CN111284049A - Graphene antibacterial modified plastic film for medicine packaging and preparation method thereof - Google Patents
Graphene antibacterial modified plastic film for medicine packaging and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention belongs to the technical field of plastic film preparation, and particularly relates to a graphene antibacterial modified plastic film for medicine packaging and a preparation method thereof, wherein graphene oxide and chitosan are firstly added and blended to generate radical reaction for tight combination, so that the uniform dispersion of the graphene oxide is promoted, and the barrier property of a medicinal packaging film is obviously improved; further, the silver zeolite antibacterial agent is dispersed in the film and has a synergistic effect with chitosan and graphene with a natural antibacterial effect, so that the antibacterial performance of the medicinal packaging film is greatly improved, the used materials are safe and nontoxic, and the safety of the medicinal packaging film is improved.
Description
Technical Field
The invention belongs to the technical field of plastic film preparation, and particularly relates to a graphene antibacterial modified plastic film for medicine packaging and a preparation method thereof.
Background
The medicinal packaging film is used for packaging medicines as the name implies, and the medicines have the following requirements on flexible packaging film materials: the main measures of preventing the deterioration of the contents are moisture resistance, air resistance, light resistance, sterility and sealing; in order to ensure the quality of the contents and the safety of the processes of filling, packaging, storing and transporting, the packaging material is required to have the sanitary performance of ensuring the stability and heat resistance of the contents and not generating harmful substance migration; the material is required to have certain sanitary performances such as stretching resistance, impact resistance, puncture resistance, tearing strength and the like. The plastic composite film package of Chinese and Western medicine granule, powder, capsule, etc. mainly comprises LDPE film, PP film, CPP film, PET film, PVDC film, vacuum aluminized film, CTFE film and multilayer medical package film. The disposable medicine packaging bag widely adopted at present is a PVC polyvinyl chloride film which has low price but has a plurality of defects, and the monomer vinyl chloride has toxicity; the other cold-stamping aluminum composite material is a novel medicine packaging material put on the market in recent years, the performance can be achieved, in terms of barrier property, an aluminum-containing composite film with high barrier property is preferentially selected as the medicine packaging material, the aluminum-plated composite film is inferior, the barrier property of a plastic composite film is poor, but the price cost is higher, and the existing materials cannot meet the requirements at present. In addition, most of the existing medicinal packaging films do not have an antibacterial function, so that the outer surfaces of the medicinal packaging films are inevitably infected with bacteria when the medicinal packaging films are used, and the safety of the medicinal packaging films is reduced.
The Chinese patent application No. 201710992274.7 discloses a graphene heat-conducting film and a preparation method thereof, wherein the graphene heat-conducting film comprises a PET (polyethylene terephthalate) film, a PI (polyimide) plastic film and an inner heat-conducting layer, the inner heat-conducting layer comprises heat-conducting wires, graphene placing positions and graphene, the graphene is located inside the graphene placing positions, the heat-conducting wires are arranged among intervals among the plurality of graphene placing positions, and the heat-conducting wires are in a curved arrangement mode. The graphene heat-conducting film and the preparation method thereof have the advantages of simple process, convenience in operation, stable quality of the obtained product, good effect and suitability for popularization and application; the heat conduction effect is better than single-layer and double-layer graphite films, and the graphene heat conduction film has flexibility, can be curled for storage, is convenient to use, has good heat conduction effect and can be widely applied to equipment such as notebook computers, mobile phones, televisions, cameras, LED lamps and automobile radiating fins.
The Chinese patent application number 201711116170.6 discloses a preparation method of a graphene multilayer co-extrusion plastic film, which comprises the following steps: A. manufacturing a base layer; B. manufacturing an inner liner; C. manufacturing an outer lining layer; D. manufacturing a surface layer; E. and D, conveying the mixtures prepared in the steps A-D to a blow molding die head through an extruder respectively, and preparing the graphene multilayer co-extrusion plastic film by using a blow molding process. The invention can improve the defects of the prior art and improve the performance of the multilayer plastic film.
The Chinese patent application No. 201610229870.5 discloses a high-wear-resistance cloth-plastic composite packaging bag, which comprises the following components in sequence from inside to outside: the plastic inner layer, the bonding layer and the cloth cover layer; wherein, the cloth surface layer is a nylon fiber braided layer, and the surface of the cloth surface layer is also coated with a printing film layer. The high-wear-resistance cloth-plastic composite packaging bag is simple in structure and reasonable in design, the plastic layer is used as the inner layer, the nylon fiber woven layer is used as the cloth layer and the outer layer, and the plastic film layer is coated and printed on the outer surface of the cloth layer; on the other hand, the plastic inner layer and the plastic film cloth layer are very convenient to clean after the packaging bag is dirty. The cloth plastic packaging bag has the advantages of high structural strength, good wear resistance, easy cleaning and long service life, can effectively reduce the waste rate of the plastic packaging bag, prolongs the service life of the plastic packaging bag, and has important practical significance for energy conservation and emission reduction.
Disclosure of Invention
Aiming at the defect that the existing medicinal packaging plastic film is poor in antibacterial performance and barrier performance, the invention provides the graphene antibacterial modified plastic film for medicine packaging and the preparation method thereof, so that the barrier performance and antibacterial performance of the medicinal packaging film are obviously improved, and the safety of the medicinal packaging film is improved.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a graphene antibacterial modified plastic film for medicine packaging comprises the steps of adding a graphene oxide dispersion liquid and a silver-series zeolite antibacterial agent into a chitosan acetic acid solution, carrying out solution blending, enabling a chitosan surface group and a graphene oxide surface group to react and be tightly combined, adding a prolamin solution containing a plasticizer, mixing, carrying out ultrasonic dispersion and stirring for 30-90min to obtain a mixed film forming liquid, adding a reducing agent to reduce graphene oxide, filling the mixed film forming liquid into a spray bottle, uniformly spraying the film forming liquid on a flat plate under high pressure, drying at low temperature and low pressure, and demoulding to obtain a chitosan-prolamin base film containing graphene and the silver-series zeolite antibacterial agent; evenly coat the binder with the glue spreader in the rubberizing equipment with the base film in packing base film both sides surface, rethread composite compression roller will coat the packing base film and glue with other membrane lamination and form the complex film, wherein the upper surface is pressed and is glued the printable polypropylene layer, and the lower surface is pressed and is glued the heat-seal layer, and the medicine packaging complex film that obtains three layer construction at last solidifies, specifically includes following step:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer, mixing, dispersing, and stirring to obtain a mixed membrane solution;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent;
s3, coating an adhesive on the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer.
Further, the preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the step of S1, wherein the mass ratio of the chitosan acetic acid solution, the graphene oxide dispersion liquid, the silver zeolite antibacterial agent and the alcohol soluble protein solution containing the plasticizer is 25-40: 10-20: 6-10: 0.5-2.
Prolamins are one of the components of plant seed storage proteins, and are found in seeds of plants such as wheat and corn; the alcohol soluble protein has strong water resistance, heat resistance and fat resistance, and is widely used in the industries of food, medicine, textile, paper making and the like; prolamins can also be used to produce biologically active peptides by enzymatic methods, and these peptides can be used in pharmaceuticals.
Further, in the preparation method of the graphene antibacterial modified plastic film for medicine packaging, in the step S1, the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 1-5%, and the plasticizer is at least one of oleic acid, stearic acid and polyethylene glycol.
Further, in the preparation method of the graphene antibacterial modified plastic film for medicine packaging, the dispersion in the step S1 is ultrasonic dispersion; the stirring speed is 350-550 r/min, and the stirring time is 30-90 min.
Further, in the preparation method of the graphene antibacterial modified plastic film for medicine packaging, the reducing agent in the step S2 is at least one of sodium borohydride, hydrazine hydrate and lithium aluminum hydride.
Further, the preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the step of S2, wherein the spraying pressure is 6-15 MPa.
Further, the preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the step of drying at low temperature and low pressure in the step of S2, wherein the temperature of drying at low temperature and low pressure is 10-20 ℃, and the pressure is 0.1-0.5 MPa.
Further, the preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the step of S3, wherein the binder is prepared from ethyl acetate, polyester polyol and isocyanate according to a volume ratio of 42-55: 35-45: 6-9.
Further, in the preparation method of the graphene antibacterial modified plastic film for medicine packaging, in the step S3, the adhesive is uniformly coated on the surfaces of the two sides of the packaging base film through the glue spreader in the gluing device.
The invention also provides the graphene antibacterial modified plastic film for medicine packaging, which is prepared by the preparation method. The antibacterial plastic is a plastic which plays a role in inhibiting or killing bacteria, mold, alcogen, algae, even viruses and the like stained on the plastic in a use environment, and keeps the plastic clean by inhibiting the propagation of microorganisms. Currently, antibacterial plastics are mainly obtained by adding a small amount of an antibacterial agent to ordinary plastics.
Related studies indicate that graphene materials have an antibacterial effect, wherein graphene oxide can destroy cell membranes of bacteria, cause outflow of intracellular substances and kill the bacteria.
According to the graphene antibacterial modified plastic film for medicine packaging, graphene oxide and chitosan are added firstly and blended to generate radical reaction and be tightly combined, so that the uniform dispersion of the graphene oxide is promoted, and the barrier property of the medicinal packaging film is remarkably improved; further, the silver zeolite antibacterial agent is dispersed in the film and has a synergistic effect with chitosan and graphene with a natural antibacterial effect, so that the antibacterial performance of the medicinal packaging film is greatly improved, the used materials are safe and nontoxic, and the safety of the medicinal packaging film is improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
The preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer to mix, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution to the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the alcohol soluble protein solution containing the plasticizer is 30:15:8: 1; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 3%, and the plasticizer is oleic acid; the stirring speed is 450r/min, and the stirring time is 60 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent; the reducing agent is hydrazine hydrate; the spraying pressure is 10 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 15 ℃, and the pressure is 0.3 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 50:40: 8.
Example 2
The preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer to mix, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution to the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the prolamin solution containing the plasticizer is 40:12:9: 0.8; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 5%, and the plasticizer is polyethylene glycol; the stirring speed is 550r/min, and the stirring time is 30 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent; the reducing agent is at least one of sodium borohydride, hydrazine hydrate and lithium aluminum hydride; the spraying pressure is 12 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 18 ℃, and the pressure is 0.5 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 45:35: 9.
Example 3
The preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer to mix, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution to the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the prolamin solution containing the plasticizer is 25:20:6: 1.5; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 1.5%, and the plasticizer is stearic acid; the stirring speed is 380r/min, and the stirring time is 45 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent; the reducing agent is lithium aluminum hydride; the spraying pressure is 6 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 10 ℃, and the pressure is 0.5 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 55:38: 7.
Example 4
The preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer to mix, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution to the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the alcohol soluble protein solution containing the plasticizer is 35:16:8: 2; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 3%, and the plasticizer is stearic acid; the stirring speed is 350r/min, and the stirring time is 90 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent; the reducing agent is sodium borohydride; the spraying pressure is 13 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 17 ℃, and the pressure is 0.2 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 45:42: 7.
Example 5
The preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer to mix, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution to the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the alcohol soluble protein solution containing the plasticizer is 40:16:10: 1; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 2.5 percent, and the plasticizer is polyethylene glycol; the stirring speed is 500r/min, and the stirring time is 50 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent; the reducing agent is hydrazine hydrate; the spraying pressure is 8 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 13 ℃, and the pressure is 0.2 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 48:36: 9.
Example 6
The preparation method of the graphene antibacterial modified plastic film for medicine packaging comprises the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer to mix, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution to the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the alcohol soluble protein solution containing the plasticizer is 30:15:8: 2; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 1%, and the plasticizer is oleic acid; the stirring speed is 480r/min, and the stirring time is 80 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent; the reducing agent is lithium aluminum hydride; the spraying pressure is 13 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 17 ℃, and the pressure is 0.4 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 44:42: 8.
Comparative example 1
The preparation method of the modified plastic film for medicine packaging comprises the following steps:
s1, adding a silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring, adding a prolamin solution containing a plasticizer, mixing, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the chitosan acetic acid solution silver zeolite antibacterial agent to the alcohol soluble protein solution containing the plasticizer is 30:8: 1; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 3%, and the plasticizer is oleic acid; the stirring speed is 450r/min, and the stirring time is 60 min;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing the membrane to obtain the chitosan-alcohol soluble protein basement membrane containing the silver zeolite antibacterial agent; the reducing agent is hydrazine hydrate; the spraying pressure is 10 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 15 ℃, and the pressure is 0.3 MPa;
s3, uniformly coating adhesives on the surfaces of the two sides of the chitosan-alcohol soluble protein base film containing the silver-based zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 50:40: 8.
Comparative example 2
The preparation method of the modified plastic film for medicine packaging comprises the following steps:
s1, stirring the graphene oxide dispersion liquid and the silver zeolite antibacterial agent, adding a prolamin solution containing a plasticizer, mixing, performing ultrasonic dispersion, and stirring to obtain a mixed membrane solution; wherein the mass ratio of the graphene oxide dispersion liquid to the silver zeolite antibacterial agent to the alcohol soluble protein solution containing the plasticizer is 15:8: 1; the mass concentration of the plasticizer in the prolamin solution containing the plasticizer is 3%, and the plasticizer is oleic acid; the stirring speed is 450r/min, and the stirring time is 60 min;
s2, filling the mixed membrane liquid obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and demoulding to obtain a prolamin base membrane containing graphene and a silver-series zeolite antibacterial agent; the reducing agent is hydrazine hydrate; the spraying pressure is 10 MPa; drying at low temperature and low pressure, wherein the temperature of the low-temperature low-pressure drying is 15 ℃, and the pressure is 0.3 MPa;
s3, uniformly coating adhesives on the surfaces of two sides of the prolamin base film containing the graphene and silver-series zeolite antibacterial agent obtained in the step S2 through a glue spreader in gluing equipment, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer; the adhesive is prepared from ethyl acetate, polyester polyol and isocyanate according to the volume ratio of 50:40: 8.
The graphene antibacterial modified plastic films for medicine packaging prepared in examples 1 to 6 and the modified plastic films for medicine packaging obtained in comparative examples 1 and 2 were used for antibacterial property tests with escherichia coli as an experimental object, the minimum inhibitory concentration (MIC value) of the antibacterial film for escherichia coli was tested, the measurement temperature was 37 ℃, the culture time was 24 hours, a blank film was used as a control, and the minimum inhibitory concentration of the antibacterial agent was measured with a film without a growth tube, and the test results were as follows.
TABLE 1
Claims (10)
1. A preparation method of a graphene antibacterial modified plastic film for medicine packaging is characterized by comprising the following steps:
s1, adding the graphene oxide dispersion liquid and the silver zeolite antibacterial agent into the chitosan acetic acid solution, stirring to enable the surface groups of the chitosan and the graphene oxide to react and be tightly combined, adding the alcohol soluble protein solution containing the plasticizer, mixing, dispersing, and stirring to obtain a mixed membrane solution;
s2, filling the mixed membrane solution obtained in the step S1 into a spray bottle, adding a reducing agent to reduce graphene oxide, uniformly spraying the reduced membrane forming solution on a flat plate, drying, and removing a membrane to obtain a chitosan-prolamin base membrane containing graphene and a silver zeolite antibacterial agent;
s3, coating an adhesive on the chitosan-alcohol soluble protein base film containing the graphene and silver zeolite antibacterial agent obtained in the step S2, laminating and adhering the coated packaging base film with an upper surface film layer and a lower surface film layer through a composite pressing roller to form a composite film, and finally curing to obtain a three-layer-structure medicine packaging composite film; the upper surface film layer is a printable polypropylene layer, and the lower surface film layer is a heat sealing layer.
2. The method for preparing the graphene antibacterial modified plastic film for medicine packaging according to claim 1, wherein the mass ratio of the chitosan acetic acid solution, the graphene oxide dispersion liquid, the silver-based zeolite antibacterial agent and the plasticizer-containing prolamin solution in the step S1 is 25-40: 10-20: 6-10: 0.5-2.
3. The method for preparing the graphene antibacterial modified plastic film for pharmaceutical packaging according to claim 1, wherein the mass concentration of the plasticizer in the prolamin solution containing the plasticizer in the step S1 is 1-5%, and the plasticizer is at least one of oleic acid, stearic acid and polyethylene glycol.
4. The method for preparing the graphene antibacterial modified plastic film for pharmaceutical packaging according to claim 1, wherein the dispersion in the step S1 is ultrasonic dispersion; the stirring speed is 350-550 r/min, and the stirring time is 30-90 min.
5. The method for preparing a graphene antibacterial modified plastic film for pharmaceutical packaging according to claim 1, wherein the reducing agent in the step S2 is at least one of sodium borohydride, hydrazine hydrate and lithium aluminum hydride.
6. The preparation method of the graphene antibacterial modified plastic film for medicine packaging as claimed in claim 1, wherein the spraying pressure in the step S2 is 6-15 MPa.
7. The preparation method of the graphene oxide reinforced and modified phenolic foam plastic according to claim 1, wherein in the step S2, the drying is performed at a low temperature and a low pressure, the temperature of the low temperature and the low pressure is 10-20 ℃, and the pressure is 0.1-0.5 MPa.
8. The preparation method of the graphene antibacterial modified plastic film for medicine packaging as claimed in claim 1, wherein the binder in the step S3 is prepared from ethyl acetate, polyester polyol and isocyanate according to a volume ratio of 42-55: 35-45: 6-9.
9. The method for preparing the graphene antibacterial modified plastic film for the medicine packaging as claimed in claim 1, wherein in the step S3, the adhesive is uniformly coated on the surfaces of the two sides of the packaging base film through a glue coating roller in a gluing device.
10. The graphene antibacterial modified plastic film for medicine packaging, which is prepared by the preparation method according to any one of claims 1 to 9.
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| CN113527867A (en) * | 2021-08-11 | 2021-10-22 | 福建师范大学泉港石化研究院 | High-resilience antibacterial TPU (thermoplastic polyurethane) foam material and preparation method thereof |
| CN114349992A (en) * | 2022-01-04 | 2022-04-15 | 陕西科技大学 | Antibacterial film and preparation method thereof |
| CN114717688A (en) * | 2022-03-09 | 2022-07-08 | 北京创新爱尚家科技股份有限公司 | Graphene aerogel fiber, graphene aerogel thermal insulation flocculus and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113527867A (en) * | 2021-08-11 | 2021-10-22 | 福建师范大学泉港石化研究院 | High-resilience antibacterial TPU (thermoplastic polyurethane) foam material and preparation method thereof |
| CN113527867B (en) * | 2021-08-11 | 2022-06-14 | 福建师范大学泉港石化研究院 | High-resilience antibacterial TPU (thermoplastic polyurethane) foam material and preparation method thereof |
| CN114349992A (en) * | 2022-01-04 | 2022-04-15 | 陕西科技大学 | Antibacterial film and preparation method thereof |
| CN114717688A (en) * | 2022-03-09 | 2022-07-08 | 北京创新爱尚家科技股份有限公司 | Graphene aerogel fiber, graphene aerogel thermal insulation flocculus and preparation method thereof |
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Application publication date: 20200616 |