simplifies the material system and product structure, avoiding the complexity, high cost, and interlayer compatibility issues associated with multi-layer composite processes.

[0015] (2) The preparation process is efficient and controllable: The advanced production method of integrated reactive extrusion granulation is adopted, which completes the grafting modification, melt blending, active component encapsulation and granulation processes in one continuous equipment. This not only improves production efficiency and reduces production costs, but more importantly, by precisely controlling process parameters such as extrusion temperature, screw speed, residence time, side feeding point and vacuum degassing, the degree of grafting reaction and the uniform dispersion of each component can be effectively controlled, and the decomposition and deactivation of active ingredients during high-temperature processing can be minimized, thus ensuring the batch stability and functional reproducibility of the product.

[0016] (3) Superior and longer-lasting antibacterial and antifungal effects: Through the synergistic effect of short-acting rapid-release and long-acting sustained-release components within the composite particles, this material can provide rapid initial antibacterial action, quickly inhibiting microbial growth while ensuring long-term effective antibacterial and antifungal protection. For example, in shoe box lining applications, it can effectively inhibit mold growth for up to 90 days and significantly reduce odor generation, far exceeding the effects of traditional single antibacterial agents or simple antifungal sheets.

[0017] (4) Flexible and diverse applications: The resulting composite granules have excellent processing properties. They can be processed by blown film, cast film, injection molding, extrusion, etc., to make antibacterial and mildew-proof films or various products. They can also be dissolved or dispersed to make stable coating liquids for surface coating of various substrates such as paper, cardboard, fabrics, and plastics. This versatility greatly expands the application range of the material, enabling it to meet a wider range of product packaging needs.

[0018] (5) Environmental friendliness and sustainability: This invention uses biodegradable polymer materials such as PBAT and PLA as the matrix, which ensures that the packaging materials can be biodegraded through composting and other methods after the end of their service life, reducing pollution to the environment and conforming to the current global trend of green environmental protection and sustainable development.

[0019] Instruction manual illustrations

[0020] Figure 1 These are physical images of the film rolls prepared in Examples 7, 8, and 9; Figure 2 Transparency test curves of the film rolls prepared in Examples 7, 8, and 9; Figure 3 Contact angle tests were conducted on the film rolls prepared in Examples 7, 8, and 9. Figure 4 This is a photograph of the antibacterial and antifungal experiment in Example Thirteen. Detailed Implementation

[0021] Example 1

[0022] The biodegradable polymer material was dried at 70°C for 4 hours to reduce the moisture content to 1 ppm; polyethylene glycol and plasticizers were dried at 40°C for 2 hours; powdered components such as inorganic metal ion carriers, antistatic agents, antioxidants, light stabilizers, anti-adhesion agents, and coupling agents were dried at 80°C for 2 hours. All liquid and heat-sensitive components maintained their chemical stability during the drying process. All dried raw materials were stored in sealed containers at a relative humidity of 1% to prevent secondary moisture absorption. The pre-dried biodegradable polymer material and inorganic metal ion carrier were precisely mixed at a weight ratio of 70:5, and then fed into a twin-screw extruder for melt blending and masterbatch production. The extrusion temperature zone was set at 140°C, and the screw speed was 150 rpm. Volatile substances were continuously discharged through a vacuum end to ensure masterbatch quality. The discharged material was cooled at 25°C and then pelletized, with the masterbatch moisture content controlled to 1 ppm. The particle size was controlled at 2 mm. The obtained masterbatch was tested for active ingredient content and dispersion uniformity to ensure uniform dispersion and stable activity of the inorganic carrier. Pre-dried biodegradable polymer materials were precisely mixed with organic antibacterial and antifungal agents at a weight ratio of 100:1, and then processed into organic antibacterial / antifungal masterbatch in another twin-screw extruder. The extrusion temperature zone was set at 140℃ and the screw speed at 120 rpm. After discharge, the material was cooled, pelletized, and dried at 40℃ for 2 hours to remove any trace volatiles. The obtained masterbatch was used for subsequent metering, and its thermal stability and the release characteristics of the antibacterial / antifungal active ingredients were tested. Pre-dried biodegradable polymer materials were used as the main material and fed into the feed section of a twin-screw reactive extruder via a constant-speed feeder, and preheated to 140℃. Grafted monomers were fed to the mixing zone side of the extruder at a dosage of 0.5%, while an initiator was added via a metering pump at the adjacent feed port. During the grafting reaction and melt blending process, the pretreated polyethylene... Glycols, plasticizers, antistatic agents, antioxidants, light stabilizers, anti-sticking agents, coupling agents, inorganic metal ion carrier masterbatches, and organic antibacterial / antifungal masterbatches are precisely added to the extruder according to the formula ratio using a high-precision loss-in-weight feeder. The screw speed is controlled at 120 rpm, and the extruder temperature is controlled in stages: the mixing section temperature is controlled at 150℃, the kneading and strengthening section temperature is controlled at 160℃, and the discharge section temperature is controlled at 165℃. The average residence time is controlled at 20 seconds to ensure sufficient grafting reaction and uniform dispersion of each component. A degassing section is set after the grafting reaction section, and unreacted monomers and low-boiling volatiles are continuously removed at a pressure of 1 mbar at the vacuum end to effectively reduce residues. The extrusion torque, extrusion temperature curve, and degassing vacuum degree are monitored in real time, and the target acid value increment is controlled at 0.1 mg / KOH, and the target residual monomer is less than 0.1%. The qualified discharge is cooled to 25℃, pelletized, dried to 1 ppm, and then stored in a sealed container to finally obtain multifunctional biodegradable composite particles with antibacterial and antifungal functions.

[0023] Example 2

[0024] The biodegradable polymer material was dried at 72°C for 6 hours to reduce the moisture content to 100 ppm; polyethylene glycol and plasticizers were dried at 50°C for 4 hours; and powdered components such as inorganic metal ion carriers, antistatic agents, antioxidants, light stabilizers, anti-adhesion agents, and coupling agents were dried at 100°C for 4 hours. All liquid and heat-sensitive components maintained their chemical stability during the drying process. All dried raw materials were stored in sealed containers at a relative humidity of 5% to prevent secondary moisture absorption. The pre-dried biodegradable polymer material and inorganic metal ion carrier were precisely mixed at a weight ratio of 85:15, and then fed into a twin-screw extruder for melt blending and masterbatch production. The extrusion temperature zone was set at 160°C, and the screw speed was 200 rpm. A vacuum end was used to continuously remove volatiles to ensure masterbatch quality. The discharged material was cooled at 30°C and then pelletized, with the masterbatch moisture content controlled at 300 ppm. The concentration was ppm, and the particle size was controlled within 3 mm. The obtained masterbatch was tested for active ingredient content and dispersion uniformity to ensure uniform dispersion and stable activity of the inorganic carrier. The pre-dried biodegradable polymer material was mixed with organic antibacterial and antifungal agents at a ratio of 100:5. The ingredients were precisely mixed in weight ratios and then processed into an organic antibacterial / antifungal masterbatch in another twin-screw extruder. The extrusion temperature zone was set at 155°C and the screw speed at 200 rpm. After discharge, the material was cooled and pelletized, and then dried at 60°C for 4 hours to remove any trace amounts of volatiles. The resulting masterbatch was used for subsequent metering, and its thermal stability and the release characteristics of the antibacterial / antifungal active ingredients were tested. Pre-dried biodegradable polymer materials were used as the main material and fed into the feed section of a twin-screw reactive extruder via a constant-speed feeder and preheated to 145°C. Grafted monomers were fed to the mixing zone side of the extruder at a dosage of 1.5%, while an initiator was added via a metering pump at the adjacent feed port. During the grafting reaction and melt blending process, pretreated polyethylene glycol, plasticizer, antistatic agent, antioxidant, light stabilizer, anti-sticking agent, coupling agent, and inorganic metal ion carrier masterbatch were added. Granules and organic antibacterial / antifungal masterbatch are precisely added to the extruder according to the formula ratio using a high-precision loss-in-weight feeder. The screw speed is controlled at 200 rpm, and the extruder temperature is controlled in stages: the mixing section temperature is controlled at 155℃, the kneading and strengthening section temperature is controlled at 170℃, and the discharge section temperature is controlled at 175℃. The average residence time is controlled at 55 seconds to ensure sufficient grafting reaction and uniform dispersion of each component. A degassing section is set after the grafting reaction section, and unreacted monomers and low-boiling volatiles are continuously removed at a pressure of 5 mbar at the vacuum end to effectively reduce residues. The extrusion torque, extrusion temperature curve, and degassing vacuum degree are monitored in real time, and the target acid value increment is controlled at 1 mg / KOH, and the target residual monomer is less than 0.1%. The qualified discharge is cooled to 33℃, granulated, dried to 250 ppm, and then stored in a sealed container to finally obtain multifunctional biodegradable composite granules with antibacterial and antifungal functions.

[0025] Example 3

[0026] The biodegradable polymer material was dried at 75°C for 8 hours to reduce the moisture content to 200 ppm; polyethylene glycol and plasticizers were dried at 60°C for 6 hours; and powdered components such as inorganic metal ion carriers, antistatic agents, antioxidants, light stabilizers, anti-adhesion agents, and coupling agents were dried at 120°C for 6 hours. All liquid and heat-sensitive components maintained their chemical stability during the drying process. All dried raw materials were stored in sealed containers at a relative humidity of 10% to prevent secondary moisture absorption. The pre-dried biodegradable polymer material and inorganic metal ion carrier were precisely mixed at a weight ratio of 95:30, and then fed into a twin-screw extruder for melt blending and masterbatch production. The extrusion temperature zone was set at 180°C, and the screw speed was 300 rpm. A vacuum end was used to continuously remove volatiles to ensure masterbatch quality. The discharged material was cooled at 40°C and then pelletized, with the masterbatch moisture content controlled at 500 ppm and the particle size controlled at 5 mm. mm; The obtained masterbatch was tested for active ingredient content and dispersion uniformity to ensure uniform dispersion and stable activity of the inorganic carrier; The pre-dried biodegradable polymer material was mixed with organic antibacterial and antifungal agents at a ratio of 100:10 The ingredients were precisely mixed in weight ratios and then processed into an organic antibacterial / antifungal masterbatch in another twin-screw extruder. The extrusion temperature zone was set at 170°C and the screw speed at 300 rpm. After discharge, the material was cooled and pelletized, and then dried at 80°C for 6 hours to remove any trace amounts of volatiles. The resulting masterbatch was used for subsequent metering, and its thermal stability and the release characteristics of the antibacterial / antifungal active ingredients were tested. Pre-dried biodegradable polymer materials were used as the main material and fed into the feed section of the twin-screw reactive extruder through a constant-speed feeder and preheated to 150°C. Grafted monomers were fed into the mixing zone side of the extruder at a dosage of 3%, while an initiator was added through a metering pump at the adjacent side feed port. During the grafting reaction and melt blending process, pretreated polyethylene glycol, plasticizer, antistatic agent, antioxidant, light stabilizer, anti-sticking agent, coupling agent, and inorganic metal ion carrier masterbatch were added. Organic antibacterial / antifungal masterbatch is precisely added to the extruder according to the formula ratio using a high-precision loss-in-weight feeder. The screw speed is controlled at 300 rpm, and the extruder temperature is controlled in stages: the mixing section temperature is controlled at 165℃, the kneading and strengthening section temperature is controlled at 175℃, and the discharge section temperature is controlled at 185℃. The average residence time is controlled at 90 seconds to ensure sufficient grafting reaction and uniform dispersion of each component. A degassing section is set after the grafting reaction section, and unreacted monomers and low-boiling volatiles are continuously removed at a pressure of 10 mbar at the vacuum end to effectively reduce residues. The extrusion torque, extrusion temperature curve, and degassing vacuum degree are monitored in real time, and the target acid value increment is controlled at 2.0 mg / KOH, and the target residual monomer is less than 0.1%. The qualified discharge is cooled to 40℃, pelletized, dried to 500 ppm, and then stored in a sealed container to finally obtain multifunctional biodegradable composite particles with antibacterial and antifungal functions.

[0027] Example 4

[0028] The composite particles prepared in Example 1 were ground using a low-temperature pulverizer to obtain micro-powder with an average particle size of 1 micrometer. Deionized water, aqueous polyurethane emulsion, wetting and dispersing agent, and defoamer were added to a high-speed mixer and premixed at 500 rpm for 15 minutes. The ground composite particles were then added, and the stirring speed was increased to 1000 rpm for 1 hour to ensure uniform particle dispersion without agglomeration. A thickener was added, and the stirring speed was adjusted to 800 rpm for 20 minutes until the viscosity of the coating liquid reached 800 mPa·s. The prepared coating liquid was filtered through a 100-mesh sieve to remove large particulate impurities, ensuring a smooth coating. Coating was performed using an industrial roller coater, with a target wet weight of 8 g / m³. 2 The coating speed is 10m / min; after coating, use a hot air circulating oven to dry at 80℃ for 15 seconds to ensure the coating is completely dry.

[0029] Example 5

[0030] The composite particles prepared in Example 2 were ground using a low-temperature pulverizer to obtain micro-powder with an average particle size of 5 micrometers. Deionized water, aqueous polyurethane emulsion, wetting and dispersing agent, and defoamer were added to a high-speed mixer and premixed at 800 rpm for 25 minutes. The ground composite particles were then added, and the stirring speed was increased to 1500 rpm for dispersion for 1.5 hours to ensure uniform particle dispersion without agglomeration. A thickener was added, and the stirring speed was adjusted to 900 rpm for 25 minutes until the viscosity of the coating liquid reached 1000 mPa·s. The prepared coating liquid was filtered through a 150-mesh sieve to remove large particulate impurities, ensuring a smooth coating. Coating was performed using an industrial roller coater, with a target wet weight of 8 g / m³. 2 The coating speed is 15m / min; after coating, use a hot air circulating oven to dry at 82℃ for 18 seconds to ensure the coating is completely dry.

[0031] Example 6

[0032] The composite particles prepared in Example 3 were ground using a low-temperature pulverizer to obtain micro-powder with an average particle size of 10 micrometers. Deionized water, aqueous polyurethane emulsion, wetting and dispersing agent, and defoamer were added to a high-speed mixer and premixed at 1000 rpm for 30 minutes. The ground composite particles were then added, and the stirring speed was increased to 2000 rpm for dispersion for 2 hours to ensure uniform particle dispersion without agglomeration. A thickener was added, and the stirring speed was adjusted to 1000 rpm for 30 minutes until the viscosity of the coating liquid reached 1200 mPa·s. The prepared coating liquid was filtered through a 200-mesh sieve to remove large particulate impurities, ensuring a smooth coating. Coating was performed using an industrial roller coater, with a target wet weight of 8 g / m³. 2The coating speed is 20m / min; after coating, use a hot air circulating oven to dry at 85℃ for 20 seconds to ensure the coating is completely dry.

[0033] Example 7

[0034] The composite particles prepared in Example 1 were vacuum dried at 60°C for 2 hours to ensure a moisture content of 1 ppm. The dried composite particles were then uniformly fed into a 50 mm diameter single-screw blown film extruder using a loss-in-weight feeder. The extruder temperature was set in stages: 128°C for the feeding section, 140°C for the compression section, 150°C for the homogenization section, 158°C for the die neck, and 160°C for the die orifice. The screw speed was 160 rpm, the melt pressure was 15 MPa, the melt temperature was 160°C, and the die gap was 1 mm. After blown film extrusion, the film underwent initial cooling and shaping via a cooling air ring at 15°C. It was then fed to a heat-setting chamber via traction rollers and set at 65°C for 30 minutes. The shaped film was then sent to a winding machine and uniformly wound up at a tension of 40 N to obtain a uniform antibacterial and mildew-resistant film roll. A picture of the film roll is shown below. Figure 1 As shown in Figure a, the film has high transparency, with a transparency of 81.5% ( Figure 2 The membrane, when applied to shoe boxes, clothing tags, and clothing packaging boxes, will not obscure the visible content on their surfaces during use. Simultaneously, wettability tests were conducted on the prepared membrane, and the results are as follows... Figure 3 As shown in Figure a, the water contact angle is 132.5°, which is hydrophobic and can prevent liquid water from entering the interior and causing mold to grow on shoe boxes, clothing tags, and clothing packaging boxes.

[0035] Example 8

[0036] The composite particles prepared in Example 2 were vacuum dried at 65°C for 3 hours to ensure a moisture content of 50 ppm. The dried composite particles were then uniformly fed into a 55mm diameter single-screw blown film extruder using a loss-in-weight feeder. The extruder temperature was set in stages: 129°C for the feeding section, 141°C for the compression section, 151°C for the homogenization section, 159°C for the die neck, and 161°C for the die orifice. The screw speed was 170 rpm, the melt pressure was 18 MPa, the melt temperature was 163°C, and the die gap was 1.1mm. After blown film extrusion, the film underwent initial cooling and shaping via a cooling air ring at 20°C. It was then fed to a heat-setting chamber via traction rollers and set at 68°C for 45 minutes. The shaped film was then sent to a winding machine and uniformly wound up with a tension of 45N to obtain a uniform antibacterial and mildew-resistant film roll. A picture of the film roll is shown below. Figure 1 As shown in Figure b, the film has high transparency, with a transparency of 78.9% ( Figure 2The membrane, when applied to shoe boxes, clothing tags, and clothing packaging boxes, will not obscure the visible content on their surfaces during use. Simultaneously, wettability tests were conducted on the prepared membrane, and the results are as follows... Figure 3 As shown in Figure b, the water contact angle is 136.7°, which is hydrophobic and can prevent liquid water from entering the interior and causing mold to grow on shoe boxes, clothing tags, and clothing packaging boxes.

[0037] Example 9

[0038] The composite particles prepared in Example 3 were vacuum dried at 70°C for 4 hours to ensure a moisture content of 100 ppm. The dried composite particles were then uniformly fed into a 60mm diameter single-screw blown film extruder using a loss-in-weight feeder. The extruder temperature was set in stages: 130°C for the feeding section, 142°C for the compression section, 152°C for the homogenization section, 160°C for the die neck, and 162°C for the die orifice. The screw speed was 180 rpm, the melt pressure was 20 MPa, the melt temperature was 165°C, and the die gap was 1.2mm. After blown film extrusion, the film underwent initial cooling and shaping via a cooling air ring at 25°C. It was then fed to a heat-setting chamber via traction rollers and set at 70°C for 60 minutes. The shaped film was then sent to a winding machine and uniformly wound up with a tension of 50N to obtain a uniform antibacterial and mildew-resistant film roll. A picture of the film roll is shown below. Figure 1 As shown in Figure c, the film has high transparency, with a transparency of 74.6% ( Figure 2 The membrane, when applied to shoe boxes, clothing tags, and clothing packaging boxes, will not obscure the visible content on their surfaces during use. Simultaneously, wettability tests were conducted on the prepared membrane, and the results are as follows... Figure 3 As shown in Figure c, the water contact angle is 133.8°, which is hydrophobic and can prevent liquid water from entering the interior and causing mold to grow on shoe boxes, clothing tags, and clothing packaging boxes.

[0039] Example 10

[0040] The antibacterial function verification experiments were conducted on the coating solutions prepared in Examples 4, 5, and 6. The main verification was carried out by detecting the inhibition rate of the prepared coating solutions against Staphylococcus aureus, Escherichia coli, and Candida albicans.

[0041] Test strain: Staphylococcus aureus (ATCC 6538) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Escherichia coli (8099) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Candida albicans (ATCC10231) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Antibacterial test procedure: (1) Melt the agar medium and pour it into a plate.

[0042] (2) Take 0.2 mL of the bacterial solution to be tested and mix it evenly in LB semi-solid medium. Immediately pour it onto agar medium and shake well so that the upper layer of medium covers the plate.

[0043] (3) Using sterile forceps, immerse sterile filter paper in the antibacterial liquid to be tested, and then place it on a sterile plate. Record and control the contact time between the filter paper immersed in the antibacterial liquid and the plate for 2, 5, 10, and 20 minutes, respectively. Use sterile saline filter paper as a control. The experimental group immersed in the antibacterial liquid to be tested is designated as the experimental group, the experimental group immersed in sterile saline and placed on a sterile plate is designated as the positive control group, and the experimental group immersed in sterile saline but not placed on a sterile plate is designated as the negative control group.

[0044] (4) Place the plate with the attached filter paper in a 37°C incubator and incubate for 1 day.

[0045] (5) Test the OD value of each experimental group separately, and obtain the antibacterial rate according to formula (1):

[0046] The test results are shown in Tables 1, 2, and 3: Table 1. Antibacterial effect of the coating solution prepared in Example 4 on the test bacteria.

[0047] Note: Negative controls showed no bacterial growth.

[0048] Table 2. Antibacterial effect of the coating solution prepared in Example 5 on the test bacteria.

[0049] Note: Negative controls showed no bacterial growth.

[0050] Table 3. Antibacterial effect of the coating solution prepared in Example 6 on the test bacteria.

[0051] Note: Negative controls showed no bacterial growth.

[0052] The results showed that the coating solutions prepared in Examples 4, 5, and 6 all had good antibacterial effects against Staphylococcus aureus, Escherichia coli, and Candida albicans.

[0053] Example 11

[0054] The antibacterial and antifungal films prepared in Examples 7, 8, and 9 were subjected to anti-inflammatory function verification experiments. The main verification was conducted by testing the antibacterial rate of the prepared dew against Staphylococcus aureus, Escherichia coli, and Candida albicans.

[0055] Test strain: Staphylococcus aureus (ATCC 6538) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Escherichia coli (8099) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Candida albicans (ATCC10231) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Antibacterial test procedure: (1) Melt the agar medium and pour it into a plate.

[0056] (2) Take 0.2 mL of the bacterial solution to be tested and mix it evenly in LB semi-solid medium. Immediately pour it onto agar medium and shake well so that the upper layer of medium covers the plate.

[0057] (3) Using sterile forceps, the prepared antibacterial and antifungal film was applied to a sterile agar plate. The contact time between the antibacterial and antifungal film and the plate was recorded and controlled at 2, 5, 10, and 20 minutes, respectively. Sterile saline filter paper was used as a control. The experimental group with the antibacterial and antifungal film was designated as the experimental group, the experimental group soaked in sterile saline and applied to a sterile agar plate was designated as the positive control group, and the experimental group soaked in sterile saline but not applied to a sterile agar plate was designated as the negative control group.

[0058] (4) Place the plate with the attached filter paper in a 37°C incubator and incubate for 1 day.

[0059] (5) Test the OD value of each experimental group separately, and obtain the antibacterial rate according to formula (1):

[0060] The test results are shown in Tables 4, 5, and 6: Table 4. Antibacterial and antifungal film prepared in Example 7 against test bacteria.

[0061] Note: Negative controls showed no bacterial growth.

[0062] Table 5. Antibacterial and antifungal film prepared in Example 8 against test bacteria.

[0063] Note: Negative controls showed no bacterial growth.

[0064] Table 6. Antibacterial and antifungal film prepared in Example 9 against test bacteria.

[0065] Note: Negative controls showed no bacterial growth.

[0066] The results showed that the antibacterial and antifungal films prepared in Examples 7, 8, and 9 all had good antibacterial effects against Staphylococcus aureus, Escherichia coli, and Candida albicans, and also had good anti-inflammatory effects.

[0067] Example 12

[0068] Meanwhile, to demonstrate the synergistic effect of the inorganic metal ion carrier, organic antibacterial agent, and antifungal agent, this embodiment will also verify the individual efficacy of the inorganic metal ion carrier, organic antibacterial agent, and antifungal agent. Using the same process as in Example 10, preparations were made using only the inorganic metal ion carrier, organic antibacterial agent, and antifungal agent for antibacterial rate experiments.

[0069] Test strain: Staphylococcus aureus (ATCC 6538) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Escherichia coli (8099) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Candida albicans (ATCC10231) 3rd generation (provided by Shanghai Beisi Biotechnology Co., Ltd.); Antibacterial test procedure: (1) Melt the agar medium and pour it into a plate.

[0070] (2) Take 0.2 mL of the bacterial solution to be tested and mix it evenly in LB semi-solid medium. Immediately pour it onto agar medium and shake well so that the upper layer of medium covers the plate.

[0071] (3) Using sterile forceps, immerse sterile filter paper in the antibacterial liquid to be tested, and then place it on a sterile plate. Record and control the contact time between the filter paper immersed in the antibacterial liquid and the plate for 2, 5, 10, and 20 minutes, respectively. Use sterile saline filter paper as a control. The experimental group immersed in the antibacterial liquid to be tested is designated as the experimental group, the experimental group immersed in sterile saline and placed on a sterile plate is designated as the positive control group, and the experimental group immersed in sterile saline but not placed on a sterile plate is designated as the negative control group.

[0072] (4) Place the plate with the attached filter paper in a 37°C incubator and incubate for 1 day.

[0073] (5) Test the OD value of each experimental group separately, and obtain the antibacterial rate according to formula (1):

[0074] The test results are shown in Table 4: Table 7. Antibacterial effect of inorganic metal ion carriers on test bacteria

[0075] Note: Negative controls showed no bacterial growth.

[0076] Table 8. Antibacterial effect of organic antibacterial agents on test bacteria

[0077] Note: Negative controls showed no bacterial growth.

[0078] Table 9. Antifungal effects of antifungal agents on test bacteria

[0079] Note: Negative controls showed no bacterial growth.

[0080] The interaction between inorganic metal ion carriers, organic antibacterial agents, and antifungal agents is calculated using the Jin Zhengjun Q-value method, as shown in formula (2):

[0081] Among them, E a+b+c The antibacterial rate of plant dew prepared by using inorganic metal ion carriers, organic antibacterial agents, and antifungal agents, E a E b and E c The values ​​represent the antibacterial rates of plant extracts prepared by using inorganic metal ion carriers, organic antibacterial agents, and antifungal agents alone. In the formula, the numerator represents the "measured combined effect," the denominator represents the "expected combined effect," and Q is the ratio of the two. If Q < 0.85, it indicates an antagonistic effect; if 0.85 ≤ Q < 1.15, it indicates an additive effect. The Q values ​​of the antibacterial rate of the antifungal and antimicrobial materials prepared in Example 3 compared to those prepared by using inorganic metal ion carriers, organic antibacterial agents, and antifungal agents alone against the test bacteria are shown in Table 10.

[0082] Table 10. Q-values ​​of the antifungal and antimicrobial material prepared in Example 3 compared to antifungal and antimicrobial materials prepared using inorganic metal ion carriers, organic antimicrobial agents, and antifungal agents alone against the test bacteria.

[0083] The results showed that the antifungal and antimicrobial materials prepared using inorganic metal ion carriers, organic antibacterial agents, and antifungal agents alone also had certain antibacterial effects, but all were lower than the antifungal effects of the antifungal and antimicrobial materials prepared using the three raw materials in Example 3. Furthermore, the results calculated by the Jinzheng mean value method showed that the Q values ​​were all greater than 1.15, indicating that the inorganic metal ion carriers, organic antibacterial agents, and antifungal agents played a synergistic role in the later-prepared antifungal and antimicrobial materials, improving their antibacterial effect.

[0084] Example 13

[0085] To further verify the antibacterial and antifungal effect of the prepared antibacterial and antifungal film roll, the antibacterial and antifungal film roll prepared in Example 9 was applied to the surface of a shoe box, and an antibacterial and antifungal experiment was conducted with a shoe box that had not undergone any treatment. The experimental conditions were a temperature of 25°C and a relative humidity of 90%, and the changes in the shoes inside the two types of shoe boxes were observed. Figure 4 As shown, after 25 days, shoes in the treated shoebox will not get moldy, while shoes in the untreated shoebox will get moldy.

[0086] Please note to all technical personnel: Although the present invention has been described according to the specific embodiments above, the inventive concept of the present invention is not limited to this invention. Any modifications that utilize the inventive concept will be included within the scope of protection of this patent.

Claims

1. An antibacterial and antifungal packaging material, characterized in that, The antibacterial and antifungal packaging material, by weight, comprises: 60-100 parts of biodegradable polymer material, 0.3-2 parts of inorganic metal ion carrier, 0.1-1 parts of organic antibacterial agent, 0.1-2 parts of antifungal agent, 1-6 parts of polyethylene glycol, 0.1-5 parts of plasticizer, 0.1-3 parts of grafted monomer, 0.1-3 parts of antistatic agent, 0.05-0.5 parts of antioxidant, 0.05-0.5 parts of light stabilizer, 0.1-2 parts of anti-adhesive, and 0.1-5 parts of coupling agent; the biodegradable polymer material is one or a combination of PBAT and PLA; the inorganic metal ion carrier is one or a combination of silver-loaded zeolite, silver-loaded oxide, zinc oxide, and copper oxide; the organic antibacterial agent is one or a combination of benzyl dodecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, phenolic resin, and paraben; The antifungal agent is one or more of the following: iodopropynyl butylcarbamate, miconazole, tea tree oil, and cinnamaldehyde; the plasticizer is one or more of the following: dioctyl adipate, sebacic acid ester, and glyceryl tartrate; the grafting monomer is one or more of the following: maleic anhydride, acrylate, and styrene; the antistatic agent is one or more of the following: fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene amine, glyceryl monostearate, alkyl phosphate, and polyether phosphate; the antioxidant is one or more of the following: phosphate ester, phosphate diester, and α,α-dimethylbenzyl; the light stabilizer is one or more of the following: benzotriazole, triazine, and benzophenone; the anti-adhesive agent is one or more of the following: micronized silica, talc, calcium carbonate, titanium dioxide, and glass microspheres; and the coupling agent is one or more of the following: methoxysilane and ethoxysilane.

2. The antibacterial and antifungal packaging material as described in claim 1, characterized in that, The preparation of the antibacterial and antifungal packaging material includes the following process: S1 involves drying biodegradable polymer materials at 70-75°C for 4-8 hours to reduce the moisture content to 1-200 ppm; drying polyethylene glycol and plasticizers at 40-60°C for 2-6 hours; and drying powdered components such as inorganic metal ion carriers, antistatic agents, antioxidants, light stabilizers, anti-adhesion agents, and coupling agents at 80-120°C for 2-6 hours. All liquid and heat-sensitive components are ensured to maintain their chemical stability during the drying process. All dried raw materials are stored in sealed containers at a relative humidity of 1-10% to prevent secondary moisture absorption. S2 involves mixing pre-dried biodegradable polymer materials with inorganic metal ion carriers at a weight ratio of 70-95:5-30, then adding the mixture to a twin-screw extruder for melt blending and masterbatch production. The extrusion temperature zone is set at 140-180℃, and the screw speed is 150-300 rpm. Volatile substances are continuously discharged through a vacuum end to ensure masterbatch quality. The discharged material is cooled at 25-40℃ and then pelletized, with the masterbatch moisture content controlled at 1-500 ppm and the particle size controlled at 2-5 mm. The resulting masterbatch is tested for active ingredient content and dispersion uniformity to ensure uniform dispersion and stable activity of the inorganic carrier. S3 precisely mixes pre-dried biodegradable polymer materials with organic antibacterial and antifungal agents at a weight ratio of 100:1~10, and then produces organic antibacterial / antifungal masterbatch in another twin-screw extruder; the extrusion temperature zone is set to 140~170℃, and the screw speed is 120~300rpm; after discharge, the material is cooled and pelletized, and dried at 40~80℃ for 2~6 hours to remove any trace volatiles that may be generated; the resulting masterbatch is used for subsequent metering, and its thermal stability and the release characteristics of antibacterial / antifungal active ingredients are tested; S4 uses pre-dried biodegradable polymer materials as the main feedstock, which are fed into the feed section of a twin-screw reactive extruder via a constant-speed feeder and preheated to 140-150°C. Grafted monomers are fed into the mixing zone of the extruder at a dosage of 0.5-3%, while an initiator is simultaneously added via a metering pump at the adjacent feed inlet. During the grafting reaction and melt blending processes, pretreated polyethylene glycol, plasticizers, antistatic agents, antioxidants, light stabilizers, anti-sticking agents, coupling agents, and inorganic additives are added. Metal ion carrier masterbatch and organic antibacterial / antifungal masterbatch are precisely added to the extruder according to the formula ratio using a high-precision loss-in-weight feeder; the screw speed is controlled at 120~300rpm, and the extruder temperature is controlled in stages: the mixing section temperature is controlled at 150~165℃, the kneading and strengthening section temperature is controlled at 160~175℃, and the discharge section temperature is controlled at 165~185℃; the average residence time is controlled at 20~90 seconds to ensure sufficient grafting reaction and uniform dispersion of each component; A degassing section is set after the S5 grafting reaction section, and unreacted monomers and low-boiling volatiles are continuously removed at a pressure of 1~10 mbar at the vacuum end to effectively reduce residues; the extrusion torque, extrusion temperature curve and degassing vacuum degree are monitored in real time, and the acid value increment is controlled to be 0.1~2.0 mg / KOH, and the residual monomer target is less than 0.1%; the qualified discharge is cooled to 25~40℃, granulated and dried to 1~500ppm and then stored in a sealed container to finally obtain multifunctional biodegradable composite particles with antibacterial and anti-mildew functions.

3. The method for preparing an antibacterial and antifungal packaging material as described in claim 2, characterized in that, The initiator described in S4 is one or more combinations of tert-butyl peroxybenzoate, benzoyl peroxide, and azobisisobutyronitrile.

4. The antibacterial and antifungal packaging material as described in any one of claims 1 to 3, used in shoe boxes, clothing hang tags, and clothing packaging boxes for antibacterial and antifungal purposes, characterized in that... The application method involves coating the prepared antibacterial and antifungal material onto the surface of shoe boxes, clothing tags, and clothing packaging boxes using a coating method, or making the prepared antibacterial and antifungal material into an antibacterial and antifungal film and then using a molding machine to adhere the antibacterial and antifungal film onto the surface of shoe boxes, clothing tags, and clothing packaging boxes.

5. The antibacterial and antifungal packaging material as described in claim 4, used in shoe boxes, clothing tags, and clothing packaging boxes, is characterized in that... The specific method for applying the prepared antibacterial and antifungal material to the surface of shoe boxes, clothing tags, and clothing packaging boxes by means of coating is as follows: S1 grinds the prepared composite particles using a low-temperature pulverizer to obtain micro powder with an average particle size of 1~10 micrometers; In step S2, deionized water, waterborne polyurethane emulsion, wetting and dispersing agent, and defoamer are added to a high-speed mixer and premixed at 500-1000 rpm for 15-30 minutes. The ground composite particles are then added, and the mixing speed is increased to 1000-2000 rpm. The mixture is dispersed for 1-2 hours to ensure uniform particle dispersion without agglomeration. A thickener is added, and the mixing speed is adjusted to 800-1000 rpm. The mixture is stirred for 20-30 minutes until the viscosity of the coating liquid reaches 800-1200 mPa·s. The wetting and dispersing agent is one or more of polyether-modified polysiloxane, sodium fatty alcohol polyoxyethylene ether sulfate, and alkylphenol polyoxyethylene ether. The defoamer is one or more of polydimethylsiloxane, ethylene oxide, and propylene oxide. The thickener is one or more of hydrophobically modified ethoxylated polyurethane, water-soluble cellulose ether, and xanthan gum. S3 filters the prepared coating solution through a 100-200 mesh sieve to remove large particulate impurities and ensure a smooth coating. S4 is applied using an industrial roller coater, with a target wet weight of 8 g / m³. 2 The coating speed is 10~20m / min; After the S5 coating is applied, use a hot air circulating oven to dry it at 80~85℃ for 15~20 seconds to ensure the coating is completely dry.

6. The antibacterial and antifungal packaging material as described in claim 4, used in shoe boxes, clothing tags, and clothing packaging boxes, is characterized in that... The specific method for preparing the antibacterial and antifungal material into an antibacterial and antifungal film, and then using a molding machine to adhere the antibacterial and antifungal film to the surface of shoe boxes, clothing tags, and clothing packaging boxes is as follows: S1. The prepared composite particles are vacuum dried at 60-70℃ for 2-4 hours to ensure a moisture content of 1-100 ppm. The dried composite particles are then uniformly fed into a single-screw blown film extruder with a diameter of 50-60 mm using a loss-in-weight feeder. The extruder temperature is set in stages: feeding section 128-130℃, compression section 140-142℃, homogenization section 150-152℃, die neck 158-160℃, and die orifice 160-162℃. The screw speed is 160-180 rpm, the melt pressure is 15-20 MPa, the melt temperature is 160-165℃, and the die orifice gap is 1-1.2 mm. After the S2 film is blown, it undergoes initial cooling and shaping through a cooling air ring at a temperature of 15~25℃. Then, it is sent to a heat setting box via a traction roller assembly and set at a temperature of 65~70℃ for 30~60 minutes. After the S3 film is shaped, it is sent to the winding machine and wound up evenly with a tension of 40~50N to obtain a uniform antibacterial and mildew-proof film roll. S4. The antibacterial and anti-mildew film roll obtained in step S3 is fed out through the unwinding device of the molding machine and aligned with the surface of the shoe box, clothing tag, or clothing packaging box that has been pre-placed or transported to the worktable of the molding machine. The antibacterial and anti-mildew film is heated and pressurized in the molding machine at a temperature of 80~120℃ and a pressure of 0.5~2.0 MPa to evenly and firmly adhere the antibacterial and anti-mildew film to the surface of the shoe box, clothing tag, or clothing packaging box. After adhesion, the composite packaging material is cooled, cut, and sorted to finally obtain a shoe box, clothing tag, or clothing packaging box with antibacterial and anti-mildew functions.

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