Antimicrobial high-molecular polymer film and preparation method therefor, and antimicrobial display cover plate and preparation method therefor

Abstract

The present application belongs to the technical field of antimicrobial materials, and specifically relates to an antimicrobial high-molecular polymer film and a preparation method therefor, and an antimicrobial display cover plate and a preparation method therefor. The preparation method for an antimicrobial high-molecular polymer film provided by the present application comprises the following steps: S1, mixing a solution of zinc acetate in absolute ethyl alcohol with a lactic acid solution for a reaction to obtain a transparent solution; S2, depositing the transparent solution onto a surface of a high-molecular polymer film, drying same, and then annealing same at 180-200°C to obtain a zinc oxide / high-molecular polymer film; and S3, performing an etching treatment on the surface of the zinc oxide / high-molecular polymer film deposited with zinc oxide by using a low-temperature plasma etching method to obtain the antimicrobial high-molecular polymer film. In the present application, the antimicrobial high-molecular polymer film is subjected to a screen printing treatment with ink and then laminated onto a surface of a glass substrate, thereby obtaining an antimicrobial display cover plate. The antimicrobial display cover plate of the present application can ensure a high transparency while achieving efficient antimicrobial performance.

Description

An antibacterial polymer film and its preparation method, and an antibacterial display cover and its preparation method.

[0001] This application claims priority to Chinese Patent Application No. 202410548048.X, filed on May 6, 2024, entitled "An antibacterial polymer film and antibacterial display cover", the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application belongs to the field of antibacterial materials technology, specifically relating to an antibacterial polymer film and its preparation method, and an antibacterial display cover plate and its preparation method. Background Technology

[0003] In daily life, electronic products are among the items people come into contact with most frequently. After prolonged use, their screens can harbor large amounts of bacteria such as E. coli and Staphylococcus aureus. Skin inevitably becomes contaminated after touching the screen, posing a significant threat to health and urgently needing to be addressed.

[0004] As people's material needs rise, electronic products are gradually developing towards foldable, lightweight, and portable designs. Flexible electronic products are showing increasingly broad market prospects, and their display cover materials are gradually evolving from polymers to ultra-thin flexible glass (UTG) with superior bending properties. Chinese patent CN116253527A discloses a method for preparing flexible antibacterial glass, which involves adding silver nitrate to potassium nitrate molten salt used for chemical tempering, and then coating the glass surface with a layer of nano-silver particles at high temperatures, thereby giving the glass surface antibacterial properties. However, this process easily contaminates the potassium nitrate molten salt required for chemical tempering of the glass and can easily cause breakage of the flexible glass.

[0005] Currently, the glass covers required for flexible electronic products are made of a multi-layer material that is produced by fully bonding both sides of flexible glass. Therefore, in daily use, the surface of flexible glass will not directly contact the air or human skin. The antibacterial effect of antibacterial flexible glass alone cannot meet the antibacterial requirements of electronic product covers. Summary of the Invention

[0006] The purpose of this application is to provide an antibacterial polymer film and its preparation method, as well as an antibacterial display cover plate and its preparation method. The antibacterial polymer film of this application, used in display cover plates, can maintain high transparency of the display cover plate while achieving highly effective antibacterial properties.

[0007] To achieve the above objectives, this application provides the following technical solution:

[0008] This application provides an antibacterial polymer film, including a zinc oxide / polymer film; the zinc oxide / polymer film is a polymer film with a zinc oxide film deposited on its surface, and the zinc oxide film has a nanoconical pattern structure.

[0009] Preferably, the material of the polymer film is selected from at least one of polyterephthalic acid, polyimide, polyurethane and polyethylene naphthalate.

[0010] Preferably, the method for preparing the antibacterial polymer film includes the following steps:

[0011] S1. Mix anhydrous ethanol solution of zinc acetate with lactic acid solution and react to obtain a transparent solution;

[0012] S2. The transparent solution is deposited on the surface of the polymer film, dried, and then annealed at 180-200°C to obtain a zinc oxide / polymer film.

[0013] S3. The zinc oxide surface of the zinc oxide / polymer film is etched using a low-temperature plasma etching method to obtain the antibacterial polymer film.

[0014] This application also provides a method for preparing an antibacterial polymer film, comprising the following steps:

[0015] S1. A transparent solution is obtained by mixing anhydrous ethanol solution of zinc acetate with lactic acid solution and reacting the mixture.

[0016] S2. Deposit the transparent solution onto the surface of the polymer film, dry it, and then anneal it at 180-200℃ to obtain a zinc oxide / polymer film.

[0017] S3. The surface of the zinc oxide / polymer film deposited with zinc oxide is etched using a low-temperature plasma etching method to obtain the antibacterial polymer film.

[0018] Preferably, in S3, the gas source used in the low-temperature plasma etching method is selected from at least one of argon, oxygen and nitrogen; the etching parameters include: power 80-200W, working pressure 0.030-0.035Torr, and processing time 1-10min.

[0019] Preferably, in S1, the reaction temperature is 30–40°C and the reaction time is 1–4 hours.

[0020] Preferably, in the anhydrous ethanol solution of zinc acetate, the molar ratio of zinc acetate to anhydrous ethanol is 1:80-95; and the mass fraction of the lactic acid solution is 30-45%.

[0021] Preferably, in S1, the mixing is performed by adding the lactic acid solution dropwise to the anhydrous ethanol solution of zinc acetate.

[0022] Preferably, in step S2, the transparent solution is spin-coated onto the surface of a polymer film at room temperature and a rotation speed of 2000–4000 rpm.

[0023] Preferably, in step S2, the drying temperature is 60–90°C and the drying time is 5–30 min.

[0024] Preferably, the annealing process takes 10 to 30 minutes.

[0025] This application also provides an antibacterial display cover, comprising a glass substrate and an antibacterial polymer film adhered to the surface of the glass substrate and treated with ink screen printing; the antibacterial polymer film is the antibacterial polymer film described in the above-described scheme or the antibacterial polymer film obtained by the preparation method described in the above-described scheme; the zinc oxide-free side of the antibacterial polymer film is adhered to the glass substrate.

[0026] Preferably, the glass substrate is ultrathin flexible glass; the thickness of the glass substrate is 20-100 μm.

[0027] This application also provides a method for preparing the antibacterial display cover plate described above, comprising the following steps: applying the antibacterial polymer film to the surface of a glass substrate after ink screen printing to obtain the antibacterial display cover plate.

[0028] Preferably, the viscosity of the ink used in the ink screen printing process is 350-450 dPa.s.

[0029] Preferably, before the ink screen printing process, the antibacterial polymer film is further subjected to sequential cleaning and drying.

[0030] Preferably, the method for preparing the antibacterial display cover further includes: uniformly coating an OCA optical adhesive on one surface of a glass substrate, and then drying it after lamination.

[0031] Preferably, the glass substrate is ultrathin flexible glass; this application does not specifically limit the preparation method of the ultrathin flexible glass, and it can be prepared by a one-time molding method or a two-time thinning method.

[0032] This application provides an antibacterial polymer film. The polymer film provided in this application is adhered to the surface of an electronic display cover, which can effectively achieve the antibacterial purpose during the use of the electronic display cover while ensuring the required transparency of the display cover.

[0033] This application also provides a method for preparing the antibacterial polymer film described in the above-mentioned scheme. As shown in Figure 1, this application uses a low-temperature plasma etching method to etch the surface of the zinc oxide / polymer film deposited with zinc oxide, thereby obtaining a nanoconical structure film surface. The nanoconical structure has anti-adhesion properties; its special morphology can reduce bacterial adhesion and growth, prevent bacteria from forming biofilms, and thus reduce the risk of bacterial infection. Secondly, the nanoconical structure can physically pierce and destroy the cell membrane of bacteria, leading to bacterial death, and has a good physical bactericidal effect. Finally, the surface of the nanoconical structure combined with zinc oxide has self-cleaning properties, which can prevent the adhesion and reproduction of microorganisms such as bacteria, mold, and viruses, keeping the surface clean and hygienic. In addition, the nanoconical structure optimizes the microstructure of the zinc oxide film, making its structure more regular, reducing scattering and refraction, and reducing the optical density of the film, making it easier for light to pass through, thereby improving transparency. The zinc oxide film with nanoconical structure provides antibacterial properties while ensuring high transparency, making it suitable for use in electronic display cover plates.

[0034] This application also provides an antibacterial display cover. The antibacterial display cover provided by this application can maintain high transparency while effectively preventing bacteria.

[0035] This application also provides a method for preparing the antibacterial display cover plate described above. The preparation method provided by this application is simple in steps and easy to operate. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 is a schematic diagram of the preparation process of the antibacterial display cover provided in this application. Detailed Implementation

[0038] To further illustrate this application, the following detailed description of the solution of this application is provided in conjunction with the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of this application.

[0039] The glass substrates used in the following examples and comparative examples are all ultra-thin flexible glass substrates, which are prepared by a secondary thinning molding process to obtain ultra-thin flexible glass with a thickness of 30±5μm, and then tempered and repaired by a glass surface micro-damage process.

[0040] Example 1

[0041] An antibacterial polymer film, the preparation method of which includes:

[0042] S1. Take 0.1 kg of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) and disperse it in 2.5 L of anhydrous ethanol under stirring and ultrasonic conditions to obtain an anhydrous ethanol solution of zinc acetate; dilute lactic acid with water to obtain a 40% lactic acid solution; add the lactic acid solution dropwise to the anhydrous ethanol solution of zinc acetate and react at 35 °C for 1.5 h to obtain a transparent solution.

[0043] S2. At room temperature and a rotation speed of 3500 rpm, the prepared transparent solution was spin-coated onto one surface of a PET film. This operation was repeated 2 to 3 times. The film was then dried at 80°C for 10 minutes. After the surface was completely dry, it was annealed at 200°C for 15 minutes to obtain a ZnO / PET film.

[0044] S3. Low-temperature etching treatment was performed on the surface of the ZnO / PET film with zinc oxide deposited using argon plasma. The plasma equipment was set to a power of 100W, a working pressure of 0.035 Torr, and a treatment time of 5 minutes to obtain an antibacterial polymer film with a nano-conical pattern structure.

[0045] An antibacterial display cover plate is prepared by means of: cleaning and drying the antibacterial polymer film, and then screen printing it with ink with a viscosity of 350 dPa.s; cleaning the ultrathin flexible glass substrate, uniformly coating one surface with OCA optical adhesive, and using a bonding device to bond the treated antibacterial polymer film onto the ultrathin flexible glass substrate so that the zinc oxide-free film surface is seamlessly bonded to the OCA-coated glass surface; cleaning and drying are then performed to obtain the antibacterial display cover plate.

[0046] Example 2

[0047] An antibacterial polymer film, the preparation method of which includes:

[0048] S1. Take 0.1 kg of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) and disperse it in 2.2 L of anhydrous ethanol under stirring and ultrasonic conditions to obtain an anhydrous ethanol solution of zinc acetate; dilute lactic acid with water to obtain a 30% lactic acid solution; add the lactic acid solution dropwise to the anhydrous ethanol solution of zinc acetate and react at 35℃ for 1 h to obtain a transparent solution.

[0049] S2. At room temperature and a rotation speed of 3500 rpm, the obtained transparent solution is spin-coated onto one surface of a PET film. This operation is repeated 2 to 3 times. The film is then dried at 80°C for 10 min. After the surface is completely dry, it is annealed at 180°C for 15 min to obtain a ZnO / PET film.

[0050] S3. Low-temperature etching of the surface of the ZnO / PET film with zinc oxide deposited was performed using argon plasma. The plasma equipment was set to a power of 100W, a working pressure of 0.030 Torr, and a processing time of 3 minutes to obtain a polymer film with a nanoconical pattern structure.

[0051] An antibacterial display cover plate is prepared in a manner that differs from that of Example 1 only in that the antibacterial polymer film is replaced with the film described in this example, while the other steps and parameters are the same as those in Example 1.

[0052] Example 3

[0053] An antibacterial polymer film, the preparation method of which includes:

[0054] S1. Take 0.1 kg of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) and disperse it in 2.5 L of anhydrous ethanol under stirring and ultrasonic conditions to obtain an anhydrous ethanol solution of zinc acetate; dilute lactic acid with water to obtain a 40% lactic acid solution; add the lactic acid solution dropwise to the anhydrous ethanol solution of zinc acetate and react at 35 °C for 1.5 h to obtain a transparent solution.

[0055] S2. At room temperature and a rotation speed of 3500 rpm, the obtained transparent solution is spin-coated onto one surface of a PET film. This operation is repeated 2 to 3 times. The film is then dried at 80°C for 10 min. After the surface is completely dry, it is annealed at 200°C for 30 min to obtain a ZnO / PET film.

[0056] S3. Low-temperature etching treatment was performed on the surface of the ZnO / PET film with zinc oxide deposited using argon plasma. The plasma equipment was set to a power of 100W, a working pressure of 0.035 Torr, and a treatment time of 5 min to obtain an antibacterial polymer film with a nanoconical pattern structure.

[0057] An antibacterial display cover plate is prepared in a manner that differs from that of Example 1 only in that the antibacterial polymer film is replaced with the film described in this example, while the other steps and parameters are the same as those in Example 1.

[0058] Comparative Example 1

[0059] An antibacterial polymer film is prepared using a method similar to that in Example 1, except that the surface of the ZnO / PET film with deposited zinc oxide is not subjected to low-temperature etching treatment. All other steps and parameters are the same as in Example 1, specifically including:

[0060] S1 is the same as in Example 1.

[0061] S2. Same as in Example 1, a ZnO / PET film is obtained.

[0062] An antibacterial display cover plate is prepared by means of: cleaning and drying the ZnO / PET film described in this comparative example, and then performing an ink screen printing process on it, with an ink viscosity of 350 dPa.s; cleaning the ultra-thin flexible glass substrate, uniformly coating one surface of it with OCA optical adhesive, and using a bonding device to bond the treated antibacterial polymer film onto the ultra-thin flexible glass substrate, so that the zinc oxide-free film surface and the OCA optical adhesive-coated glass surface are seamlessly bonded; cleaning and drying are performed to obtain the antibacterial display cover plate.

[0063] Comparative Example 2

[0064] An antibacterial polymer film, prepared by a method identical to that of Example 1, except that the PET film is not subjected to zinc oxide deposition treatment, while all other steps and parameters are the same as in Example 1. Specifically, the preparation method includes:

[0065] Argon plasma was used to perform low-temperature etching on the surface of a PET film. The plasma equipment was set to operate at a power of 100W, a working pressure of 0.035 Torr, and a processing time of 5 minutes to obtain a polymer film with a nanoconical pattern structure.

[0066] An antibacterial display cover plate is prepared by means of: cleaning and drying the polymer film with nano-conical pattern structure described in this comparative example, and then performing an ink screen printing process on it, with an ink viscosity of 350 dPa.s; cleaning the ultrathin flexible glass substrate, uniformly coating one surface of it with OCA optical adhesive, and using a bonding device to bond the treated antibacterial polymer film to the ultrathin flexible glass substrate, so that the film and the glass surface coated with OCA optical adhesive are seamlessly bonded; cleaning and drying are performed to obtain the antibacterial display cover plate.

[0067] The performance of the antibacterial display covers obtained in Examples 1-3 and Comparative Examples 1-2 was tested, and the performance data are shown in Table 1. The antibacterial performance was characterized using the inhibition zone test, the light transmittance was characterized using a UV-Vis spectrophotometer, and the bending performance was characterized by the number of R1 bends.

[0068] Table 1. Performance data of antibacterial display cover plate

[0069] Although the above embodiments have provided a detailed description of this application, they are only some embodiments of this application, not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of this application.

Claims

1. An antibacterial polymer film, characterized in that, It includes a zinc oxide / polymer film; the zinc oxide / polymer film is a polymer film with a zinc oxide film deposited on its surface, and the zinc oxide film has a nanoconical pattern structure.

2. The antibacterial polymer film according to claim 1, characterized in that, The material of the polymer film is selected from at least one of polyterephthalic acid, polyimide, polyurethane and polyethylene naphthalate.

3. The antibacterial polymer film according to claim 1, characterized in that, The method for preparing the antibacterial polymer film includes the following steps: S1. Mix anhydrous ethanol solution of zinc acetate with lactic acid solution and react to obtain a transparent solution; S2. The transparent solution is deposited on the surface of the polymer film, dried, and then annealed at 180-200°C to obtain a zinc oxide / polymer film. S3. The zinc oxide surface of the zinc oxide / polymer film is etched using a low-temperature plasma etching method to obtain the antibacterial polymer film.

4. A method for preparing an antibacterial polymer film, characterized in that, Includes the following steps: S1. Mix anhydrous ethanol solution of zinc acetate with lactic acid solution and react to obtain a transparent solution; S2. The transparent solution is deposited on the surface of the polymer film, dried, and then annealed at 180-200°C to obtain a zinc oxide / polymer film. S3. The zinc oxide surface of the zinc oxide / polymer film is etched using a low-temperature plasma etching method to obtain the antibacterial polymer film.

5. The preparation method according to claim 4, characterized in that, In S3, the gas source used in the low-temperature plasma etching method is selected from at least one of argon, oxygen and nitrogen; the etching parameters include: power 80-200W, working pressure 0.030-0.035Torr, and processing time 1-10min.

6. The preparation method according to claim 4 or 5, characterized in that, In S1, the reaction temperature is 30–40°C and the reaction time is 1–4 hours.

7. The preparation method according to claim 4 or 5, characterized in that, In S1, the molar ratio of zinc acetate to anhydrous ethanol in the zinc acetate anhydrous ethanol solution is 1:80-95; the mass fraction of the lactic acid solution is 30-45%.

8. The preparation method according to claim 4 or 5, characterized in that, In S1, the mixing process involves adding the lactic acid solution dropwise to the anhydrous ethanol solution of zinc acetate.

9. The preparation method according to any one of claims 4 to 5, characterized in that, In S2, the transparent solution is spin-coated onto the surface of a polymer film at room temperature and a rotation speed of 2000–4000 rpm.

10. The preparation method according to any one of claims 4 to 5, characterized in that, In S2, the drying temperature is 60–90°C, and the drying time is 5–30 min.

11. The preparation method according to any one of claims 4 to 5, characterized in that, In S2, the annealing process takes 10 to 30 minutes.

12. An antibacterial display cover, characterized in that it comprises a glass substrate and an antibacterial polymer film adhered to the surface of the glass substrate and treated with ink screen printing; the antibacterial polymer film is the antibacterial polymer film according to any one of claims 1 to 2 or the antibacterial polymer film obtained by the preparation method according to any one of claims 3 to 9; the zinc oxide-free side of the antibacterial polymer film is adhered to the glass substrate.

11. The antibacterial display cover plate according to claim 10, wherein the glass substrate is ultra-thin flexible glass; and the thickness of the glass substrate is 20-100 μm.

12. A method for preparing the antibacterial display cover plate according to any one of claims 10-11, characterized in that, Includes the following steps: The antibacterial polymer film is screen-printed with ink and then bonded to the surface of a glass substrate to obtain the antibacterial display cover.

13. The preparation method according to claim 12, characterized in that, The viscosity of the ink used in the ink screen printing process is 350-450 dPa.s.

14. The preparation method according to claim 12 or 13, characterized in that, Also includes: OCA optical adhesive is uniformly coated on one surface of a glass substrate and then dried after bonding.

15. The preparation method according to claim 12, characterized in that, Before the ink screen printing process, the antibacterial polymer film is sequentially cleaned and dried.

16. The preparation method according to claim 12, characterized in that, The glass substrate is ultra-thin flexible glass; the ultra-thin flexible glass is prepared by a one-time molding method or a two-time thinning method.

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