Anti-atomic-oxygen anti-static black flexible film as well as preparation method and application thereof

Abstract

The invention relates to an anti-atomic oxygen anti-static black flexible film as well as a preparation method and application thereof. The anti-atomic oxygen anti-static black flexible film comprises a black flexible substrate, and a non-compact laminated structure and an anti-static coating which are formed on the surface of the black flexible substrate, the black flexible substrate comprises a black polyimide film, a black polyester film or a black polyethylene film; preferably, the solar absorptivity alpha s of the black flexible substrate is larger than or equal to 0.88, and the hemispherical emissivity epsilon H of the black flexible substrate is larger than or equal to 0.78.

Description

Technical Field

[0001] The invention relates to an anti-oxygen antistatic black flexible film and a preparation method and application thereof, which is mainly applied to a thermal control system of a spacecraft and belongs to the technical field of aerospace material application. Background Art

[0002] Polymer materials have the advantages of good flexibility, light weight, low cost, and easy processing, and are an important component of aerospace materials. Black flexible films with high solar absorption ratios have good light-shielding properties and can be used as stray light absorbing materials. For example, polyimide polymer materials have outstanding comprehensive performance, and their high and low temperature stability, high strength, good flexibility, light weight, radiation resistance, and low outgassing rate make them irreplaceable polymer materials in the aerospace field. At the same time, different types of polyimides also have their own special performance advantages and are widely used in spacecraft thermal control, power supply, and structural systems. Among them, the black composite film obtained by carbon doping of polyimide film has good light-shielding properties and can be used as electronic materials, electromagnetic interference elimination materials, and stray light absorbing materials. It is also a space material that has received widespread attention in recent years. Its high solar absorption ratio characteristics can be used in spacecraft thermal control systems and structural systems. However, during the service in space, the problem of adaptability to the space environment needs to be further solved. When used in the low-orbit space environment, when atomic oxygen collides with a high-speed spacecraft in orbit, the bombardment energy of atomic oxygen can reach 4 to 5 eV. When atomic oxygen with high energy and strong oxidizing properties acts on the surface of polymer materials, it is easy to corrode. Conventional black polyimide films used on the surface of low-orbit spacecraft will be severely corroded by atomic oxygen, etc. The black polyimide film can be completely etched away in a few months, and atomic oxygen protection must be carried out. When used on the outer surface of devices that are sensitive to charge and discharge in higher orbits or low orbits, it is also necessary to have anti-static function. In addition, the current solar absorption ratio of black polyimide films is usually around 0.92. With the development of spacecraft, the demand for further improvement of the solar absorption ratio of black flexible films has been proposed. Summary of the invention

[0003] In order to solve the above problems, the present invention utilizes the fact that the black flexible film substrate itself contains highly absorptive components such as carbon black. Based on the solar absorption characteristics of the substrate with a solar absorption ratio of αs≥0.90, the material system is stable in the space environment and has a low refractive index. Through surface modification, the anti-proton oxygen antistatic function is achieved at the same time, and the solar absorption ratio of the black flexible film is further increased.

[0004] In one aspect, the present invention provides an anti-oxygen antistatic black flexible film, comprising: a black flexible substrate, and a non-dense laminated structure and an antistatic coating formed on the surface of the black flexible substrate; the black flexible substrate comprises a black polyimide film, a black polyester film, or a black polyethylene film; preferably, the solar absorption ratio of the black flexible substrate is α s ≥0.88, hemispherical emissivity ε H ≥0.78.

[0005] Specifically, the present invention creatively proposes a low-orbit space environment protection idea of ​​constructing a scaly laminated bionic structure coating based on hydrotalcite or hydrotalcite-like layered nanomaterials. Specifically, a silane coupling agent is used to modify the hydrotalcite or hydrotalcite-like nanosheet coating and combine it with the black flexible film surface activation treatment to construct a strong anti-proton oxygen film layer on the surface of the black flexible substrate film. Moreover, the present invention also prepares an antistatic layer to reduce the accumulation of static electricity generated by long-term service in a low-orbit environment containing charged particles, avoid the impact of charging and discharging on the material itself and internal devices, especially electronic components, and prevent the material itself and internal components from failing.

[0006] In the present invention, the metal oxide generated by the reaction of hydrotalcite or hydrotalcite-like nanosheets and the antistatic film layer with atomic oxygen is inert to atomic oxygen, and the atomic oxygen inert substance will not react with atomic oxygen to generate volatile substances, and can isolate atomic oxygen. The arrangement of the hydrotalcite or hydrotalcite-like nanosheets parallel to the substrate direction is equivalent to infinitely extending the erosion path of atomic oxygen to the substrate, which can effectively prevent atomic oxygen from invading the substrate and greatly improve the substrate's anti-proton oxygen erosion performance. The coating not only has relatively excellent anti-proton oxygen performance, but also the arrangement of the layered hydrotalcite or hydrotalcite-like nanosheets or the porous antistatic nanomaterial non-dense structure has the advantages of good flexibility and resistance to peeling and cracking, and the coating has excellent firmness and durability. In addition, the non-dense micro-nano structure of the coating is used to reduce the refractive index and reflectivity, which can further improve the solar absorption ratio.

[0007] Preferably, the black polyimide film comprises: a polyimide film containing an inorganic black filler and / or an organic black filler, or a polyimide film coated with an inorganic black filler and / or an organic black filler; the inorganic black filler comprises at least one of black metal oxide, carbon black and graphite; the organic black filler comprises at least one of perylene black and aniline black; Preferably, the black polyimide film is a polyimide film doped with carbon black, the content of carbon black is 0.2-20wt%, and the total content of carbon element in the black polyimide is 65-85wt%; Preferably, the thickness of the black polyimide matrix is ​​3 to 100 μm. Among them, the black flexible matrix is ​​preferably a black polyimide matrix with excellent performance, which can be prepared by adding various light-shielding fillers to the polyimide precursor (polyamic acid), such as black metal oxides, carbon black, graphite, perylene black, aniline black and other inorganic or organic black fillers, and then preparing the film by salivation drying and high-temperature imidization treatment; or making these light-shielding materials into slurry and coating them on the polyimide film. Preferably, the black polyimide is preferably a heat-resistant inorganic black filler modified polyimide, such as carbon-containing polyimide doped with carbon black.

[0008] Preferably, the black polyimide matrix has carboxyl groups, hydroxyl groups or amine groups on its surface; the black polyimide matrix is ​​subjected to surface activation treatment to obtain a black polyimide matrix having carboxyl groups, hydroxyl groups or amine groups on its surface.

[0009] Preferably, the non-dense laminated structure is formed by cross-linking at least one of hydrotalcite nanosheets or hydrotalcite-like nanosheets and a silane coupling agent. The chemical composition of the hydrotalcite nanosheets or hydrotalcite-like nanosheets is [M 2+ 1-x M 3+ x (OH) 2 ] x+ A n- x / n ·mH 2 O, where M 2+ is a divalent metal cation, preferably selected from Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ , Cu 2+ At least one of 3+ is a trivalent metal cation, preferably selected from Al 3+ Cr 3+ , Fe 3+ Sc 3+ At least one of n- is an anion, preferably selected from CO 3 2- 、NO 3 - , Cl - OH - 、SO 4 2- ,PO 4 3- , C 6 H 4 (COO) 2 2-At least one of the following; x is in the range of 0.1 to 0.5, preferably 0.2 to 0.33; more preferably, the divalent metal cation is Mg 2+ , the trivalent metal cation is Al 3+ , most preferably Mg 2+ :Al 3+ =2:1.

[0010] Preferably, the hydrotalcite nanosheet or hydrotalcite-like nanosheet has a nearly regular hexagon or a circle; the diameter of the circumscribed circle of the circle or nearly hexagon is between 50 and 1000 nm, and the thickness of the hydrotalcite nanosheet is between 1 and 50 nm.

[0011] In the present invention, the surface micro-nano structure of the non-dense film layer of the anti-oxygen can be further adjusted by controlling the size of the hydrotalcite or hydrotalcite-like nanosheets, and the arrangement structure and refractive index of the film layer can be adjusted by controlling the size of the hydrotalcite or hydrotalcite-like nanosheets and the amount of the silane coupling agent added to increase the solar absorption ratio. In addition, the technology of the present invention has the characteristics of low raw material and preparation price and easy implementation and operation.

[0012] Preferably, the silane coupling agent is selected from at least one of aminohydrocarbon silane, 3-mercaptopropyltrimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; the aminohydrocarbon silane is selected from at least one of N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-aminopropyltriethoxysilane, preferably 3-aminopropyltriethoxysilane; The silane coupling agent simultaneously undergoes bonding reactions with the flexible substrate and the hydrotalcite or hydrotalcite-like nanosheets.

[0013] Preferably, the antigenic oxygen-resistant hydrotalcite coating further comprises a silane coupling agent modified layer distributed between the polymer matrix and the porous coating; the thickness of the silane coupling agent modified layer is 10 nm to 1000 nm.

[0014] Preferably, the ratio of hydrotalcite nanosheets or at least one of hydrotalcite-like nanosheets to silane coupling agent in the scale-like laminated bionic micro-nanostructure layer is (5-40) mg: (5-30) μL; the interlayer spacing of the hydrotalcite or hydrotalcite-like nanosheets is as large as possible, and the scale-like laminated bionic micro-nanostructure layer should be as loose as possible to minimize the refractive index of the film layer while meeting the requirements of coating firmness and anti-proton oxygen performance; the total thickness of the scale-like laminated bionic micro-nanostructure layer is 50 nm to 10 μm.

[0015] Preferably, the antistatic layer is a transparent conductive oxide material, and the material system is preferably selected from at least one of ITO film, indium oxide, tin oxide, zinc oxide and cadmium oxide; the structure of the antistatic layer is preferably a non-dense structure; the thickness of the antistatic layer does not exceed 100 μm. The material structure of the antistatic layer is preferably a non-dense structure to reduce the refractive index, the thickness of the antistatic layer does not exceed 100 μm to reduce the impact on the photothermal performance, and is not less than 10 nm to form a continuous conductive film.

[0016] In another aspect, the present invention provides a method for preparing an anti-oxygen antistatic black flexible film, comprising: (1) adding a silane coupling agent to an aqueous dispersion containing at least one of hydrotalcite nanosheets or hydrotalcite-like nanosheets and mixing, then coating the mixture on a surface of a black flexible substrate, and heat treating the mixture at 80 to 300° C. for 1 to 72 hours to obtain a hydrotalcite or hydrotalcite-like coating with a scale-like laminated bionic micro-nano structure; (2) An antistatic layer is prepared on the surface of a hydrotalcite or hydrotalcite-like coating by a wet chemical method or a vacuum coating method to obtain an anti-oxygen-resistant antistatic black flexible film.

[0017] Preferably, the black flexible film is preferably a black polyimide substrate. Before coating, the black polyimide substrate is subjected to a surface activation treatment; preferably, the surface activation treatment includes: wet chemical treatment, ultraviolet radiation treatment, plasma treatment, and corona treatment; more preferably, the wet chemical treatment is acid-base modification, and the alkali-acid modification includes alkali treatment and acid treatment; most preferably, the polyimide substrate is treated in a NaOH solution with a concentration of 0.1 to 6 mol / L and an acetic acid solution with a concentration of 0.1 to 6 mol / L for 0.2 to 6 h, respectively, and then washed and dried to obtain a polymer matrix with surface active groups (hydroxyl, carboxyl or amine).

[0018] Preferably, the concentration of the aqueous dispersion containing at least one of the hydrotalcite nanosheets or the hydrotalcite-like nanosheets is 5 to 100 mg / mL; and the mixing method is stirring or ultrasonic dispersion.

[0019] Preferably, the coating is performed at least once; the coating includes spin coating, drip coating, spray coating, scraping, coating or static pulling.

[0020] On the other hand, the present invention also provides an application of an anti-proton oxygen antistatic black flexible film in the aerospace field. The anti-proton oxygen coating can protect the internal materials from damage by atomic oxygen in the low-orbit space environment, and is particularly suitable for the design requirements of different subsystems of low-orbit long-life spacecraft. Utilizing its high absorption ratio characteristics, the flexible film can be used in the optical systems of various spacecraft, strongly absorb light in a certain wavelength range, reduce the stray light and astigmatism of the system, such as the back of the satellite antenna and the camera tube to eliminate stray light, and eliminate or avoid the interference of various stray lights on the imaging system and sensor. The high solar absorption ratio and high emissivity characteristics of the flexible film can be widely used in the thermal control system of spacecraft to achieve high absorption of light in the solar radiation band and high emission of light in the infrared band. Preferably, the flexible film also has an anti-static function, which can protect the internal materials and components from the interference of charging and discharging, and is particularly suitable for use on the outside of electronic components that are sensitive to charged particles.

[0021] Beneficial effects of the present invention: (1) The present invention provides an anti-proton oxygen antistatic black flexible film, which utilizes hydrotalcite or hydrotalcite-like layered nanomaterials combined with an antistatic film layer to simultaneously achieve excellent anti-proton oxygen function, antistatic performance and high solar absorption ratio function; (2) The present invention provides an anti-proton oxygen antistatic black flexible film, which has excellent resistance to space environment radiation. Its base material is a black flexible film material, the outermost layer exposed to the space environment is a transparent conductive oxide material, and the second outer layer is a hydrotalcite or hydrotalcite-like coating layered inorganic nanomaterial. The coating itself has excellent anti-proton oxygen and antistatic properties. On the one hand, the transparent conductive oxide antistatic layer itself can prevent the erosion of atomic oxygen to a certain extent. On the other hand, the hydrotalcite tends to form a scale-like laminated structure parallel to the direction of the substrate, which can fully utilize the spontaneous adsorption of highly active atomic oxygen after entering the protective layer to capture and stably convert atomic oxygen, which is equivalent to infinitely extending the erosion path of atomic oxygen to the substrate, thereby effectively preventing the erosion of the substrate by atomic oxygen, and has excellent anti-proton oxygen performance. In addition, the inorganic indium tin oxide antistatic layer exposed to the space environment and the inner layer of the hydrotalcite coating and the polyimide-like black matrix have good tolerance to ultraviolet rays, electrons, and protons, so that the anti-proton oxygen antistatic black flexible film of the present invention has the beneficial effect of resistance to space environment radiation; (3) The present invention provides an anti-proton oxygen antistatic black flexible film, which further improves the solar absorption ratio on the basis of making full use of the light absorption characteristics of conventional black polyimide films. Different from the current idea of ​​achieving high solar absorption ratios using carbon nanotubes or black paint materials, the anti-proton oxygen antistatic black flexible film of the present invention combines the characteristics of the substrate and the surface modification technology, and while achieving high space environment stability, it also makes full use of the micro-nano structure regulation to further improve the high solar absorption ratio. On the one hand, it makes full use of the characteristics of the black flexible substrate that already contains light-absorbing materials such as carbon black to achieve the absorption of sunlight; on the other hand, it makes full use of the micro-nano structure characteristics of the material to prepare a material with a low refractive index on the surface of the black flexible substrate, and the refractive index gradient from vacuum or atmospheric environment to black polyimide takes into account the high absorption of sunlight by carbon materials and the anti-reflection effect of the surface film layer on sunlight. Unlike conventional carbon materials and other solar absorption ratio materials, it is difficult to utilize the above-mentioned high solar absorption ratio regulation mechanism, and the stability of the low-orbit space environment is poor or excessive pursuit of high solar absorption ratio uses too loose structures to lose the firmness of the film layer, affecting subsequent use and processing. The present invention improves the solar absorption ratio of commercial black polyimide film from about 0.92 to above 0.96 while achieving high space environment stability; (4) The bonding force between different layers of the anti-proton oxygen antistatic black flexible film is strong, and the excellent adhesion between different film layers is mainly achieved through chemical bonding. The hydrotalcite or hydrotalcite-like coating is formed by in-situ construction of the surface of the black flexible substrate after surface activation by a silane coupling agent. The silane coupling agent that can react with the active groups such as hydroxyl groups on the surface of the black flexible substrate after surface activation treatment forms a strong chemical bond with the hydrotalcite coating and the black flexible substrate. In addition, a small amount of small molecular silane coupling agent reacts and diffuses into the black flexible substrate after surface activation treatment to form a thinner chemically bonded diffusion reaction film layer to achieve a strong bond. At the same time, the silane coupling agent can react and bond with the hydroxyl groups on the surface of the transparent conductive oxide nanoparticles, especially the surface of the aqueous solution of the transparent conductive oxide nanoparticles has more hydroxyl groups. In terms of flexibility, unlike the existing dense inorganic coatings that are easy to peel off and crack, the non-dense arrangement structure of this coating can release stress to a certain extent, and it is not easy to crack and fall off during the bending process. However, it is dense in the direction of atomic oxygen erosion, and can fully capture and transform atomic oxygen to make it lose its corrosiveness, thus achieving the coordinated optimization of the film refractive index and the mechanical properties of the coating. The film has excellent protective performance and is strong and durable. (5) The hydrotalcite or hydrotalcite-like coating structure used in the present invention is composed of positive charges between the main layers and anions in the interlayer guest. Therefore, the chemical composition of the layers, the internal space composition of the layers, the internal grain size and distribution, and the type and number of anions between the layers are all controllable, which is very suitable for the multifunctional design of micro-nano structure control and composition. For example, its inorganic layers can scatter and absorb a small amount of ultraviolet rays, and the exchangeability of the interlayer guest allows organic anions with ultraviolet absorption properties to enter the hydrotalcite or hydrotalcite-like interlayer to achieve ultraviolet shielding. In addition, by introducing transition metals to synthesize hydrotalcite with ternary metal components, and further through sulfurization, the microstructure band gap is narrowed in two steps, and the narrowing of the band gap can effectively improve the conductivity and anti-ultraviolet performance, and further improve its overall antistatic performance, which is beneficial for its use at different orbital altitudes and different spacecraft subsystems; (6) The anti-proton oxygen antistatic black flexible film of the present invention has the advantage of being easy to cut and process like conventional flexible film materials, and can be used after being cut at will, and can also be used in combination with other flexible thermal control materials. Moreover, the film itself is easy to paste and construct, and is convenient to paste and implement on-site on the surface of a spacecraft, and can meet the needs of multi-scenario use of a spacecraft; (7) The raw materials of the anti-oxygen high solar absorption ratio flexible film of the present invention are commonly used commercial materials, which can be purchased in bulk at a relatively low price. At the same time, it has low requirements for equipment, does not have the requirements of conventional coating solutions for vacuum control, has a simple process, is easy to operate, and has no process factors that limit its large-scale implementation, which is conducive to low-cost, batch development and easy to further promote and apply in the civilian field. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The schematic diagram of the structure of the anti-proton oxygen antistatic black flexible film disclosed in the present invention is that the flexible film is constructed by coating hydrotalcite or hydrotalcite-like nanosheets modified by a silane coupling agent on the surface of a black polyimide substrate to construct a scale-laminated bionic structure coating, and further adding a transparent conductive oxide layer on the surface of the hydrotalcite or hydrotalcite-like coating to improve the antistatic performance; Figure 2 This is an electron microscope photo of the sample surface in Example 1. It can be seen from the figure that the coating surface has a certain degree of roughness and is not a smooth and flat dense structure; Figure 3 This is a high-power electron microscope photo of the sample surface in Example 1. Figure 2 and Figure 3 It can be seen that the microstructure of the coating is formed by hydrotalcite or hydrotalcite-like nanosheets arranged in a scale-like stacking manner, which is a non-dense film layer; Figure 4This is an EDS image of the sample surface in Example 1. It can be seen from the figure that the coating contains elements such as magnesium, aluminum, silicon, carbon, nitrogen, and oxygen. Since the depth of the EDS test signal is greater than the thickness of the coating, the test signal will contain information about the matrix elements, but magnesium, aluminum, and silicon are not matrix components, indicating that a coating containing silane coupling agent-modified hydrotalcite nanosheets has been successfully prepared, in which magnesium, aluminum, and silicon can play a role in atomic oxygen protection; Figure 5 This is an electron microscope photograph of the sample surface in Example 2. It can be seen from the figure that the surface has a certain degree of roughness after being coated with the antistatic coating, and it is not a smooth and dense structure. Figure 6 This is the EDS image of the sample surface in Example 2. It can be seen from the figure that the coating contains elements such as indium, tin, magnesium, aluminum, silicon, carbon, nitrogen, and oxygen, wherein the contents of indium and tin are 9.9at% and 2.24at%, respectively. Since the depth of the EDS test signal is greater than the thickness of the coating, the test signal will contain information on the internal material elements, but indium and tin elements are not components before coating, indicating that the ITO coating was successfully prepared. DETAILED DESCRIPTION

[0023] The present invention is further described below by the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, but not to limit the present invention.

[0024] In the present disclosure, the anti-proton oxygen antistatic black flexible film comprises: a black flexible substrate, and a scale-like laminated structure coating and an antistatic layer formed on the surface of the black flexible substrate, which is composed of a laminated structure formed by hydrotalcite nanosheets or hydrotalcite-like nanosheets with a certain sheet size and a small amount of silane coupling agent.

[0025] In an optional embodiment, the chemical composition of the hydrotalcite nanosheets or hydrotalcite-like nanosheets of a certain size can be expressed as [M 2+ 1-x M 3+ x (OH) 2 ] x+ A n- x / n ·mH 2 O. Among them M 2+ For divalent metal cations, such as Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ , Cu 2+ etc.; M 3+ For trivalent metal cations, such as Al 3+ Cr 3+ , Fe 3+ Sc 3+ etc. n-Anions, such as CO 3 2- 、NO 3 - , Cl - OH - 、SO 4 2- ,PO 4 3- , C 6 H 4 (COO) 2 2- Inorganic and organic ions and complex ions; x ranges from 0.1 to 0.5, preferably from 0.2 to 0.33. The preferred composition is a hydrotalcite-like nanosheet with a magnesium-aluminum ratio of 2:1, wherein the divalent metal cation, trivalent metal cation, and anion are Mg 2+ 、Al 3+ , Cl - , and Mg 2+ :Al 3+ =2:1.

[0026] In an optional embodiment, the hydrotalcite or hydrotalcite-like nanosheets of a certain size can be prepared in large quantities by a two-step method of co-precipitation and hydrothermal treatment, and the sheet layers are nearly regular hexagons or circles, the circle diameter or the hexagonal circumscribed circle diameter is in the range of 50nm to 1000nm, and the thickness of the hydrotalcite or hydrotalcite-like nanosheets is 1 to 50nm.

[0027] In an optional embodiment, the antistatic layer is a transparent conductive oxide material, and the material system is preferably selected from at least one of ITO film, indium oxide, tin oxide, zinc oxide and cadmium oxide; the material structure is preferably a non-dense structure to reduce the refractive index, and the thickness of the antistatic layer does not exceed 100 μm.

[0028] The following is an exemplary description of the method for preparing the anti-oxygen antistatic black flexible film of the present invention.

[0029] Preparation of black polyimide substrate surface activation layer. After the black polyimide substrate is cleaned, it is subjected to surface activation treatment by wet chemical treatment, ultraviolet irradiation treatment or plasma treatment to prepare an activation layer having carboxyl, hydroxyl or amine groups on the surface. Preferably, the surface activation treatment is a wet chemical treatment; more preferably, the surface of the polymer substrate is subjected to alkali-acid modification; the alkali-acid modification includes alkali treatment and acid treatment, and then washed and dried to obtain a black polyimide substrate with surface active groups (hydroxyl, carboxyl, amine). Among them, the thickness of the black polyimide substrate is not less than 3μm, and it is a type of modified black polyimide substrate in which carboxyl, hydroxyl and amine groups are generated on the surface of the black polyimide after surface activation treatment, including but not limited to: black polyimide modified by inorganic or organic black fillers such as black metal oxides, carbon black, graphite, perylene black, aniline black, such as carbon black modified black polyimide and black polyimide substrate film using polyacrylonitrile as a light shielding agent. The content of carbon black is generally 0.2-20wt%

[0030] Preparation of an aqueous dispersion containing hydrotalcite nanosheets or / and hydrotalcite-like nanosheets. Preferably, the dispersion is prepared by a two-step method of coprecipitation and hydrothermal method. Taking the preferred magnesium-aluminum hydrotalcite-like nanosheets as an example, the steps of preparing the hydrotalcite-like nanosheets by the two-step method of coprecipitation and hydrothermal method include: preparing a solution of magnesium chloride hexahydrate, aluminum chloride hexahydrate, and water in a molar ratio of (3-x): 3x: 350 (wherein the range of x is between 0.1 and 0.5, preferably 0.2 to 0.33), adding ammonia water and stirring to adjust the pH to 9 to 10, and standing after stirring. The resulting suspension is centrifuged and washed with deionized water to a pH of 8 to 9. It is then placed in an oven at 80 to 300°C for hydrothermal treatment for 24 hours.

[0031] A certain amount of aminoalkylsilane is added as a crosslinking agent to the aqueous dispersion containing hydrotalcite nanosheets or / and hydrotalcite-like nanosheets, and then after stirring for a certain period of time, it is coated on the polymer substrate modified by alkali / acid in two steps to form a wet film. The coating method is any one of spin coating, drop coating, spray coating, blade coating, coating or hysteresis pulling.

[0032] In an optional embodiment, the heat treatment temperature may be a temperature value within 80 to 300° C. or a gradient change formed by several temperature values. The total time of the heat treatment may be 1 to 48 hours. Preferably, the heat treatment process is 80° C., 110° C., 150° C. for 1 hour, 1 hour, and 3 hours, respectively.

[0033] Preparation of antistatic layer: For example, the ITO antistatic layer is coated on the surface of the hydrotalcite modified layer with an ITO coating having a thickness of about 100 to 2000 nm by wet chemical method (such as spin coating or hysteresis pulling method), or ITO having a thickness of about 30 to 100 nm can be plated by magnetron sputtering.

[0034] Performance Testing: The surface morphology and composition of the samples were tested using a scanning electron microscope combined with an energy dispersive X-ray spectrometer. Refer to GJB 2502.2 Test Method for Thermal Control Coatings of Spacecraft Part 2: Solar Absorption Ratio Test to test the solar absorption ratio of the coating surface; refer to GJB 2502.3 Test Method for Thermal Control Coatings of Spacecraft Part 3: Emissivity Test to test the hemispherical emissivity of the coating surface; refer to GJB 2704 General Specification for Thermal Control Coatings of Spacecraft to use 3M610 tape (nominal tension 4.7N / cm) to test the adhesion; refer to GB / T 6742 Paint and Varnish Bend Test (Cylindrical Mandrel) to test the surface cracking of the surface modified surface after the bending test (180°) of a cylindrical bending tester with a bending diameter of 2mm; refer to GJB 2502.8 Test Method for Thermal Control Coatings of Spacecraft Part 8: Thermal Cycle Test to carry out hot and cold alternating tests, and test the appearance and thermal radiation performance after 100 high and low temperature alternations at -110℃~+150℃; refer to GJB 2502.5 Test method for thermal control coatings of spacecraft Part 5: Vacuum-ultraviolet irradiation test Carry out ultraviolet irradiation test to check the thermal radiation performance after vacuum-ultraviolet irradiation test with cumulative dose of 2000ESH; refer to GJB 2502.7 Test method for thermal control coatings of spacecraft Part 7: Vacuum-electron irradiation test with cumulative dose of 2.5×10 15 e / cm 2 Thermal radiation performance after electron irradiation test; refer to GJB 2502.6 Spacecraft Thermal Control Coating Test Method Part 6: Vacuum-Proton Irradiation Test Inspection Cumulative Dose 2.5×10 15 p / cm 2 The thermal radiation performance after proton irradiation test; refer to GJB 2502.9 Test Method for Thermal Control Coatings of Spacecraft Part 9: Atomic Oxygen Test to carry out atomic oxygen irradiation test, and check the cumulative dose of 2.61×10 21 atoms / cm 2 The mass loss and thermal radiation performance after atomic oxygen irradiation test; refer to GB / T 1410 Test method for volume resistivity and surface resistivity of solid insulating materials to test the surface resistance of the sample; refer to GJB 2704 General specification for thermal control coatings of spacecraft, use an ultra-fine dust-free cloth dipped in acetone (chemically pure) to gently wipe the surface along the surface direction of the modified layer, wipe it 3 times and observe the appearance with the naked eye to check its cleaning resistance.

[0035] The following further examples are given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the scope of protection of the present invention. The specific process parameters and the like in the following examples are also only examples within a suitable range, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values ​​​​exemplified below.

[0036] Example 1 According to the technical scheme of the present invention, an anti-oxygen-resistant and antistatic black polyimide flexible film material is prepared. (1) Preparation of the black polyimide substrate surface activation layer. The HB-N-25 black polyimide film product produced by Shenzhen Ruihuatai Film Technology Co., Ltd. was used, which had a solar absorption ratio of 0.92 and a hemispherical emissivity of 0.88. The polyimide flexible substrate was scrubbed with a dust-free cloth dipped in a mixture of ethanol and acetone to remove dust, oil stains and other contamination during the preparation and transportation process; the PI film was placed in a 1 mol / L sodium hydroxide alkaline solution for 1 hour, and then the residual alkaline solution was rinsed with deionized water and ethanol. The rinsed PI film was then placed in a 1 mol / L acetic acid acid solution for 1 hour, and then rinsed clean. Finally, the wet film was dried at room temperature to obtain an alkali-acid modified PI substrate; (2) Preparation of aqueous dispersion of magnesium-aluminum hydrotalcite nanosheets. Dissolve 0.6449 g of magnesium chloride hexahydrate and 1.9314 g of aluminum chloride hexahydrate in 50 mL of deionized water to prepare a precursor solution. Quickly add ammonia water and stir to adjust the pH to 9-10. After stirring, let it stand for aging. The resulting white suspension was centrifuged and washed with deionized water several times to a precipitate with a pH of 8-9. After washing, add a certain amount of deionized water to the precipitate and stir evenly to obtain a dispersion with a mass concentration of 18 mg / mL. The dispersion was then hydroheated in an oven at 150°C for 24 hours. Finally, a magnesium-aluminum hydrotalcite nanosheet dispersion with a nearly regular hexagonal shape and a circumscribed circle diameter of approximately 320 nm and a thickness of approximately 7.3 nm was obtained; (3) Preparation of hydrotalcite-like flaky laminated structure on the surface of black polyimide matrix. Add 3-aminopropyltriethoxysilane (50 μL) (wherein the ratio of at least one of the hydrotalcite nanosheets to the silane coupling agent is 9 mg:5 μL) to the above-mentioned magnesium-aluminum hydrotalcite nanosheet dispersion (5 mL). After stirring, coat it on the surface of the surface-modified black polyimide film, and then place it in an air atmosphere at 60, 90, 120°C, and 150°C for heat treatment for 1h, 1h, 3h, and 3h, respectively, to obtain the above-mentioned fish-scale-like, non-dense structured anti-proton oxygen hydrotalcite coating with a thickness of about 1 μm;

[0037] The material properties and environmental adaptability tests were carried out systematically for the anti-oxygen antistatic black flexible film material prepared according to the above steps. The results showed that the treated surface was dark black, with no obvious foreign matter or stains on the surface, the film layer was uniform in color, without peeling or shedding, and the appearance was intact; under a scanning electron microscope, the surface showed a scale-like laminated structure, with Mg, Al, and Si contents of 10.61at%, 5.16at%, and 3.98at%, respectively; the solar absorption ratio α s is 0.96~0.97, about 0.96, hemispherical emissivity ε H The film has a thermal radiation performance of high solar absorption ratio and high hemispherical emissivity. After the 3M610 pull-off test, the film has no blistering and no obvious shedding, and the film has good adhesion. After the bending test (180°, 100 times) of a cylindrical bending tester with a bending diameter of 2mm, the film has no obvious shedding, and has excellent resistance to peeling and cracking. The film is kept at -110℃~+150℃, with 100 cycles, and the residence time at high and low temperatures is 5 minutes, and the transfer time is less than 10s. After the test, the appearance is intact, without blistering, peeling, or shedding. There is no obvious change in the solar absorption ratio and hemispherical emissivity before and after the test, and the film has excellent resistance to cold and hot alternation. The vacuum degree is better than 1.3×10 -3 Pa vacuum condition, after the vacuum-ultraviolet irradiation test with a cumulative dose of 2000ESH (equivalent solar hours), the solar absorption ratio and hemispherical emissivity have no obvious changes, and have excellent ultraviolet radiation resistance; after the total electron irradiation agent of 2.5×10 15 e / cm 2 After the energy irradiation test, the solar absorption ratio and hemispherical emissivity have no obvious changes, and have excellent resistance to electron irradiation; in a vacuum degree better than 1.3×10 -3 Pa vacuum condition, the total proton irradiation dose was 2.5×10 14 p / cm 2 After the energy irradiation test, the solar absorption ratio and hemispherical emissivity did not change significantly, and the sample had good proton irradiation resistance. 21 atoms / cm 2 After atomic oxygen irradiation, there is no obvious mass loss, no significant change in solar absorption ratio and hemispherical emissivity, and the substrate is intact without any signs of corrosion, indicating that the black polyimide flexible film with a hydrotalcite-like flaky laminated structure coating on the surface has excellent anti-atomic oxygen performance. The surface square resistance of the test is 10 13 Ω / □, the distance is usually the anti-static requirement of thermal control coating of spacecraft (≤10 9In addition, the sample also has a certain degree of washing resistance. After being lightly wiped three times with an ultra-fine dust-free cloth dipped in acetone (chemically pure), there is no obvious foreign matter or pollution on the surface. The surface modification layer is dark black in appearance. The surface modification layer is uniform, without peeling or shedding. Combined with the adhesion and bending tests, it can be seen that the film layer has excellent firmness and durability.

[0038] Example 2 The preparation process of the anti-proton oxygen antistatic black flexible film in this Example 2 is similar to that in Example 1, with the only difference being: Step (4) preparation of the antistatic layer: 1 g of indium tin oxide (ITO) nanopowder was dissolved in 100 mL of water, stirred and ultrasonically dispersed, and then coated on the surface of the hydrotalcite coating treated in step (3), and the connection between the indium tin oxide (ITO) nanopowders was promoted by heat treatment to form a conductive network, and the heat treatment conditions were heat treatment in an air atmosphere at 60, 90, 120°C, and 150°C for 1 h, 1 h, 3 h, and 3 h, respectively.

[0039] The non-dense structure of the ITO antistatic layer gives the material an antistatic function, and its surface resistance varies slightly at different locations, which is 10 5 ~10 6 Ω / □, meeting the application requirements of anti-static thermal control coatings for spacecraft. Figure 5 As shown in Figure 1, the surface of the prepared ITO layer is relatively rough, not a smooth and dense structure. The EDS spectrum of the sample surface is shown in Figure 1. Figure 6 As shown in the figure, it can be seen that the coating contains indium, tin, magnesium, aluminum, silicon, carbon, nitrogen, oxygen and other elements, among which the indium and tin contents are 9.9at% and 2.24at%, respectively. Since the depth of the EDS test signal is greater than the coating thickness, the test signal will contain internal material element information, but indium and tin elements are not pre-coating components, indicating that the ITO coating was successfully prepared. Solar absorption ratio α s It is about 0.96, which is slightly lower than before adding ITO anti-static. This is mainly because the refractive index of ITO is slightly higher than that of hydrotalcite. However, due to the non-dense structure of ITO, the solar absorption ratio does not change much within a certain range of ITO thickness. The hemispherical emissivity ε H The film has a thermal radiation performance of high solar absorption ratio and high hemispherical emissivity. After the 3M610 pull-off test, the film has no blistering and no obvious shedding, and the film has good adhesion. After the bending test (180°, 100 times) of a cylindrical bending tester with a bending diameter of 2 mm, the film has no obvious shedding, and has excellent resistance to peeling and cracking. After the test at -110℃~+150℃ and 100 cycles, the appearance is intact, without blistering, peeling or shedding. There is no obvious change in the solar absorption ratio and hemispherical emissivity before and after the test, and the resistance to cold and hot alternation is excellent. The sample has been subjected to a cumulative flux of 2.61×10 21atoms / cm 2 After atomic oxygen irradiation, there is no obvious mass loss, and the solar absorption ratio and hemispherical emissivity have no obvious changes. At the same time, the substrate is intact without any signs of corrosion, indicating that the black polyimide flexible film with surface constructed ITO coating and hydrotalcite coating has excellent anti-atomic oxygen properties.

[0040] Example 3 The preparation process of the hydrotalcite-like flaky laminated structure coating in Example 3 is similar to that in Example 2, except that the hydrotalcite dispersion is heated at 80°C. When the dispersion in Example 3 is heated in an oven at 80°C for 24 hours, the prepared magnesium-aluminum hydrotalcite nanosheets are still nearly regular hexagonal, and the diameter of the circumscribed circle is about 120nm. The results show that the treated surface is dark black in appearance; the solar absorption ratio α s is 0.95~0.96, about 0.96, hemispherical emissivity ε H The black polyimide flexible film has a cumulative flux of 2.61×10 21 atoms / cm 2 After atomic oxygen irradiation, there is no obvious mass loss, the substrate is intact without any signs of corrosion, and the solar absorption ratio and hemispherical emissivity have no obvious changes; at the same time, the surface resistivity is 10 5 ~10 6 Ω / □, has excellent anti-oxygen performance and meets the application requirements of anti-static thermal control coatings for spacecraft.

[0041] Example 4 The preparation process of the hydrotalcite-type flaky laminated structure coating in this Example 4 is similar to that in Example 2, except that the amount of silane coupling agent added is different. In this Example 4, 3-aminopropyltriethoxysilane (25 μL) is added to the above-mentioned magnesium-aluminum hydrotalcite nanosheet dispersion (5 mL) (wherein the ratio of hydrotalcite nanosheet to silane coupling agent is 18 mg: 5 μL). The results show that the treated surface has a dark black appearance; the solar absorption ratio α s is 0.95~0.96, about 0.96, hemispherical emissivity ε H The black polyimide flexible film has a cumulative flux of 2.61×10 21 atoms / cm 2 After atomic oxygen irradiation, there is no obvious mass loss, the substrate is intact without any signs of corrosion, and the solar absorption ratio and hemispherical emissivity have no obvious changes; at the same time, the surface resistivity is 10 5 ~10 6 Ω / □, has excellent anti-oxygen performance and meets the application requirements of anti-static thermal control coatings for spacecraft.

[0042] Example 5 The preparation process of the hydrotalcite-type flaky laminated structure coating in this Example 5 refers to that in Example 2, with the only difference being the amount of silane coupling agent added. In this Example 5, N-aminoethyl-3-aminopropyltriethoxysilane (50 μL) was added to the above-mentioned magnesium-aluminum hydrotalcite nanosheet dispersion (5 mL) (wherein the ratio of hydrotalcite nanosheets to silane coupling agent was 9 mg: 5 μL). The results showed that the treated surface had a dark black appearance, with no obvious foreign matter or stains on the surface, the film layer had uniform color, no peeling or shedding, and an intact appearance; the solar absorption ratio α s is 0.95~0.96, about 0.96, hemispherical emissivity ε H The black polyimide flexible film has a cumulative flux of 2.61×10 21 atoms / cm 2 After atomic oxygen irradiation, there is no obvious mass loss, the substrate is intact without any signs of corrosion, and the solar absorption ratio and hemispherical emissivity have no obvious changes; at the same time, the surface resistivity is 10 5 ~10 6 Ω / □, has excellent anti-oxygen performance and meets the application requirements of anti-static thermal control coatings for spacecraft.

[0043] Comparative Example 1 If the conventional black polyimide film (HB-N-25 product of Shenzhen Ruihuatai Film Technology Co., Ltd.) used in the present invention is not surface treated, its solar absorption ratio is α s is 0.92, and the hemispherical emissivity ε H is 0.88, after 2.61×10 21 atoms / cm 2 After atomic oxygen irradiation, the etched polyimide material has been completely etched away. The erosion rate of polyimide materials does not change much with the increase of atomic oxygen dose. The mass loss increases linearly with the increase of atomic oxygen dose. 20 atoms / cm 2 ) Mass loss under atomic oxygen test is 0.40 mg / cm 2 Calculation, 2.61×10 21 atoms / cm 2 The theoretical mass loss after atomic oxygen irradiation is about 9.49 mg / cm 2The etched thickness is 66.84μm, far exceeding the actual film thickness of 25μm. This comparison also shows that if conventional commercial black polyimide film is used in a low-orbit atomic oxygen environment, the influence of atomic oxygen must be considered. Due to the high erosion rate of atomic oxygen, it is difficult to achieve long-term service in a low-orbit by using multiple layers of conventional commercial black polyimide film. The surface square resistance of the test is 10 13 Ω / □, the distance is usually the anti-static requirement of thermal control coating of spacecraft (≤10 9 Ω / □) has a large gap.

[0044] Comparative Example 2 Widely used conventional polyimide films (such as the commonly used PMDA-ODA polyimide films without carbon black) are yellow transparent flexible films. Most visible light will pass through the polyimide film, and its solar absorption is relatively low. The solar absorption ratio of a 25μm thick film is less than 0.40 (tested by subtracting transmission and reflection). For example, the solar absorption ratio of Kapton 100HN type (about 25μm thick) yellow polyimide film tested is about 0.24, and the hemispherical emissivity is about 0.48; after increasing the film thickness to 50μm, the solar absorption ratio of Kapton 200HN type film is only 0.30, and the hemispherical emissivity is about 0.60; Ruihuatai's 50μm thick KHN type film has a solar absorption ratio of 0.24 and a hemispherical emissivity of about 0.61; although the emissivity of the polymer film can be improved by increasing its thickness, the widely used conventional yellow polyimide film has a relatively low solar absorption, which is far from meeting the requirements of high solar absorption ratio, and the emissivity is also lower than that of black polyimide film.

[0045] Comparative Example 3 See Example 1, the difference is: a conventional 25μm thick Kapton 100HN polyimide film is selected. Its absorptivity and emissivity are tested. The solar absorptivity of the sample using Kapton 100HN polyimide film is about 0.25, and the hemispherical emissivity is about 0.52; the results show that the solar absorptivity of the conventional yellow polyimide film is extremely limited by the method of the present invention. At the same time, although the emissivity of the conventional yellow polyimide film can be increased by the method of the present invention, it is still lower than that of the black polyimide film. The realization of high solar absorptivity and high emissivity must be achieved in combination with the selection of the substrate.

[0046] Comparative Example 4 See Example 2, the difference is: a conventional 25μm thick Kapton 100HN polyimide film is selected. Its absorptivity and emissivity are tested. The solar absorptivity of the sample using Kapton 100HN polyimide film is about 0.26, and the hemispherical emissivity is about 0.53; the results show that the solar absorptivity of the conventional yellow polyimide film is extremely limited by the method of the present invention. At the same time, although the emissivity of the conventional yellow polyimide film can be increased by the method of the present invention, it is still lower than that of the black polyimide film. The realization of high solar absorptivity and high emissivity must be achieved in combination with the selection of the substrate.

[0047] The raw materials listed in the present invention, as well as the upper and lower limits and interval values ​​of the raw materials of the present invention, and the upper and lower limits and interval values ​​of the process parameters can all realize the present invention, and the embodiments are not listed one by one here.

[0048] Finally, it is necessary to explain here that the above embodiments are only used to further illustrate the technical solution of the present invention in detail and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the above content of the present invention all fall within the scope of protection of the present invention.

Claims

1. An anti-oxygen antistatic black flexible film, characterized in that: include: A black flexible substrate, and a non-dense laminated structure and an antistatic coating formed on the surface of the black flexible substrate; The black flexible substrate comprises a black polyimide film, a black polyester film, or a black polyethylene film; preferably, the solar absorption ratio of the black flexible substrate is α s ≥0.88, hemispherical emissivity ε H ≥0.

78.

2. The anti-proton oxygen antistatic black flexible film according to claim 1, characterized in that: The black polyimide film includes: a polyimide film containing an inorganic black filler and / or an organic black filler, or a polyimide film coated with an inorganic black filler and / or an organic black filler; the inorganic black filler includes at least one of black metal oxide, carbon black, and graphite; the organic black filler includes at least one of perylene black and aniline black; Preferably, the black polyimide film is a polyimide film doped with carbon black, the content of carbon black is 0.2-20wt%, and the total content of carbon element in the black polyimide is 65-85wt%; Preferably, the thickness of the black polyimide matrix is ​​3-100 μm.

3. The anti-proton oxygen antistatic black flexible film according to claim 1, characterized in that: The surface of the black polyimide matrix has carboxyl groups, hydroxyl groups or amine groups; the black polyimide matrix is ​​subjected to surface activation treatment to obtain a black polyimide matrix having carboxyl groups, hydroxyl groups or amine groups on the surface.

4. The anti-proton oxygen antistatic black flexible film according to claim 1, characterized in that: The chemical composition of the hydrotalcite nanosheet or hydrotalcite-like nanosheet is [M 2+ 1-x M 3+ x (OH)2] x+ A n- x / n mH2O, where M 2+ is a divalent metal cation, preferably selected from Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ , Cu 2+ At least one of 3+ is a trivalent metal cation, preferably selected from Al 3+ Cr 3+ , Fe 3+ Sc 3+ At least one of n- is an anion, preferably selected from CO3 2- 、NO3 - , Cl - OH - 、SO4 2- PO4 3- 、C6H4(COO)2 2- At least one of the following; x is in the range of 0.1 to 0.5, preferably 0.2 to 0.33; more preferably, the divalent metal cation is Mg 2+ , the trivalent metal cation is Al 3+ , most preferably Mg 2+ :Al 3+ =2:

1.

5. The anti-proton oxygen antistatic black flexible film according to claim 1, characterized in that: The sheet layer of the hydrotalcite nanosheet or hydrotalcite-like nanosheet is nearly regular hexagonal or circular; the diameter of the circumscribed circle of the circular or nearly hexagonal shape is between 50 and 1000 nm, and the thickness of the hydrotalcite nanosheet is 1 to 50 nm.

6. The anti-proton oxygen antistatic black flexible film according to claim 1, characterized in that: The silane coupling agent is selected from at least one of aminohydrocarbon silane, 3-mercaptopropyltrimethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; the aminohydrocarbon silane is selected from at least one of N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-aminopropyltriethoxysilane, preferably 3-aminopropyltriethoxysilane; The silane coupling agent simultaneously undergoes bonding reactions with the flexible substrate and the hydrotalcite or hydrotalcite-like nanosheets.

7. The anti-proton oxygen antistatic black flexible film according to claim 1, characterized in that: The anti-proton oxygen hydrotalcite coating further comprises a silane coupling agent modified layer distributed between the polymer matrix and the porous coating; the thickness of the silane coupling agent modified layer is 10nm to 1000nm.

8. The anti-proton oxygen antistatic black flexible film according to any one of claims 1 to 7, characterized in that: The ratio of at least one of the hydrotalcite nanosheets or hydrotalcite-like nanosheets to the silane coupling agent in the scale-like laminated bionic micro-nanostructure layer is (5-40) mg: (5-30) μL; The total thickness of the scale-like laminated bionic micro-nano structure layer is 50nm-10μm.

9. The anti-proton oxygen antistatic black flexible film according to any one of claims 1 to 7, characterized in that: The antistatic layer is a transparent conductive oxide material, and the material system is preferably selected from at least one of ITO film, indium oxide, tin oxide, zinc oxide and cadmium oxide; the structure of the antistatic layer is preferably a non-dense structure; the thickness of the antistatic layer does not exceed 100 μm.

10. A method for preparing an anti-oxygen antistatic black flexible film according to any one of claims 1 to 9, characterized in that: include: (1) adding a silane coupling agent to an aqueous dispersion containing at least one of hydrotalcite nanosheets or hydrotalcite-like nanosheets and mixing, then coating the mixture on a surface of a black flexible substrate, and heat treating the mixture at 80 to 300° C. for 1 to 72 hours to obtain a hydrotalcite or hydrotalcite-like coating with a scale-like laminated bionic micro-nano structure; (2) An antistatic layer is prepared on the surface of a hydrotalcite or hydrotalcite-like coating by a wet chemical method or a vacuum coating method to obtain an anti-oxygen-resistant antistatic black flexible film.

11. The preparation method according to claim 10, characterized in that: When the black flexible substrate is a black polyimide film, the black polyimide substrate is subjected to a surface activation treatment before coating; preferably, the surface activation treatment includes: wet chemical treatment, ultraviolet radiation treatment, plasma treatment, and corona treatment; more preferably, the wet chemical treatment is acid-base modification, and the alkali-acid modification includes alkali treatment and acid treatment; most preferably, the polyimide substrate is treated in a NaOH solution with a concentration of 0.1 to 6 mol / L and an acetic acid solution with a concentration of 0.1 to 6 mol / L for 0.2 to 6 h, respectively, and then washed and dried to obtain a polymer matrix with surface active groups (hydroxyl, carboxyl or amine groups).

12. The preparation method according to claim 10, characterized in that: The concentration of the aqueous dispersion containing at least one of the hydrotalcite nanosheets or the hydrotalcite-like nanosheets is 5-100 mg / mL; the mixing method is stirring or ultrasonic dispersion.

13. The preparation method according to any one of claims 10 to 12, characterized in that: The coating is performed at least once; the coating includes spin coating, drip coating, spray coating, scraping coating, spreading or static pulling.

14. Use of the anti-oxygen antistatic black flexible film according to any one of claims 1 to 9 in the aerospace field.

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