CN115782322B - Aluminum foil titanium-containing antibacterial packaging element and preparation method thereof - Google Patents
Aluminum foil titanium-containing antibacterial packaging element and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an aluminum foil titanium-containing antibacterial packaging element and a preparation method thereof; the titanium-containing antibacterial aluminum foil packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein the inner film layer comprises the following components in percentage by mass: 3.5 to 7.9 percent of nano titanium dioxide, 0.6 to 1.0 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the outer film layer comprises the following components in percentage by mass: 4.0-8.5% of nano silicon dioxide, 1.0-5.4% of composite antibacterial agent, 0.5-0.9% of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin used for the inner film layer and the outer film layer is modified polypropylene. The aluminum foil titanium-containing antibacterial packaging element provided by the invention has the advantages of high barrier property, high extensibility, heat aging resistance, corrosion resistance, high stability and long-acting antibacterial property, is simple in production process, and can be normally used at an environmental temperature of 220 ℃.
Description
Technical Field
The invention belongs to the technical field of packaging elements, and particularly relates to an aluminum foil titanium-containing antibacterial packaging element and a preparation method thereof.
Background
The aluminum foil paper is used as an industrial manufacturing raw and auxiliary material, and the product is mainly applied to packaging protection, articles for daily use, buildings and the like. The existing antibacterial aluminum foil applied to air-conditioning pipelines, heat exchangers and medicine packaging generally adopts an antibacterial coating coated on the surface of the aluminum foil to achieve the antibacterial effect, the antibacterial coating in the aluminum foil inevitably has hidden troubles of microbial pollution in the production and packaging processes, and the antibacterial coating has complicated working procedures in the production and low production efficiency. The aluminum-titanium foil is an all-metal foil with super-strong barrier property, can block bacteria, light, air and water vapor, is prepared by using aluminum and titanium elements through multiple rolling, processing and heat treatment processes, does not contain plasticizer, and has the antibacterial rate of more than 99%.
The patent with application number 202111150272.6 provides an efficient and low-cost antibacterial foil for food packaging and a preparation method thereof, and the antibacterial foil provided by the invention comprises the following components in percentage by mass: 0.05 to 0.15 percent of Si, 0.3 to 0.7 percent of Fe0.05 to 0.15 percent of Cu0.05 percent of Mn, less than or equal to 0.01 percent of Zn, less than or equal to 0.03 percent of Ti and the balance of Al, and the aluminum-based single-layer aluminum foil is prepared by the procedures of smelting, casting and rolling, rough rolling, homogenizing annealing, rough rolling, trimming, finish rolling, finished product annealing, slitting and the like. The multilayer barrier material is a mode for improving the barrier property, ductility, corrosion resistance and tear strength of an aluminum foil, a patent with the application number of 202010232234.4 provides a corrosion-resistant flexible packaging film and a processing technology thereof, the corrosion-resistant flexible packaging film comprises a nanoscale silicon dioxide layer from outside to inside, an aluminum foil layer, a polyurethane adhesive layer and a polypropylene layer, the patent coats nanoscale silicon dioxide on the surface of the aluminum foil layer, a compact protective layer can be formed, the corrosion resistance and the mechanical property of the aluminum foil are improved, the problems that the existing aluminum-plastic flexible packaging film is not corrosion-resistant and the leakage problem caused by poor corrosion resistance are solved, the protective layer also has excellent chemical resistance and moisture barrier property, but the nanoscale silicon dioxide layer is poor in wear resistance, the coating is easy to generate defects, the requirement on equipment is high during coating, the coverage of the aluminum foil is incomplete, the yield is guaranteed, and the polyurethane adhesive layer and the polypropylene layer in the corrosion-resistant flexible packaging film are both high molecular polymers, the heat resistance is poor, and the corrosion-resistant flexible packaging film is difficult to be normally used at the temperature of more than 180 ℃.
Therefore, the development of an aluminum foil titanium-containing antibacterial packaging element with high barrier property, high extensibility, high antibacterial rate, heat aging resistance, corrosion resistance and high stability is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an aluminum foil titanium-containing antibacterial packaging element which has excellent barrier property, extensibility, bacteriostasis, thermal aging resistance, corrosion resistance and high stability; the invention also discloses a preparation method of the titanium-containing antibacterial aluminum foil packaging element.
The technical scheme adopted by the invention for realizing the purpose is as follows:
an aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein the inner film layer comprises the following components in percentage by mass: 3.5 to 7.9 percent of nano titanium dioxide, 0.6 to 1.0 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the outer film layer comprises the following components in percentage by mass: 4.0-8.5% of nano silicon dioxide, 1.0-5.4% of composite antibacterial agent, 0.5-0.9% of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the polyolefin resin used in the inner film layer and the outer film layer is modified polypropylene, and the preparation method of the modified polypropylene comprises the following steps:
s1, sequentially adding polypropylene (PP), dibenzoyl peroxide (BPO) and 4-vinylphenylboronic acid into a mixed solution of xylene and acetone in a nitrogen atmosphere, stirring and mixing uniformly, continuing to stir at 95-105 ℃ for 3.0-4.5h, cooling to room temperature, performing solid-liquid separation, taking a solid, heating and dissolving the solid in the xylene, stirring and refluxing for 3-5h, cooling for 20-30min, adding acetone, shaking uniformly, standing for precipitation, filtering, taking filter residues, washing and drying to obtain PP-1;
s2, sequentially adding PP-1, tetramethyl dihydroxy disiloxane and xylene obtained in the step S1 into a reactor, heating to 110-120 ℃, stirring for 2-3h, cooling to room temperature, filtering, washing filter residues, and drying to obtain modified polypropylene;
the synthetic route of the modified polypropylene is as follows:
the invention takes polypropylene as a reaction raw material, takes dibenzoyl peroxide as a free radical initiator, and generates a free radical grafting reaction with 4-vinylphenylboronic acid in the presence of xylene and acetone to obtain PP-1, wherein the PP-1 contains phenylboronic acid, and the phenylboronic acid and diol in a tetramethyl dihydroxy disiloxane structure generate esterification and cyclization reactions to obtain the modified polypropylene.
In order to improve the free radical grafting rate and the esterification and cyclization reaction rates of polypropylene and ensure the consistency of products, the mass ratio of polypropylene, dibenzoyl peroxide and 4-vinylphenylboronic acid in the step S1 is 10.5-0.7, the volume ratio of xylene to acetone in a mixed solution of xylene and acetone is 2-3; in the step S2, the mass ratio of PP-1 to tetramethyl dihydroxy disiloxane is 10.4-0.6; washing in the step S1 is washing by using diethyl ether and acetone in sequence, washing in the step S2 is washing by using cyclohexane and acetone in sequence, and drying in the steps S1 and S2 is vacuum drying for 20-24h at 45-50 ℃.
In order to improve the ductility, the machinability and the antibacterial property of the aluminum foil layer, the aluminum foil layer comprises the following components in percentage by mass: 0.23 to 0.25 percent of silicon, 0.66 to 0.95 percent of iron, 3.3 to 6.1 percent of copper, 0.33 to 0.71 percent of manganese, 1.5 to 1.8 percent of magnesium, 0.04 to 0.11 percent of chromium, 0.15 to 0.30 percent of zinc, 0.10 to 0.22 percent of titanium and the balance of aluminum.
In order to ensure that all layers of the packaging element are combined more tightly and have better compatibility, bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers are made of silica gel bonding agents.
Furthermore, the thickness of the inner film layer is 40-60 μm, the thickness of the aluminum foil layer is 20-40 μm, the thickness of the adhesive layer is 10-15 μm, and the thickness of the outer film layer is 50-70 μm.
In order to improve the performance of the film materials of the inner film layer and the outer film layer and improve the water vapor and air barrier performance, the packaging element achieves the effect of synergistic antibacterial inside and outside, the particle size of the nano titanium dioxide is 20-30nm, and the particle size of the nano silicon dioxide is 15-25nm; the preparation method of the composite antibacterial agent comprises the following steps: heating deionized water to 70-90 deg.C, adding chitosan, preparing suspension, adding silver nitrate solution into the suspension, stirring for 20-30min, adding chitosan, stirring for 10-15min, cooling to room temperature, filtering, washing the residue, and drying; wherein the total amount of the chitosan added twice in the deionized water is 3-7g/L, and the mass ratio of the chitosan to the silver nitrate is 1.
The polyolefin resin of the invention selects modified polypropylene, and has good heat insulation, mechanical property, stress cracking resistance and cyclic regeneration property; the polypropylene is chemically modified, an aromatic ring structure which is difficult to move is introduced into the polypropylene structure, so that molecular movement can be inhibited, the heat resistance of the polypropylene material is improved, meanwhile, the polypropylene is subjected to free radical grafting modification, free radical reaction sites in a polypropylene molecular chain are occupied, and the aging resistance of the material is improved; the boron-containing siloxane is introduced into the polypropylene structure, and the synergistic effect of boron and silicon endows the polypropylene material with good thermal stability, oxidation resistance and mechanical properties, compatibility and adhesion with other materials, and synergistic effect with a silica gel adhesive, so that the bonding strength between layers is obviously enhanced, each layer is not easy to fall off, and further the composite strength and product stability of the packaging element are improved; the nano titanium dioxide and the nano silicon dioxide are added into the modified polypropylene, so that micropores on a polymer film material can be filled on a nano level, the barrier property of the material is improved, the enhancement and the toughening of a polypropylene matrix are realized, the mechanical property, the aging resistance, the thermal stability and the synergistic antibacterial property of the material are improved, the surface of the nano silicon dioxide is of a mesoporous structure, the super-strong adsorption capacity is realized, the release of an antibacterial agent in the film material can be slowed down, and the long-acting antibacterial property is endowed to the material; by compounding octadecylamine polyoxyethylene ether, the dispersibility and antistatic property of the material are improved.
The invention also provides a preparation method of the titanium-containing aluminum foil antibacterial packaging element, which is used for preparing the titanium-containing aluminum foil antibacterial packaging element and comprises the following steps: respectively bonding the inner film layer and the outer film layer on two sides of the aluminum foil layer, curing for 24-30h in a constant-temperature curing chamber at 50-55 ℃ after pressing, and rolling to obtain the titanium-containing aluminum foil antibacterial packaging element.
The invention has the following beneficial effects: according to the invention, polypropylene is chemically modified, and aromatic rings and boron-containing siloxane are introduced into the polypropylene structure, so that the heat resistance, aging resistance, stability and mechanical properties of the polypropylene material, as well as the compatibility and adhesiveness with other materials are improved; the modified polypropylene, the nano particles, the octadecylamine polyoxyethylene ether and the like are compounded to prepare an inner film layer and an outer film layer, and the inner film layer, the outer film layer and the aluminum foil layer are compounded, so that the corrosion resistance and the mechanical property of the aluminum foil layer are improved; the aluminum foil titanium-containing antibacterial packaging element provided by the invention has the advantages of high barrier property, high extensibility, heat aging resistance, corrosion resistance, high stability and long-acting antibacterial property, is simple in production process, and can be normally used at an ambient temperature of 220 ℃.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The raw materials used in the following examples and comparative examples are all common commercial products. Nanometer titanium dioxide, model Brofos-TiO2-J20, nanometer silicon dioxide, model Brofos-SiO2-15, all available from Bowss nanotechnology (Ningbo) Inc.; octadecylamine polyoxyethylene ether, model AC1812, available from full and informative biotechnology limited of wuhan; polypropylene, model B130F, available from new materials ltd, shanghai li; chitosan with 80 meshes, purchased from sierra bioengineering ltd; 4-vinyl phenylboronic acid CAS number 2156-04-9; tetramethyldydroxydisiloxane CAS number 1118-15-6.
Example 1
A preparation method of modified polypropylene comprises the following steps:
s1, sequentially adding a mixed solution of 5kg of polypropylene, 0.3kg of dibenzoyl peroxide, 0.4kg of 4-vinylphenylboronic acid, 200L of xylene and 100L of acetone into a reactor in a nitrogen atmosphere, stirring and mixing uniformly, then continuously stirring for 3h at 105 ℃, cooling to room temperature, carrying out solid-liquid separation, taking a solid, dissolving in 400L of xylene at 120 ℃, stirring and refluxing for 4h, cooling for 30min, adding 200L of acetone, shaking uniformly, standing for precipitation, filtering, taking filter residue, sequentially washing with diethyl ether and acetone, and carrying out vacuum drying for 24h at 45 ℃ to obtain PP-1;
s2, sequentially adding 4kg of PP-1 obtained in the step S1, 0.2kg of tetramethyl dihydroxy disiloxane and 240L of xylene into a reactor, heating to 110 ℃, stirring for 2h, cooling to room temperature, filtering, taking filter residue, sequentially washing with cyclohexane and acetone, and vacuum-drying at 45 ℃ for 24h to obtain modified polypropylene;
the synthetic route of the modified polypropylene is as follows:
example 2
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers adopt silica gel adhesives; the inner film layer comprises the following components in percentage by mass: 4.1 percent of nano titanium dioxide, 0.6 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.23% of silicon, 0.75% of iron, 4.4% of copper, 0.50% of manganese, 1.6% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.16% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 6.1 percent of nano silicon dioxide, 3.5 percent of composite antibacterial agent, 0.5 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin is the modified polypropylene prepared in example 1, the particle size of the nano titanium dioxide is 20nm, the particle size of the nano silicon dioxide is 15nm, the thickness of the inner membrane layer is 40 μm, the thickness of the aluminum foil layer is 22 μm, the thickness of the adhesive layer is 10 μm, and the thickness of the outer membrane layer is 50 μm; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan/silver nitrate composite material.
A method for preparing an aluminum foil titanium-containing antibacterial packaging element comprises the following steps:
a1, preparing an inner membrane layer: weighing nanometer titanium dioxide, octadecylamine polyoxyethylene ether and polyolefin resin according to weight percentage, adding into an extruder, melting and blending at 260 ℃, extruding into a T-shaped die head, casting onto the roll surface of a cooling roller with the temperature of 15 ℃ at the speed of 12m/min, controlling the film thickness to be 40 mu m, and cutting edges to obtain an inner film layer;
a2, preparing an outer membrane layer: weighing nano silicon dioxide, octadecylamine polyoxyethylene ether, a composite antibacterial agent and polyolefin resin according to weight percentage, adding into an extruder, melting and blending at 260 ℃, extruding into a T-shaped die head, casting to the roll surface of a cooling roller with the temperature of 15 ℃ at the speed of 12m/min, controlling the film thickness to be 50 mu m, and cutting edges to obtain an outer film layer;
a3, preparing an aluminum foil layer: preparing materials according to the mass percentage of each component of the aluminum foil layer, melting the materials, controlling the melting temperature to be 750 ℃ and the time to be 45min, pouring the materials into a standing furnace at 740 ℃ after melt refining treatment, standing and preserving the temperature for 15min, and obtaining a 6.8mm aluminum-titanium coil through cast rolling; rolling the aluminum-titanium coil by two passes until the rolling thickness is 2.5mm, carrying out first annealing, heating to 560 ℃, preserving heat for 24h, then cooling to 530 ℃, preserving heat for 3h, cooling to room temperature, and discharging; rolling the aluminum-titanium coil subjected to the first annealing for two passes until the rolling thickness is 0.57mm, performing second annealing, heating to 320 ℃, preserving heat for 3.5 hours, then cooling to 280 ℃, preserving heat for 0.5 hour, cooling to room temperature, and discharging; and rolling the aluminum-titanium coil subjected to the second annealing for one pass to reduce the rolling thickness to 0.26mm, shearing the aluminum-titanium coil under a rewinding device to produce the aluminum-titanium coil with the required width, rolling the aluminum-titanium coil by two passes to reduce the rolling thickness to 0.022mm, annealing the finished product (third annealing), heating to 220 ℃ and preserving heat for 15 hours, then cooling to 200 ℃ and preserving heat for 2 hours, cooling to room temperature, discharging from the furnace, and slitting to the width of the finished product to obtain the aluminum-titanium coil.
And A4, coating adhesive layers on the surfaces of the two sides of the aluminum foil layer, standing at room temperature for 5min, respectively adhering the inner film layer and the outer film layer to the two sides of the aluminum foil layer, pressing, curing at the pressure of 1.5MPa in a constant-temperature curing chamber at 50 ℃ for 24h, and rolling to obtain the titanium-containing aluminum foil antibacterial packaging element.
Example 3
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers adopt silica gel adhesives; the inner film layer comprises the following components in percentage by mass: 3.5 percent of nano titanium dioxide, 0.6 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.24% of silicon, 0.75% of iron, 5.0% of copper, 0.50% of manganese, 1.6% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.16% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 4.0 percent of nano silicon dioxide, 3.5 percent of composite antibacterial agent, 0.5 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin is the modified polypropylene prepared in example 1, the particle size of the nano titanium dioxide is 20nm, the particle size of the nano silicon dioxide is 15nm, the thickness of the inner membrane layer is 40 μm, the thickness of the aluminum foil layer is 22 μm, the thickness of the adhesive layer is 10 μm, and the thickness of the outer membrane layer is 50 μm; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan nano-particles.
Example 4
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers are made of silica gel bonding agents; the inner film layer comprises the following components in percentage by mass: 4.5 percent of nano titanium dioxide, 0.7 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.25% of silicon, 0.75% of iron, 4.4% of copper, 0.60% of manganese, 1.6% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.16% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 5.0 percent of nano silicon dioxide, 3.5 percent of composite antibacterial agent, 0.6 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin is the modified polypropylene prepared in the embodiment 1, the particle size of the nano titanium dioxide is 20nm, the particle size of the nano silicon dioxide is 15nm, the thickness of the inner membrane layer is 40 μm, the thickness of the aluminum foil layer is 22 μm, the thickness of the adhesive layer is 10 μm, and the thickness of the outer membrane layer is 50 μm; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan nano-particles.
Example 5
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers adopt silica gel adhesives; the inner film layer comprises the following components in percentage by mass: 5.5 percent of nano titanium dioxide, 0.8 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.23% of silicon, 0.70% of iron, 4.4% of copper, 0.60% of manganese, 1.5% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.16% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 7.0 percent of nano silicon dioxide, 2.0 percent of composite antibacterial agent, 0.7 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin is the modified polypropylene prepared in example 1, the particle size of the nano titanium dioxide is 20nm, the particle size of the nano silicon dioxide is 15nm, the thickness of the inner membrane layer is 40 μm, the thickness of the aluminum foil layer is 22 μm, the thickness of the adhesive layer is 10 μm, and the thickness of the outer membrane layer is 50 μm; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan nano-particles.
Example 6
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers adopt silica gel adhesives; the inner film layer comprises the following components in percentage by mass: 5.5 percent of nano titanium dioxide, 1.0 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.23% of silicon, 0.85% of iron, 6.0% of copper, 0.50% of manganese, 1.6% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.20% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 8.0 percent of nano silicon dioxide, 5.0 percent of composite antibacterial agent, 0.8 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin is the modified polypropylene prepared in the embodiment 1, the particle size of the nano titanium dioxide is 20nm, the particle size of the nano silicon dioxide is 15nm, the thickness of the inner membrane layer is 40 μm, the thickness of the aluminum foil layer is 22 μm, the thickness of the adhesive layer is 10 μm, and the thickness of the outer membrane layer is 50 μm; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan nano-particles.
Comparative example 1
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers adopt silica gel adhesives; the inner film layer comprises the following components in percentage by mass: 0.6 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.23% of silicon, 0.75% of iron, 4.4% of copper, 0.50% of manganese, 1.6% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.16% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 3.5 percent of composite antibacterial agent, 0.5 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; wherein the polyolefin resin is the modified polypropylene prepared in example 1, the thickness of the aluminum foil layer is 22 μm, the thickness of the adhesive layer is 10 μm, and the thickness of the outer film layer is 50 μm; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan nano-particles.
Compared with example 2, comparative example 1 is different from the case where nano titania is not added to the inner film layer and nano silica is not added to the outer film layer.
Comparative example 2
An aluminum foil titanium-containing antibacterial packaging element comprises an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein bonding layers are arranged between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, and the bonding layers adopt silica gel adhesives; the inner film layer comprises the following components in percentage by mass: 4.1% of nano titanium dioxide, 0.6% of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the aluminum foil layer comprises the following components in percentage by mass: 0.23% of silicon, 0.75% of iron, 4.4% of copper, 0.50% of manganese, 1.6% of magnesium, 0.07% of chromium, 0.24% of zinc, 0.16% of titanium and the balance of aluminum; the outer film layer comprises the following components in percentage by mass: 6.1% of nano silicon dioxide, 3.5% of composite antibacterial agent, 0.5% of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the polyolefin resin is polypropylene, the particle size of the nano titanium dioxide is 20nm, the particle size of the nano silicon dioxide is 15nm, the thickness of the inner membrane layer is 40 mu m, the thickness of the aluminum foil layer is 22 mu m, the thickness of the bonding layer is 10 mu m, and the thickness of the outer membrane layer is 50 mu m; the preparation method of the composite antibacterial agent comprises the following steps: heating 100L of deionized water to 90 ℃, adding 300g of chitosan to prepare a suspension, adding 7.4L of 0.1mol/L silver nitrate solution into the suspension, stirring for 30min, adding 200g of chitosan, continuing stirring for 10min, cooling to room temperature, filtering, taking filter residue, washing with deionized water for 3 times, and vacuum-drying at 60 ℃ for 20h to obtain the chitosan nano-particles.
The difference of comparative example 1 compared to example 2 is that the polyolefin resin added to the inner and outer film layers is polypropylene.
The titanium-containing aluminum foil antibacterial packaging members described in examples 3-6 and comparative examples 1-2 were prepared according to the process described in example 2.
Comparative example 3
An aluminum foil titanium-containing antibacterial packaging element sold in domestic markets is purchased from plastic packaging Limited company in Jiangyin City.
Test example 1
The aluminum foil titanium-containing antibacterial packaging elements prepared in the examples 2 to 6 and the comparative examples 1 to 3 were subjected to related performance tests, and the water vapor transmission amount was tested according to GB/T1037-1988 cup-type test method for testing the water vapor permeability of plastic films and sheets; the oxygen permeability is tested according to GB/T19789-2005 coulometer detection method for oxygen permeability test of packaging material plastic films and sheets; elongation testing was carried out according to GB/T15821-1995, method for measuring ductility of a metal coating; the temperature of the heat aging resistance test box is (220 +/-5) DEG C, and a sample is placed in the test box for 72h and does not deform or become brittle; carrying out corrosion resistance test according to GB1763-1979 method for measuring chemical reagent resistance of paint film; performing an antibacterial test according to QB/T2591-2003, namely an antibacterial performance test method and an antibacterial effect of antibacterial plastic, and cutting a sample into 1 cm by 10cm sample pieces, wherein the environmental temperature is 25.0 ℃ and the humidity is 51%; the results of the experiment are shown in table 1.
TABLE 1 test results of performance of titanium-containing aluminum foil antibacterial packaging element
As can be seen from the results in Table 1, the aluminum foil titanium-containing antibacterial packaging members prepared in examples 2-6 have water vapor barrier properties, oxygen barrier properties, salt spray resistance, salt water resistance, thermal aging resistance, extensibility and antibacterial properties that are significantly better than those of comparative examples 1-3, wherein the aluminum foil titanium-containing antibacterial packaging member prepared in example 2 has the best overall performance; from examples 2-6, it can be seen that the percentage of polyolefin resin, nano titanium dioxide, nano silicon dioxide, iron, silicon, copper, manganese, magnesium, titanium in the inner film layer, aluminum foil layer, and outer film layer materials can all affect the performance of the packaging element; compared with the comparative examples 1-3, the compound of polypropylene, nano particles, octadecylamine polyoxyethylene ether and the like has an unobvious effect on improving the performance of the aluminum foil titanium-containing antibacterial packaging element, the polypropylene is subjected to chemical modification, aromatic rings and boron-containing siloxane are introduced into the polypropylene structure, and the polypropylene structure is compounded with the nano particles, octadecylamine polyoxyethylene ether and the like, so that the barrier property, the corrosion resistance, the heat aging resistance, the extensibility and the antibacterial performance of the packaging element can be obviously improved.
The polyolefin resin of the invention selects modified polypropylene, and has good heat insulation, mechanical property, stress cracking resistance and cyclic regeneration property; the polypropylene is chemically modified, and aromatic rings and boron-containing siloxane are introduced into the polypropylene structure, so that the heat resistance, aging resistance, stability and mechanical properties of the polypropylene material, as well as the compatibility and adhesiveness with other materials are improved; the modified polypropylene is compounded with nano particles, octadecylamine polyoxyethylene ether and the like to prepare an inner film layer and an outer film layer, and the inner film layer, the outer film layer and the aluminum foil layer are compounded, so that the corrosion resistance and the mechanical property of the aluminum foil layer are improved; the aluminum foil titanium-containing antibacterial packaging element provided by the invention has the advantages of high barrier property, high extensibility, high antibacterial rate, heat aging resistance, corrosion resistance and high stability, is simple in production process, and can be normally used at an ambient temperature of 220 ℃.
Although embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The titanium-containing antibacterial aluminum foil packaging element is characterized by comprising an inner film layer, an aluminum foil layer and an outer film layer from inside to outside, wherein the inner film layer comprises the following components in percentage by mass: 3.5 to 7.9 percent of nano titanium dioxide, 0.6 to 1.0 percent of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the outer film layer comprises the following components in percentage by mass: 4.0-8.5% of nano silicon dioxide, 1.0-5.4% of composite antibacterial agent, 0.5-0.9% of octadecylamine polyoxyethylene ether and the balance of polyolefin resin; the polyolefin resin used in the inner film layer and the outer film layer is modified polypropylene, and the preparation method of the modified polypropylene comprises the following steps:
s1, sequentially adding polypropylene, dibenzoyl peroxide and 4-vinylphenylboronic acid into a mixed solution of dimethylbenzene and acetone in a nitrogen atmosphere, stirring and mixing uniformly, continuing stirring at 95-105 ℃ for 3.0-4.5h, cooling to room temperature, carrying out solid-liquid separation, heating and dissolving a solid in dimethylbenzene, stirring and refluxing for 3-5h, cooling for 20-30min, adding acetone, shaking uniformly, standing for precipitation, filtering, washing filter residues, and drying to obtain PP-1, wherein the structural formula of the PP-1 is as follows:
s2, sequentially adding PP-1, tetramethyl dihydroxy disiloxane and xylene obtained in the step S1 into a reactor, heating to 110-120 ℃, stirring for 2-3h, cooling to room temperature, filtering, washing filter residues, and drying to obtain modified polypropylene, wherein the structural formula of the modified polypropylene is as follows:
2. the titanium-containing antibacterial packaging element for aluminum foil as recited in claim 1, wherein the mass ratio of polypropylene, dibenzoyl peroxide to 4-vinylphenylboronic acid in step S1 is 10.5 to 0.7, the volume ratio of xylene to acetone in the mixed solution of xylene and acetone is 2 to 3.
3. The aluminum foil titanium-containing antibacterial packaging element as claimed in claim 1, wherein the mass ratio of PP-1 to tetramethyldihydroxydisiloxane in step S2 is 10.4-0.6.
4. The aluminum foil titanium-containing antibacterial packaging element as claimed in claim 1, wherein the washing in step S1 is washing with diethyl ether and acetone in sequence, the washing in step S2 is washing with cyclohexane and acetone in sequence, and the drying in steps S1 and S2 is vacuum drying at 45-50 ℃ for 20-24h.
5. The aluminum foil titanium-containing antimicrobial packaging element of claim 1 wherein the aluminum foil layer comprises the following components in mass percent: 0.23 to 0.25 percent of silicon, 0.66 to 0.95 percent of iron, 3.3 to 6.1 percent of copper, 0.33 to 0.71 percent of manganese, 1.5 to 1.8 percent of magnesium, 0.04 to 0.11 percent of chromium, 0.15 to 0.30 percent of zinc, 0.10 to 0.22 percent of titanium and the balance of aluminum.
6. The aluminum foil titanium-containing antimicrobial packaging component of claim 1 wherein an adhesive layer is disposed between the inner film layer and the aluminum foil layer and between the aluminum foil layer and the outer film layer, wherein the adhesive layer is a silicone adhesive.
7. The titanium-containing aluminum foil antibacterial packaging element as claimed in claim 6, wherein the thickness of the inner film layer is 40-60 μm, the thickness of the aluminum foil layer is 20-40 μm, the thickness of the adhesive layer is 10-15 μm, and the thickness of the outer film layer is 50-70 μm.
8. The aluminum foil titanium-containing antibacterial packaging element as claimed in claim 1, wherein the nano titanium dioxide has a particle size of 20-30nm, and the nano silicon dioxide has a particle size of 15-25nm; the preparation method of the composite antibacterial agent comprises the following steps: heating deionized water to 70-90 deg.C, adding chitosan, preparing suspension, adding silver nitrate solution into the suspension, stirring for 20-30min, adding chitosan, stirring for 10-15min, cooling to room temperature, filtering, washing the residue, and drying.
9. The aluminum foil titanium-containing antibacterial packaging element as claimed in claim 8, wherein the total amount of chitosan added twice in deionized water is 3-7g/L, and the mass ratio of chitosan to silver nitrate is 1.
10. A method for preparing an aluminum foil titanium-containing antibacterial packaging element, which is used for preparing the aluminum foil titanium-containing antibacterial packaging element as claimed in any one of claims 1 to 9, and comprises the following steps: respectively bonding the inner film layer and the outer film layer on two sides of the aluminum foil layer, curing for 24-30h in a constant-temperature curing chamber at 50-55 ℃ after pressing, and rolling to obtain the titanium-containing aluminum foil antibacterial packaging element.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2915543A (en) * | 1957-09-24 | 1959-12-01 | American Cyanamid Co | Preparation of compounds containing silicon and boron |
| CN106626590A (en) * | 2016-12-07 | 2017-05-10 | 滁州瑞林包装材料有限公司 | Compression-resistance anti-bacteria pharmaceutical packaging composite film |
| CN107298737A (en) * | 2017-06-20 | 2017-10-27 | 西南科技大学 | A kind of polyacrylic preparation method of Three-Dimensional Dynamic |
| CN107474184A (en) * | 2017-07-12 | 2017-12-15 | 浙江大学 | A kind of phenyl boric acid based aquagel and preparation method thereof |
| CN110204732A (en) * | 2019-06-25 | 2019-09-06 | 荆州市江汉精细化工有限公司 | A kind of preparation method of boracic silane coupling agent copolymer |
| CN110343327A (en) * | 2019-07-19 | 2019-10-18 | 泉州师范学院 | A kind of chitosan loaded nanometer silver antimicrobial polypropylene material and preparation method thereof |
| CN111331967A (en) * | 2020-03-27 | 2020-06-26 | 安徽捷诚包装制品有限公司 | Corrosion-resistant flexible packaging film and processing technology thereof |
| CN213733838U (en) * | 2020-08-26 | 2021-07-20 | 上海春宜药品包装材料有限公司 | Environment-friendly composite film for packaging aluminum-polypropylene medicines and foods |
| CN113292671A (en) * | 2021-07-08 | 2021-08-24 | 南方科技大学 | Polymer crosslinking agent containing phenylboronic acid group, biological adhesive prepared from polymer crosslinking agent, and preparation method and application of biological adhesive |
| CN114058108A (en) * | 2021-11-30 | 2022-02-18 | 泛海海工(山东)智能装备有限公司 | Long-acting broad-spectrum antibacterial polyethylene material and preparation method thereof |
| CN114874397A (en) * | 2022-05-12 | 2022-08-09 | 安徽大学 | Method for toughening polylactic acid based on reversible covalent crosslinking |
| CN115353775A (en) * | 2022-10-19 | 2022-11-18 | 广东骊虹新材料有限公司 | High-barrier high-strength composite packaging film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2381749A (en) * | 2001-11-08 | 2003-05-14 | Alan John Taylor | Powders having contact biocidal properties comprising a polymer and silver |
| US6767981B1 (en) * | 2002-09-26 | 2004-07-27 | The United States Of America As Represented By The Secretary Of The Navy | Thermoset and ceramic containing silicon and boron |
| FR3040172B1 (en) * | 2015-08-20 | 2020-01-24 | Ecole Superieure De Physique Et De Chimie Industrielles De La Ville De Paris | POLYMER COMPOSITIONS COMPRISING CROSSLINKED POLYMERS COMPRISING BORONIC ESTER FUNCTIONS, ALLOWING EXCHANGE REACTIONS, METHOD OF PREPARATION AND USE |
-
2023
- 2023-02-06 CN CN202310066007.2A patent/CN115782322B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2915543A (en) * | 1957-09-24 | 1959-12-01 | American Cyanamid Co | Preparation of compounds containing silicon and boron |
| CN106626590A (en) * | 2016-12-07 | 2017-05-10 | 滁州瑞林包装材料有限公司 | Compression-resistance anti-bacteria pharmaceutical packaging composite film |
| CN107298737A (en) * | 2017-06-20 | 2017-10-27 | 西南科技大学 | A kind of polyacrylic preparation method of Three-Dimensional Dynamic |
| CN107474184A (en) * | 2017-07-12 | 2017-12-15 | 浙江大学 | A kind of phenyl boric acid based aquagel and preparation method thereof |
| CN110204732A (en) * | 2019-06-25 | 2019-09-06 | 荆州市江汉精细化工有限公司 | A kind of preparation method of boracic silane coupling agent copolymer |
| CN110343327A (en) * | 2019-07-19 | 2019-10-18 | 泉州师范学院 | A kind of chitosan loaded nanometer silver antimicrobial polypropylene material and preparation method thereof |
| CN111331967A (en) * | 2020-03-27 | 2020-06-26 | 安徽捷诚包装制品有限公司 | Corrosion-resistant flexible packaging film and processing technology thereof |
| CN213733838U (en) * | 2020-08-26 | 2021-07-20 | 上海春宜药品包装材料有限公司 | Environment-friendly composite film for packaging aluminum-polypropylene medicines and foods |
| CN113292671A (en) * | 2021-07-08 | 2021-08-24 | 南方科技大学 | Polymer crosslinking agent containing phenylboronic acid group, biological adhesive prepared from polymer crosslinking agent, and preparation method and application of biological adhesive |
| CN114058108A (en) * | 2021-11-30 | 2022-02-18 | 泛海海工(山东)智能装备有限公司 | Long-acting broad-spectrum antibacterial polyethylene material and preparation method thereof |
| CN114874397A (en) * | 2022-05-12 | 2022-08-09 | 安徽大学 | Method for toughening polylactic acid based on reversible covalent crosslinking |
| CN115353775A (en) * | 2022-10-19 | 2022-11-18 | 广东骊虹新材料有限公司 | High-barrier high-strength composite packaging film and preparation method thereof |
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