CN118085444B - Antibacterial sealing film and preparation method thereof - Google Patents
Antibacterial sealing film and preparation method thereof Download PDFInfo
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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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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 47
- 238000007789 sealing Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 170
- 239000011787 zinc oxide Substances 0.000 claims abstract description 85
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 11
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 11
- 239000011976 maleic acid Substances 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000009966 trimming Methods 0.000 claims abstract description 7
- 238000005086 pumping Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 22
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 16
- 239000005770 Eugenol Substances 0.000 claims description 16
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 16
- 229960002217 eugenol Drugs 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000004475 Arginine Substances 0.000 claims description 12
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007987 MES buffer Substances 0.000 claims description 11
- 244000028419 Styrax benzoin Species 0.000 claims description 11
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 11
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 11
- 229960002130 benzoin Drugs 0.000 claims description 11
- 235000019382 gum benzoic Nutrition 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims 2
- 239000004698 Polyethylene Substances 0.000 abstract description 16
- 239000003242 anti bacterial agent Substances 0.000 abstract description 15
- 229920000573 polyethylene Polymers 0.000 abstract description 15
- 235000013305 food Nutrition 0.000 abstract description 11
- -1 polyethylene Polymers 0.000 abstract description 10
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000005022 packaging material Substances 0.000 abstract description 4
- 244000005700 microbiome Species 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 210000000170 cell membrane Anatomy 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
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- 238000004659 sterilization and disinfection Methods 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241001360526 Escherichia coli ATCC 25922 Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000637 arginyl group Chemical group N[C@@H](CCCNC(N)=N)C(=O)* 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229960000274 lysozyme Drugs 0.000 description 1
- 239000004325 lysozyme Substances 0.000 description 1
- 235000010335 lysozyme Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
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
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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