CN117141077A - Barrier type polyethylene single-material composite antibacterial film and preparation method thereof - Google Patents
Barrier type polyethylene single-material composite antibacterial film and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- -1 polyethylene Polymers 0.000 title claims abstract description 40
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 40
- 230000004888 barrier function Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 156
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 59
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000002135 nanosheet Substances 0.000 claims abstract description 30
- 239000002346 layers by function Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 15
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 15
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 14
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 17
- 239000004408 titanium dioxide Substances 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052582 BN Inorganic materials 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
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- 239000002064 nanoplatelet Substances 0.000 claims description 5
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
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- 239000004814 polyurethane Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
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- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 13
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- 238000002474 experimental method Methods 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000002845 discoloration Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
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Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the field of polyolefin films, and discloses a barrier type polyethylene single-material composite antibacterial film and a preparation method thereof. The composite antibacterial film comprises an outer protection BOPE layer, a bonding layer and an inner functional layer which are sequentially arranged from top to bottom; the inner functional layer is a five-layer structure layer obtained by coextrusion process and comprises an A layer, an E1 layer and a B layer which are sequentially arranged from top to bottomLayer E2 and layer C; the master batch of the layer A is prepared by blending and granulating organically modified boron nitride nano-sheets and LDPE; the master batch of the layer B is prepared by blending and granulating organically modified boron nitride nano-sheets and HDPE; the master batch of the layer C is organic modified nano TiO 2 Blending with MPE and LLDPE, granulating; both the E1 layer and the E2 layer are LLDPE layers. The composite antibacterial film disclosed by the invention is single in material, can enhance the gas barrier property and mechanical property of the polyethylene film, and has a remarkable antibacterial effect.
Description
Technical Field
The invention belongs to the field of polyolefin films, and particularly relates to a barrier type polyethylene single-material composite antibacterial film and a preparation method thereof.
Background
With the rapid development of economy and society, the living standard of people is continuously improved, and the requirements of people on food safety are far surpassed simple non-toxic and harmless, but are extended to pursue health and environmental protection concepts, so that the demands of the market on functional environmental protection packages are continuously increased.
On the one hand, the traditional single packaging material often cannot meet the requirements of foods and the like on the packaging barrier performance, the packaging products on the market are often packaged by adopting multiple layers and multiple materials, and in the material composition, different plastic layers, aluminum foils, coatings and the like are often contained, so that the sorting and classifying processes are complicated and difficult, and the recycling rate is low. Under the influence of environmental protection policies and sustainable development concepts, plastic packaging materials using a single material are increasingly gaining importance. On the premise of ensuring the packaging performance requirement, a single material is adopted as much as possible so as to be beneficial to recycling, which has become the consensus of industry health development. The single material is that only one main material of the material is adopted, and the content of other materials in the single material package is generally considered to be not more than 5% in the packaging industry, and the material which is not beneficial to recycling is not contained.
On the other hand, the antibacterial package is a comprehensive method which combines packaging materials and preservatives to improve the shelf life and the safety of foods and skillfully combines various factors which restrict the preservation of the foods. Antibacterial packaging systems generally consist of packaging materials, antibacterial agents and foods. The antimicrobial agent is typically coated on, incorporated into, fixed to, or modified into the packaging material. However, the antibacterial packaging material made of a single material has single functionality, and cannot well meet the requirements of food on packaging other properties such as mechanical properties and barrier properties.
Therefore, it is highly desirable to provide a barrier type polyethylene composite antibacterial film and a preparation method thereof, which can effectively solve the problem of poor barrier property of a single material film on the basis of ensuring the recovery property of the single material, improve the mechanical property of the single material film to a certain extent, and endow the single material film with antibacterial function.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a barrier type polyethylene single-material composite antibacterial film and a preparation method thereof. The composite antibacterial film disclosed by the invention is single in material, can enhance the gas barrier property and mechanical property of the polyethylene film, and has a remarkable antibacterial effect.
In order to achieve the above purpose, the present invention provides a barrier type polyethylene single material composite antibacterial film, which comprises an outer protective BOPE layer, a bonding layer and an inner functional layer, which are sequentially arranged from top to bottom;
the inner functional layer is a five-layer structure layer obtained by a coextrusion process, and the five-layer structure layer comprises an A layer, an E1 layer, a B layer, an E2 layer and a C layer which are sequentially arranged from top to bottom;
the master batch of the layer A is prepared by blending and granulating organically modified boron nitride nano sheets (BNSs) and LDPE (low density polyethylene); the master batch of the layer B is prepared by blending and granulating organically modified boron nitride nano-sheets and HDPE (high-density polyethylene); the master batch of the C layer is organically modified nano TiO 2 Blending with MPE (metallocene polyethylene) and LLDPE (linear low density base ethylene) and granulating to obtain the final product; the E1 layer and the E2 layer are LLDPE layers.
According to the present invention, preferably, the thickness of the inner functional layer is 50-100 μm; the thickness ratio of the layer A, the layer E1, the layer B, the layer E2 and the layer C is (3.5-4.5): (0.8-1.2): (1.5-2.5): (0.8-1.2): (3.5-4.5).
In the present invention, the E1 layer and the E2 layer serve as transitions and bonds for the A, B, C layer.
According to the present invention, preferably, the content of the organically modified boron nitride nanoplatelets of the master batch of the a layer is 1% to 5% based on the total weight of the master batch of the a layer.
According to the present invention, preferably, the content of the organically modified boron nitride nanoplatelets of the masterbatch of the B layer is 1% to 5% based on the total weight of the masterbatch of the B layer.
According to the present invention, preferably, the organically modified nano TiO is based on the total weight of the master batch of the C layer 2 The content of (2) is 1% -5%; the mass ratio of MPE to LLDPE is (1.5-4): 1.
in the invention, the barrier property enhancement mechanism of the barrier type polyethylene single material composite antibacterial film is as follows: the boron nitride nano-sheet is used as a two-dimensional nano-layered material, has extremely high aspect ratio, and can effectively prolong the permeation path of permeation molecules and reduce the diffusion rate when being dispersed into polyolefin materials, thereby effectively improving the barrier property of the polyethylene film.
The antibacterial mechanism and the characteristics of the barrier type polyethylene single material composite antibacterial film are as follows: the nano titanium dioxide can decompose bacteria under the photocatalysis effect to achieve the antibacterial effect, is safe and nontoxic to human body, and has no irritation to skin; the antibacterial capability is strong, and the antibacterial range is wide; no odor, strange smell, and small smell; the water-washing resistance and the storage period are long; has good thermal stability, no discoloration at high temperature, no decomposition, no volatilization, and no deterioration.
In the present invention, since the inorganic nano-particles (boron nitride nano-sheets and nano-titania) which have not undergone surface treatment have poor compatibility with the organic material, are liable to cause agglomeration thereof in the organic matrix material to be unevenly dispersed, the boron nitride nano-sheets and nano-titania need to undergo organic modification to enhance their compatibility and dispersibility in the polyethylene resin material.
According to the present invention, preferably, the method for preparing the organically modified boron nitride nanoplatelets comprises: under the air condition, carrying out high-temperature calcination treatment on nano hexagonal boron nitride (h-BN), cooling, taking out, mixing with water, and carrying out primary ultrasonic dispersion to obtain a first dispersion liquid; and regulating the pH value of the first dispersion liquid to 4-5, mixing the first dispersion liquid with a first silane coupling agent, and sequentially performing secondary ultrasonic dispersion, stirring, centrifugation, supernatant removal, drying, precipitation and grinding to obtain the organically modified boron nitride nano-sheet.
According to the present invention, preferably, in the preparation of the organically modified boron nitride nanoplatelets:
the average grain diameter of the nano hexagonal boron nitride is less than or equal to 1000nm;
the conditions of the high temperature calcination treatment include: the calcination temperature is 800-1000 ℃, the heating rate is 10-20 ℃/min, and the heat preservation time is 20-40min;
the dosage ratio of the nano hexagonal boron nitride after high-temperature calcination treatment to water to the first silane coupling agent is (1-2): (200-400): (1-2) g/mL/mL;
the time of primary ultrasonic dispersion is 30-60min;
adjusting the pH of the first dispersion to 4-5 with formic acid and/or acetic acid;
the first silane coupling agent is at least one of KH-540, KH-550, KH-560 and A-151;
the secondary ultrasonic dispersion time is 20-30min;
stirring for 0.8-1.2h under the water bath condition of 60-80 ℃;
the conditions for drying the precipitate include: the drying temperature is 100-140 ℃ and the drying time is 24-36h.
In the invention, the preparation method of the master batch of the layer A comprises the following steps: mixing the organically modified boron nitride nanosheets with LDPE to obtain a mixed material, extruding and granulating the mixed material by using a double screw extruder, and setting proper processing conditions according to different polyethylene types to finally obtain the master batch of the layer A (BNSs modified LDPE).
In the invention, the preparation method of the master batch of the B layer comprises the following steps: mixing the organically modified boron nitride nanosheets with HDPE to obtain a mixed material, extruding and granulating the mixed material by a double screw extruder, and setting proper processing conditions according to different polyethylene types to finally obtain the B-layer master batch (BNSs modified HDPE).
In the invention, the preparation method of the master batch of the C layer comprises the following steps: organic modified nano TiO 2 Mixing with MPE and LLDPE to obtain a mixed material, extruding and granulating the mixed material with a double screw extruder, and setting appropriate processing conditions according to different polyethylene types to obtain C-layer master batch (nanometer TiO) 2 Modified MPE/LLDPE).
According to the present invention, preferably, the organically modified nano TiO 2 The preparation method of (2) comprises the following steps: mixing titanium dioxide, an organic solvent and a second silane coupling agent, and performing ultrasonic dispersion for one time to obtain a second dispersion liquid; adjusting the pH of the second dispersion liquid to 4-5, sequentially performing secondary ultrasonic dispersion, stirring, centrifugation, supernatant removal, drying, precipitation and grinding to obtain the organic modified nano TiO 2 。
According to the present invention, preferably, in the organic modified nano TiO 2 In the preparation of (2):
the average grain diameter of the titanium dioxide is less than or equal to 100nm; the organic solvent is ethanol water solution with the mass fraction of 45-55%; the second silane coupling agent is at least one of KH-540, KH-550, KH-560 and A-151;
the dosage ratio of the titanium dioxide to the organic solvent to the second silane coupling agent is (1-2): (200-400): (1-2) g/mL/mL;
the time of primary ultrasonic dispersion is 30-40min;
adjusting the pH of the second dispersion to 4-5 with formic acid and/or acetic acid;
the secondary ultrasonic dispersion time is 20-30min;
stirring for 0.8-1.2h under the water bath condition of 60-80 ℃;
the conditions for drying the precipitate include: the drying temperature is 100-140 ℃ and the drying time is 24-36h.
According to the present invention, the thickness of the outer protective BOPE layer is preferably 15-30 μm.
According to the invention, preferably, the outer protective BOPE layer is formed by molding PE master batch through a biaxial stretching process, and the PE master batch is at least one of HDPE, LDPE and LLDPE.
In the invention, the outer protective BOPE layer is a BOPE film layer, the BOPE film is prepared by molding PE through a biaxial stretching process, which is known to those skilled in the art, has very high molecular weight orientation and crystallization orientation, and excellent impact resistance, puncture resistance and low temperature resistance, compared with the traditional blow molding PE film, the tensile strength of the BOPE film is improved by 2-8 times, the tensile modulus and dart impact performance are both improved by 2-5 times after the BOPE film is molded through the biaxial stretching process, good toughness and mechanical strength can be maintained at low temperature, and the mechanical property of the BOPE film is superior to that of the blow molding film under the condition that the thickness is reduced by 30% -60%, thus the use requirement can be met, and the use of resources and the consumption of energy by packaging materials can be effectively reduced.
According to the present invention, it is preferable that the thickness of the adhesive layer is 3-6 μm.
According to the present invention, preferably, the material of the adhesive layer is a two-component solvent-free polyurethane adhesive and/or a solvent-type polyurethane adhesive.
The invention also provides a preparation method of the barrier type polyethylene single material composite antibacterial film, which comprises the following steps: and carrying out solvent-free compounding and/or dry compounding on the outer protective BOPE layer, the bonding layer and the inner functional layer to obtain the barrier type polyethylene single-material composite antibacterial film.
In the invention, the bonding layer is used for bonding the outer protection BOPE layer and the inner functional layer, a two-component solvent-free polyurethane adhesive is used when a solvent-free compounding process is adopted, and a solvent-free polyurethane adhesive is used when a dry compounding process is adopted.
The technical scheme of the invention has the following beneficial effects:
the invention prepares BOPE by biaxial stretching technology and BNNS and TiO by biaxial stretching technology 2 The modified inner functional layer is compounded to form the barrier type polyethylene single material composite antibacterial film. The composite antibacterial film prepared by adopting the processes of blending modification, multilayer coextrusion, compounding and the like can enhance the gas barrier property and the mechanical property of the polyethylene film and endow the film with remarkable antibacterial effectAnd (5) fruits.
The composite antibacterial film ensures that all layers are made of the same material and the content of other materials is not more than 5% on the premise that the mechanical property, the barrier property and the antibacterial property meet the food packaging requirement, so that the composite antibacterial film is beneficial to recycling. The invention is green and environment-friendly, has superior performance, simple preparation, safety, reliability, innocuity and innocuity, has the feasibility of industrialized production, has wide potential application scene and has certain application value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
Fig. 1 shows a schematic structural diagram of a barrier type polyethylene single material composite antibacterial film provided by the invention.
1-an outer protective BOPE layer; 2-a bonding layer; a layer A; an E1 layer; a layer B; an E2 layer; and C layer.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a barrier type polyethylene single-material composite antibacterial film, as shown in fig. 1, wherein the composite antibacterial film comprises an outer protection BOPE layer 1, a bonding layer 2 and an inner functional layer which are sequentially arranged from top to bottom; the inner functional layer is a five-layer structure layer obtained by a coextrusion process, and the five-layer structure layer comprises an A layer, an E1 layer, a B layer, an E2 layer and a C layer which are sequentially arranged from top to bottom;
the thickness of the outer protection BOPE layer 1 is 15 mu m, the outer protection BOPE layer is made of PE master batch through molding by a biaxial stretching process, and the PE master batch is HDPE;
the thickness of the bonding layer 2 is 3 mu m, and the bonding layer is made of a two-component solvent-free polyurethane adhesive;
the thickness of the inner functional layer is 60 μm; the thickness ratio of the layer A, the layer E1, the layer B, the layer E2 and the layer C is 4:1:2:1:4.
the master batch of the layer A is prepared by blending and granulating organically modified boron nitride nano sheets and LDPE, and the content of the organically modified boron nitride nano sheets is 3% based on the total weight of the master batch of the layer A; the master batch of the layer B is prepared by blending and granulating organically modified boron nitride nano-sheets and HDPE, and the content of the organically modified boron nitride nano-sheets is 3% based on the total weight of the master batch of the layer B; the master batch of the C layer is organically modified nano TiO 2 Is prepared by blending and granulating with MPE and LLDPE, and organically modified nano TiO is prepared by taking the total weight of the master batch of the layer C as the basis 2 3%, 77% MPE and 20% LLDPE; the E1 layer and the E2 layer are LLDPE layers.
The preparation of the master batch of the layer A and the master batch of the layer B comprises the following steps:
(1) The preparation of the organically modified boron nitride nanosheets comprises the following steps: selecting nano hexagonal boron nitride (h-BN) with the average particle size of 800nm, placing the nano hexagonal boron nitride (h-BN) into a hearth of a high-temperature resistance furnace in the presence of air for high-temperature calcination treatment, increasing the temperature in the furnace to 900 ℃ at a heating rate of 15 ℃/min, keeping for 30min, cooling and taking out for later use. Taking 1g of nano hexagonal boron nitride subjected to high-temperature calcination treatment, adding the nano hexagonal boron nitride into 200mL of deionized water, performing ultrasonic dispersion for 30min to obtain a first dispersion liquid, slowly dropwise adding an acetic acid solution into the first dispersion liquid, adjusting the pH of the first dispersion liquid to 5.0, adding 1mL of silane coupling agent KH-560, continuing ultrasonic treatment for 30min, and stirring for 1 h under the water bath condition of 60 ℃. Finally, centrifuging the stirred dispersion liquid at a high speed, removing supernatant, placing the rest part in an oven, drying for 24 hours at 120 ℃, and grinding after drying to obtain organically modified boron nitride nano-sheets (BNSs);
(2) Masterbatch of layer a: taking 3g of BNSs obtained in the step (1) and 97g of LDPE, mechanically mixing to obtain a mixed material, extruding and granulating the mixed material by using a double-screw extruder, setting the processing temperature of each section to be 160 ℃, 175 ℃, 190 ℃, 185 ℃ and 180 ℃ in sequence, setting the screw rotating speed to be 30r/min, and obtaining a layer A master batch (BNSs modified LDPE) through blending, melting, extruding, cooling and shearing;
masterbatch of layer B: and (3) mechanically mixing 3g of BNSs obtained in the step (1) with 97g of HDPE to obtain a mixed material, extruding and granulating the mixed material by using a double-screw extruder, setting the processing temperature of each section to be 180 ℃, 190 ℃, 195 ℃, 210 ℃ and 200 ℃ in sequence, setting the screw rotating speed to be 30r/min, and obtaining the B-layer master batch (BNSs modified HDPE) through blending, melting, extruding, cooling and shearing.
The preparation of the master batch of the layer C comprises the following steps:
s1: the organic modified nano TiO 2 Is prepared from the following steps: 1g of titanium dioxide (TiO) having an average particle diameter of 60nm was selected 2 ) Adding the mixture into 200mL of 50% ethanol water solution, uniformly stirring, adding 1mL of silane coupling agent KH-560, and performing ultrasonic treatment for 30min to obtain second dispersion; slowly dropwise adding acetic acid solution into the second dispersion, regulating the pH of the second dispersion to 5.0, continuing ultrasonic treatment for 10min, and stirring for 1 hour under the water bath condition of 60 ℃. Finally, after high-speed centrifugation of the stirred dispersion liquid, removing supernatant, putting the rest part into a baking oven, drying for 24 hours at 120 ℃, and grinding after drying to obtain the organic modified nano TiO 2 ；
S2: taking 3g of the organic modified nano TiO obtained in the step S1 2 Mechanically mixing with 77g MPE and 20g LLDPE to obtain a mixed material, extruding and granulating the mixed material by using a double-screw extruder, setting the processing temperature of each section to be 150 ℃, 160 ℃, 175 ℃, 180 ℃ and 170 ℃ in sequence, setting the screw rotating speed to be 30r/min, and obtaining a C-layer master batch (nano TiO) through blending, melting, extruding, cooling and shearing 2 Modified MPE/LLDPE).
The preparation method of the barrier type polyethylene single material composite antibacterial film comprises the following steps: and performing solvent-free compounding on the outer protective BOPE layer, the bonding layer and the inner functional layer to obtain the barrier type polyethylene single-material composite antibacterial film (BOPE/Tie/G-PE).
Example 2
The present embodiment provides a barrier type polyethylene composite antibacterial film, and the difference between the present embodiment and embodiment 1 is that:
the thickness of the outer protection BOPE layer 1 is 20 mu m;
the bonding layer is made of solvent polyurethane bonding agent;
the thickness of the inner functional layer is 80 mu m;
the master batch of the layer A is prepared by blending and granulating organically modified boron nitride nano sheets and LDPE, and the content of the organically modified boron nitride nano sheets is 4% based on the total weight of the master batch of the layer A;
the master batch of the layer B is prepared by blending and granulating organically modified boron nitride nano-sheets and HDPE, and the content of the organically modified boron nitride nano-sheets is 2% based on the total weight of the master batch of the layer B;
the master batch of the C layer is organically modified nano TiO 2 Is prepared by blending and granulating with MPE and LLDPE, and organically modified nano TiO is prepared by taking the total weight of the master batch of the layer C as the basis 2 4%, 66% MPE and 30% LLDPE;
the preparation method of the barrier type polyethylene single material composite antibacterial film comprises the following steps: and carrying out dry-process compounding on the outer protective BOPE layer, the bonding layer and the inner functional layer to obtain the barrier type polyethylene single-material composite antibacterial film.
Example 3
The present embodiment provides a barrier type polyethylene composite antibacterial film, and the difference between the present embodiment and embodiment 1 is that:
the thickness of the outer protection BOPE layer 1 is 30 mu m, the outer protection BOPE layer is formed by molding PE master batch through a biaxial stretching process, and the PE master batch is LLDPE;
the thickness of the adhesive layer 2 is 5 μm;
the thickness of the inner functional layer is 100 mu m;
the master batch of the layer A is prepared by blending and granulating organically modified boron nitride nano sheets and LDPE, and the content of the organically modified boron nitride nano sheets is 2% based on the total weight of the master batch of the layer A;
the master batch of the layer B is prepared by blending and granulating organically modified boron nitride nano-sheets and HDPE, and the content of the organically modified boron nitride nano-sheets is 2% based on the total weight of the master batch of the layer B;
the master batch of the C layer is organically modified nano TiO 2 Is prepared by blending and granulating with MPE and LLDPE, and organically modified nano TiO is prepared by taking the total weight of the master batch of the layer C as the basis 2 5%, 55% MPE and 40% LLDPE;
the preparation method of the barrier type polyethylene single material composite antibacterial film is the same as that of the embodiment 1.
Comparative example 1
This comparative example provides a polyethylene-based composite film, which differs from example 1 only in that:
the inner functional layer is only a single-layer LDPE, and is not subjected to multilayer coextrusion;
the compounding method of the polyethylene-based composite film is the same as that of example 1, and BOPE/Tie/LDPE is obtained.
Test case
The test example adopts the method described in national standard GB/T1038.1-2022 to measure the gas permeability of the films of comparative example 1 and example 1 so as to evaluate the barrier property; film stretching experiments of comparative example 1 and example 1 were performed using methods described in national standards GB/T1040.1-2006, GB/T1040.3-2006 to evaluate the tensile strength of the films; the antibacterial property of the films was evaluated by performing the surface antibacterial experiments of the films of comparative example 1 and example 1 using the method described in national standard GB/T31402-2015. The test shows that: under the condition of the same thickness, compared with the BOPE/Tie/G-PE (example 1), the antibacterial rate of the BOPE/Tie/G-PE to the escherichia coli and the staphylococcus aureus is improved from 0% to 95-100%, the oxygen permeability is reduced by 60% -80%, namely, the barrier property is improved by 60% -80%, and the tensile strength is improved by 80% -120%.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. The composite antibacterial film is characterized by comprising an outer protective BOPE layer, a bonding layer and an inner functional layer which are sequentially arranged from top to bottom;
the inner functional layer is a five-layer structure layer obtained by a coextrusion process, and the five-layer structure layer comprises an A layer, an E1 layer, a B layer, an E2 layer and a C layer which are sequentially arranged from top to bottom;
the master batch of the layer A is prepared by blending and granulating organically modified boron nitride nano-sheets and LDPE; the master batch of the layer B is prepared by blending and granulating organically modified boron nitride nano-sheets and HDPE; the master batch of the C layer is organically modified nano TiO 2 Blending with MPE and LLDPE, granulating; the E1 layer and the E2 layer are LLDPE layers.
2. The barrier-type polyethylene-based single-material composite antibacterial film according to claim 1, wherein the thickness of the inner functional layer is 50-100 μm; the thickness ratio of the layer A, the layer E1, the layer B, the layer E2 and the layer C is (3.5-4.5): (0.8-1.2): (1.5-2.5): (0.8-1.2): (3.5-4.5).
3. The barrier type polyethylene-based single-material composite antibacterial film according to claim 1, wherein,
the content of the organically modified boron nitride nano-sheets of the master batch of the layer A is 1 to 5 percent based on the total weight of the master batch of the layer A;
the content of the organically modified boron nitride nano-sheets of the master batch of the B layer is 1-5 percent based on the total weight of the master batch of the B layer;
organically modified nano TiO based on the total weight of the master batch of the layer C 2 The content of (2) is 1% -5%; the mass ratio of MPE to LLDPE is (1.5-4): 1.
4. the barrier-type polyethylene-based single-material composite antibacterial film according to claim 1, wherein the preparation method of the organically modified boron nitride nano-sheet comprises the following steps: under the air condition, carrying out high-temperature calcination treatment on nano hexagonal boron nitride, cooling, taking out, mixing with water, and carrying out primary ultrasonic dispersion to obtain a first dispersion liquid; and regulating the pH value of the first dispersion liquid to 4-5, mixing the first dispersion liquid with a first silane coupling agent, and sequentially performing secondary ultrasonic dispersion, stirring, centrifugation, supernatant removal, drying, precipitation and grinding to obtain the organically modified boron nitride nano-sheet.
5. The barrier-type polyethylene-based single-material composite antibacterial film according to claim 4, wherein, in the preparation of the organically modified boron nitride nanoplatelets:
the average grain diameter of the nano hexagonal boron nitride is less than or equal to 1000nm;
the conditions of the high temperature calcination treatment include: the calcination temperature is 800-1000 ℃, the heating rate is 10-20 ℃/min, and the heat preservation time is 20-40min;
the dosage ratio of the nano hexagonal boron nitride after high-temperature calcination treatment to water to the first silane coupling agent is (1-2): (200-400): (1-2) g/mL/mL;
the time of primary ultrasonic dispersion is 30-60min;
adjusting the pH of the first dispersion to 4-5 with formic acid and/or acetic acid;
the first silane coupling agent is at least one of KH-540, KH-550, KH-560 and A-151;
the secondary ultrasonic dispersion time is 20-30min;
stirring for 0.8-1.2h under the water bath condition of 60-80 ℃;
the conditions for drying the precipitate include: the drying temperature is 100-140 ℃ and the drying time is 24-36h.
6. The barrier-type polyethylene-based single-material composite antibacterial film according to claim 1, wherein the organically modified nano-TiO 2 The preparation method of (2) comprises the following steps: mixing titanium dioxide, an organic solvent and a second silane coupling agent, and performing ultrasonic dispersion for one time to obtainTo a second dispersion; adjusting the pH of the second dispersion liquid to 4-5, sequentially performing secondary ultrasonic dispersion, stirring, centrifugation, supernatant removal, drying, precipitation and grinding to obtain the organic modified nano TiO 2 。
7. The barrier-type polyethylene-based single-material composite antibacterial film according to claim 6, wherein, in the organically modified nano-TiO 2 In the preparation of (2):
the average grain diameter of the titanium dioxide is less than or equal to 100nm; the organic solvent is ethanol water solution with the mass fraction of 45-55%; the second silane coupling agent is at least one of KH-540, KH-550, KH-560 and A-151;
the dosage ratio of the titanium dioxide to the organic solvent to the second silane coupling agent is (1-2): (200-400): (1-2) g/mL/mL;
the time of primary ultrasonic dispersion is 30-40min;
adjusting the pH of the second dispersion to 4-5 with formic acid and/or acetic acid;
the secondary ultrasonic dispersion time is 20-30min;
stirring for 0.8-1.2h under the water bath condition of 60-80 ℃;
the conditions for drying the precipitate include: the drying temperature is 100-140 ℃ and the drying time is 24-36h.
8. The barrier-type polyethylene-based single-material composite antibacterial film according to claim 1, wherein the thickness of the outer protective BOPE layer is 15-30 μm;
the outer protection BOPE layer is made of PE master batch through bi-directional stretching process molding, and the PE master batch is at least one of HDPE, LDPE and LLDPE.
9. The barrier-type polyethylene-based single-material composite antibacterial film according to claim 1, wherein the thickness of the adhesive layer is 3-6 μm;
the material of the bonding layer is a two-component solvent-free polyurethane adhesive and/or a solvent-type polyurethane adhesive.
10. The preparation method of the barrier type polyethylene-based single material composite antibacterial film as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps: and carrying out solvent-free compounding and/or dry compounding on the outer protective BOPE layer, the bonding layer and the inner functional layer to obtain the barrier type polyethylene single-material composite antibacterial film.
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