CN118085444B - Antibacterial sealing film and preparation method thereof - Google Patents

Antibacterial sealing film and preparation method thereof Download PDF

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CN118085444B
CN118085444B CN202410524301.8A CN202410524301A CN118085444B CN 118085444 B CN118085444 B CN 118085444B CN 202410524301 A CN202410524301 A CN 202410524301A CN 118085444 B CN118085444 B CN 118085444B
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zinc oxide
nano zinc
antibacterial
sealing film
parts
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CN118085444A (en
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宋治福
杜心文
陈晓峰
王黎明
叶玲燕
张恩强
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Hangzhou Super Star Packaging Material Co ltd
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Abstract

The invention discloses an antibacterial sealing film and a preparation method thereof, which relate to the technical field of packaging materials and comprise the following steps: putting PE resin, modified nano zinc oxide, maleic acid and stearic acid into a stirrer to be uniformly mixed, pumping into a dehumidifying dryer, drying for 4-6 hours at 70-90 ℃, and carrying out extrusion casting, mirror face opposite pressing, cooling, trimming, pressurizing and rolling to obtain the antibacterial sealing film; according to the invention, the nano zinc oxide is modified by adding the organic-inorganic synergistic antibacterial agent, so that the antibacterial property and the broad spectrum of the film are improved, the problem of poor antibacterial property of the common polyethylene film is solved, the mechanical property of the film is improved to a certain extent, and the requirements of various food packages can be met.

Description

Antibacterial sealing film and preparation method thereof
Technical Field
The invention relates to the technical field of packaging materials, in particular to an antibacterial sealing film and a preparation method thereof.
Background
At present, plastic products have become one of the most important food packaging materials, and are mainly produced by processing polymers such as resins. Commonly used packaging materials are Polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polycarbonate (PC) and the like. PP is a thermoplastic material with good properties. The processing method is simple and various. It is safe, reliable and nontoxic. It is used in automobile, clothing, food and medicine fields. The plastic surface is easy to attach a large amount of microorganisms, so that the quality of packaged goods can be affected, and the surfaces of machines such as instruments and the like can be infected, so that potential safety hazards of equipment are caused. With increasing importance of food safety, the demands for high-quality, green and safe foods with longer shelf life are increasing. Traditionally, the addition of preservatives and preservatives to foods may not only change the original flavor of the food, but also result in the consumption of nutrients. Active substances such as a bacteriostatic agent are added into the packaging material by utilizing the existing processing technology so as to protect the basic quality of food, effectively prevent and inhibit the growth of microorganisms and achieve the effect of keeping fresh and prolonging the shelf life. This has become an important research direction for food packaging, with good application base and safety.
Bacteriostats are generally: three main types, organic, inorganic and natural.
(1) The organic antibacterial agent is mainly composed of organic substances such as alcohol phenols, pyridines, quaternary ammonium salts, etc. Can act on the cell wall membrane, genetic material or enzyme system of the microorganism to affect the physiological metabolic activity of the microorganism, resulting in self-extinguishment of the microorganism. The organic antibacterial agent has the characteristics of various types and high sterilization speed, but has the defects of poor safety and stability.
(2) Inorganic antibacterial agents include two major classes, namely, metallic elements (e.g., cu, ag, zn, etc.) and compounds (e.g., tiO2, siO2, znO, etc.). Elemental metals are mainly responsible for the functional disorders caused by the blockage of the physiological metabolism of microorganisms by slow release dispersion of the spatial conformation of the protein molecules acting on the microorganisms. Photocatalytic compounds, such as TiO2, are photocatalytic and produce strong oxidative radicals that alter cell membrane permeability, thereby killing microorganisms. The inorganic antibacterial agent has the characteristic of good heat resistance and stability, but has higher use cost.
(3) Natural antibacterial agents, mostly derived from the release of active parts of natural materials, such as animals, plants and microorganisms, are commonly known as plant essential oils, chitosan, lysozyme, etc. The chitosan is extracted from chitin, has the characteristics of antibacterial property, no toxicity or harm to human, and has been widely used by research and development personnel. The preparation method has the advantages of wide distribution, high yield and easy acquisition, and is favored in the fields of foods and medicines. Compared with other antibacterial agents, the natural antibacterial agent is more green and environment-friendly, but has the problems of difficult extraction and purification of active ingredients, poor stability and the like.
The Chinese patent document CN111410785A discloses a film for an antibacterial packaging bag and a preparation method thereof, wherein the film is prepared by mixing the following components in parts by mass: 10-15 parts of low-density polyethylene; 35-45 parts of high-density polyethylene; 5-10 parts of maleic anhydride grafted polyethylene; 10-18 parts of thermoplastic polyurethane elastic rubber; 3-6 parts of filler; 8-12 parts of nano zinc oxide-chitosan composite antibacterial agent.
The antibacterial agent of the antibacterial film in the prior art has poor compatibility with the matrix, and the duration of the antibacterial effect is not long.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide the antibacterial sealing film and the preparation method thereof, and the organic-inorganic synergistic antibacterial agent is added to modify the nano zinc oxide, so that the antibacterial property and the broad spectrum of the film are improved, the problem of poor antibacterial property of the common polyethylene film is solved, the mechanical property of the film is improved to a certain extent, and the requirements of various food packages can be met.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The antibacterial sealing film is prepared from the following components in parts by weight: 100-130 parts of PE resin, 10-20 parts of modified nano zinc oxide, 2-8 parts of maleic acid and 0.5-3 parts of stearic acid.
Preferably, the PE resin is linear low-density polyethylene, the density is 0.93-0.94 g/cm < 3 >, and the melt flow rate is 5-20 g/10min.
Preferably, the preparation method of the modified nano zinc oxide comprises the following steps:
(1) Adding KH580 into ethanol/water mixed solution for hydrolysis, then adding nano zinc oxide, performing ultrasonic dispersion, and stirring for reaction to obtain sulfhydrylation nano zinc oxide;
The structural formula is as follows:
In the method, in the process of the invention, Refers to nano zinc oxide;
Preferably, in the step (1), the particle size of the nano zinc oxide is 10-100 nm.
More preferably, in the step (1), the particle size of the nano zinc oxide is 50nm.
Preferably, in the step (1), the volume ratio of ethanol to water in the ethanol/water mixed solution is 5: 1-5; KH580, ethanol/water mixed solution and nano zinc oxide with the mass ratio of 0.5-3: 50-100: 10.
More preferably, in the step (1), the volume ratio of ethanol to water in the ethanol/water mixed solution is 5:3, a step of; KH580, ethanol/water mixed solution and nano zinc oxide with mass ratio of 2:100:10.
Preferably, in the step (1), the hydrolysis time is 15-45 min, the ultrasonic dispersion time is 30-60 min, and the stirring reaction condition is 40-60 ℃ for 3-5 h.
(2) Dispersing sulfhydrylation nano zinc oxide and eugenol into DMF, then adding benzoin dimethyl ether, fully mixing, reacting under the action of ultraviolet light, washing and drying the product to obtain grafted nano zinc oxide;
The structural formula is as follows:
Preferably, in the step (2), the mass ratio of the sulfhydrylation nano zinc oxide, eugenol, DMF and benzoin dimethyl ether is 10: 6-14: 50-100: 0.5-2.
More preferably, in the step (2), the mass ratio of the sulfhydrylation nano zinc oxide, eugenol, DMF and benzoin dimethyl ether is 10:10:100:1.5.
Preferably, in the step (2), the reaction condition is stirring reaction for 5-8 hours at room temperature.
(3) Dissolving arginine in MES buffer solution, then adding EDC and NHS, stirring and activating, then adding grafted nano zinc oxide, heating and stirring for reaction, and filtering, washing with alcohol and drying after the reaction is finished to obtain the modified nano zinc oxide.
The structural formula is as follows:
Preferably, in the step (3), the concentration of the MES buffer solution is 0.05-0.5 mol/L, and the pH is 4-6.
Preferably, in the step (3), the dosage ratio of arginine, MES buffer, EDC, NHS and grafted nano zinc oxide is 1-3 g: 50-100 mL: 1-5 g: 1-4 g:5g.
More preferably, in the step (3), the dosage ratio of arginine, MES buffer, EDC, NHS and grafted nano zinc oxide is 2g:100mL:3g:2.5g:5g.
Preferably, in the step (3), the activation time is 30-90 min, and the reaction is carried out for 12-18 h under the conditions of temperature rising and stirring at 45-60 ℃.
The invention also claims a preparation method of the antibacterial sealing film, which comprises the following steps: and (3) putting PE resin, modified nano zinc oxide, maleic acid and stearic acid into a stirrer for uniform mixing, pumping into a dehumidifying dryer, drying for 4-6 hours at 70-90 ℃, and carrying out extrusion casting, mirror surface opposite pressing, cooling, trimming, pressurizing and rolling to obtain the antibacterial sealing film.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention provides an antibacterial sealing film, which improves the antibacterial property and broad spectrum of the film by adding organic-inorganic synergistic antibacterial agent modified nano zinc oxide, overcomes the problem of poor antibacterial property of the common polyethylene film, improves the mechanical property of the film to a certain extent, and can meet the requirements of various food packages.
2) The invention provides a modified nano zinc oxide, which is prepared by firstly treating nano zinc oxide by KH580 to obtain sulfhydrylation nano zinc oxide, wherein after sulfhydrylation treatment, the compatibility between the nano zinc oxide and a polyethylene matrix can be increased, and the modified nano zinc oxide is inlaid in a film matrix, so that the mechanical property of the film is improved, precipitation of the modified nano zinc oxide can be avoided, and the long-term maintenance of an antibacterial effect is facilitated; then under photoinitiation and ultraviolet irradiation of benzoin dimethyl ether, utilizing unsaturated double bond in eugenol to react with mercapto alkene on mercapto nano zinc oxide surface mercapto, grafting antibacterial active substance eugenol on zinc oxide particle surface, introducing benzene ring to improve rigidity and heat resistance of film material, obtaining grafted nano zinc oxide; finally, arginine is bonded to the surface of the nano zinc oxide through the esterification reaction of hydroxyl in eugenol and arginine carboxyl, and guanidine groups with antibacterial activity are introduced to obtain the modified nano zinc oxide with organic-inorganic synergistic antibacterial effect.
3) The invention provides a modified nano zinc oxide, which is an inorganic antibacterial agent, and has an antibacterial action mechanism that superoxide anion O2-and hydroxyl radical OH which are very strong in chemical activity are generated through photocatalysis, and newly generated radicals have very strong chemical activity, when encountering bacteria, the newly generated radicals directly attack cell walls, cell membranes or components in cells of the bacteria, so that organic matters in the bacteria are degraded, and the bacteria are killed and decomposed; eugenol is an organic antibacterial agent, can endow a material with a certain sterilization effect, and can synergistically improve the antibacterial performance of zinc oxide by grafting the eugenol onto the surface of nano zinc oxide; the guanidine group in arginine carries positive charge, can interact with bacterial microbial cell membranes through electrostatic action and is combined with phosphate groups near the area with the largest negative charge on the cell membranes, so that the phosphate forms mosaic aggregation, and then bacterial cell membranes are broken to cause bacterial microbial death; the invention prepares the organic-inorganic synergistic antibacterial agent by grafting eugenol and guanidine groups on the surface of nano zinc oxide, has excellent antibacterial property and broad spectrum, and has stable and durable antibacterial effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
The preparation method of the antibacterial sealing film comprises the following steps:
(1) Adding 0.5-3 g KH580 into 50-100 g ethanol/water mixed solution (the volume ratio of ethanol to water is 5:1-5) for hydrolysis for 15-45 min, adding 10g nano zinc oxide, performing ultrasonic dispersion for 30-60 min, and stirring at 40-60 ℃ for reaction for 3-5 h to obtain sulfhydrylation nano zinc oxide;
(2) Dispersing 10g of sulfhydrylation nano zinc oxide and 6-14 g of eugenol into 50-100 g of DMF, then adding 0.5-2 g of benzoin dimethyl ether, fully mixing, stirring at room temperature under the action of ultraviolet light for reacting for 5-8 h, washing and drying the product to obtain grafted nano zinc oxide;
(3) Dissolving 1-3 g of arginine in 50~100mL 0.05~0.5mol/L MES buffer solution (pH is 4-6), then adding 1-5 g of EDC and 1-4 g of NHS, stirring and activating for 30-90 min, adding 5g of grafted nano zinc oxide, heating to 45-60 ℃, stirring and reacting for 12-18 h, filtering, washing with alcohol and drying after the reaction is finished to obtain the modified nano zinc oxide;
(4) 100-130 parts of PE resin, 10-20 parts of modified nano zinc oxide, 2-8 parts of maleic acid and 0.5-3 parts of stearic acid are put into a stirrer to be mixed uniformly, then the mixture is pumped into a dehumidifying dryer, dried for 4-6 hours at 70-90 ℃, and then the antibacterial sealing film is obtained through extrusion casting, mirror face opposite pressing, cooling, edge cutting and pressurizing rolling.
The casting process is direct casting, the casting roller is a chromeplated steel roller, the chromeplated layer is 0.01-0.015 mm thick, the diameter of the steel roller is 500mm, and the middle height of the steel roller is 0.20-0.25 mm; the temperature of the steel roller is set to be 35-40 ℃.
The pressurizing and rolling process is to pressurize and roll on a 60-65A liquid silica gel rubber roller, and the pressurizing pressure is 5kgf.
The invention will be further illustrated by the following examples.
Example 1
The preparation method of the antibacterial sealing film comprises the following steps:
(1) Adding 3g KH580 into 100g ethanol/water mixed solution (volume ratio of ethanol to water is 5:3) for hydrolysis for 45min, adding 10g nano zinc oxide, performing ultrasonic dispersion for 60min, and stirring at 60 ℃ for 3h to obtain sulfhydrylation nano zinc oxide;
(2) Dispersing 10g of sulfhydrylation nano zinc oxide and 14g of eugenol into 100g of DMF, then adding 2g of benzoin dimethyl ether, fully mixing, stirring at room temperature under the action of ultraviolet light for reaction for 8 hours, washing and drying the product to obtain grafted nano zinc oxide;
(3) 3g of arginine is dissolved in 100mL of 0.05mol/L MES buffer solution (pH is 4-6), then 5g of EDC and 4g of NHS are added, after stirring and activation for 90min, 5g of grafted nano zinc oxide is added, the temperature is raised to 60 ℃ and stirring is carried out for 12h, and after the reaction is finished, filtration, alcohol washing and drying are carried out, so that the modified nano zinc oxide is obtained;
(4) 120 parts of PE resin, 20 parts of modified nano zinc oxide, 5 parts of maleic acid and 2 parts of stearic acid are put into a stirrer to be uniformly mixed, then the mixture is pumped into a dehumidifying dryer, dried for 5 hours at 80 ℃, and then the antibacterial sealing film with the thickness of 32 mu m is obtained through extrusion casting, mirror face opposite pressing, cooling, trimming and pressurizing rolling.
Example 2
The preparation method of the antibacterial sealing film comprises the following steps:
(1) Adding 1.7g KH580 into 75g ethanol/water mixed solution (volume ratio of ethanol to water is 5:2) for hydrolysis for 30min, adding 10g nano zinc oxide, performing ultrasonic dispersion for 45min, and stirring at 50 ℃ for reaction for 4h to obtain sulfhydryl nano zinc oxide;
(2) Dispersing 10g of sulfhydrylation nano zinc oxide and 10g of eugenol into 80g of DMF, then adding 1.2g of benzoin dimethyl ether, fully mixing, stirring at room temperature under the action of ultraviolet light for reaction for 6.5h, washing and drying the product to obtain grafted nano zinc oxide;
(3) Dissolving 2g of arginine in 80mL of 0.05mol/L MES buffer solution (pH is 4-6), then adding 3g of EDC and 2.5g of NHS, stirring and activating for 60min, adding 5g of grafted nano zinc oxide, heating to 55 ℃, stirring and reacting for 15h, filtering, washing with alcohol and drying after the reaction is finished to obtain the modified nano zinc oxide;
(4) 120 parts of PE resin, 15 parts of modified nano zinc oxide, 5 parts of maleic acid and 2 parts of stearic acid are put into a stirrer to be uniformly mixed, then the mixture is pumped into a dehumidifying dryer, dried for 5 hours at 80 ℃, and then the antibacterial sealing film with the thickness of 28 mu m is obtained through extrusion casting, mirror surface opposite pressing, cooling, trimming and pressurizing rolling.
Example 3
The preparation method of the antibacterial sealing film comprises the following steps:
(1) Adding 0.5g KH580 into 50g ethanol/water mixed solution (volume ratio of ethanol to water is 5:2) for hydrolysis for 15min, then adding 10g nano zinc oxide, performing ultrasonic dispersion for 30min, and stirring at 40 ℃ for reaction for 5h to obtain sulfhydryl nano zinc oxide;
(2) Dispersing 10g of sulfhydrylation nano zinc oxide and 6g of eugenol into 50g of DMF, then adding 0.5g of benzoin dimethyl ether, fully mixing, stirring at room temperature under the action of ultraviolet light for reaction for 5h, washing and drying the product to obtain grafted nano zinc oxide;
(3) Dissolving 1g of arginine in 50mL of 0.05mol/L MES buffer solution (pH is 4-6), then adding 1g of EDC and 1g of NHS, stirring and activating for 30min, adding 5g of grafted nano zinc oxide, heating to 45 ℃, stirring and reacting for 18h, filtering, washing with alcohol and drying after the reaction is finished to obtain the modified nano zinc oxide;
(4) 120 parts of PE resin, 10 parts of modified nano zinc oxide, 5 parts of maleic acid and 2 parts of stearic acid are put into a stirrer to be uniformly mixed, then the mixture is pumped into a dehumidifying dryer, dried for 5 hours at 80 ℃, and then extruded and cast, mirror surface opposite-pressed, cooled, cut edge, pressurized and rolled to obtain the antibacterial sealing film with the thickness of 30 mu m.
Comparative example 1
A preparation method of a sealing film comprises the following steps:
(1) Adding 3g KH580 into 100g ethanol/water mixed solution (volume ratio of ethanol to water is 5:3) for hydrolysis for 45min, adding 10g nano zinc oxide, performing ultrasonic dispersion for 60min, and stirring at 60 ℃ for 3h to obtain sulfhydrylation nano zinc oxide;
(2) Dispersing 10g of sulfhydrylation nano zinc oxide and 14g of eugenol into 100g of DMF, then adding 2g of benzoin dimethyl ether, fully mixing, stirring at room temperature under the action of ultraviolet light for reaction for 8 hours, washing and drying the product to obtain grafted nano zinc oxide;
(3) 120 parts of PE resin, 20 parts of grafted nano zinc oxide, 5 parts of maleic acid and 2 parts of stearic acid are put into a stirrer to be uniformly mixed, then the mixture is pumped into a dehumidifying dryer, dried for 5 hours at 80 ℃, and then the sealing film with the thickness of 30 mu m is obtained through extrusion casting, mirror surface opposite pressing, cooling, trimming and pressing rolling.
Comparative example 2
A preparation method of a sealing film comprises the following steps:
(1) Adding 3g KH580 into 100g ethanol/water mixed solution (volume ratio of ethanol to water is 5:3) for hydrolysis for 45min, adding 10g nano zinc oxide, performing ultrasonic dispersion for 60min, and stirring at 60 ℃ for 3h to obtain sulfhydrylation nano zinc oxide;
(2) 120 parts of PE resin, 20 parts of sulfhydrylation nanometer zinc oxide, 5 parts of maleic acid and 2 parts of stearic acid are put into a stirrer to be uniformly mixed, then are pumped into a dehumidifying dryer to be dried for 5 hours at 80 ℃, and then are subjected to extrusion casting, mirror surface pressurizing, cooling, trimming and pressurizing rolling to obtain the sealing film with the thickness of 30 mu m.
Performance tests were carried out on the films prepared in examples 1 to 3 and comparative examples 1 to 2, with reference to GB/T1040.2-2022 "determination of tensile Properties of plastics section 2: test conditions for molded and extruded plastics the tensile strength of which was tested; inoculating escherichia coli ATCC25922, staphylococcus aureus ATCC 6538 and candida albicans ATCC 10231 into nutrient broth, activating for 3 times, diluting the bacterial liquid with physiological saline, oscillating to obtain bacterial suspension of 107cfu/mL, coating 0.4mL of bacterial suspension on the (50 mm multiplied by 50 mm) surfaces of the films prepared in the examples 1-3 and the comparative examples 1-2, placing the films on a culture dish, culturing the films in an illuminated incubator at 37 ℃ and 50% relative humidity for 24 hours, leaching the bacterial suspension with the nutrient broth, and measuring the number of viable bacteria and calculating the antibacterial rate by a pouring method after the bacterial suspension is properly diluted with the physiological saline; the specific data are shown in Table 1.
TABLE 1 film Performance test results
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Tensile Strength (MPa) 34.3 33.8 33.5 31.4 30.1
Coliform bacteria inhibition rate (%) >99.9 >99.9 >99.9 87.2 81.7
Staphylococcus aureus antibacterial rate (%) 98.3 98.1 97.5 85.4 76.3
Candida albicans antibacterial ratio (%) 95.2 95.1 94.8 77.9 68.5
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (9)

1. The antibacterial sealing film is characterized by being prepared from the following components in parts by weight: 100-130 parts of PE resin, 10-20 parts of modified nano zinc oxide, 2-8 parts of maleic acid and 0.5-3 parts of stearic acid;
The preparation method of the modified nano zinc oxide comprises the following steps:
(1) Adding KH580 into ethanol/water mixed solution for hydrolysis, then adding nano zinc oxide, performing ultrasonic dispersion, and stirring for reaction to obtain sulfhydrylation nano zinc oxide;
(2) Dispersing sulfhydrylation nano zinc oxide and eugenol into DMF, then adding benzoin dimethyl ether, fully mixing, reacting under the action of ultraviolet light, washing and drying the product to obtain grafted nano zinc oxide;
(3) Dissolving arginine in MES buffer solution, then adding EDC and NHS, stirring and activating, then adding grafted nano zinc oxide, heating and stirring for reaction, and filtering, washing with alcohol and drying after the reaction is finished to obtain the modified nano zinc oxide.
2. The antimicrobial seal film of claim 1, wherein in step (1), the volume ratio of ethanol to water in the ethanol/water mixture is 5: 1-5; KH580, ethanol/water mixed solution and nano zinc oxide with the mass ratio of 0.5-3: 50-100: 10.
3. The antibacterial sealing film according to claim 1, wherein in the step (1), the hydrolysis time is 15-45 min, the ultrasonic dispersion time is 30-60 min, and the stirring reaction condition is 40-60 ℃ for 3-5 h.
4. The antibacterial sealing film according to claim 1, wherein in the step (2), the mass ratio of the mercapto nano zinc oxide, eugenol, DMF and benzoin dimethyl ether is 10: 6-14: 50-100: 0.5-2.
5. The antibacterial sealing film according to claim 1, wherein in the step (2), the reaction condition is stirring reaction at room temperature for 5 to 8 hours.
6. The antimicrobial seal film of claim 1, wherein in step (3), the MES buffer concentration is 0.05 to 0.5mol/L and the pH is 4 to 6.
7. The antibacterial sealing film according to claim 1, wherein in the step (3), the dosage ratio of arginine, MES buffer, EDC, NHS, grafted nano zinc oxide is 1 to 3g: 50-100 mL: 1-5 g: 1-4 g:5g.
8. The antibacterial sealing film according to claim 1, wherein in the step (3), the activation time is 30-90 min, and the reaction is carried out for 12-18 h at 45-60 ℃ under the condition of heating and stirring.
9. A method for preparing the antibacterial sealing film according to any one of claims 1 to 8, comprising the steps of: and (3) putting PE resin, modified nano zinc oxide, maleic acid and stearic acid into a stirrer for uniform mixing, pumping into a dehumidifying dryer, drying for 4-6 hours at 70-90 ℃, and carrying out extrusion casting, mirror surface opposite pressing, cooling, trimming, pressurizing and rolling to obtain the antibacterial sealing film.
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