Insulating waterproof antibacterial coating structure and preparation method thereof

Abstract

The preparation method comprises the following steps: depositing an Al2O3 layer on the surface of a cleaned sample by using an atomic layer, then depositing a layer of polymer conformal coating, growing a layer of Ag on the surface by using a pulling dipping method, and finally growing a ZnO coating on the surface by using atomic layer deposition. On one hand, the problem that the coating is easy to fall off on the surface of the sample is solved, a multi-layer film mode is adopted, the compatibility between the films is good, the advantages of the coatings in the insulating, waterproof and antibacterial fields can be fully utilized, the function of the to-be-modified sample is comprehensively improved, and the application prospect is wide. The coating can be used for insulating, waterproof, antibacterial and mildew-proof protection of electronic devices, medical apparatuses and instruments, device packaging, cultural relic printed matters and the like. The invention further provides a preparation method, the adopted technological method has good shape preserving performance, comprehensive modification of complex structures and surfaces can be achieved, the maturity of equipment and the technology is high, cost is low, and batch production is easy.

Description

Technical Field

[0001] The invention relates to the field of surface modification, and in particular to an insulating waterproof and antibacterial coating structure and a preparation method, in particular to the preparation of a functional coating on the surface of a product. Background Art

[0002] Insulating, waterproof and antibacterial coatings are widely used in various fields, such as waterproofing, insulation and packaging of electronic devices, waterproofing, mildew-proofing and antibacterial of medical devices, especially biomedical materials implanted in the human body, waterproofing, antibacterial and mildew-proof protection of printed materials such as cultural relics. Different products have different requirements for protective coatings. On the one hand, the coating needs to have the requirements of waterproofing, mildew-proofing, insulation and antibacterial. On the other hand, compatibility with the surface needs to be considered to ensure the long-term stability of the product. Therefore, the development of an insulating, waterproof and antibacterial coating is a bottleneck to further improve product performance. Breakthroughs in coating structure, technology and cost are the focus of enhancing my country's competitive advantage in different fields at this stage.

[0003] The insulating, waterproof and antibacterial coating structure provided by the present invention not only has good electrical and protective properties, but also has very good biocompatibility. It can meet the Class VI standard for biomedical materials. It is a material that can be used for a long time and has waterproof, insulating, antibacterial, mildew-proof and wear-resistant properties. It can effectively replace the performance improvement needs of most products currently used in the market. Summary of the invention

[0004] The purpose of the present invention is to provide an insulating, waterproof and antibacterial coating structure, which can modify the surface of a product and improve its electrical insulation performance and chemical stability.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned insulating waterproof and antibacterial coating structure.

[0006] The purpose of the present invention is achieved through the following scheme: an insulating waterproof antibacterial coating structure, comprising the following structure: an Al2O3 layer, a polymer conformal coating, an Ag layer and a ZnO coating are sequentially included on the surface of the sample to be modified.

[0007] Furthermore, when the sample to be modified is made of silver, the surface modification layers are sequentially Al2O3 layer, polymer conformal coating and surface ZnO coating.

[0008] The present invention also provides a method for preparing the above insulating waterproof and antibacterial coating structure, which at least comprises the following steps: (1) First, an Al2O3 layer is deposited on the surface of the sample to be modified by atomic layer deposition; (2) depositing a polymer conformal coating on the surface of the sample obtained in step (1); (3) For non-silver samples to be repaired, a layer of Ag is grown on the surface by using the Czochralski method; (4) Growing a ZnO coating on the surface of step (2) or step (3) by atomic layer deposition.

[0009] The method of preparing the Al2O3 nanolayer on the substrate by using the atomic layer deposition technology is as follows: Raise the temperature of the atomic layer deposition system cavity to 100-200°C, open the cavity, and place the sample in the sample pool; When the pressure in the chamber drops below 50 hPa, the reaction chamber is purged with inert gas; Trimethylaluminum is introduced into the reaction chamber with a pulse time of 4 to 10 s; then an inert gas is introduced with a pulse time of 20 to 60 s; then an oxygen precursor is introduced with a pulse time of 4 to 10 s; finally, the unreacted oxygen precursor is cleaned with an inert gas to complete a cycle of Al2O3 deposition; this process is repeated to obtain an Al2O3 layer deposited on the substrate surface for 500 to 1000 cycles.

[0010] The polymer conformal coating is a p-xylene polymer, at least one of dichloro p-xylene dimer and octafluoro p-xylene dimer, and the coating thickness is 25-40 microns.

[0011] The method of growing a layer of Ag on the surface by the pulling and dipping method is as follows: immerse the sample in a silver nitrate aqueous solution with a mass concentration of 10-15% for 10 seconds, take it out and dry it; then immerse it in an ascorbic acid or sodium borohydride aqueous solution with a mass concentration of 20-30% for 15-30 seconds, take it out and dry it, which is one cycle; repeat the above steps for 0-10 times.

[0012] The method for growing a ZnO coating on a surface by atomic layer deposition is as follows: To prepare the ZnO nanolayer on the substrate, first raise the temperature of the atomic layer deposition system chamber to 100-250°C, open the chamber, and place the sample in the sample cell; When the pressure in the chamber drops below 50 hPa, the reaction chamber is purged with inert gas; Diethyl zinc was introduced into the reaction chamber with a pulse time of 4 to 10 s; Then, inert gas is introduced with a pulse time of 20s to 60s; Then, oxygen precursor was introduced with a pulse time of 4 s to 10 s; Finally, the unreacted oxygen precursor is purged with an inert gas to complete a cycle of ZnO deposition; this process is repeated to deposit a ZnO coating with a thickness of 5 to 10 nm on the substrate surface.

[0013] On the one hand, the present invention solves the problem that the coating is easy to fall off on the sample surface. By adopting a multilayer film method, each layer of the film has good compatibility, and can fully utilize the advantages of each coating in the fields of insulation, waterproofing, and antibacterial, to achieve an all-round improvement in the function of the sample to be modified. This technology can be used for insulation, waterproofing, antibacterial and mildew-proof protection of electronic devices, medical devices, device packaging, cultural relics and printed materials, etc. The process used in the method provided by the present invention has good conformality, can achieve all-round modification of complex structures and surfaces, has high equipment and process maturity, low cost, and is easy to mass produce. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a schematic diagram of the multilayer film structure of the present invention; Figure 2 The figures are the salt spray test results of the modified and unmodified silver coins of the present invention. DETAILED DESCRIPTION

[0015] Embodiment 1: An insulating waterproof antibacterial coating structure, such as Figure 1 The slide is shown as the sample to be etched, and on its surface there are Al2O3 layer, polymer conformal coating, Ag coating and ZnO coating from bottom to top, which are prepared according to the following steps: (1) Preparation of Al2O3 layer: Raise the temperature of the atomic layer deposition system chamber to 100°C, open the chamber, and place the glass slide in the sample pool; reduce the pressure in the chamber to below 50 hPa, and purge the reaction chamber with inert gas; introduce trimethylaluminum into the reaction chamber with a pulse time of 10 s; then introduce inert gas with a pulse time of 60 s; then introduce water with a pulse time of 10 s; finally, purge the unreacted water with inert gas to complete a cycle of Al2O3 deposition; repeat this process to deposit 500 cycles of Al2O3 layer on the surface of the glass slide; (2) depositing a layer of dichloroparaxylene dimer coating on the surface of the sample obtained in step (1) to obtain a polymer conformal coating with a thickness of 25 μm; (3) Immerse the sample obtained in step (2) in a 10% silver nitrate aqueous solution for 10 seconds, remove and air dry; then immerse it in a 20% ascorbic acid aqueous solution for 15 seconds, remove and air dry to complete one cycle; repeat the above cycle 5 times to obtain a Ag-coated sample substrate; (4) The sample substrate obtained in step (3) is placed in an atomic layer deposition sample cell with the inner chamber temperature raised to 100°C; the pressure in the chamber is reduced to below 50 hPa, and the reaction chamber is purged with an inert gas; diethyl zinc is introduced into the reaction chamber with a pulse time of 10 s; then an inert gas is introduced with a pulse time of 60 s; then water is introduced with a pulse time of 10 s; finally, unreacted oxygen precursor water is purged with an inert gas to complete a cycle of depositing ZnO; this is repeated to deposit a ZnO coating with a thickness of 10 nm on the substrate surface.

[0016] The antibacterial activity value of this example against Staphylococcus aureus ATCC6538P is greater than 5.4.

[0017] Embodiment 2: The surface of the silver coin is modified. The modified silver coin is used as a base, and an Al2O3 layer, a polymer conformal coating and a ZnO coating are sequentially provided on the surface from bottom to top. The preparation steps are as follows: The steps include: (1) Raise the temperature of the atomic layer deposition system chamber to 150°C, open the chamber, and place the sample in the sample pool; reduce the pressure in the chamber to below 50 hPa, and purge the reaction chamber with inert gas; introduce trimethylaluminum into the reaction chamber with a pulse time of 5 s; then introduce inert gas with a pulse time of 40 s; then introduce water with a pulse time of 10 s; finally, purge the unreacted water with inert gas to complete a cycle of Al2O3 deposition; repeat this process to deposit 600 cycles of Al2O3 layers on the surface of the silver coin; (2) depositing a layer of dichloroparaxylene dimer coating on the sample obtained in step (1) to obtain a polymer conformal coating with a thickness of 30 μm; (3) The sample obtained in step (2) is placed in an atomic layer deposition sample cell with the inner chamber temperature raised to 200°C; the pressure in the chamber is reduced to below 50 hPa, and the reaction chamber is purged with an inert gas; diethyl zinc is introduced into the reaction chamber with a pulse time of 5 s; then an inert gas is introduced with a pulse time of 40 s; then water is introduced with a pulse time of 10 s; finally, unreacted oxygen precursor water is purged with an inert gas to complete a cycle of depositing ZnO; this is repeated to deposit a ZnO coating with a thickness of 10 nm on the substrate surface.

[0018] Figure 2 This is the salt spray test of the silver coin with the coating grown in this embodiment. Figure 2 A is the modified sample of this example and Figure 2 B is an unmodified silver coin. It can be seen that after the coating is grown, the anti-corrosion performance of the silver coin can be effectively improved.

[0019] Embodiment 3: The surface of the PP plastic sheet is modified, and there are Al2O3 layer, polymer conformal coating, Ag coating and ZnO coating on the surface from bottom to top, which are prepared according to the following steps: (1) Raise the temperature of the atomic layer deposition system chamber to 200°C, open the chamber, and place the PP plastic sheet into the sample pool; reduce the pressure in the chamber to below 50 hPa, and purge the reaction chamber with inert gas; introduce trimethylaluminum into the reaction chamber with a pulse time of 5 s; then introduce inert gas with a pulse time of 20 s; then introduce water with a pulse time of 4 s; finally, purge the unreacted water with inert gas to complete a cycle of Al2O3 deposition; repeat this process to deposit 500 cycles of Al2O3 layer on the substrate surface; (2) depositing a layer of dichloroparaxylene dimer coating on the surface of the sample obtained in step (1) to obtain a polymer conformal coating with a thickness of 40 μm; (3) The sample obtained in step (2) was immersed in a 15% mass concentration silver nitrate aqueous solution for 10 s, taken out and dried, and then immersed in a 30% mass concentration ascorbic acid aqueous solution for 15 s, taken out and dried, and the above cycle was repeated 10 times to obtain a sample substrate with an Ag coating; (4) The sample substrate obtained in step (3) is placed in an atomic layer deposition sample cell with the inner chamber temperature raised to 200°C; the pressure in the chamber is reduced to below 50 hPa, and the reaction chamber is purged with an inert gas; diethyl zinc is introduced into the reaction chamber with a pulse time of 10 s; then an inert gas is introduced with a pulse time of 60 s; then water is introduced with a pulse time of 10 s; finally, unreacted oxygen precursor water is purged with an inert gas to complete a cycle of depositing ZnO; this is repeated to deposit a ZnO coating with a thickness of 7 nm on the substrate surface.

[0020] The antibacterial activity value of the modified PP plastic sheet against Staphylococcus aureus ATCC6538P is greater than 5.4, and the antibacterial activity value against Escherichia coli ATCC8739 is greater than 6.1.

Claims

1. An insulating, waterproof and antibacterial coating structure, characterized in that: The method comprises the following structure: an Al2O3 layer, a polymer conformal coating, an Ag layer and a ZnO coating are sequentially included on the surface of a sample to be modified.

2. The insulating, waterproof and antibacterial coating structure according to claim 1, characterized in that: When the sample to be modified is made of silver, the surface modification layers are Al2O3 layer, polymer conformal coating and surface ZnO coating in sequence.

3. A method for preparing the insulating waterproof and antibacterial coating structure according to claim 1 or 2, characterized in that: At least the following steps are included: (1) First, an Al2O3 layer is deposited on the surface of the sample to be modified by atomic layer deposition; (2) depositing a polymer conformal coating on the surface of the sample obtained in step (1); (3) For non-silver samples to be modified, a layer of Ag is grown on the surface by using the Czochralski method; (4) Growing a ZnO coating on the surface of step (2) or step (3) by atomic layer deposition.

4. The method for preparing an insulating waterproof and antibacterial coating structure according to claim 3, characterized in that: The method of depositing the Al2O3 layer by atomic layer includes the following steps: Raise the temperature of the atomic layer deposition system cavity to 100-200°C, open the cavity, and place the sample in the sample pool; When the pressure in the chamber drops below 50 hPa, the reaction chamber is purged with inert gas; Trimethylaluminum is introduced into the reaction chamber with a pulse time of 4 to 10 s; then an inert gas is introduced with a pulse time of 20 to 60 s; then an oxygen precursor is introduced with a pulse time of 4 to 10 s; finally, the unreacted oxygen precursor is cleaned with an inert gas to complete a cycle of Al2O3 deposition; this process is repeated to deposit 500 to 1000 cycles of Al2O3 layers on the substrate surface.

5. The method for preparing an insulating waterproof and antibacterial coating structure according to claim 3, characterized in that: The polymer conformal coating is a p-xylene polymer, at least one of dichloro p-xylene dimer and octafluoro p-xylene dimer, and the coating thickness is 25-40 microns.

6. The method for preparing an insulating waterproof and antibacterial coating structure according to claim 3, characterized in that: The above-mentioned method of growing a layer of Ag on the surface by the pulling and dipping method is as follows: immerse the sample in a silver nitrate aqueous solution with a mass concentration of 10-15% for 10 seconds, take it out and dry it, then immerse it in an ascorbic acid or sodium borohydride aqueous solution with a mass concentration of 20-30% for 15-30 seconds, take it out and dry it, which is one cycle; repeat the above cycle 0-10 times.

7. The method for preparing an insulating waterproof and antibacterial coating structure according to claim 3, characterized in that: The ZnO coating is grown on the surface by atomic layer deposition according to the following steps: Raise the temperature of the atomic layer deposition system cavity to 100-250°C, open the cavity, and place the sample in the sample pool; When the pressure in the chamber drops below 50 hPa, the reaction chamber is purged with inert gas; Diethyl zinc is introduced into the reaction chamber with a pulse time of 4 to 10 s; then an inert gas is introduced with a pulse time of 20 to 60 s; then an oxygen precursor is introduced with a pulse time of 4 to 10 s; finally, the unreacted oxygen precursor is cleaned with an inert gas to complete a cycle of ZnO deposition; this process is repeated to deposit a ZnO coating with a thickness of 5 to 10 nm on the substrate surface.

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