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CN112430343B - Antibacterial food packaging film and preparation method and application thereof - Google Patents

Antibacterial food packaging film and preparation method and application thereof Download PDF

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Publication number
CN112430343B
CN112430343B CN202011374017.5A CN202011374017A CN112430343B CN 112430343 B CN112430343 B CN 112430343B CN 202011374017 A CN202011374017 A CN 202011374017A CN 112430343 B CN112430343 B CN 112430343B
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packaging film
chx
food packaging
solution
mesoporous silica
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CN112430343A (en
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邢振雷
迟建国
徐利
高颖
田海龙
张家树
李刚
李玲
李晓华
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Shandong Ruibosi Tobacco Co ltd
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Shandong Ruibosi Tobacco Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/042Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/06Coating with compositions not containing macromolecular substances
    • C08J7/065Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • C08J7/123Treatment by wave energy or particle radiation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12Homopolymers or copolymers of methyl methacrylate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04Polysiloxanes
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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Abstract

The invention relates to the technical field of food packaging, in particular to an antibacterial food packaging film and a preparation method and application thereof. The preparation method comprises the following steps: 1) Mixing the CHX solution with MSN to obtain CHX-MSN material with CHX embedded in MSN; 2) Adding the CHX-MSN material obtained in the step 1) into a PDMS solution to obtain a pre-cured CHX-MSN/PDMS solution; 3) Pretreatment of a PMMA resin packaging film: sequentially treating the PMMA resin packaging film by using IPA, oxygen plasma and APTES solution to activate the surface of the PMMA resin and form a self-assembled layer; 4) Applying the precured CHX-MSN/PDMS solution obtained in the step 2) as a thin layer to the PMMA resin packaging film pretreated in the step 3), and then carrying out heat treatment to obtain the antibacterial food packaging film.

Description

Antibacterial food packaging film and preparation method and application thereof
Technical Field
The invention relates to the technical field of food packaging, in particular to an antibacterial food packaging film and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polymethyl methacrylate (PMMA) is an acrylic resin that has good biocompatibility and is not degradable, and can be used as a food packaging film due to its easy handling, high cost performance and good aesthetics. However, PMMA films have surface defects of high porosity and are prone to adsorption of microorganisms and bacteria. The antibacterial agent is added into the packaging film, so that the growth of microorganisms on the surface of food in the package can be effectively inhibited, and the addition amount of the antibacterial agent in the food is reduced. However, the addition of the antibacterial agent directly to the PMMA film may affect the mechanical properties thereof and hinder the polymerization, and also affect the amount of the antibacterial agent and the antibacterial effect, etc.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide an antibacterial food packaging film and a preparation method and application thereof.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing an antibacterial food packaging film, comprising the steps of:
(1) Mixing and stirring a chlorhexidine diacetate (CHX) solution and Mesoporous Silica Nanoparticles (MSN), and embedding the CHX in the MSN to obtain CHX-MSN particles;
(2) Adding the CHX-MSN particles into a Polydimethylsiloxane (PDMS) solution, stirring the mixture and carrying out ultrasonic oscillation to obtain a precured CHX-MSN/PDMS solution;
(3) Pretreatment of a PMMA resin packaging film: cleaning the packaging film by using Isopropanol (IPA), then treating the packaging film by using oxygen plasma, and finally soaking the packaging film in a 3-Aminopropyltriethoxysilane (APTES) solution to activate the surface of PMMA resin to form a self-assembled layer;
(4) And (3) applying the precured CHX-MSN/PDMS solution obtained in the step (2) as a thin layer on a PMMA resin packaging film, and then carrying out heat treatment to obtain the antibacterial food packaging film.
In a second aspect of the present invention, there is provided an antibacterial food packaging film produced by the method for producing an antibacterial food packaging film according to the first aspect.
In a third aspect of the present invention, there is provided a use of the antibacterial food packaging film of the second aspect in food packaging.
The specific embodiment of the invention has the following beneficial effects:
the mesoporous silica nano-particles which are biocompatible and adsorb CHX are used and applied to the antibacterial coating technology, so that the safety of the antibacterial coating is ensured, and the slow-release effect of the antibacterial agent is improved;
the mesoporous silica nanoparticles for adsorbing CHX are dissolved by PDMS, and are applied to the coating technology, so that the antibacterial property of the food packaging film is enhanced on the premise of not influencing the mechanical property of the PMMA packaging film, and the using amount of the antibacterial agent in food can be effectively reduced;
(3) The invention has simple operation process, safe material and high cost performance, and is convenient for large-scale production; the food additive is used for various food systems, has good universality and is widely applied.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the release profile of CHX concentration in the CHX-MSN coated PMMA packaging films prepared in examples 1-3;
FIG. 2 is a graph of the bacteriostatic effect of the CHX-MSN coated PMMA packaging film prepared in example 1;
fig. 3 is a bacteriostatic effect graph of the uncoated PMMA food packaging film of comparative example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In one embodiment of the present invention, there is provided a method for preparing an antibacterial food packaging film, comprising the steps of:
(1) Mixing a chlorhexidine diacetate (CHX) solution with Mesoporous Silica Nanoparticles (MSN) to obtain a CHX-MSN material with CHX embedded in MSN;
(2) Adding the CHX-MSN material obtained in the step (1) into a Polydimethylsiloxane (PDMS) solution to obtain a pre-cured CHX-MSN/PDMS solution;
(3) Pretreatment of a PMMA resin packaging film: sequentially treating the PMMA resin packaging film by using Isopropanol (IPA), oxygen plasma and 3-Aminopropyltriethoxysilane (APTES) to activate the surface of the PMMA resin and form a self-assembled layer;
(4) And (3) applying the precured CHX-MSN/PDMS solution obtained in the step (2) as a thin layer to the PMMA resin packaging film pretreated in the step (3), and then carrying out heat treatment to obtain the antibacterial food packaging film.
Chlorhexidine (CHX) has quite strong broad-spectrum antibacterial and bactericidal effects, and is a better bactericidal disinfectant; the Mesoporous Silica Nanoparticles (MSN) can be used for adsorbing CHX, enhancing the anti-biofilm effect thereof, and slowly releasing an antibacterial agent to exert a lasting antibacterial effect due to their excellent physicochemical properties, excellent biocompatibility, high loading capacity, and excellent sustained-release properties.
PDMS is a heat-curable elastomer polymer, has fast diffusion and high bonding capability, high biocompatibility and excellent transparency, can be compatible with various materials, dissolves MSN loaded with CHX in PDMS and coats a PMMA film, and can improve the antibacterial property of the PMMA packaging film without influencing the mechanical property of the PMMA packaging film.
In the step (3), the PMMA resin packaging film is treated by using Isopropanol (IPA), oxygen plasma and 3-Aminopropyltriethoxysilane (APTES) in sequence, so that the surface of the PMMA resin can be activated to form a self-assembled layer.
In a specific embodiment, the solvent in the chlorhexidine diacetate (CHX) solution in step (1) is selected from ethanol, methanol, isopropanol and acetonitrile, preferably ethanol;
in a specific embodiment, the ratio (mass ratio) of the chlorhexidine diacetate (CHX) to the Mesoporous Silica Nanoparticles (MSN) in step (1) is: 1;
in a specific embodiment, the Mesoporous Silica Nanoparticles (MSN) have a pore volume of 0.98cm 3 (ii)/g, pore size 2.5nm;
in a specific embodiment, the step (1) of mixing the chlorhexidine diacetate (CHX) solution with the Mesoporous Silica Nanoparticles (MSN) further comprises the steps of stirring, centrifuging, washing and drying;
preferably, the stirring conditions are: physically stirring at the room temperature for 24h at the speed of 300 rpm;
preferably, the conditions of centrifugation are: centrifuging at 6000rpm for 10min with a microcentrifuge;
preferably, the washing is to remove unencapsulated CHX using ethanol and distilled water;
preferably, the drying condition is drying at 90 ℃ for 10min under vacuum condition.
In a specific embodiment, the Polydimethylsiloxane (PDMS) in step (2) is prepared from a mixture of materials in a weight ratio of 5:1, the base material is dimethyl siloxane, and the curing agent is Dow Corning 184.
In a specific embodiment, in step (2), the CHX-MSN material is added in an amount of 0.2-0.6wt% based on the mass of PDMS.
In a specific embodiment, the step (2) of adding the CHX-MSN material to the aqueous solution of Polydimethylsiloxane (PDMS) further comprises the steps of stirring, ultrasonic oscillation and vacuum pumping;
preferably, the stirring time is 1h;
preferably, the time of ultrasonic oscillation is 30min;
preferably, the time for evacuation is 20min until the bubbles are removed.
In a specific embodiment, the specific operation steps of step (3) are as follows: cleaning the packaging film with Isopropanol (IPA), treating the packaging film with oxygen plasma, and finally soaking the packaging film in a 3-Aminopropyltriethoxysilane (APTES) solution;
preferably, the power of the oxygen plasma is 70W, and the treatment time is 10min;
preferably, the 3-Aminopropyltriethoxysilane (APTES) is 5 volume percent of 3-Aminopropyltriethoxysilane (APTES) water solution;
preferably, the soaking temperature is 85 ℃, and the soaking time is 10min;
in a specific embodiment, the temperature of the heat treatment in the step (4) is 80 ℃ and the time is 2 hours.
In one embodiment of the invention, the antibacterial food packaging film prepared by the preparation method of the antibacterial food packaging film is provided.
In one embodiment of the invention, the application of the antibacterial food packaging film in food packaging is provided.
The invention will be further explained and illustrated with reference to the following examples.
Example 1
The preparation method of the antibacterial food packaging film comprises the following steps:
(1) Dissolving 50mg of chlorhexidine diacetate (CHX) in 5mL of ethanol to prepare a CHX solution; subsequently, the pore volume was set to 0.98cm 3 (ii)/g Mesoporous Silica Nanoparticles (MSN) with a pore size of 2.5nm mixed with CHX solutionAnd, physically stirring at room temperature for 24 hours using an electromagnetic stirrer at a speed of 300rpm, collecting MSN-embedded CHX by centrifugation at 6000rpm for 10min using a microcentrifuge, and washing with ethanol and distilled water to remove unencapsulated CHX, after washing, drying at 90 ℃ for 10min using a vacuum drying oven, and collecting final CHX-MSN particles;
(2) 0.2wt% of CHX-MSN particles was added to a solution of 3g of Polydimethylsiloxane (PDMS) made up of 5:1, base material and curing agent; stirring the mixture for 1h by using an electromagnetic stirrer, ultrasonically oscillating for 30min, and then vacuumizing for 20min to remove bubbles to obtain a precured CHX-MSN/PDMS solution;
(3) Production of food packaging film using PMMA resin: cleaning a packaging film by using Isopropanol (IPA), and treating the film for 10min by using oxygen plasma under the power of 70W; next, the packaging film was immersed in a 5% (v/v) aqueous solution of 3-Aminopropyltriethoxysilane (APTES) at 85 ℃ for 10min to activate the surface of the resin sample, forming a self-assembled layer; subsequently, the precured CHX-MSN coating solution was applied as a thin layer on the resin sample, and then the coated sample was heat-treated in an oven at 80 ℃ for 2h to obtain a CHX-MSN coated PMMA antibacterial food packaging film.
Example 2
The preparation method of the antibacterial food packaging film comprises the following steps:
(1) 100mg of chlorhexidine diacetate (CHX) was dissolved in 10mL of ethanol to prepare a CHX solution, and then the pore volume was set to 0.98cm 3 (ii)/g, mesoporous Silica Nanoparticles (MSN) with a pore size of 2.5nm are mixed with CHX solution; physically stirring at room temperature for 36h using an electromagnetic stirrer at 300rpm, collecting MSN-embedded CHX by centrifugation at 8000rpm for 20min using a microcentrifuge, and washing with ethanol and distilled water to remove unencapsulated CHX; after washing, the final CHX-MSN particles were collected after drying for 15min at 90 ℃ using a vacuum oven.
(2) 0.4wt% of CHX-MSN particles was added to a solution of 3g of Polydimethylsiloxane (PDMS) made up of 5:1, base material and curing agent; stirring the mixture for 2h by using an electromagnetic stirrer, ultrasonically oscillating for 45min, and then vacuumizing for 30min until bubbles are removed to obtain a precured CHX-MSN/PDMS solution;
(3) Production of food packaging film using PMMA resin: cleaning a packaging film by using Isopropanol (IPA), and treating the film for 15min by using oxygen plasma under the power of 70W; next, the packaging film was immersed in a 5% (v/v) aqueous solution of 3-Aminopropyltriethoxysilane (APTES) at 85 ℃ for 20min to activate the surface of the resin sample, forming a self-assembled layer; subsequently, the precured CHX-MSN coating solution was applied as a thin layer on the resin sample, and then the coated sample was heat-treated in an oven at 80 ℃ for 3 hours to obtain a CHX-MSN coated PMMA antibacterial food packaging film.
Example 3
The preparation method of the antibacterial food packaging film comprises the following steps:
(1) 150mg of chlorhexidine diacetate (CHX) was dissolved in 10mL of ethanol to prepare a CHX solution, and then the pore volume was set to 0.98cm 3 (ii)/g, mesoporous Silica Nanoparticles (MSN) with a pore size of 2.5nm are mixed with CHX solution; physically stirring at room temperature for 36h using an electromagnetic stirrer at 300rpm, collecting MSN-embedded CHX by centrifugation for 20min at 8000rpm using a microcentrifuge, and washing with ethanol and distilled water to remove unencapsulated CHX; after washing, the final CHX-MSN particles were collected after drying for 15min at 90 ℃ using a vacuum oven.
(2) 0.6wt% of CHX-MSN particles was added to a solution of 3g of Polydimethylsiloxane (PDMS) made up of 5:1, base material and curing agent; stirring the mixture for 2h by using an electromagnetic stirrer, ultrasonically oscillating for 45min, and then vacuumizing for 30min until bubbles are removed to obtain a precured CHX-MSN/PDMS solution;
(3) Production of food packaging film using PMMA resin: cleaning a packaging film by using Isopropanol (IPA), and treating the film for 15min by using oxygen plasma under the power of 70W; next, the packaging film was immersed in a 5% (v/v) aqueous solution of 3-Aminopropyltriethoxysilane (APTES) at 85 ℃ for 20min to activate the surface of the resin sample, forming a self-assembled layer; subsequently, the precured CHX-MSN coating solution was applied as a thin layer on the resin sample, and then the coated sample was heat-treated in an oven at 80 ℃ for 3 hours to obtain a CHX-MSN coated PMMA antibacterial food packaging film.
Comparative example 1
The PMMA food packaging film is directly manufactured by using PMMA resin without adding an antibacterial coating.
Comparative example 2
(1) A CHX solution was prepared by dissolving 50mg of chlorhexidine diacetate in 5mL of ethanol. Subsequently, the pore volume was set to 0.98cm 3 (ii)/g mesoporous silica nanoparticles with a pore size of 2.5nm were mixed with the CHX solution. The mixture was physically stirred at room temperature for 24h using a magnetic stirrer at 300 rpm. The MSN encapsulated CHX was collected by centrifugation at 6000rpm for 10min using a microcentrifuge and washed with ethanol and distilled water to remove unencapsulated CHX. After washing, the final CHX-MSN particles were collected after drying at 90 ℃ for 10min using a vacuum oven.
(2) 0.2wt% CHX-MSN particles were added to a solution of 3g polylactic acid matrix resin in methylene chloride, the mixture was stirred for 1h using an electromagnetic stirrer, ultrasonically shaken for 30min, and then vacuumed for 20min to remove air bubbles, resulting in a pre-cured solution.
(3) A food packaging film was produced using PMMA resin by first washing the packaging film with isopropyl alcohol and then treating the film with oxygen plasma at a power of 70W for 10min. Next, the packaging film was immersed in a 5% (v/v) aqueous solution of 3-aminopropyltriethoxysilane at 85 ℃ for 10min to activate the surface of the resin sample, forming a self-assembled layer. Subsequently, the pre-cured coating solution was applied as a thin layer onto the resin sample, and then the coated sample was heat treated in an oven at 80 ℃ for 2h.
Examples of the experiments
The antibacterial food packaging film prepared in example 1 and the food packaging film of comparative example 1 were subjected to a bacteriostasis test. The cold fresh meat was packaged by example 1 and comparative example 1, respectively, and the total number of bacterial colonies (APC) of the cold fresh meat was measured according to the method of international standard (AFNOR), and 10g of the cold fresh meat sample was accurately weighed into a sterile sampling bag containing 90mL of physiological saline, and the sampling bag containing the cold fresh meat sample was patted for 2min using a patting homogenizer. 1mL of the sample solution was diluted in a concentration gradient and transferred to a petri dish, then 15mL of agar medium was added to the petri dish at 46 ℃, the petri dish was shaken to ensure homogeneous mixing of the inoculum, and the medium was cooled at room temperature until it solidified. The prepared culture dish is turned over and placed in an incubator with relative humidity of 27 +/-1 ℃ for 48 +/-2 h, and then the total number of colonies of each plate is recorded. The test results are shown in fig. 2 and 3, from which it can be seen that: the food protective film added with the antibacterial coating is basically free from bacteria, and the food packaging film without the antibacterial coating is obviously polluted by bacteria.
The packaging films of examples 1 to 3 and comparative examples 1 to 2 were subjected to mechanical property tests, and the data are shown in the following table:
test items Tensile strength, MPa Elongation at break,% Film thickness (μm)
Example 1 115.9±6.5 12.1±0.1 35.8±0.5
Example 2 112.3±13.6 13.3±0.2 36.8±0.4
Example 3 115.2±5.9 12.8±0.4 40.0±0.3
Comparative example 1 120.2±2.8 14.2±0.3 34.7.8±0.8
Comparative example 2 60.5±3.1 6.1±2.5 35.1±2.2
It can be seen that the food antibacterial films coated with the CHX-MSN pre-cured coating solution (examples 1 to 3) have better mechanical strength than comparative example 2, which shows that the method for preparing the antibacterial food packaging film of the present invention has less influence on the mechanical properties of the PMMA resin packaging film and can effectively add the antibacterial agent to the PMMA resin packaging film to achieve good antibacterial effect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. The preparation method of the antibacterial food packaging film is characterized by comprising the following steps:
(1) Mixing and stirring a chlorhexidine diacetate solution and mesoporous silica nanoparticles, and embedding chlorhexidine diacetate in the mesoporous silica nanoparticles to obtain a chlorhexidine diacetate-mesoporous silica nanoparticle material;
(2) Adding the chlorhexidine diacetate-mesoporous silica nanoparticle material into a polydimethylsiloxane solution, stirring the mixture and carrying out ultrasonic oscillation to obtain a pre-cured chlorhexidine diacetate-mesoporous silica nanoparticle/polydimethylsiloxane solution;
(3) Pretreatment of a PMMA resin packaging film: cleaning the packaging film by using isopropanol, then treating the packaging film by using oxygen plasma, and finally soaking the packaging film in a 3-aminopropyltriethoxysilane solution to form a self-assembled layer;
(4) Applying the precured chlorhexidine diacetate-mesoporous silica nano-particle/polydimethylsiloxane solution obtained in the step (2) as a thin layer to a PMMA resin packaging film, and then carrying out heat treatment to obtain an antibacterial food packaging film;
the specific operation steps of the step (1) are as follows: dissolving chlorhexidine diacetate into a solvent to form a solution, mixing with mesoporous silica nanoparticles, stirring, centrifuging, washing and drying to obtain a chlorhexidine diacetate-mesoporous silica nanoparticle material with the chlorhexidine diacetate embedded in the mesoporous silica nanoparticles; the stirring conditions were: physically stirring at the room temperature for 24h at the speed of 300 rpm; the conditions of centrifugation were: centrifuging at 6000rpm for 10min with a microcentrifuge; washing is to remove unencapsulated CHX using ethanol and distilled water; the drying condition is drying at 90 ℃ for 10min under vacuum condition;
the step (2) of adding the chlorhexidine diacetate-mesoporous silicon dioxide nano particle material into the polydimethylsiloxane solution further comprises the steps of stirring, ultrasonic oscillation and vacuumizing; the stirring time is 1h; the ultrasonic oscillation time is 30min; vacuumizing for 20min until bubbles are removed;
in the step (3), the power of the oxygen plasma is 70W, and the processing time is 10min; the concentration of the 3-aminopropyltriethoxysilane in the 3-aminopropyltriethoxysilane aqueous phase solution is 5% by volume; soaking at 85 deg.C for 10min;
the temperature of the heat treatment in the step (4) is 80 ℃, and the time is 2 hours;
the addition amount of the chlorhexidine diacetate-mesoporous silica nanoparticle material is 0.2-0.6wt% of the mass of the polydimethylsiloxane.
2. The method for preparing an antibacterial food packaging film according to claim 1, wherein the solvent in step (1) is selected from the group consisting of ethanol, methanol, isopropanol and acetonitrile.
3. The method of manufacturing an antibacterial food packaging film according to claim 2, wherein the solvent is ethanol.
4. The method of preparing an antibacterial food packaging film according to claim 1, wherein the mesoporous silica nanoparticles have a pore volume of 0.98cm 3 (ii)/g, pore diameter 2.5 nm.
5. The antibacterial food packaging film produced by the method for producing an antibacterial food packaging film according to any one of claims 1 to 4.
6. Use of the antibacterial food packaging film according to claim 5 in food packaging.
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US5929133A (en) * 1996-02-16 1999-07-27 Hitachi Chemical Filtec, Inc. Anti-bacterial film suitable for food packaging
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