CN111909411A - Plastic film with self-disinfection function and preparation method thereof - Google Patents
Plastic film with self-disinfection function and preparation method thereof Download PDFInfo
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention belongs to the technical field of plastic films, and relates to a plastic film with a self-disinfection function and a preparation method thereof. The plastic film with the self-disinfection function sequentially comprises a self-disinfection layer and a base layer to form a single-sided self-disinfection material, or sequentially comprises a self-disinfection layer, a base layer and a self-disinfection layer to form a double-sided self-disinfection material, wherein the self-disinfection layer contains 0.005-0.010% of beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound, 40-60% of waterborne polyurethane, 5-10% of film forming agent, 0.01-0.05-polylysine and 0.1-0.5% of surfactant by mass, and the base layer is a high-molecular plastic film. The invention also provides a preparation method of the plastic film, so that the plastic film has good self-disinfection capability and wide application space.
Description
Technical Field
The invention belongs to the technical field of plastic films, and relates to a plastic film with a self-disinfection function and a preparation method thereof.
Background
There are a variety of plastic products in daily life, which are used to store food and come into direct or indirect contact with people. Due to the fact that the surface temperature and humidity of the plastic product are proper, bacteria are easy to breed, and the requirement for cleanliness of living goods is higher. Some pathogenic microorganisms in bacteria, fungi and viruses carried by the articles can be transferred to human bodies. Therefore, antimicrobial processing of such materials is highly desirable.
Therefore, a self-disinfection polyurethane plastic film which has good self-disinfection property, high film strength, low cost of preparation raw materials and simple and easily-controlled preparation process is urgently needed.
Chinese patent CN200710008507.1 discloses a photosensitizer beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine conjugate, which is enriched on the surface of tumor cells by utilizing a target marker of the photosensitizer, namely polylysine, and can be used as a carrier of energy and a bridge for reaction to kill the tumor cells, and a good effect is achieved in an in vitro photodynamic therapy experiment of the tumor cells.
Disclosure of Invention
The invention aims to provide a plastic film with a self-disinfection function, so that the plastic film has good self-disinfection capability.
The invention is realized by adopting the following technical scheme:
the invention provides a plastic film with a self-disinfection function, which is a single-sided self-disinfection material sequentially composed of a self-disinfection layer and a base layer, or a double-sided self-disinfection material sequentially composed of the self-disinfection layer, the base layer and the self-disinfection layer, wherein the self-disinfection layer contains 0.005-0.010 mass percent of beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound, 40-60 mass percent of waterborne polyurethane, 5-10 mass percent of film forming agent, 0.01-0.05-polylysine and 0.1-0.5 mass percent of surfactant, and the base layer is a high molecular plastic film.
The invention also provides a preparation method of the plastic film with the self-disinfection function, which comprises the following steps:
(1) dissolving the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupler in an organic mixed solvent, adding polylysine and a surfactant, and uniformly stirring to obtain an antibacterial mother solution;
(2) putting the waterborne polyurethane into a mixer, adding water, stirring, and continuously adding the film forming agent; keeping the temperature in the stirring equipment of the mixer at 80-90 ℃;
(3) adding the antibacterial mother liquor obtained in the step (1) into the mixed feed liquid melted in the step (2), and continuously stirring to obtain a self-disinfection polyurethane liquid;
(4) coating the self-disinfecting polyurethane liquid on the substrate by adopting a coating and thermosetting process, and curing.
Preferably, the organic mixed solvent in the step (1) comprises methanol/formic acid or ethyl acetate/formic acid, and the surfactant is a cationic long-chain quaternary ammonium salt.
Specifically, the mass fraction of the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound in the organic mixed solvent is 0.005-0.010%, and the mass ratio of the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound to the polylysine to the surfactant is 1 (2-5) to (30-50).
Preferably, the film forming agent in the step (2) is polyvinylpyrrolidone or vinylpyrrolidone, and the mass ratio of the film forming agent, the waterborne polyurethane and the water is 1 (5-8) to (8-10). The polyvinylpyrrolidone (PVP) may be ｃA vinylpyrrolidone homopolymer (PVP-K) or ｃA vinylpyrrolidone copolymer (PVP-A).
Preferably, the mass ratio of the antibacterial mother liquor to the mixed liquor in the step (3) is 1 (20-25).
Preferably, the bonding temperature of the coating heat curing process in the step (4) is controlled to be 50-90 ℃.
The invention has the beneficial effects that:
the self-disinfection polyurethane plastic film prepared by the invention consists of a self-disinfection antibacterial layer and a base layer, wherein the disinfection layer mainly consists of a beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound and a surfactant, and the surfactant can enable the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound to form dispersed monomers so as to ensure the antibacterial performance of the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound; the base layer is a plastic film without self-disinfection function. The plastic film prepared by the invention has high adhesion, so that the plastic film has good self-disinfection property and high chemical stability.
The beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine conjugate has a dual antimicrobial mechanism, the first mechanism of which is: beta-monocarboxyl substituted zinc phthalocyanine has photocatalysis to destroy the synthesis of microorganism organelles; the second mechanism is: the polypeptide group of the pentapoly-lysine coupling compound carried by the polypeptide is in a high-polymerization multivalent cation state, can destroy the cell structure of microorganisms, cause interruption of material, energy and information transmission of cells, and can be combined with ribosome in the cells to influence the synthesis of biomacromolecules, thereby finally leading to cell death.
The self-disinfecting polyurethane plastic film prepared by the invention has the advantages of high self-disinfecting antibacterial property, high strength, simple preparation method and low preparation cost, and is suitable for large-scale popularization.
Detailed Description
The present invention will be described in further detail in order to make the object and technical solution of the present invention more apparent. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the specific techniques or conditions are not indicated in the examples, and the techniques or conditions are described in the literature in the field or according to the product specification; the reagents and materials are commercially available, unless otherwise specified.
The preparation method of the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound refers to a preparation scheme disclosed in an example in Chinese patent CN 200710008507.1.
Waterborne polyurethane was purchased from Anhui Dahuatai New materials, Inc., Cat # AH-1802A.
The film-forming agent is polyvinylpyrrolidone (PVP) available from Shanghai Allantin Biotechnology, Inc., Cat P110608. The polyvinylpyrrolidone (PVP) may be ｃA vinylpyrrolidone homopolymer (PVP-K) or ｃA vinylpyrrolidone copolymer (PVP-A).
The surfactant is a cationic long-chain quaternary ammonium salt, and is available from Shanghai Aladdin Biotechnology, Inc., Cat number H108985.
Polylysine is a homotypic monomer polymer containing 25-30 lysine residues and is called polylysine (-PL).
The plastic film base layer is plastic films such as a polypropylene film (BOPP), a low density polyethylene film (LDPE), a polyester film (PET), a nylon film (PA), a cast polypropylene film (CPP), an aluminum-plated film and the like.
Preparation of plastic film with self-disinfection function
Example 1
(1) Dissolving 0.5g of beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound in a mixed solvent of 450g of methanol and 50g of formic acid, adding 1g of polylysine and 10g of surfactant, and uniformly stirring to obtain the antibacterial mother liquor.
(2) Putting 4.5kg of waterborne polyurethane into a mixer, adding 5kg of water, stirring, and continuously adding 0.5kg of vinyl pyrrolidone homopolymer; the temperature in the mixer stirring equipment was kept at 80 ℃.
(3) And (3) adding the antibacterial mother liquor obtained in the step (1) into the mixed liquor melted in the step (2) according to the mass ratio of 1:20, and continuously stirring for 10min to obtain the self-disinfection polyurethane liquor.
(4) The self-disinfection polyurethane liquid is coated on a polyester film (PET) by adopting a coating and thermosetting process, the temperature is controlled to be 50-60 ℃, and the curing is carried out for 24 hours.
Example 2
(1) Dissolving 0.75g of beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound in a mixed solvent of 440g of methanol and 60g of formic acid, adding 2g of polylysine and 25g of surfactant, and uniformly stirring to obtain the antibacterial mother liquor.
(2) Putting 4.5kg of waterborne polyurethane into a mixer, adding 4kg of water, stirring, and continuously adding 0.5kg of vinyl pyrrolidone; the temperature in the mixer stirring equipment was kept at 80 ℃.
(3) And (3) adding the antibacterial mother liquor obtained in the step (1) into the mixed liquor melted in the step (2) according to the mass ratio of 1:20, and continuously stirring for 10min to obtain the self-disinfection polyurethane liquor.
(4) The self-disinfection polyurethane liquid is coated on a low-density polyethylene film (LDPE) by adopting a coating and thermosetting process, the temperature is controlled to be 50-60 ℃, and the curing is carried out for 48 hours.
Example 3
(1) Dissolving 0.8g of beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound in a mixed solvent of 430g of methanol and 70g of formic acid, adding 1g of polylysine and 30g of surfactant, and uniformly stirring to obtain the antibacterial mother liquor.
(2) Putting 4.5kg of waterborne polyurethane into a mixer, adding 4kg of water, stirring, and continuously adding 0.5kg of vinyl pyrrolidone homopolymer; the temperature in the mixer stirring equipment was kept at 80 ℃.
(3) And (3) adding the antibacterial mother liquor obtained in the step (1) into the mixed liquor melted in the step (2) according to the mass ratio of 1:20, and continuously stirring for 10min to obtain the self-disinfection polyurethane liquor.
(4) The self-disinfection polyurethane liquid is coated on a polypropylene film (BOPP) by adopting a coating and thermosetting process, the temperature is controlled to be 70-80 ℃, and the curing is carried out for 30 hours.
Comparative example 1
Unlike example 3, the antibacterial mother liquor was not used in this example.
(1) Putting 4.5kg of waterborne polyurethane into a mixer, adding 4kg of water, stirring, and continuously adding 0.5kg of vinyl pyrrolidone homopolymer; keeping the temperature in the mixer stirring equipment at 80 ℃, and preparing the polyurethane solution without adding the antibacterial mother solution.
(2) The polyurethane liquid is coated on a polypropylene film (BOPP) by adopting a coating and thermosetting process, the temperature is controlled to be 70-80 ℃, and the curing is carried out for 30 h.
Second, the antibacterial property test of the plastic film with self-disinfection function
1. Covering film
A polyethylene film having a standard size of (40. + -. 2) mm X (40. + -.2) mm and a thickness of 0.05mm to 0.10 mm. If the overall dimension of the test sample is smaller, the size of the covering film can be reduced according to the area of the sample, and the concentration of bacteria laid on the position of the covering film of the sample is ensured to be unchanged. Soaking in 70% ethanol solution for 1min, washing with sterile water, and naturally drying.
2. Sample (I)
2.1 negative control samples
Number A, inner plate of a sterile plate with a diameter of 90mm or 100 mm.
2.2 blank control sample
No. B, a plastic film to which no antibacterial component was added, having a standard size of (50. + -.2) mm X (50. + -.2) mm and a thickness of not more than 5 mm. It is also possible to cut directly from a plain plastic article (comparative example 1) and to select as flat a surface as possible. If the size is less than 50mm multiplied by 50mm, the size should not be less than 20mm multiplied by 20mm, otherwise, the size needs to be processed again to be standard.
2.3 antimicrobial Plastic film samples
The number C is a plastic film (examples 1 to 3) to which an antibacterial component is added, and it is recommended that the plastic film has a standard size of (50. + -.2) mm X (50. + -.2) mm and a thickness of not more than 5 mm. If the size is less than 50mm multiplied by 50mm, the size should not be less than 20mm multiplied by 20mm, and the area of the covering film is correspondingly reduced, otherwise the covering film is reprocessed into a standard size.
All samples in 2.2 above were sterilized before testing, the surface of the samples was wiped with a disinfectant (70% ethanol solution), rinsed with sterile water after 1min, and dried naturally.
3. Testing of samples
3.1 preparation of bacterial suspension (Using E.coli suspension) selected bacterial liquid concentration of 5.0X 105cfu/mL～10.0×105cfu/mL, eluent physiological saline.
3.2 dropping 0.2mL of test bacterial liquid on the negative control sample (A), the blank control sample (B) and the antibacterial plastic sample (C). Each sample was run in 5 replicates. The samples (A), (B) and (C) were covered with sterile cover films with sterile tweezers, and the samples were placed in sterile petri dishes at 37+1 ℃ and a relative humidity of 90% for a predetermined period of time.
3.3 taking out the sample cultured for the corresponding test time, respectively adding 20mLPBS eluent, repeatedly washing the sample (A), the sample (B), the sample (C) and the covering film (preferably using tweezers to clamp the film for washing), fully shaking up, inoculating a certain amount of the mixture into a nutrient agar culture medium (NA), culturing at the temperature of 37 +/-1) DEG C for 24-48 h, counting viable bacteria, and measuring the viable bacteria number according to the GB/T4789.2-2016 method. The above experiment was repeated twice.
4 calculation of test results
Multiplying the result of the viable count determined in 3.3 by 100 to obtain the actual value of the recovered viable count after culturing the samples A, B and C for 24 hours, wherein the values are A, B, C respectively, so that the test result can meet the following requirements, otherwise, the test is invalid:
the 5 parallel viable bacteria values of the same blank control sample B meet (the highest logarithm value-the lowest logarithm value)/the average viable bacteria value logarithm value is not more than 0.3;
the actual recovery viable bacteria value A of the sample A should be not less than 1.0 multiplied by 105cfu/piece, and the actual recovery viable bacteria value B of the sample B should not be less than 1.0 x 104cfu/tablet.
The antibacterial rate was calculated as follows.
R(％)＝(B-C)/B×100
In the formula:
r; antibacterial rate,%;
b: average recovery bacteria number of blank control sample, cfu/piece;
c: the average recovery bacteria number of the antibacterial plastic sample is cfu/piece.
The plastic films obtained in examples 1 to 3 and comparative example 1 were analyzed for antibacterial rate, and the results are shown in Table 1:
TABLE 1 anti-colibacillus test result table for plastic film
The time in the table represents the contact time of the bacterial liquid and the plastic film.
The results show that the plastic film prepared in example 3 has a significant antibacterial effect improvement compared to comparative example 1, and the polyester film (PET) and the low density polyethylene film (LDPE) selected in examples 1 and 2 have a significant antibacterial effect except for the polypropylene material. Therefore, the plastic film prepared by the invention has good self-disinfection property.
The plastic films obtained in examples 1-3 and comparative example 1 were contacted with the bacterial solution for 10min, the bacterial solution was dropped repeatedly, the contacted bacterial solution was taken out and tested, and then new bacterial solution was dropped and repeated for 5 times to analyze the antibacterial rate, and the results are shown in table 2:
TABLE 2 repeated colibacillus resistance test result table for plastic film
| Object | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Material of | Polyester film | Low density polyethylene film | Polypropylene film | Polypropylene film |
| For the first time | 99.10％ | 99.50％ | 99.90％ | 0％ |
| For the second time | 99.0％ | 98.50％ | 99.20％ | 0％ |
| The third time | 98.2％ | 97.80％ | 99.20％ | 0％ |
| Fourth time | 96.1％ | 95.50％ | 94.50％ | 0％ |
| Fifth time | 92.5％ | 91.50％ | 92.20％ | 0％ |
It can be seen from table 2 that the self-disinfecting plastic film sample prepared by the present invention can continuously kill the repeatedly added bacterial liquid when the bacterial liquid is repeatedly infected.
Third, the long-acting antibacterial performance experiment of the plastic film with self-disinfection function
1. The plastic film obtained in example 1 was cut into a plurality of 25cm pieces2And small membranes are respectively placed under the irradiation of 1400lux of a fluorescent lamp and subjected to the experiment after 0, 6, 16 and 24h of exposure.
Then, a certain amount of bacterial suspension (Staphylococcus aureus ATCC6538) is smeared on a TSA agar plate and is stuck to the plate for 25cm2Culturing and counting after 5 min; the control used the opposite side of the self-sterilizing clinker film (substrate side without antimicrobial coating) for the exposure time. The results are shown in Table 3:
TABLE 3 Long-acting antibacterial property test meter for plastic film with self-disinfection function
As can be seen from Table 3, the self-disinfecting plastic film has a log antibacterial value of more than 2 (antibacterial rate > 99%) in a 5-minute contact time after being placed under indoor lamp light irradiation for 0, 6, 16 and 24 hours.
2. The plastic films obtained in examples 1 to 3 and comparative example 1 were subjected to "Disinfection technical Specification (Ministry of health, 2002 edition) -2.1.11.3.4 (stability test method)": and (3) accelerating sample retention in an acceleration test, placing the film in a constant temperature box at 37 ℃ for 3 months, and taking out the film sample for antibacterial test. The sterilization rate or the bacteriostasis rate of the product reaches more than or equal to 90 percent through an accelerated test at 37 ℃, and the effective period of the sterilization or bacteriostasis of the product is at least 2 years at room temperature. The results are shown in Table 4. Meanwhile, the self-disinfection performance of the self-disinfection plastic film is 2 years of validity period, and the chemical stability of the self-disinfection coating on the self-disinfection plastic film is verified.
TABLE 4. test result table for plastic film accelerated stability sample retention and anti-colibacillus
| Object | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Material of | Polyester film | Low density polyethylene film | Polypropylene film | Polypropylene film |
| 5min | 91％ | 92％ | 93.5％ | 0％ |
| 10min | 95.10％ | 95.50％ | 94.90％ | 1％ |
| 24h | 91.90％ | 90.99％ | 90.15％ | 3％ |
The time in the table represents the contact time of the bacterial liquid and the plastic film.
Fourth, the antiviral test of the plastic film with self-disinfecting function
According to the test method for the virus inactivation performance of the antiviral material ISO18184:2014E, a sample of the transparent PET film with the self-disinfection function (example 1) prepared in example 1 and the plastic film prepared in comparative example 1 are taken as a control sample to carry out an inactivation test for inactivating the influenza A virus H1N1, and the results are shown in Table 5.
TABLE 5 test results of plastic film for resisting influenza A virus H1N1 virus
The results show that the self-sterilized PET plastic film prepared in example 1, which can be tested under indoor natural lighting conditions, exhibits 99.92% antiviral activity.
Fifthly, testing physical and chemical properties of plastic film with self-disinfection function
The plastic films obtained in examples 1-3 and comparative example 1 were tested for physical and chemical properties by the tensile property test method of GB/T13022-1991 plastic film and the peeling test method of GB/T8808-1988 soft composite plastic material, and the results are shown in Table 6.
TABLE 6 comparison table of physicochemical properties of plastic films having self-sterilizing function
It should be understood that the above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents may be made in the technical solutions described in the foregoing embodiments, or some technical features may be substituted. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A plastic film with a self-disinfection function is characterized in that a self-disinfection layer and a base layer form a single-side self-disinfection material in sequence, or a self-disinfection layer, a base layer and a self-disinfection layer form a double-side self-disinfection material in sequence, the self-disinfection layer contains 0.005-0.010 mass percent of beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound, 40-60 mass percent of waterborne polyurethane, 5-10 mass percent of film forming agent, 0.01-0.05-polylysine and 0.1-0.5 mass percent of surfactant, and the base layer is a high polymer plastic film.
2. A method for preparing a plastic film having a self-sterilizing function according to claim 1, comprising the steps of:
(1) dissolving the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupler in an organic mixed solvent, adding polylysine and a surfactant, and uniformly stirring to obtain an antibacterial mother solution;
(2) putting the waterborne polyurethane into a mixer, adding water, stirring, and continuously adding the film forming agent; keeping the temperature in the stirring equipment of the mixer at 80-90 ℃;
(3) adding the antibacterial mother liquor obtained in the step (1) into the mixed feed liquid melted in the step (2), and continuously stirring to obtain a self-disinfection polyurethane liquid;
(4) coating the self-disinfecting polyurethane liquid on the substrate by adopting a coating and thermosetting process, and curing.
3. The method for preparing a plastic film with a self-disinfecting function as claimed in claim 2, wherein the organic mixed solvent in the step (1) comprises methanol/formic acid or ethyl acetate/formic acid, and the surfactant is cationic long-chain quaternary ammonium salt.
4. The method for preparing a plastic film with a self-disinfecting function as claimed in claim 3, wherein the mass fraction of the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound in the organic mixed solvent is 0.005-0.010%, and the mass ratio of the beta-monocarboxyl substituted zinc phthalocyanine-pentapolylysine coupling compound to the polylysine to the surfactant is 1 (2-5) to (30-50).
5. The method for preparing a plastic film with a self-disinfecting function according to claim 2, wherein the film forming agent in the step (2) is polyvinylpyrrolidone or vinylpyrrolidone, and the mass ratio of the film forming agent, the waterborne polyurethane and the water is 1 (5-8) to (8-10).
6. The method for preparing a plastic film with a self-sterilization function according to claim 2, wherein the mass ratio of the antibacterial mother liquor to the mixed liquor in the step (3) is 1 (20-25).
7. The method for preparing a plastic film with a self-sterilization function according to claim 2, wherein the bonding temperature of the coating heat curing process in the step (4) is controlled to be 50 ℃ to 90 ℃.
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| CN109422893A (en) * | 2017-09-05 | 2019-03-05 | 江南大学 | A kind of antibacterial film and preparation method |
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| US20110237706A1 (en) * | 2010-03-25 | 2011-09-29 | Cheng-Chien Yang | Germs resisting and self cleaning infiltration thin film and manufacturing method thereof |
| CN102755647A (en) * | 2012-07-23 | 2012-10-31 | 中国科学院福建物质结构研究所 | Application of pentamer lysinephthalocyanine zinc in killing staphylococcus aureus |
| CN106637992A (en) * | 2015-10-29 | 2017-05-10 | 中国科学院福建物质结构研究所 | Photodynamic antibacterial cellulose material and preparation method thereof |
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