CN116144110B - Antibacterial and antiviral plastic film and preparation method and application thereof - Google Patents
Antibacterial and antiviral plastic film and preparation method and application thereof Download PDFInfo
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- CN116144110B CN116144110B CN202310124333.4A CN202310124333A CN116144110B CN 116144110 B CN116144110 B CN 116144110B CN 202310124333 A CN202310124333 A CN 202310124333A CN 116144110 B CN116144110 B CN 116144110B
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Abstract
The application relates to the technical field of plastics, and particularly discloses an antibacterial and antiviral plastic film, a preparation method and application thereof, wherein the antibacterial and antiviral plastic film comprises the following components in parts by weight based on the total weight of the antibacterial and antiviral plastic film: 90-120 parts of plastic resin, 1-6 parts of graphene oxide, 1-5 parts of antibacterial agent, 10-30 parts of high molecular polymer and 1-10 parts of plastic auxiliary agent; wherein, based on the total weight of the antibacterial agent, the antibacterial agent comprises the following components in parts by weight: 2-5 parts of modified chitosan, 10-20 parts of nano titanium dioxide, 4-7 parts of nano zinc oxide and 0.1-0.3 part of hexadecyl trimethyl silver ammonium bromide. The antibacterial and antiviral plastic film can be used for packaging materials of foods and medical products, and has the advantages that: the lasting antibacterial and antiviral effects of the plastic film are improved.
Description
Technical Field
The application relates to the technical field of plastics, in particular to an antibacterial and antiviral plastic film, a preparation method and application thereof.
Background
With the economic development at home and abroad, the processes of urbanization, urbanization and globalization are accelerated, new and sudden viral infectious diseases are in an increasing trend, and the threat to human health is not only represented as causing serious infection and even death of individuals, but also because the serious infectious diseases can be mutated into high-induced virus strains through frequent mutation or the potential threat of rapid transmission between animals and people and between people is obtained, the disastrous harm is brought to people, and people are forced to research the antibacterial and antiviral technology in various fields.
Plastic is used as a main packaging material in the current market, and is widely applied to the fields of food, medical treatment and the like by virtue of the characteristics of light weight, high strength, water resistance, oil resistance and the like. The food and medicine packaging materials can be in direct contact with food or medicine, so the food and medicine industries have higher requirements on sterility of the packaging materials, meanwhile, along with global temperature rise and frequent outbreaks of influenza viruses, the pursuit of public health is more and more important, and the products with antibacterial and antiviral surfaces are more popular with consumers, so the sterility of plastic products and the durability research on antibacterial and antiviral performances of the plastic products are more and more widely focused.
Disclosure of Invention
In order to improve the lasting antibacterial and antiviral effects of the plastic film, the application provides an antiviral plastic film, and a preparation method and application thereof.
In a first aspect, the present application provides an antibacterial and antiviral plastic film, which adopts the following technical scheme:
an antibacterial and antiviral plastic film comprises the following components in parts by weight based on the total weight of the antibacterial and antiviral plastic film: 90-120 parts of plastic resin, 1-6 parts of graphene oxide, 1-5 parts of antibacterial agent, 10-30 parts of high molecular polymer and 1-10 parts of plastic auxiliary agent; wherein, based on the total weight of the antibacterial agent, the antibacterial agent comprises the following components in parts by weight: 2-5 parts of modified chitosan, 10-20 parts of nano titanium dioxide, 4-7 parts of nano zinc oxide and 0.1-0.3 part of hexadecyl trimethyl silver ammonium bromide.
By adopting the technical scheme, the antibacterial and antiviral film is prepared by taking plastic resin as a matrix and introducing antibacterial agent, graphene oxide, high molecular polymer and plastic auxiliary agent to blend. The antibacterial agent and the graphene oxide are added, so that the prepared plastic film has antibacterial and antiviral effects.
When graphene oxide is in direct contact with bacteria, the sharp edges of the lamellar layers can damage the cell membrane directly through mechanical damage or damage the cell membrane through large-scale direct extraction of phospholipid molecules on the cell membrane, so that the damage of the structure and the dysfunction of the bacteria are caused; meanwhile, graphene oxide has large specific surface area and hydrophobicity, and can effectively adsorb phospholipid molecules combined with the surface of bacterial viruses in a contact or insertion mode and the like so as to destroy the cell membrane structure of the graphene oxide and further cause bacterial virus death.
In addition, the antibacterial agent in the application adopts particles with antibacterial and antiviral functions, such as modified chitosan, nano titanium dioxide, nano zinc oxide, cetyl trimethyl silver ammonium bromide and the like, so that the lasting antibacterial and antiviral effects of the plastic film can be improved. The addition of the high polymer enables the combination of the graphene oxide, the antibacterial agent and the plastic resin to be more stable, reduces precipitation of the antibacterial agent, and effectively improves the lasting antibacterial and antiviral functions of the plastic film.
Preferably, the antibacterial agent comprises the following components in parts by weight: 3-4 parts of modified chitosan, 12-16 parts of nano titanium dioxide, 5-6 parts of nano zinc oxide and 0.2-0.3 part of hexadecyl trimethyl silver ammonium bromide.
Preferably, the antibacterial agent comprises the following components in parts by weight: 3 parts of modified chitosan, 14 parts of nano titanium dioxide, 5 parts of nano zinc oxide and 0.2 part of cetyl trimethyl silver ammonium bromide.
By adopting the technical scheme, the nano titanium dioxide has strong ultraviolet shielding capability, good chemical stability and thermal stability, and the antibacterial action mechanism of the nano titanium dioxide is that the nano titanium dioxide generates chemically active strong superoxide anion free radical O through photocatalysis 2 - And hydroxyl radical OH, the newly generated radical has very strong chemical activity, when encountering bacteria, directly attacks the cell wall, cell membrane or constituent components in cells of the bacteria, so that organic matters in the bacteria are degraded, thereby killing the bacteria and decomposing the bacteria, and the photocatalysis of the nano titanium dioxide is lasting, thus effectively improving the lasting antibacterial and antiviral effects of the plastic film.
Similarly, the nano zinc oxide has a similar action mechanism to that of nano titanium dioxide, and is also antibacterial through photocatalysis.
Cetyl trimethyl silver ammonium bromide is a quaternary ammonium salt with silver ions; the silver ions are positively charged, the microorganisms are generally negatively charged, and the silver ions are attracted according to the action of coulomb attraction, when the surface of the microorganisms is accumulated to a certain concentration of silver ions, the silver ions can effectively break down the cell wall of the microorganisms and permeate into the cells of the microorganisms to react with sulfhydryl groups of proteins, so that the proteins of the microorganisms are coagulated, and protease is inactivated, so that the cells of the microorganisms lose the division and reproduction capacity, and meanwhile, the silver ions also have extremely high reduction potential, so that atomic oxygen can be generated in surrounding spaces, and the antibacterial effect is greatly improved; and the quaternary ammonium salt gradually enters cells through the combination of silver ions on the surfaces of microorganisms to destroy cell membranes, so that the cell contents are discharged outwards to cause cell death, thereby inhibiting the proliferation of microorganisms.
The chitosan contains a large amount of amino groups, and the amino groups are protonated to ensure that the chitosan is positively charged, so that adsorption effect is generated on bacteria, and the adsorption effect interacts with negative charges on the surfaces of the bacteria to inhibit the growth of the bacteria. The chitosan is used as a natural macromolecule, can be used as a dispersing agent and a stabilizing agent of nano titanium dioxide, nano zinc oxide and cetyl trimethyl silver ammonium bromide in a plastic film, so that agglomeration of the nano titanium dioxide and the nano zinc oxide is reduced, nano titanium dioxide and nano zinc oxide particles can be more stably dispersed in the plastic film, the service life is prolonged, and the maximum antibacterial effect is exerted. Meanwhile, the modified chitosan adopted in the application has a rougher surface and a more complex micropore structure, namely the surface area of the modified chitosan is larger, and further more silver ions in cetyl trimethyl silver ammonium bromide can be adsorbed, so that the plastic film has better antibacterial performance.
The modified chitosan, the nano zinc oxide, the nano titanium dioxide and the cetyl trimethyl silver ammonium bromide which are prepared according to the proportion have a synergistic antibacterial effect, so that the antibacterial and antiviral properties of the plastic film are further improved, and meanwhile, the antibacterial property of the plastic film can be improved.
Preferably, the preparation method of the modified chitosan comprises the following steps:
2-3 parts of chitosan is weighed and dissolved in 10-15 parts of 0.1mol/L hydrochloric acid solution to form chitosan solution, then 0.2-0.3 part of paraformaldehyde and 1-2 parts of catechol are sequentially added into the chitosan solution to be uniformly mixed, then Mannich reaction is carried out at the temperature of 60 ℃ for 12 hours, then reduced pressure distillation is carried out, the volume of the solution is reduced to be one fifth of the original volume, and then spongy solid modified chitosan is obtained through freeze drying.
By adopting the technical scheme, the catechol and the paraformaldehyde are adopted to carry out Mannich reaction modification on the chitosan, and the prepared modified chitosan is changed into an amorphous state from a crystal, so that the modified chitosan has a rougher surface and a more complex micropore structure, the modified chitosan can be used as an adsorption carrier of cetyl trimethyl silver ammonium bromide, the capability of the modified chitosan for adsorbing bacteria and viruses is stronger, and the limitation that the chitosan can only inhibit bacteria under an acidic condition is broken through by the modified chitosan, namely, the modified chitosan can still maintain higher antibacterial performance under a neutral or alkaline condition, so that the antibacterial and antiviral performance of the plastic film is effectively improved; meanwhile, compared with the common chitosan, the chitosan modified by catechol can improve the mechanical property of the prepared plastic film.
Preferably, the high molecular polymer is at least one selected from the group consisting of polymethacrylic acid, polyvinyl alcohol, polyethylene glycol, chitosan biguanide hydrochloride and sodium alginate.
Through adopting above-mentioned technical scheme, adopt above-mentioned polymer and antiseptic and graphene oxide to cooperate each other, the plastic film of preparation not only can last effectual sterilization antiviral, but also has better mechanical properties, has promoted plastic film's comprehensive performance. The chitosan biguanide hydrochloride combines the biological activities of chitosan and guanidyl compounds, shows stronger and broad-spectrum antibacterial activity and antifungal activity than chitosan, improves the water solubility of the chitosan, and can effectively improve the antibacterial and antiviral properties of the plastic film when being added into the plastic film.
Preferably, the plastic auxiliary comprises at least one of an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant and a dispersing agent.
By adopting the technical scheme, the antioxidant has high antioxidation efficiency, has strong protection effect on plastic resin in the plastic film, can effectively inhibit the aging of the plastic film mainly induced by factors such as light, heat, oxygen and the like, delays the aging speed of the plastic film, and prolongs the service life of the plastic film; the ultraviolet absorber can effectively reduce the damage of ultraviolet to the plastic film, has long-acting anti-oxidation and anti-yellowing effects, has high-quality synergistic effect with the antioxidant, and can improve the weather resistance and the thermo-oxidative stability of the plastic film. After absorbing light energy in an aerobic state, the hindered amine light stabilizer can be converted into corresponding nitroxide free radicals, and the nitroxide free radicals not only can capture alkyl active free radicals generated in photooxidation degradation of a high polymer material, but also have a regeneration function in a light stabilization process, so that chain reaction is inhibited to achieve the aim of protection, and the hindered amine light stabilizer has a good protection effect on thick and thin products. The dispersing agent can uniformly disperse the graphene oxide, the antibacterial agent and the high polymer in the plastic film, so that the antibacterial and antiviral properties of the graphene oxide, the antibacterial agent and the high polymer are effectively improved, and the lasting antibacterial property of the plastic film is further improved.
Preferably, the weight ratio of the graphene oxide to the antibacterial agent to the high molecular polymer is 2-5:3-4:13-15.
Preferably, the weight ratio of the graphene oxide to the antibacterial agent to the high molecular polymer is 2:4:15.
by adopting the technical scheme, the graphene oxide, the antibacterial agent and the high polymer in the weight ratio can generate a synergistic effect, and the lasting antibacterial and antiviral effects of the plastic film can be effectively improved.
In a second aspect, the present application provides a method for preparing an antibacterial and antiviral plastic film, which adopts the following technical scheme:
the preparation method of the antibacterial and antiviral plastic film comprises the following steps:
s1, taking plastic resin, graphene oxide, an antibacterial agent, a high molecular polymer and a plastic auxiliary agent according to a set proportion, and stirring and mixing to obtain a mixed material;
s2, collecting the mixed materials in the step S1, placing the mixed materials in a double-screw extruder, collecting the extruded materials, and performing film blowing or film casting to obtain the antibacterial and antiviral plastic film.
By adopting the technical scheme, the preparation method is simple in steps, convenient and fast to operate, free of complex processes or large-scale equipment, capable of effectively saving labor cost, high in production efficiency and applicable to industrial production.
In a third aspect, the application provides an application of an antibacterial and antiviral plastic film in food and medical product packaging.
Through adopting above-mentioned technical scheme, use the plastic film that this application prepared in food, medicine goods packing field, can effectively reduce food packing, medicine goods packing and produce the possibility that bacterium and virus pollute because of contacting the external world, be favorable to personnel's health.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, the plastic resin is used as a matrix, and the antibacterial agent, the graphene oxide, the high polymer and the plastic additive are introduced to blend to prepare the antiviral film, so that the prepared antiviral film has antibacterial and antiviral effects.
2. The preparation method has the advantages of simple steps, convenient operation, no need of complex process or large-scale equipment, effective saving of labor cost, improvement of production efficiency and applicability to industrial production.
3. The plastic film prepared by the application is applied to the field of food and medical product packaging, can effectively reduce the possibility of bacterial and viral pollution caused by contact of the food packaging and the medical product packaging with the outside, and is beneficial to personnel health.
Detailed Description
The present application is further described in detail below in connection with the preparation examples and examples.
The specific description is: unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The experimental reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the raw materials, instruments, equipment, etc. used in the following examples are all commercially available or available by existing methods; the dosage of the experimental reagent is the dosage of the reagent in the conventional experimental operation if no special description exists; the experimental methods are conventional methods unless otherwise specified.
The antibacterial and antiviral plastic film provided by the application comprises the following components in parts by weight based on the total weight of the antibacterial and antiviral plastic film: 90-120 parts of plastic resin, 1-6 parts of graphene oxide, 1-5 parts of antibacterial agent, 10-30 parts of high molecular polymer and 1-10 parts of plastic auxiliary agent; wherein, based on the total weight of the antibacterial agent, the antibacterial agent comprises the following components in parts by weight: 2-5 parts of modified chitosan, 10-20 parts of nano titanium dioxide, 4-7 parts of nano zinc oxide and 0.1-0.3 part of hexadecyl trimethyl silver ammonium bromide.
In some specific embodiments, the weight ratio of graphene oxide, antimicrobial agent, and high molecular polymer may be 2-3:3-4:13-15, 2-4:3-4:13-15, 2-5:3-4:13-14, 2-5:3-4:14-15, 2-3:3-4:13-14, 2-3:3-4:14-15, 2-4:3-4:13-14, 2-4:3-4:14-15, 3-5:3-4:13-15, 3-5:3-4:13-14, 3-5:3-4:14-15, 3-4:3-4:13-15, 3-4:3-4:13-14, 3-4:3-4:14-15, 4-5:3-4:13-15, 4-5:3-4:13-14, 4-5:3-4:14-15.
Preferably, the weight ratio of the graphene oxide to the antibacterial agent to the high molecular polymer is 2-5:3-4:13-15.
In a specific embodiment, the weight ratio of graphene oxide, antimicrobial agent, and high molecular polymer may be 2:4:13, 2:4:14, 2:4:15, 2:3:13, 2:3:14, 2:3:15, 3:4:13, 3:4:14, 3:4:15, 3:3:13, 3:3:14, 3:3:3:15.
Preferably, the weight ratio of the graphene oxide to the antibacterial agent to the high molecular polymer is 2:4:15.
preferably, the transverse dimension of the graphene oxide material is 100-200 nm.
Further preferably, the oxygen-containing group content of the graphene oxide material is 20% -30%.
Preferably, the plastic resin is selected from one of polyethylene, polystyrene and polypropylene.
Further preferably, the plastic resin is polypropylene.
Preferably, the high molecular polymer is at least one selected from the group consisting of polymethacrylic acid, polyvinyl alcohol, polyethylene glycol, chitosan biguanide hydrochloride and sodium alginate.
Further preferably, the high molecular polymer is chitosan biguanide hydrochloride.
Preferably, the plastic auxiliary comprises at least one of an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant and a dispersing agent.
The ultraviolet absorber, hindered amine light stabilizer, antioxidant, and dispersant are not particularly limited, and known ultraviolet absorbers, hindered amine light stabilizers, antioxidants, and dispersants can be used.
For example, the ultraviolet absorber is selected from any one of 2-hydroxybenzophenone, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and phenyl orthohydroxybenzoate.
Further preferably, the ultraviolet absorber is phenyl o-hydroxybenzoate.
Preferably, the ultraviolet absorber is also selected from Beijing Tiangang auxiliary agent Limited liability companyUV-531、/>UV-570、/>Any one of UV-237.
Preferably, the hindered amine light stabilizer is a light stabilizer 944.
Preferably, the antioxidants can be phenols, amines, phosphites, organosulfides.
Further preferably, the antioxidant is selected from any one of pentaerythritol 2, 6-di-tert-butyl-p-methylphenol, pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, N-stearyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N '-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
Preferably, the antioxidant is selected from the group consisting of Beijing Tiangang auxiliary, incAO-1076、AO-DLTDP、/>AO-B277.
Preferably, the dispersing agent is selected from any one of paraffin oil, polyethylene wax and oxidized polyethylene wax.
Preferably, the antibacterial agent comprises the following components in parts by weight: 3-4 parts (such as 3 parts and 4 parts) of modified chitosan, 12-16 parts (such as 12 parts, 13 parts, 14 parts, 15 parts and 16 parts) of nano titanium dioxide, 5-6 parts (such as 5 parts and 6 parts) of nano zinc oxide, and 0.2-0.3 part (such as 0.2 part and 0.3 part) of cetyltrimethyl silver ammonium bromide.
Preferably, the antibacterial agent comprises the following components in parts by weight: 3 parts of modified chitosan, 14 parts of nano titanium dioxide, 5 parts of nano zinc oxide and 0.2 part of cetyl trimethyl silver ammonium bromide.
Preferably, the average particle size of the nano titanium dioxide is 10-20nm.
Preferably, the average particle size of the nano zinc oxide is 10-100nm.
When the average particle diameters of the nano titanium dioxide and the nano zinc oxide are smaller than the above ranges, the agglomeration phenomenon of the nano particles is easy to occur, so that the mechanical property and the antibacterial property of the plastic film are reduced. And when the average particle diameters of the nano titanium dioxide and the nano zinc oxide are larger than the above range, the antibacterial and antiviral effects are reduced. Therefore, when the average particle diameters of the nano titanium dioxide and the nano zinc oxide are controlled within the above ranges, the nano titanium dioxide and the nano zinc oxide can be well dispersed in the plastic film, and the inhibition effect on bacteria and viruses can be increased.
Preferably, the preparation method of the modified chitosan comprises the following steps:
2-3 parts of chitosan is weighed and dissolved in 10-15 parts of 0.1mol/L hydrochloric acid solution to form chitosan solution, then 0.2-0.3 part of paraformaldehyde and 1-2 parts of catechol are sequentially added into the chitosan solution to be uniformly mixed, then Mannich reaction is carried out at the temperature of 60 ℃ for 12 hours, then reduced pressure distillation is carried out, the volume of the solution is reduced to be one fifth of the original volume, and then spongy solid modified chitosan is obtained through freeze drying.
Further preferably, 2-3 parts of chitosan is weighed and dissolved in 10-15 parts of 0.1mol/L hydrochloric acid solution to form chitosan solution, then 0.2-0.3 part of paraformaldehyde and 1-2 parts of catechol are sequentially added into the chitosan solution to be uniformly mixed, then the temperature is controlled to be 60 ℃ for 12 hours to carry out Mannich reaction, then the solution after Mannich reaction is placed into a dialysis bag with the molecular weight cutoff of 3500KD to carry out dialysis for 48 hours, then the dialysis solution is tested by UV-Vis to detect whether the catechol is completely removed, the solution after dialysis is distilled under reduced pressure at 60 ℃, and after the volume of the solution is reduced to be one fifth of the original volume, the spongy solid modified chitosan is obtained through freeze drying.
The application also provides a preparation method of the antibacterial and antiviral plastic film, which comprises the following steps:
s1, taking plastic resin, graphene oxide, an antibacterial agent, a high molecular polymer and a plastic auxiliary agent according to a set proportion, and stirring and mixing to obtain a mixed material;
s2, collecting the mixed materials in the step S1, placing the mixed materials in a double-screw extruder, collecting the extruded materials, and performing film blowing or film casting to obtain the antibacterial and antiviral plastic film.
Finally, the application provides an application of the antibacterial and antiviral plastic film in packaging of foods and medical products.
According to the preparation method, the plastic resin is used as a matrix, and the antibacterial agent, the graphene oxide, the high polymer and the plastic additive are introduced to blend to prepare the antiviral film, so that the prepared antiviral film has antibacterial and antiviral effects. Meanwhile, the plastic film prepared by the method is applied to the field of food and medical product packaging, so that the possibility of bacterial and viral pollution caused by contact of the food packaging and the medical product packaging with the outside can be effectively reduced, and the method is beneficial to personnel health.
Preparation example of antibacterial agent
Preparation example 1
The antibacterial agent comprises the following components in parts by weight: 2 parts of modified chitosan, 10 parts of nano titanium dioxide, 4 parts of nano zinc oxide and 0.1 part of hexadecyl trimethyl silver ammonium bromide; wherein the average particle diameter of the nano titanium dioxide is 15nm, and the average particle diameter of the nano zinc oxide is 50nm.
The preparation of the antibacterial agent comprises the following steps:
2.42g of chitosan is weighed and dissolved in 0.1mol/L hydrochloric acid solution to form chitosan solution, then 0.23g of paraformaldehyde and 1.65g of catechol are sequentially added into the chitosan solution to be uniformly mixed, then the Mannich reaction is carried out for 12 hours at the temperature of 60 ℃, then the solution after the Mannich reaction is placed into a dialysis bag with the molecular weight cutoff of 3500KD for dialysis for 48 hours, then the dialysis solution is tested by UV-Vis to detect whether the catechol is completely removed, the solution after the dialysis is distilled under reduced pressure at the temperature of 60 ℃, and the volume of the solution is reduced to one fifth of the original volume, and then the spongy solid modified chitosan is obtained through freeze drying.
According to the proportion, the modified chitosan prepared by the steps is mixed with nano titanium dioxide, nano zinc oxide and cetyltrimethyl silver ammonium bromide and then uniformly stirred to obtain the antibacterial agent.
PREPARATION EXAMPLES 2 to 17
Preparation examples 2 to 17 respectively provide different antibacterial agents, and the difference from preparation example 1 is that the antibacterial agents are different in the component proportions, and are shown in Table 1.
TABLE 1 proportions of the components in the antibacterial agents of preparation examples 1 to 17
| Project | Modified chitosan | Nanometer titanium dioxide | Nano zinc oxide | Sixteen kinds ofAlkyl trimethyl silver ammonium bromide |
| Preparation example 1 | 2 | 10 | 4 | 0.1 |
| Preparation example 2 | 2 | 15 | 6 | 0.3 |
| Preparation example 3 | 2 | 20 | 7 | 0.2 |
| Preparation example 4 | 3 | 14 | 5 | 0.2 |
| Preparation example 5 | 2 | 14 | 5 | 0.2 |
| Preparation example 6 | 4 | 14 | 5 | 0.2 |
| Preparation example 7 | 5 | 14 | 5 | 0.2 |
| Preparation example 8 | 10 | 10 | 4 | 0.1 |
| Preparation example 9 | / | 10 | 4 | 0.1 |
| Preparation example 10 | 2 | 5 | 4 | 0.1 |
| PREPARATION EXAMPLE 11 | 2 | 25 | 4 | 0.1 |
| Preparation example 12 | 2 | / | 4 | 0.1 |
| Preparation example 13 | 2 | 10 | 1 | 0.1 |
| PREPARATION EXAMPLE 14 | 2 | 10 | 15 | 0.1 |
| Preparation example 15 | 2 | 10 | / | 0.1 |
| PREPARATION EXAMPLE 16 | 2 | 10 | 4 | / |
| Preparation example 17 | 2 | 10 | 4 | 1 |
In Table 1 "/" represents no addition.
PREPARATION EXAMPLE 18
The antibacterial agent provided in preparation example 18 is different from preparation example 1 in that the antibacterial agent prepared in preparation example 18 is conventional chitosan, the CAS number is 9012-76-4, and the antibacterial agent is purchased from Shanghai Ala Biotechnology Co., ltd., product number: c299272|purity: more than or equal to 75 percent (deacetylated).
Examples
Example 1
An antibacterial and antiviral plastic film comprises the following components in parts by weight: 115 parts of polypropylene, 1 part of graphene oxide (with the transverse dimension of 100-200 nm and the oxygen-containing group content of 25%), 1 part of an antibacterial agent, 10 parts of chitosan biguanide hydrochloride, 2 parts of an ultraviolet absorber, 1 part of a hindered amine light stabilizer, 2 parts of an antioxidant and 3 parts of polyethylene wax.
Wherein the antibacterial agent is the antibacterial agent prepared in preparation example 1;
the ultraviolet absorbent is fructus Toosendan Summit, beijingUV-531；
The antioxidant is Beijing Tiangang auxiliary agent Limited liability companyAO-1076；
The hindered amine light stabilizer is a light stabilizer 944 of the company responsible for the assistant, limited, beijing, tiangang.
The preparation method of the antibacterial and antiviral plastic film comprises the following steps:
s1, according to a set proportion, placing plastic resin, graphene oxide, an antibacterial agent, a high polymer and a plastic additive into a mixer for stirring and mixing to obtain a mixed material;
s2, collecting the mixed materials in the step S1, placing the mixed materials in a double-screw extruder, controlling the temperature of the double-screw extruder from a feed inlet and a machine head to 160 ℃ and 240 ℃ and the rotating speed of a screw to 110rpm, collecting the extruded materials, cooling the extruded materials to 50 ℃ and cutting the materials for drying, and then collecting the extruded materials, and carrying out film blowing or casting on the film to obtain the antibacterial and antiviral plastic film.
Examples 2 to 15
Examples 2 to 15 respectively provide an antibacterial and antiviral plastic film, which is different from example 1 in the weight ratio of graphene oxide, antibacterial agent and high molecular polymer, and is shown in table 2.
TABLE 2 weight ratio of graphene oxide, antimicrobial agent and high molecular Polymer in examples 1 to 15
Examples 16 to 21
Examples 16-21 each provide an antimicrobial and antiviral plastic film, differing from example 6 in that the antimicrobial agent was the antimicrobial agent of a different preparation, as shown in Table 3.
TABLE 3 examples 16-21 antibacterial agents selected from different preparations
| Project | Preparation example |
| Example 1 | Preparation example 1 |
| Example 16 | Preparation example 2 |
| Example 17 | Preparation example 3 |
| Example 18 | Preparation example 4 |
| Example 19 | Preparation example 5 |
| Example 20 | Preparation example 6 |
| Example 21 | Preparation example 7 |
Comparative example
Comparative example 1
Comparative examples 1 to 11 respectively provide an antibacterial and antiviral plastic film, which is different from example 1 in that antibacterial agents of different preparation examples are used as antibacterial agents, as shown in Table 4.
Table 4 comparative examples 1-11 antibacterial agents in different preparations were selected
Comparative examples 12 to 14
Comparative examples 12 to 14 respectively provide an antibacterial and antiviral plastic film, which is different from example 1 in the ratio of graphene oxide, antibacterial agent and high molecular polymer, as shown in table 5.
TABLE 5 proportions of graphene oxide, antibacterial agent and high molecular Polymer in example 1 and comparative examples 12 to 14
| Project | Oxidized graphene | Antibacterial agent | Chitosan biguanideHydrochloride salt |
| Example 1 | 1 | 1 | 10 |
| Comparative example 12 | / | 1 | 10 |
| Comparative example 13 | 1 | / | 10 |
| Comparative example 14 | 1 | 1 | / |
In Table 5 "/" represents no addition.
Performance test
Detection method
Performance tests were performed on examples 1-21 and comparative examples 1-14, respectively.
1. Tensile strength: the test was carried out according to GB/T1040.2-2006 determination of Plastic-tensile Properties.
2. Antibacterial rate: the test is carried out according to GB/T31402-2015 test method for antibacterial property of Plastic-Plastic surface. Testing strains: the strain is a mixture of candida albicans ATCC 10231, staphylococcus aureus ATCC 6538 and escherichia coli ATCC25922, and the adding proportion of the candida albicans ATCC 10231, the staphylococcus aureus ATCC 6538 and the escherichia coli ATCC25922 is the same.
3. Antiviral activity rate: measured according to ISO21702:2019 determination of antiviral Activity of plastics and other non-porous surfaces. The test virus is influenza a virus H1N1.
4. Antibacterial timeliness test: the antibacterial and antiviral activity rates of the obtained plastic film before and after accelerated aging were measured according to the above-mentioned method. Wherein the accelerated aging test is as follows: placing the antibacterial and antiviral plastic film into a container with the temperature of 70+/-3 ℃ and a refrigerator with the temperature of-20+/-3 ℃ for 3 hours respectively, and drying by ultraviolet irradiation for 24 hours under the condition that the ambient temperature is 22+/-3 ℃ after 5 times of circulation.
The test results are shown in Table 6.
TABLE 6 test results of the plastic films of examples 1-21 and comparative examples 1-14
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As can be seen from the combination of examples 1-21 and comparative examples 1-14 and the combination of Table 6, the application takes plastic resin as a matrix, and an antibacterial agent, graphene oxide, a high molecular polymer and a plastic additive are introduced and blended to prepare an antiviral film, so that the prepared antiviral film has lasting antibacterial and antiviral effects.
As can be seen from the combination of examples 1 to 15 and comparative examples 12 to 14 and the combination of Table 6, examples 1 to 15 and comparative examples 12 to 14 adjust the proportions of graphene oxide, antibacterial agent and high molecular polymer in the antibacterial and antiviral plastic film, and the proportions of graphene oxide, antibacterial agent and high molecular polymer are changed, so that the mechanical properties, antibacterial rate and antiviral activity of the antibacterial and antiviral plastic film are all affected to a certain extent. Wherein, the weight ratio of graphene oxide, antibacterial agent and high molecular polymer is 2-5:3-4:13-15, the mechanical property, the antibacterial rate and the antiviral activity of the antibacterial and antiviral plastic film are all improved.
The weight ratio of graphene oxide, antibacterial agent and high molecular polymer in example 6 was 2:4:15, the tensile strength of the antibacterial and antiviral plastic reached 22.2MPa, the antibacterial rate and antiviral activity reached 99.9% and 99.99%, and after the accelerated aging test, the antibacterial rate and antiviral activity were 98.1% and 98.8%.
As can be seen from the combination of examples 16-21 and comparative examples 1-11 and the combination of Table 6, examples 16-21 and comparative examples 1-11 use different antibacterial agents according to different preparation examples, and the antibacterial agents according to different preparation examples are prepared by adjusting different compositions and proportions of components in the antibacterial agents, and the different antibacterial agents have certain effects on the mechanical properties, antibacterial rate and antiviral activity of antibacterial and antiviral plastics.
The antibacterial agent in the preparation example 4 adopted in the example 18 has the optimal effect, the tensile strength of the antibacterial and antiviral plastic reaches 27.8MPa, the antibacterial rate and the antiviral activity reach 99.9% and 99.9999%, and the antiviral activity is improved by two orders of magnitude; and after an accelerated aging test, the antibacterial rate and the antiviral activity are 98.8% and 99.2%, which shows that the antibacterial and antiviral plastic prepared by the application can last for effective antibacterial and antiviral.
As can be seen from the combination of examples 1 and comparative examples 1-2 and 11 and the combination of Table 6, the antibacterial agent of comparative example 1 has 10 parts of modified chitosan, the antibacterial agent of comparative example 2 has no modified chitosan, and the antibacterial agent of comparative example 11 has ordinary chitosan, which results in a reduction in mechanical properties, antibacterial rate and antiviral activity of the antibacterial and antiviral plastic film prepared in comparison with example 1.
Likewise, in the antimicrobial agents of comparative examples 3-5, nano titania was added beyond the ratio range defined herein or nano titania was not added (comparative example 5); in the antimicrobial agents of comparative examples 6 to 8, the added nano zinc oxide is out of the range of the ratio defined in the application or the nano zinc oxide is not added (comparative example 8); in the antibacterial agent of comparative example 9, cetyltrimethyl silver ammonium bromide was not added, and in comparative example 10, 1 part of cetyltrimethyl silver ammonium bromide was added; compared with the embodiment 1, the mechanical property, the antibacterial rate and the antiviral activity of the prepared antibacterial and antiviral plastic film are reduced to a certain extent.
The description limits the proportion range of the modified chitosan, the nano titanium dioxide, the nano zinc oxide and the hexadecyl trimethyl silver ammonium bromide to the range limited by the application, and can effectively improve the mechanical property, the antibacterial rate and the antiviral activity of the antibacterial and antiviral plastic film.
In conclusion, the antibacterial and antiviral plastic prepared by the application has good mechanical properties and durable antibacterial and antiviral capabilities, can be applied to the field of food and medical product packaging, effectively reduces possible virus infection caused by contact of food packaging and medical product packaging, and is beneficial to personnel health.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (8)
1. An antibacterial and antiviral plastic film, characterized in that the total weight of the antibacterial and antiviral plastic film is taken as the basis
The antibacterial and antiviral plastic film comprises the following components in parts by weight: 90-120 parts of plastic resin, 1-6 parts of graphene oxide, 1-5 parts of antibacterial agent, 10-30 parts of high molecular polymer and 1-10 parts of plastic auxiliary agent; wherein, based on the total weight of the antibacterial agent, the antibacterial agent comprises the following components in parts by weight: 2-5 parts of modified chitosan, 10-20 parts of nano titanium dioxide, 4-7 parts of nano zinc oxide and 0.1-0.3 part of hexadecyl trimethyl silver ammonium bromide;
the plastic resin is selected from one of polyethylene, polystyrene and polypropylene;
the high molecular polymer is at least one selected from polymethacrylic acid, polyvinyl alcohol, polyethylene glycol, chitosan biguanide hydrochloride and sodium alginate;
the preparation method of the modified chitosan comprises the following steps:
2-3 parts of chitosan is weighed and dissolved in 10-15 parts of 0.1mol/L hydrochloric acid solution to form chitosan solution, then 0.2-0.3 part of paraformaldehyde and 1-2 parts of catechol are sequentially added into the chitosan solution to be uniformly mixed, then Mannich reaction is carried out at the temperature of 60 ℃ for 12 hours, then reduced pressure distillation is carried out, the volume of the solution is reduced to be one fifth of the original volume, and then spongy solid modified chitosan is obtained through freeze drying.
2. The antimicrobial antiviral plastic film according to claim 1, wherein the antimicrobial agent comprises the following weight
The components in parts by weight: 3-4 parts of modified chitosan, 12-16 parts of nano titanium dioxide, 5-6 parts of nano zinc oxide and 0.2-0.3 part of hexadecyl trimethyl silver ammonium bromide.
3. An antimicrobial antiviral plastic film according to claim 2, wherein: the antibacterial agent comprises the following components by weight
The components in parts by weight: 3 parts of modified chitosan, 14 parts of nano titanium dioxide, 5 parts of nano zinc oxide and 0.2 part of cetyl trimethyl silver ammonium bromide.
4. An antimicrobial antiviral plastic film according to claim 1, wherein: the plastic auxiliary agent comprises at least one of an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant and a dispersing agent.
5. An antimicrobial antiviral plastic film according to claim 1, wherein: the weight ratio of the graphene oxide to the antibacterial agent to the high molecular polymer is 2-5:3-4:13-15.
6. The antibacterial and antiviral plastic film according to claim 5, wherein: the weight ratio of the graphene oxide to the antibacterial agent to the high molecular polymer is 2:4:15.
7. the method for preparing the antibacterial and antiviral plastic film according to any one of claims 1 to 6, comprising the steps of:
s1, taking plastic resin, graphene oxide, an antibacterial agent, a high molecular polymer and a plastic auxiliary agent according to a set proportion, and stirring and mixing to obtain a mixed material;
s2, collecting the mixed material in the step S1, placing the mixed material in a double-screw extruder, collecting the extruded material, and performing film blowing or casting
The antibacterial and antiviral plastic film can be prepared by the film.
8. Use of the antibacterial and antiviral plastic film according to any one of claims 1-6 in packaging of food and pharmaceutical products.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016047568A1 (en) * | 2014-09-22 | 2016-03-31 | 富士フイルム株式会社 | Antibacterial sheet, antibacterial coat, laminated body, and antibacterial fluid |
| KR20170043424A (en) * | 2015-10-13 | 2017-04-21 | 주식회사 에이유 | Bioplastic with improved insect-proof and antimicrobial and a method there of |
| CN112552578A (en) * | 2020-12-14 | 2021-03-26 | 台州市路桥瑞康家庭用品厂 | Antibacterial film product and preparation process thereof |
| CN113004667A (en) * | 2021-03-24 | 2021-06-22 | 北京悦康塑料制品有限公司 | Complex plastic product and production process thereof |
| CN114832506A (en) * | 2021-01-15 | 2022-08-02 | 中国科学院化学研究所 | Antibacterial air filtering material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016047568A1 (en) * | 2014-09-22 | 2016-03-31 | 富士フイルム株式会社 | Antibacterial sheet, antibacterial coat, laminated body, and antibacterial fluid |
| KR20170043424A (en) * | 2015-10-13 | 2017-04-21 | 주식회사 에이유 | Bioplastic with improved insect-proof and antimicrobial and a method there of |
| CN112552578A (en) * | 2020-12-14 | 2021-03-26 | 台州市路桥瑞康家庭用品厂 | Antibacterial film product and preparation process thereof |
| CN114832506A (en) * | 2021-01-15 | 2022-08-02 | 中国科学院化学研究所 | Antibacterial air filtering material and preparation method and application thereof |
| CN113004667A (en) * | 2021-03-24 | 2021-06-22 | 北京悦康塑料制品有限公司 | Complex plastic product and production process thereof |
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