A protective reinforcement film and a method for manufacturing the same

Abstract

This disclosure provides a protective enhancement film and its preparation method that simultaneously achieves ultraviolet protection and atomic oxygen protection, as well as enhanced transmission performance for light in a desired anti-transmittance band or enhanced reflection performance for light in a desired anti-reflection band. The protective enhancement film comprises a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from ultraviolet absorbers or ultraviolet blockers. The protective enhancement film has at least one layer, wherein the thickness of the outermost layer is one-quarter of the wavelength of the incident light in the desired anti-transmittance band in the medium, or an odd multiple thereof, or one-half of the wavelength of the incident light in the desired anti-reflection band in the medium, or an integer multiple thereof. The above-mentioned protective enhancement film is suitable for use as a film for spacecraft optoelectronic devices.

Description

Technical Field

[0001] This disclosure relates to the fields of materials engineering and aerospace technology, and in particular to a protective enhancement film for spacecraft optoelectronic devices and a method for preparing the same. Background Technology

[0002] Various flexible aerospace devices, due to their foldable size and excellent mechanical properties, have become one of the key technologies for future aerospace technology, especially for the construction and development of space stations. However, in the specific environment of low Earth orbit, aerospace devices face long-term exposure to strong ultraviolet radiation and high-energy atomic oxygen, thus requiring the use of flexible encapsulation materials for protection. Transparent flexible surface coating materials, such as tetrafluoroethylene, polyimide, and polyethylene, have been widely used in cutting-edge fields such as flexible solar cells due to their excellent light transmittance in the initial stage.

[0003] It is worth noting that currently, the surface coating materials of various aerospace devices can only protect against one or more types of damage, such as ultraviolet rays or atomic oxygen. They cannot enhance the performance of the protected devices, such as improving the light utilization rate of solar cells or reducing photothermal accumulation in the devices while providing protection.

[0004] Therefore, there is a need for a protective enhancement film technology for spacecraft optoelectronic devices that can simultaneously achieve ultraviolet protection and atomic oxygen protection, as well as enhance the transmission or reflection performance of light in the required wavelength range. Summary of the Invention

[0005] In view of the above-mentioned technical problems existing in the prior art, the purpose of this disclosure is to provide a protective enhancement film that can be used in spacecraft optoelectronic devices and can simultaneously achieve ultraviolet protection and atomic oxygen protection, as well as enhance the transmission performance of light in the desired anti-transmittance band or the reflection performance of light in the desired anti-reflection band.

[0006] The purpose of this disclosure is also to provide a method for manufacturing the aforementioned protective reinforcing film.

[0007] This disclosure includes the following technical solutions.

[0008] [1] A protective reinforcing film comprising a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from ultraviolet absorbers or ultraviolet blocking agents.

[0009] The aforementioned protective enhancement film has at least one layer, wherein the thickness of the outermost layer is 1 / 4 of the wavelength of the incident light in the desired light transmission band in the medium of the layer or an odd multiple thereof, or 1 / 2 of the wavelength of the incident light in the desired light reflection band in the medium of the layer or an integer multiple thereof.

[0010] [2] The protective reinforcing film as described in [1], wherein the protective reinforcing film has:

[0011] A first polyimide layer comprising the above-mentioned polyimide resin, the above-mentioned siloxane compound, and the above-mentioned ultraviolet absorber.

[0012] [3] The protective reinforcing film as described in [1], wherein the protective reinforcing film has:

[0013] The first polyimide layer comprising the above-mentioned polyimide resin, the above-mentioned siloxane compound, and the above-mentioned ultraviolet absorber, and

[0014] A second polyimide layer comprising the above-mentioned polyimide resin and the above-mentioned siloxane compound.

[0015] [4] The protective reinforcing film as described in [1], wherein the protective reinforcing film has:

[0016] The first polyimide layer comprising the above-mentioned polyimide resin, the above-mentioned siloxane compound, and the above-mentioned ultraviolet absorber, and

[0017] An atomic oxygen protective layer containing an atomic oxygen protective agent.

[0018] [5] The protective reinforcing film as described in [1], wherein the protective reinforcing film has:

[0019] A second polyimide layer comprising the above-mentioned polyimide resin and the above-mentioned siloxane compound, and

[0020] An ultraviolet protection layer containing the aforementioned ultraviolet blocking agent.

[0021] [6] The protective reinforcing film as described in any one of [1] to [5], wherein,

[0022] The aforementioned siloxane compounds are selected from hexamethyldisiloxane, siloxanes containing at least one group selected from vinyl, propenyl, amino, phenyl, hydroxyl and carboxyl groups, as well as aminopropylheptyl-cage polysemi-siloxane, trisilylphenyl cage polysemi-siloxane, N-[(heptaisobutyl cage polysemi-siloxane)propyl]3,5-diaminobenzamide, trisilanol isobutyl cage polysemi-siloxane, trans-cyclohexanediol heptayl-cage polysemi-siloxane, 1,2-propanediol... At least one of the following: isobutyl alcohol cage polysiloxane, aminopropylheptyl-cage polysilsesquioxane, N-phenylamino cage polysilsesquioxane, acryloylisobutyl cage polysilsesquioxane, allyl cage polysiloxane, isooctyl ester cage polysilsesquioxane, octaisobutyl cage polysilsesquioxane, tetramethylammonium cage polysilsesquioxane, tetrasilane cage polysilsesquioxane, trisilyl isooctyl cage polysilsesquioxane, and trisilyl phenyl cage polysilsesquioxane;

[0023] The aforementioned ultraviolet absorber is at least one selected from 2,(2-hydroxy-5-methylphenyl)benzotriazole, hexamethylphosphoric triamine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxy-phenol, and nano-cerium oxide;

[0024] The aforementioned ultraviolet blocking agent is selected from at least one of titanium dioxide, aluminum oxide, cerium oxide, zinc oxide, and indium tin oxide.

[0025] [7] The protective reinforcement film as described in [4], wherein the atomic oxygen protective agent is at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide and indium tin oxide.

[0026] [8] As described in [1], in the case where the protective reinforcement film is a protective antireflective film, when the thickness of the outermost layer of the protective reinforcement film is set as d, the thickness d of the outermost layer satisfies the following formula (1):

[0027]

[0028] Where λ is the required value. Enhanced transparency The wavelength of light or the optimized wavelength for peak device performance, where n is the refractive index of the outermost layer and k is a natural number.

[0029] [9] As described in [1], in the case where the protective reinforcement film is a protective anti-reflective film, when the thickness of the outermost layer of the protective reinforcement film is set as d, the thickness d of the outermost layer also satisfies the following formula (2):

[0030]

[0031] Where λ1 is the required value. Increase and decrease The optimal wavelength for optical wavelength or peak performance of a device, where n is the refractive index of the outermost layer and k is a natural number greater than 1.

[0032]

[10] The protective reinforcement film as described in any one of [1] to [5], wherein the protective reinforcement film is attached to the surface of the spacecraft optoelectronic device.

[0033]

[11] A method for manufacturing a protective reinforcing film, comprising:

[0034] A first polyimide layer is formed by adhering a composition comprising dianhydride monomer, diamine monomer, siloxane compound, and ultraviolet absorber to the surface of a spacecraft optoelectronic device and then curing it.

[0035] Optionally, a composition comprising a dianhydride monomer, a diamine monomer, and a siloxane compound is attached to the first polyimide layer and then cured to form a second polyimide layer; or an atomic oxygen protective layer comprising an atomic oxygen protective agent is formed on the first polyimide layer by a dry process.

[0036]

[12] A method for manufacturing a protective reinforcing film, comprising:

[0037] A second polyimide layer is formed by adhering a composition comprising dianhydride monomers, diamine monomers, and siloxane compounds to the surface of a spacecraft optoelectronic device and then curing it.

[0038] A first polyimide layer is formed by attaching a composition comprising a dianhydride monomer, a diamine monomer, a siloxane compound, and a UV absorber onto the second polyimide layer and then curing it; or a UV protection layer comprising a UV blocker is formed on the second polyimide layer by a dry process.

[0039]

[13] The method for manufacturing the protective reinforcing film as described in

[11] or

[12] above, wherein,

[0040] The dianhydride monomers mentioned above are selected from at least one of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1S,2S,4R,5R-cyclohexanetetracarboxylic acid dianhydride, and pyromellitic dianhydride.

[0041] The diamine monomer mentioned above is selected from at least one of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(3-(trifluoromethyl)aniline), 1,4-bis(2-trifluoromethyl4-aminophenoxy)benzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane;

[0042] The aforementioned siloxane compound is selected from at least one of hexamethyldisiloxane, siloxanes containing at least one group selected from vinyl, amino, phenyl, hydroxyl and carboxyl groups, and cage-type siloxanes.

[0043] Beneficial effects

[0044] According to this disclosure, a protective enhancement film can be provided that can be used in spacecraft optoelectronic devices and can simultaneously achieve ultraviolet protection and atomic oxygen protection, as well as enhance the transmission performance of light in the desired anti-transmittance band or the reflection performance of light in the desired anti-reflection band.

[0045] Other aspects, features, and advantages of this disclosure will become apparent in the following detailed description. Attached Figure Description

[0046] Figure 1 A photograph of the protective reinforcement film of Embodiment 1 of the present invention;

[0047] Figure 2 The transmittance of the protective enhancement film of Embodiment 1 of the present invention before (solid line) and after (dashed line) ultraviolet irradiation is shown.

[0048] Figure 3 For reference, the transmittance of a silicon-containing polyimide film before (solid line) and after (dashed line) ultraviolet irradiation;

[0049] Figure 4 The transmittance of the protective reinforcement film of Embodiment 2 of the present invention before (solid line) and after (dashed line) atomic oxygen irradiation is shown.

[0050] Figure 5 The transmittance of the protective enhancement film of Embodiment 3 of the present invention before (solid line) and after (dashed line) ultraviolet irradiation is shown. Detailed Implementation

[0051] The following terms have the following meanings in this disclosure.

[0052] In this disclosure, "membrane" includes single-layer membranes and multilayer membranes.

[0053] In this disclosure, "protective enhancement film" refers to a film that has ultraviolet protection and atomic oxygen protection properties, and at the same time has the properties of enhancing the transmission performance of light in the desired anti-reflection band or the reflection performance of light in the desired anti-reflection band; "protective anti-reflection film" refers to a film that has ultraviolet protection and atomic oxygen protection properties, and at the same time has the properties of enhancing the transmission performance of light in the desired anti-reflection band; "protective anti-reflection film" refers to a film that has ultraviolet protection and atomic oxygen protection properties, and at the same time has the properties of enhancing the reflection performance of light in the desired anti-reflection band.

[0054] The tilde "~" indicating a numerical range means that the values ​​recorded before and after it are included as the lower and upper limits. In the numerical ranges described hierarchically in this disclosure, the upper or lower limit of one numerical range can be replaced with the upper or lower limit of other numerical ranges described hierarchically. Furthermore, the upper or lower limit of the numerical ranges described in this disclosure can also be replaced with the values ​​shown in the embodiments.

[0055] The term "layer" includes not only the case where it forms over the entire region when observing the area where the layer exists, but also the case where it forms only over a part of the region.

[0056] The protective enhancement film disclosed herein comprises a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from ultraviolet absorbers or ultraviolet blocking agents. The protective enhancement film has at least one layer, wherein the thickness of the outermost layer is 1 / 4 or an odd multiple of the wavelength of incident light in the desired light transmittance band in the medium, or 1 / 2 or an integer multiple of the wavelength of incident light in the desired light reflectance band in the medium.

[0057] In the protective reinforcement film disclosed herein, the polyimide resin is a flexible, transparent resin with excellent high and low temperature resistance, mechanical properties, insulation properties, space radiation resistance, and flame-retardant self-extinguishing characteristics, making it suitable as a substrate for use in spacecraft optoelectronic devices. The polyimide resin contains siloxane compounds; by introducing silicon atoms (or silicon-containing groups) into the polyimide molecular structure, the silicon atoms can react with atomic oxygen to form a passivation layer, imparting anti-atomic oxygen properties to the polyimide and thus improving the anti-atomic oxygen properties of the polyimide film. Furthermore, the protective reinforcement film improves its UV resistance by including an anti-UV compound selected from UV absorbers or UV blockers.

[0058] The protective reinforcing film disclosed herein has at least one layer. For example, the protective reinforcing film can be a single-layer film or a multi-layered film. When the protective reinforcing film is a single-layer film, the outermost layer is the protective reinforcing film itself. When the protective reinforcing film is a multi-layered film, the outermost layer is the outermost surface layer of the protective reinforcing film.

[0059] In the protective enhancement film disclosed herein, the thickness of the outermost layer is one-quarter of the wavelength of the incident light in the desired anti-reflection band within the medium, or an odd multiple thereof. Specifically, when the wavelength of the incident light in a specific light band (e.g., 400–750 nm) in a vacuum is denoted as λ, and the refractive index of the film medium is denoted as n, the wavelength λ of the incident light in the film medium is... n The thickness of the film (the outermost layer in the case of a multilayer film) is λ / n, where the thickness is equal to the wavelength λ of the incident light in the film medium. n The wavelength of light is 1 / 4 or an odd multiple thereof, which can increase the transmittance of the incident light in the film, thereby enhancing the utilization rate of light with wavelength λ, that is, achieving the effect of anti-reflection and anti-reflection. At the same time, for light with wavelengths that are 1 / 2 or integer multiples of the incident light wavelength λ, the film (the outermost layer in the case of a laminated film) can enhance the reflectivity of the light, achieving the effect of anti-reflection and anti-reflection, thereby reducing the heat accumulation on the optoelectronic device caused by the light.

[0060] The protective enhancement film disclosed herein, through the above-described configuration, can achieve ultraviolet protection and atomic oxygen protection, as well as enhance the transmission performance of light in the desired anti-transmittance band or the reflection performance of light in the desired anti-reflection band. Therefore, when used in spacecraft optoelectronic devices, it can provide ultraviolet protection and atomic oxygen protection for spacecraft optoelectronic devices, and can enhance the light utilization rate of spacecraft optoelectronic devices such as solar cells, and reduce photothermal accumulation caused by specific light rays, which is beneficial to extending the service life of optoelectronic devices.

[0061] The following description illustrates the protective reinforcement film of this disclosure with preferred embodiments. This is intended to illustrate the invention and not limit it. The protective reinforcement film of the present invention is not limited to the following embodiments.

[0062] [First Implementation Method]

[0063] The protective reinforcement film 1 of the first embodiment has a first polyimide layer comprising a polyimide resin, a siloxane compound, and an ultraviolet absorber.

[0064] The aforementioned protective reinforcement film 1 has a first polyimide layer as a single layer. The thickness of the first polyimide layer is 1 / 4 of the wavelength of the incident light in the desired light transmission band in the medium of the layer or an odd multiple thereof, or 1 / 2 of the wavelength of the incident light in the desired light reflection band in the medium of the layer or an integer multiple thereof.

[0065] (First polyimide layer)

[0066] The first polyimide layer comprises a polyimide resin, a siloxane compound, and a UV absorber.

[0067] As for the polyimide resin, any transparent and flexible polyimide resin is acceptable. The polyimide resin used in this invention preferably possesses excellent high and low temperature resistance, mechanical properties, insulation properties, space radiation resistance, and flame-retardant self-extinguishing characteristics, making it suitable as a substrate for use in spacecraft optoelectronic devices.

[0068] The polyimide resin of this invention can be obtained by reacting a dianhydride monomer and a diamine monomer in an organic solvent to obtain a polyamic acid solution, and then imidizing the polyamic acid to obtain polyimide. In some preferred embodiments, the molar ratio of the dianhydride monomer and the diamine monomer used in the synthesis of the polyimide resin is 1:(0.9 to 1.2), preferably 1:(0.9 to 1.1), and particularly preferably 1:1.

[0069] Examples of the aforementioned dianhydride monomers include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, and 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene. [1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, norbornane-2-spirocyclic-α-cyclopentanone-α'-spirocyclic-2”-norbornane-5,5”,6,6”-tetracarboxylic acid dianhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methyleneisobenzofuran) Aliphatic or alicyclic tetracarboxylic dianhydrides such as sobenzofuran-1,3-dione; pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, Aromatic tetracarboxylic anhydrides such as 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene phthalic anhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,3,3',4'-biphenyltetracarboxylic anhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, and bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride.From the perspective of readily obtaining polyimide resins with excellent flexibility, aliphatic or alicyclic tetracarboxylic dianhydrides are preferred; from the perspective of readily obtaining polyimide resins with excellent heat resistance, aromatic tetracarboxylic dianhydrides are preferred. In some preferred embodiments, the dianhydride monomer is at least one selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride, with 1,2,3,4-cyclobutanetetracarboxylic dianhydride or pyromellitic dianhydride being particularly preferred.

[0070] Examples of diamine monomers mentioned above include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(3-(trifluoromethyl)aniline), 1,4-bis(2-trifluoromethyl4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenylmethane, and 3,3'-diaminodiphenylmethane. 4,4'-Diaminodiphenylethane, 3,3'-Diaminodiphenylethane, 3,3'-Diaminobiphenyl, 3,3'-Diaminodiphenyl ether, 2,2-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-Diaminobenzophenone, 3,3'-Diaminobenzophenone, 9,9-bis(4-aminophenyl)fluorene, p-diaminobenzene, m-diaminobenzene, o- Diaminobenzene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 3,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-[1,3-phenylenebis(1-methyl-ethylene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methyl-ethylene)]bisaniline, 3,3'-diaminodiphenyl sulfone, 4,4'-diamino 4,4'-Diaminodiphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzoylaniline, o-toluidine sulfone, 2,3,5,6-tetramethyl-1,4-phenylene diamine, 3,3',5,5'-tetramethylbenzidine, 1,5-bis(4-aminophenoxy)pentane, 4,4'-diaminotriphenylamine, 1,4-bis(4-aminobenzoyl)piperazine, 2-phenoxy-1,4-diaminobenzene, bis(4-aminophenyl)terephthalate, N 1 N4 - bis(4-aminophenyl)terephthalamide, bis(4-aminophenyl)[1,1'-biphenyl]-4,4'-dicarboxylic acid ester, 4,4'-diamino-p-terphenyl, N,N'-bis(4-aminobenzoyl)-p-phenylene diamine, bis[4-(4-aminophenoxy)phenyl]one, 4-aminophenyl-4-aminobenzoate, [1,1'-biphenyl]-4,4'-dimethylbis(4-aminobenzoate), etc. In some preferred embodiments, the diamine monomer is selected from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-di... At least one of aminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(3-(trifluoromethyl)aniline), 1,4-bis(2-trifluoromethyl4-aminophenoxy)benzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, particularly preferably 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, or 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

[0071] As the aforementioned siloxane compound, at least one of hexamethyldisiloxane, siloxanes containing at least one of vinyl, propenyl, amino, phenyl, hydroxyl and carboxyl groups, and cage-type siloxanes is preferred.

[0072] Examples of cage-like siloxanes include, for instance, aminopropylheptyl-cage-like polysemi-siloxane, trisilylphenyl-cage-like siloxane, N-[(heptaisobutylcage-like siloxane)propyl]3,5-diaminobenzamide, trisilanol isobutylcage-like siloxane, trans-cyclohexanediol heptayl-cage-like polysemi-cage-like siloxane, 1,2-propanediol isobutylcage-like siloxane, and aminopropylheptyl- Cage-shaped polysilsesquioxanes, N-phenylamino cage-shaped polysilsesquioxanes, acryloyl isobutyl cage-shaped polysilsesquioxanes, allyl cage-shaped polysiloxanes, isooctyl ester cage-shaped polysilsesquioxanes, octaisobutyl cage-shaped polysilsesquioxanes, tetramethylammonium cage-shaped polysilsesquioxanes, tetrasilane cage-shaped polysilsesquioxanes, trisilyl isooctyl cage-shaped polysilsesquioxanes, trisilyl phenyl cage-shaped polysilsesquioxanes, etc.

[0073] Examples of siloxanes containing at least one of vinyl, propenyl, amino, phenyl, hydroxyl, and carboxyl groups include methacryloxypropylsiloxane, propenyloxypropylsiloxane, and dodecylbenzenesiloxane.

[0074] The aforementioned siloxane compound is further preferably hexamethyldisiloxane, trisilylphenyl cage-type siloxane, or a siloxane containing at least one of vinyl, phenyl, and hydroxyl groups.

[0075] The aforementioned siloxane compounds can be used alone or in combination of two or more.

[0076] Examples of UV absorbers include triazine-based UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, cyanoacrylate-based UV absorbers, hydroxybenzoate-based UV absorbers, nano zinc oxide, nano titanium dioxide, and nano cerium oxide. In some preferred embodiments, the UV absorber is at least one selected from 2-[2-hydroxy-3,5-di(1,1-dimethylpropylphenyl)]-2H-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,(2-hydroxy-5-methylphenyl)benzotriazole, hexamethylphosphoryltriamine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, and nano cerium oxide; particularly preferred are 2-[2-hydroxy-3,5-di(1,1-dimethylpropylphenyl)]-2H-benzotriazole or nano cerium oxide. Among them, cerium oxide particles with a particle size of less than 100 nm are preferred as nano-cerium oxide.

[0077] In the first polyimide layer, the content of the aforementioned siloxane compound is not particularly limited, as long as a protective reinforcing film with atomic oxygen protection properties can be obtained. In some preferred embodiments, the content of the siloxane compound relative to 100% by weight of the polyimide resin is 0 to 30% by weight, preferably 1 to 30% by weight, more preferably 10 to 25% by weight, and even more preferably 15 to 25% by weight. When the siloxane compound is contained within the above range, it is easier to obtain good atomic oxygen protection properties.

[0078] In the first polyimide layer, the content of the aforementioned ultraviolet absorber is not particularly limited, as long as a protective reinforcing film with ultraviolet protection properties can be obtained. In some preferred embodiments, the content of the ultraviolet absorber is 0.1 to 10% by weight, preferably 0.3 to 8% by weight, and more preferably 0.5 to 5% by weight, relative to 100% by weight of the polyimide resin. When the ultraviolet absorber is contained within the above range, it is easier to obtain good ultraviolet protection performance.

[0079] (Thickness of the first polyimide layer)

[0080] As described above, the protective reinforcement film 1 has a first polyimide layer as a single layer. Therefore, the first polyimide layer is the outermost layer of the protective reinforcement film 1. In this embodiment, the thickness of the first polyimide layer is 1 / 4 of the wavelength of the incident light in the desired anti-transmission band in the medium of this layer, or an odd multiple thereof.

[0081] In some preferred embodiments, when the protective reinforcing film 1 is a protective antireflective film, and the thickness of the first polyimide layer is set to d, the thickness d of the first polyimide layer satisfies the following formula (1):

[0082]

[0083] Where λ is the desired wavelength for enhanced light transmission or the optimized wavelength for peak device performance, n is the refractive index of the outermost layer, and k is a natural number, preferably 0.

[0084] The protective reinforcement film 1, by having the aforementioned first polyimide layer, can achieve enhanced light transmission for incident light with wavelength λ, thereby improving the utilization rate of the incident light.

[0085] In some preferred embodiments, when the protective reinforcing film 1 is a protective antireflective film, and the thickness of the first polyimide layer is set to d, the thickness d of the first polyimide layer satisfies the following formula (2):

[0086]

[0087] Where λ1 is the required value. Increase and decrease The optimal wavelength for optical wavelength or peak performance of a device, where n is the refractive index of the outermost layer and k is a natural number greater than 1.

[0088] The protective reinforcement film 1, by having the first polyimide layer described above, can achieve enhanced reflectivity for incident light with a wavelength of λ1, thereby preventing photothermal accumulation caused by the incident light.

[0089] The thickness of the first polyimide layer in the protective reinforcing film 1 can be controlled, for example, by controlling the coating thickness and number of coating cycles of the coating liquid as described in the manufacturing method below.

[0090] (Manufacturing method of protective reinforcing film 1)

[0091] The manufacturing method of the protective reinforcement film 1 in this embodiment will now be described.

[0092] The method for manufacturing the protective reinforcement film 1 includes: attaching a composition comprising a dianhydride monomer, a diamine monomer, a siloxane compound and an ultraviolet absorber to the surface of a spacecraft optoelectronic device and then curing it to form a first polyimide layer.

[0093] In the manufacturing method of the protective reinforcement film 1, the types of dianhydride monomer, diamine monomer, siloxane compound and ultraviolet absorber are as described above, and their preferred forms are also the same.

[0094] In some preferred embodiments, the protective reinforcing film 1 can be manufactured by a method including the following steps:

[0095] (1) Dissolve the dianhydride monomer and the diamine monomer in a polar organic solvent at a molar percentage of 1:(0.9~1.2) to obtain a polyamic acid solution; add 0~30% by weight of a siloxane compound relative to the weight of the polyamic acid to the polar organic solvent, stir evenly, and obtain a siloxane solution.

[0096] (2) Dissolve 0.1 to 10% by weight of UV absorber relative to the weight of polyamic acid in a polar organic solvent and disperse it evenly by ultrasonic stirring to obtain a solution containing UV absorber.

[0097] (3) Slowly drop the cerium-containing colloid obtained in step (2) into the polyamic acid solution and siloxane solution obtained in step (1) to obtain a polyamic acid solution containing ultraviolet absorber and a siloxane solution containing ultraviolet absorber.

[0098] (4) The siloxane solution containing UV absorber obtained in step (3) is added dropwise to the polyamic acid solution containing UV absorber at an injection rate of 2-10 mL / min for mixing and reaction, and then allowed to stand for 24-48 hours to obtain a polyamic acid composition solution.

[0099] (5) The polyamic acid composition solution obtained above is attached to the surface of the spacecraft optoelectronic device and left to stand until the solution is evenly distributed and reaches a semi-cured state. Then it is cured to obtain the first polyimide layer.

[0100] In the above manufacturing method, the molar percentage of the dianhydride monomer and the diamine monomer is further preferably 1:(0.9 to 1.1), and particularly preferably 1:1.

[0101] In the above manufacturing method, the polar organic solvent is preferably DMF, DMAc or NMP, with DMAc being particularly preferred.

[0102] In the above manufacturing method, the ultraviolet absorber is preferably selected from at least one of 2-[2-hydroxy-3,5-di(1,1-dimethylpropylphenyl)]-2H-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,(2-hydroxy-5-methylphenyl)benzotriazole, hexamethylphosphoric triamine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, and nano-cerium oxide.

[0103] In the above manufacturing method, in step (5), the "attachment" is preferably spraying, spin coating, direct coating, casting, or additive manufacturing. When the device is small, spin coating is preferred; when the device is large or has an irregular curved surface, spraying is preferred. When using spraying for adhesion, it is preferred to spray under conditions of 0.2 to 0.5 MPa and a spray valve operating speed of 50 to 200 mm / s, and particularly preferred to spray under conditions of 0.3 MPa and a spray valve operating speed of 100 mm / s.

[0104] In the above manufacturing method, in step (5), the curing conditions are preferably baking at 200-300°C for 60-240 minutes, more preferably baking at 250°C for 120-240 minutes, and particularly preferably baking at 250°C for 120 minutes.

[0105] (Effects)

[0106] The protective enhancement film 1 of this embodiment has a first polyimide layer as described above, which is a transparent and flexible coating that can achieve ultraviolet protection and atomic oxygen protection, as well as enhance the transmission performance of light in the desired anti-transmittance band or the reflection performance of light in the desired anti-reflection band. It is suitable for application on the surface of various spacecraft optoelectronic devices such as flexible, rigid, and irregular curved surfaces. It can provide ultraviolet protection and atomic oxygen protection for spacecraft optoelectronic devices, and can enhance the light utilization rate of spacecraft optoelectronic devices such as solar cells, and reduce photothermal accumulation caused by specific light.

[0107] [Second Implementation]

[0108] The protective reinforcement film 2 of the second embodiment has: a first polyimide layer comprising a polyimide resin, a siloxane compound and an ultraviolet absorber, and a second polyimide layer comprising a polyimide resin and a siloxane compound.

[0109] The stacking order of the first polyimide layer and the second polyimide layer in the protective reinforcement film 2 is not particularly limited. For example, the base layer can be the first polyimide layer, and the second polyimide layer can be further stacked on it as the outermost layer; or the base layer can be the second polyimide layer, and the first polyimide layer can be further stacked on it as the outermost layer. Note that regardless of the stacking order, the outermost layer of the protective reinforcement film 2 must satisfy the following requirement: its thickness must be 1 / 4 or an odd multiple of the wavelength of the incident light in the desired anti-reflection band in the medium, or 1 / 2 or an integer multiple of the wavelength of the incident light in the desired anti-reflection band in the medium.

[0110] The morphology of the protective reinforcing film 2, which has a second polyimide layer as the base layer and a first polyimide layer as the outermost layer, will be described below.

[0111] (First polyimide layer)

[0112] The first polyimide layer has the same structure as the first polyimide layer in the protective reinforcing film 1 described in the first embodiment above. The outermost first polyimide layer has the same thickness as the first polyimide layer in the first embodiment, and its preferred shape is also the same.

[0113] For the sake of simplicity, repeated descriptions of the first polyimide layer are omitted.

[0114] (Second polyimide layer)

[0115] The second polyimide layer is a base layer formed directly on the surface of the spacecraft optoelectronic device, and contains polyimide resin and siloxane compound.

[0116] The polyimide resin in the second polyimide layer is the same as the polyimide resin in the first polyimide layer described in the first embodiment above, and its preferred form is also the same.

[0117] The siloxane compound in the second polyimide layer is the same as the siloxane compound in the first polyimide layer described in the first embodiment above, and its preferred form is also the same.

[0118] (Thickness of the second polyimide layer)

[0119] There is no particular limitation on the thickness of the second polyimide layer, which serves as the base layer, as long as the thickness of the second polyimide layer does not affect the purpose of the present invention.

[0120] The thickness of the second polyimide layer can be the same as or different from the thickness of the first polyimide layer.

[0121] The thickness of the second polyimide layer in the protective reinforcing film 2 can be controlled, for example, by controlling the coating thickness and number of coating cycles of the coating liquid as described in the manufacturing method below.

[0122] (Manufacturing method of protective reinforcing film 2)

[0123] The manufacturing method of the protective reinforcement film 2 in this embodiment will now be described.

[0124] The method for manufacturing the protective reinforcement film 2 includes: attaching a composition comprising a dianhydride monomer, a diamine monomer, and a siloxane compound to the surface of a spacecraft optoelectronic device and then curing it to form a second polyimide layer; and attaching a composition comprising a dianhydride monomer, a diamine monomer, a siloxane compound, and an ultraviolet absorber to the second polyimide layer and then curing it to form a first polyimide layer.

[0125] In the above manufacturing method, the dianhydride monomer, diamine monomer, siloxane compound, and ultraviolet absorber are the same as those described in the first embodiment, and their preferred forms are also the same.

[0126] Furthermore, the first polyimide layer in this embodiment can be manufactured using the same manufacturing steps as the first polyimide layer in the first embodiment.

[0127] In some preferred embodiments, the second polyimide layer in this embodiment can be manufactured by a method including the following steps:

[0128] (1) Dissolve the dianhydride monomer and the diamine monomer in a polar organic solvent at a molar percentage of 1:(0.9~1.2) to obtain a polyamic acid solution; add 0~30% by weight of a siloxane compound relative to the weight of the polyamic acid to the polar organic solvent, stir evenly, and obtain a siloxane solution.

[0129] (2) The siloxane solution obtained in step (1) is added dropwise to the polyamic acid solution at an injection rate of 2 to 10 mL / min and mixed to react. After standing for 24 to 48 hours, a polyamic acid composition solution containing siloxane is obtained.

[0130] (3) The above-obtained siloxane-containing polyamic acid composition solution is attached to the surface of the spacecraft optoelectronic device and left to stand until the solution is evenly distributed and reaches a semi-cured state. Then it is cured to obtain the second polyimide layer.

[0131] In the above manufacturing method, the molar percentage of the dianhydride monomer and the diamine monomer is further preferably 1:(0.9 to 1.1), and particularly preferably 1:1.

[0132] In the above manufacturing method, the polar organic solvent is preferably DMF, DMAc or NMP, with DMAc being particularly preferred.

[0133] In the above manufacturing method, in step (3), the "attachment" is preferably spraying, spin coating, direct coating, casting, or additive manufacturing. When the device is small, spin coating is preferred; when the device is large or has an irregular curved surface, spraying is preferred.

[0134] In the above manufacturing method, in step (3), the curing conditions are preferably baking at 200-300°C for 60-240 minutes, more preferably baking at 250°C for 120-240 minutes, and particularly preferably baking at 250°C for 120 minutes.

[0135] (Effects)

[0136] The protective enhancement film 2 of this embodiment has a second polyimide layer as a base layer and a first polyimide layer as the outermost layer. Both the first and second polyimide layers are transparent and flexible coatings. The first polyimide layer provides ultraviolet and atomic oxygen protection, and enhances the transmission performance of light in the desired anti-transmittance wavelength range or the reflection performance of light in the desired anti-reflection wavelength range. The second polyimide layer provides atomic oxygen protection. When the protective enhancement film 2 is applied to the surface of a spacecraft optoelectronic device, it can provide ultraviolet and atomic oxygen protection to the spacecraft optoelectronic device, and can enhance the light utilization rate of the spacecraft optoelectronic device, such as a solar cell, and reduce photothermal accumulation caused by specific light rays.

[0137] It should be noted that the above description describes the morphology of the protective reinforcing film 2 having a second polyimide layer as the base layer and a first polyimide layer as the outermost layer. However, those skilled in the art can easily obtain the protective reinforcing film 2 having a first polyimide layer as the base layer and a second polyimide layer as the outermost layer by making appropriate combinations and modifications based on the content disclosed herein.

[0138] [Third Implementation Method]

[0139] The protective reinforcement film 3 of the third embodiment has: a first polyimide layer comprising a polyimide resin, a siloxane compound and an ultraviolet absorber, and an atomic oxygen protective layer comprising an atomic oxygen protectant.

[0140] The stacking order of the first polyimide layer and the atomic oxygen protective layer in the protective reinforcement film 3 is not particularly limited. For example, the base layer can be the first polyimide layer, and then a further layer can be stacked on top of it as the outermost atomic oxygen protective layer; alternatively, the base layer can be the atomic oxygen protective layer, and then a further layer can be stacked on top of it as the outermost first polyimide layer. Note that regardless of the stacking order, the outermost layer of the protective reinforcement film 3 must satisfy the following requirement: its thickness must be 1 / 4 of the wavelength of the incident light in the desired anti-reflection band in the medium of this layer, or an odd multiple thereof; or 1 / 2 of the wavelength of the incident light in the desired anti-reflection band in the medium of this layer, or an integer multiple thereof.

[0141] The morphology of the protective reinforcement film 3, which has a first polyimide layer as the base layer and an atomic oxygen protective layer as the outermost layer, will be described below.

[0142] (First polyimide layer)

[0143] The first polyimide layer has the same composition as the first polyimide layer in the protective reinforcing film 1 described in the first embodiment above. There is no particular limitation on the thickness of the first polyimide layer, as long as the thickness does not affect the purpose of the present invention.

[0144] For the sake of simplicity, repeated descriptions of the first polyimide layer are omitted.

[0145] (Atomic oxygen protective layer)

[0146] The atomic oxygen protective layer is a layer containing an atomic oxygen protective agent, which is formed on the first polyimide layer.

[0147] As an atomic oxygen protectant, at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide and indium tin oxide is preferred, and titanium dioxide, silicon dioxide or cerium oxide is more preferred.

[0148] In some preferred embodiments, the atomic oxygen protective layer is formed on the first polyimide layer by a dry process. Examples of dry processes include physical vapor deposition (hereinafter also referred to as "PVD"), chemical vapor deposition (hereinafter also referred to as "CVD"), etc.

[0149] Examples of PVD methods include vacuum evaporation, sputtering, ion plating, and pulsed laser deposition; any of these methods can be used. For sputtering, any of the following can be used: DC sputtering, RF sputtering, magnetron sputtering, single (multi) target sputtering, and hybrid target sputtering. Considering excellent productivity, widespread industrial use, and the ability to obtain a highly dense film with uniform thickness and strong adhesion to the first polyimide layer, sputtering is preferred, and magnetron sputtering is particularly preferred.

[0150] Examples of CVD methods include plasma CVD, thermal CVD, and catalytic CVD; any of these methods can be used. Among these, plasma CVD is preferred due to its superior productivity, wide industrial applicability, and ability to produce a highly dense film with uniform thickness and strong adhesion to the first polyimide layer.

[0151] (Thickness of the atomic oxygen protective layer)

[0152] As described above, the protective enhancement film 3 has an atomic oxygen protective layer as the outermost layer. In this embodiment, the thickness of the atomic oxygen protective layer is 1 / 4 or an odd multiple of the wavelength of the incident light in the desired light transmission band in the medium, or 1 / 2 or an integer multiple of the wavelength of the incident light in the desired light reflection band in the medium.

[0153] In some preferred embodiments, when the protective reinforcement film 3 is a protective antireflection film, and the thickness of the atomic oxygen protective layer is set as d, the thickness d of the atomic oxygen protective layer satisfies the following formula (1):

[0154]

[0155] Where λ is the desired wavelength for enhanced light transmission or the optimized wavelength for peak device performance, n is the refractive index of the outermost layer, and k is a natural number, preferably 0.

[0156] The protective enhancement film 3, by having the aforementioned atomic oxygen protective layer, can achieve enhanced light transmission for incident light with a wavelength of λ, thereby improving the utilization rate of the incident light.

[0157] In some preferred embodiments, when the protective reinforcement film 3 is a protective anti-reflective film, and the thickness of the atomic oxygen protective layer is set as d, the thickness d of the atomic oxygen protective layer satisfies the following formula (2):

[0158]

[0159] Where λ1 is the required value. Increase and decrease The optimal wavelength for optical wavelength or peak performance of a device, where n is the refractive index of the outermost layer and k is a natural number greater than 1.

[0160] The protective enhancement film 3, by having the aforementioned atomic oxygen protective layer, can achieve enhanced reflectivity for incident light with a wavelength of λ1, thereby preventing photothermal accumulation caused by the incident light.

[0161] The thickness of the atomic oxygen protective layer in the protective reinforcement film 3 can be controlled, for example, by the sputtering time described in the manufacturing method below.

[0162] (Manufacturing method of protective reinforcing film 3)

[0163] The manufacturing method of the protective reinforcement film 3 in this embodiment will now be described.

[0164] The method for manufacturing the protective reinforcement film 3 includes: attaching a composition comprising a dianhydride monomer, a diamine monomer, a siloxane compound and an ultraviolet absorber to the surface of a spacecraft optoelectronic device and then curing it to form a first polyimide layer, and forming an atomic oxygen protective layer comprising an atomic oxygen protective agent on the first polyimide layer by a dry process.

[0165] In the above manufacturing method, the dianhydride monomer, diamine monomer, siloxane compound, and ultraviolet absorber are the same as those described in the first embodiment, and their preferred forms are also the same.

[0166] Furthermore, the first polyimide layer in this embodiment can be manufactured using the same manufacturing steps as the first polyimide layer in the first embodiment.

[0167] As the atomic oxygen protective agent used to form the atomic oxygen protective layer, it is preferable to use at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide and indium tin oxide, and more preferably titanium dioxide, silicon dioxide or cerium oxide.

[0168] In some preferred embodiments, the dry method used to form the atomic oxygen protective layer is preferably PVD, more preferably sputtering, and even more preferably any one of DC sputtering, RF sputtering, magnetron sputtering, single (multi) target sputtering, and hybrid target sputtering, with magnetron sputtering being particularly preferred.

[0169] When forming an atomic oxygen protective layer on the first polyimide layer using magnetron sputtering, the thickness of the atomic oxygen protective layer is controlled by adjusting the magnetron sputtering time.

[0170] The conditions for magnetron sputtering can be those known in the art. For example, an atomic oxygen protective layer containing silicon dioxide can be formed by sputtering in an inert gas atmosphere such as argon using a silicon dioxide target.

[0171] (Effects)

[0172] The protective enhancement film 3 of this embodiment has a first polyimide layer as a base layer and an atomic oxygen protection layer as the outermost layer. The first polyimide layer is a transparent and flexible coating, and the atomic oxygen protection layer is a transparent layer. The first polyimide layer can achieve both ultraviolet protection and atomic oxygen protection, while the atomic oxygen protection layer can enhance the transmission performance of light in the desired anti-transmittance wavelength range or the reflection performance of light in the desired anti-reflection wavelength range while achieving atomic oxygen protection. When the protective enhancement film 3 is applied to the surface of a spacecraft optoelectronic device, it can provide ultraviolet protection and atomic oxygen protection for the spacecraft optoelectronic device, and can enhance the light utilization rate of spacecraft optoelectronic devices such as solar cells, and reduce photoheat accumulation caused by specific light rays.

[0173] It should be noted that the above description describes the morphology of the protective reinforcement film 3 having a first polyimide layer as the base layer and an atomic oxygen protection layer as the outermost layer. However, those skilled in the art can easily obtain the protective reinforcement film 3 having an atomic oxygen protection layer as the base layer and a first polyimide layer as the outermost layer by making appropriate combinations and modifications based on the content disclosed herein.

[0174] [Fourth Implementation Method]

[0175] The protective reinforcement film 4 of the fourth embodiment has: a second polyimide layer comprising a polyimide resin and a siloxane compound, and an ultraviolet protection layer comprising an ultraviolet blocking agent.

[0176] The stacking order of the second polyimide layer and the ultraviolet protection layer in the protective reinforcement film 4 is not particularly limited. For example, the base layer can be the second polyimide layer, and then a further layer can be stacked on top of it as the outermost ultraviolet protection layer; alternatively, the base layer can be the ultraviolet protection layer, and then a further layer can be stacked on top of it as the outermost second polyimide layer. Note that regardless of the stacking order, the outermost layer of the protective reinforcement film 4 must have a thickness that is 1 / 4 of the wavelength of the incident light in the desired anti-transmittance band in the medium of this layer, or an odd multiple thereof, or 1 / 2 of the wavelength of the incident light in the desired anti-reflection band in the medium of this layer, or an integer multiple thereof.

[0177] The morphology of the protective reinforcement film 4, which has a second polyimide layer as the base layer and an ultraviolet protection layer as the outermost layer, will be described below.

[0178] (Second polyimide layer)

[0179] The second polyimide layer has the same composition as the second polyimide layer in the protective reinforcing film 2 described in the second embodiment above. There is no particular limitation on the thickness of the second polyimide layer, as long as the thickness does not affect the purpose of the present invention.

[0180] For the sake of simplicity, the repeated description of the second polyimide layer is omitted.

[0181] (UV protection layer)

[0182] The ultraviolet protection layer is a layer containing an ultraviolet blocking agent, which is formed on the second polyimide layer.

[0183] As a UV blocking agent, at least one selected from titanium dioxide, aluminum oxide, cerium oxide, zinc oxide and indium tin oxide is preferred, and titanium dioxide, zinc oxide or cerium oxide is more preferred.

[0184] In some preferred embodiments, the UV protection layer is formed on the second polyimide layer by a dry process. Examples of dry processes include physical vapor deposition (hereinafter also referred to as "PVD"), chemical vapor deposition (hereinafter also referred to as "CVD"), etc.

[0185] Examples of PVD methods include vacuum evaporation, sputtering, ion plating, and pulsed laser deposition; any of these methods can be used. For sputtering, any of the following can be used: DC sputtering, RF sputtering, magnetron sputtering, single (multi) target sputtering, and hybrid target sputtering. Considering excellent productivity, widespread industrial use, and the ability to obtain a very dense film with uniform thickness and high adhesion to the second polyimide layer, sputtering is preferred, and magnetron sputtering is particularly preferred.

[0186] Examples of CVD methods include plasma CVD, thermal CVD, and catalytic CVD; any of these methods can be used. Among these, plasma CVD is preferred due to its superior productivity, wide industrial applicability, and ability to produce a highly dense film with uniform thickness and strong adhesion to the second polyimide layer.

[0187] (Thickness of the UV protection layer)

[0188] As described above, the protective enhancement film 4 has an ultraviolet protection layer as the outermost layer. In this embodiment, the thickness of the ultraviolet protection layer is 1 / 4 or an odd multiple of the wavelength of the incident light in the desired light transmission band in the medium, or 1 / 2 or an integer multiple of the wavelength of the incident light in the desired light reflection band in the medium.

[0189] In some preferred embodiments, when the protective enhancement film 4 is a protective antireflection film, and the thickness of the ultraviolet protective layer is set as d, the thickness d of the ultraviolet protective layer satisfies the following formula (1):

[0190]

[0191] Where λ is the desired wavelength for enhanced light transmission or the optimized wavelength for peak device performance, n is the refractive index of the outermost layer, and k is a natural number, preferably 0.

[0192] The protective enhancement film 4, by having the aforementioned ultraviolet protection layer, can achieve enhanced light transmission for incident light with a wavelength of λ, thereby improving the utilization rate of the incident light.

[0193] In some preferred embodiments, when the protective enhancement film 4 is a protective antireflective film, and the thickness of the ultraviolet protective layer is set as d, the thickness d of the ultraviolet protective layer satisfies the following formula (2):

[0194]

[0195] Where λ1 is the required value. Increase and decrease The optimal wavelength for optical wavelength or peak performance of a device, where n is the refractive index of the outermost layer and k is a natural number greater than 1.

[0196] The protective enhancement film 4, by having the aforementioned ultraviolet protection layer, can achieve enhanced reflectivity for incident light with a wavelength of λ1, thereby preventing photothermal accumulation caused by the incident light.

[0197] The thickness of the ultraviolet protection layer in the protective enhancement film 4 can be controlled, for example, by the sputtering time described in the manufacturing method below.

[0198] (Manufacturing method of protective reinforcement film 4)

[0199] The manufacturing method of the protective reinforcement film 4 in this embodiment will now be described.

[0200] The method for manufacturing the protective reinforcement film 4 includes: attaching a composition comprising a dianhydride monomer, a diamine monomer and a siloxane compound to the surface of a spacecraft optoelectronic device and then curing it to form a second polyimide layer, and forming an ultraviolet protection layer comprising an ultraviolet blocking agent on the second polyimide layer by a dry process.

[0201] In the above manufacturing method, the dianhydride monomer, diamine monomer, and siloxane compound are the same as those described in the first embodiment, and their preferred forms are also the same.

[0202] Furthermore, the second polyimide layer in this embodiment can be manufactured using the same manufacturing steps as the second polyimide layer in the second embodiment.

[0203] As the ultraviolet blocking agent used to form the ultraviolet protective layer, it is preferred to use at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, zinc oxide and indium tin oxide, and more preferably titanium dioxide, zinc oxide or cerium oxide.

[0204] In some preferred embodiments, the dry method used to form the ultraviolet protective layer is preferably PVD, more preferably sputtering, and even more preferably any one of DC sputtering, RF sputtering, magnetron sputtering, single (multi) target sputtering, and hybrid target sputtering, with magnetron sputtering being particularly preferred.

[0205] When forming an ultraviolet (UV) protective layer on the second polyimide layer using magnetron sputtering, the thickness of the UV protective layer is controlled by adjusting the magnetron sputtering time.

[0206] The conditions for magnetron sputtering can be those known in the art. For example, an atomic oxygen protective layer containing cerium oxide can be formed by sputtering in an inert gas atmosphere such as argon using a cerium oxide target.

[0207] (Effects)

[0208] The protective enhancement film 4 of this embodiment has a second polyimide layer as a base layer and an ultraviolet (UV) protective layer as the outermost layer. The second polyimide layer is a transparent and flexible coating, and the UV protective layer is a transparent layer. The second polyimide layer can achieve atomic oxygen protection, and the UV protective layer can enhance the transmission performance of light in the desired anti-transmittance wavelength range or the reflection performance of light in the desired anti-reflection wavelength range while achieving UV protection. When the protective enhancement film 4 is applied to the surface of spacecraft optoelectronic devices, it can provide UV and atomic oxygen protection for the spacecraft optoelectronic devices, and can enhance the light utilization rate of spacecraft optoelectronic devices such as solar cells, and reduce photoheat accumulation caused by specific light rays.

[0209] It should be noted that the above description describes the morphology of the protective reinforcement film 4 having a second polyimide layer as the base layer and an ultraviolet protection layer as the outermost layer. However, those skilled in the art can easily obtain the protective reinforcement film 4 having an ultraviolet protection layer as the base layer and a second polyimide layer as the outermost layer by making appropriate combinations and modifications based on the content disclosed herein.

[0210] [use]

[0211] The protective enhancement film disclosed herein can enhance the transmission performance of light in the desired light transmission band or the reflection performance of light in the desired light reflection band while achieving ultraviolet protection and atomic oxygen protection. Therefore, it is suitable for use as a film for optoelectronic devices in spacecraft, and is particularly suitable for surface protection of solar cells, space solar cell arrays, etc. in spacecraft.

[0212] Example

[0213] The following examples further illustrate the structure and advantages of the present invention. However, it should be understood that the following examples are merely illustrative of implementing the present invention and are not intended to limit the scope of protection of the present invention.

[0214] [Example 1]

[0215] The protective reinforcing film m1 of the present invention having a structure comprising a first polyimide layer comprising a polyimide resin, a siloxane compound, and an ultraviolet absorber is manufactured by the following steps.

[0216] (1) 100g of a mixture of cyclobutanetetracarboxylic dianhydride (as a dianhydride unit) and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (as a diamine unit) was dissolved in 566.6g of DMAc to obtain a polyamic acid solution; in addition, 25g of trisilanol phenylsiloxane (as a siloxane compound) was added to 100g of DMAc and stirred until homogeneous to obtain a siloxane solution;

[0217] (2) Dissolve 2g of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, which is used as a UV absorber, in 5g of DMAc and disperse it evenly by ultrasonic stirring to obtain a solution containing UV absorber.

[0218] (3) Slowly drip the solution containing ultraviolet absorber obtained in step (2) into the polyamic acid solution and siloxane solution obtained in step (1) to obtain a polyamic acid solution containing ultraviolet absorber and a siloxane solution containing ultraviolet absorber.

[0219] (4) The siloxane solution containing ultraviolet absorber obtained in step (3) is added dropwise to the polyamic acid solution containing ultraviolet absorber at an injection rate of 5 ml / min for mixing and reaction. After standing for 48 hours, a polyamic acid composition solution without bubbles and without layering is obtained.

[0220] (5) Spray the polyamic acid composition solution obtained in step (4) directly onto the surface of the solar cell array under the conditions of 0.3 MPa and spray valve running speed of 100 mm / s. After standing and waiting for the solution to be evenly distributed and reach a semi-cured state, set the baking temperature of 250℃ and baking time of 120 minutes to cure the coating until it is completely cured.

[0221] (6) Repeat step (5) to perform multiple spraying and curing operations, so that the thickness of the final protective reinforcement film m1 reaches 29.92μm.

[0222] The refractive index of the obtained protective reinforcement film m1 was compared with the refractive index of the standard database, and the result was 1.6.

[0223] Furthermore, the resulting protective reinforcement film m1 is a transparent, flexible film, such as... Figure 1 As shown in the photo.

[0224] (UV resistance test)

[0225] The obtained protective reinforcement film m1 was subjected to an ultraviolet radiation resistance test.

[0226] First, before ultraviolet irradiation, the transmittance of the protective enhancement film m1 was measured and used as the transmittance before ultraviolet irradiation; then, the protective enhancement film m1 was irradiated with ultraviolet light with wavelengths of 115–400 nm at a power density of 27 mW / cm². -2 Irradiate for 30 hours, then measure the transmittance after ultraviolet irradiation.

[0227] The transmittance (solid line) and transmittance (dashed line) of the protective reinforcement film m1 before ultraviolet irradiation are shown in the figure. Figure 2 middle.

[0228] according to Figure 2 It can be seen that the transmittance of the protective reinforcement film m1 did not decrease significantly after ultraviolet irradiation, which indicates that the protective reinforcement film m1 can achieve ultraviolet protection function.

[0229] (Atomic Oxygen Exposure Test)

[0230] The protective reinforcement film m1 and the control film (pure polyimide resin film) were respectively subjected to high-speed atomic oxygen irradiation at an intensity of 2.5 × 10⁻⁶. 20 atoms cm -2After irradiation with the specified dose, the mass loss of the protective reinforcement film m1 was only 1.5 wt%, while the mass loss of the control film (pure polyimide resin film) was 10.9 wt%. This result indicates that the atomic resistance of the protective reinforcement film m1 is significantly improved.

[0231] (Anti-reflective and anti-reflective properties)

[0232] In this embodiment, the protective enhancement film m1 has a thickness d of 29.92 μm and a refractive index n of 1.6. This protective enhancement film m1 has an anti-reflection effect on light with a wavelength of about 500.00 nm (k = 191) and an anti-reflection effect on light with a wavelength of about 625.00 nm (k = 153). Therefore, it can improve the utilization rate of light with a wavelength of about 500.00 nm required by solar cells and reduce the heat accumulation caused by light with a wavelength of about 625.00 nm.

[0233] [Reference Example]

[0234] In the reference example, except that 2-[2-hydroxy-3,5-bis(1,1-dimethylpropylphenyl)]-2H-benzotriazole as an ultraviolet absorber was not added, the process was carried out in the same manner as in Example 1. Specifically, the silicon-containing polyimide film of the reference example was manufactured by the following steps.

[0235] (1) 100g of a mixture of cyclobutanetetracarboxylic dianhydride (as a dianhydride unit) and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (as a diamine unit) was dissolved in 566.6g of DMAc to obtain a polyamic acid solution; in addition, 25g of trisilanol phenylsiloxane (as a siloxane compound) was added to 100g of DMAc and stirred until homogeneous to obtain a siloxane solution;

[0236] (2) The siloxane solution obtained in step (1) is added dropwise to the polyamic acid solution at an injection rate of 5 mL / min for mixing and reaction, and then allowed to stand for 48 hours to obtain the polyamic acid composition solution.

[0237] (3) The polyamic acid composition solution obtained in step (2) is directly sprayed onto the surface of the solar cell array under the conditions of 0.3 MPa and spray valve running speed of 100 mm / s. After standing and waiting for the solution to be evenly distributed and reach a semi-cured state, the coating is cured by setting parameters such as baking temperature of 250℃ and baking time of 120 minutes until it is completely cured.

[0238] (4) Repeat step (3) to perform multiple spraying and curing operations so that the thickness of the final protective reinforcement film m1 reaches 30.5 μm.

[0239] (UV resistance test)

[0240] The obtained silicon-containing polyimide film was subjected to an ultraviolet radiation resistance test.

[0241] First, the transmittance of the silicon-containing polyimide film was measured before ultraviolet irradiation, and this was used as the transmittance before ultraviolet irradiation. Then, the silicon-containing polyimide film was irradiated with ultraviolet light with wavelengths of 115–400 nm at a power density of 27 mW / cm². -2 Irradiate for 30 hours, then measure the transmittance after ultraviolet irradiation.

[0242] The transmittance (solid line) and transmittance (dashed line) of the silicon-containing polyimide film before ultraviolet irradiation are shown in the figure. Figure 3 middle.

[0243] according to Figure 3 It can be seen that after ultraviolet irradiation, the transmittance of the film (especially near the wavelength of 400nm) decreases, indicating that the silicon-containing polyimide film cannot effectively protect against ultraviolet rays.

[0244] [Example 2]

[0245] The protective reinforcement film m2 of the present invention having a structure comprising a first polyimide layer comprising a polyimide resin, a siloxane compound and an ultraviolet absorber, and an atomic oxygen protective layer is manufactured by the following steps.

[0246] (1) 100g of a mixture of cyclobutanetetracarboxylic dianhydride (as a dianhydride unit) and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane (as a diamine unit) was dissolved in 566.6g of DMAc to obtain a polyamic acid solution; in addition, 25g of hexamethyldisiloxane (as a siloxane compound) was added to 100g of DMAc and stirred until homogeneous to obtain a siloxane solution;

[0247] (2) Dissolve 2g of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, which is used as a UV absorber, in 5g of DMAc and disperse it evenly by ultrasonic stirring to obtain a solution containing UV absorber.

[0248] (3) Slowly drip the solution containing ultraviolet absorber obtained in step (2) into the polyamic acid solution and siloxane solution obtained in step (1) to obtain a polyamic acid solution containing ultraviolet absorber and a siloxane solution containing ultraviolet absorber.

[0249] (4) The siloxane solution containing ultraviolet absorber obtained in step (3) is added dropwise to the polyamic acid solution containing ultraviolet absorber at an injection rate of 5 ml / min for mixing and reaction. After standing for 48 hours, a polyamic acid composition solution without bubbles and without layering is obtained.

[0250] (5) Spray the polyamic acid composition solution obtained in step (4) directly onto the surface of the solar cell array under the conditions of 0.3 MPa and spray valve running speed of 100 mm / s. After standing and waiting for the solution to be evenly distributed and reach a semi-cured state, set the baking temperature of 250℃ and baking time of 120 minutes to cure the coating until it is completely cured.

[0251] (6) Repeat step (5) to perform multiple spraying and curing operations, so that the thickness of the first polyimide layer reaches 30.50 μm.

[0252] (7) Using a silicon dioxide target, silicon dioxide was sputtered on the surface of the obtained first polyimide layer at a speed of 1.5 Å / s at room temperature by magnetron sputtering to obtain an atomic oxygen protective layer containing silicon dioxide with a thickness of 84.46 nm.

[0253] The refractive index of the silica sputtered layer in the obtained protective reinforcement film m2 was compared with that of a standard database, and the result was 1.48.

[0254] (Atomic Oxygen Exposure Test)

[0255] The protective reinforcement film m2 and the control film (pure polyimide resin film) were respectively subjected to high-speed atomic oxygen irradiation at 2.5 × 10⁻⁶. 20 atoms cm -2 After irradiation with the specified dose, the mass loss of the protective reinforcement film m2 was 0.8 wt%, while that of the control film (pure polyimide resin film) was 10.9 wt%. This result indicates that the atomic resistance of the protective reinforcement film m2 is significantly improved, and its atomic resistance is superior to that of the protective reinforcement film m1 (mass loss 1.5 wt%).

[0256] In addition, the transmittance of the protective reinforcement film m2 before and after atomic oxygen irradiation was measured, and the transmittance before atomic oxygen irradiation (solid line) and the transmittance after atomic oxygen irradiation (dashed line) are shown in the figure. Figure 4 middle.

[0257] according to Figure 4 It can be seen that the transmittance of the protective reinforcement membrane m2 did not decrease significantly after atomic oxygen irradiation, which indicates that the protective reinforcement membrane m2 can achieve the atomic oxygen irradiation function.

[0258] (Anti-reflective and anti-reflective properties)

[0259] In this embodiment, the atomic oxygen protective layer, which serves as the surface layer in the protective enhancement film m2, has a thickness d of 84.46 nm and a refractive index n of 1.48. This atomic oxygen protective layer has an anti-reflection effect (k = 0) for light with a wavelength of approximately 500.00 nm and an anti-reflection effect (k = 1) for light with a wavelength of approximately 250.00 nm. Therefore, it can improve the utilization rate of light with a wavelength of around 500.00 nm required by the solar cell and reduce the heat accumulation caused by light with a wavelength of around 250.00 nm.

[0260] [Example 3]

[0261] The protective reinforcement film m3 of the present invention having a structure comprising a second polyimide layer containing a polyimide resin and a siloxane compound, and an ultraviolet protection layer is manufactured by the following steps.

[0262] (1) 100g of a mixture of pyromellitic dianhydride as a dianhydride unit and 4,4'-diaminodiphenyl ether as a diamine unit (molar percentage of dianhydride unit to diamine unit is 1:1) was dissolved in 566.6g of DMAc to obtain a polyamic acid solution; in addition, 25g of trisilylphenyl cage polysiloxane as a siloxane compound was added to 100g of DMAc and stirred evenly to obtain a siloxane solution;

[0263] (2) The siloxane solution obtained in step (1) is added dropwise to the polyamic acid solution at an injection rate of 5 mL / min for mixing and reaction, and then allowed to stand for 48 hours to obtain a polyamic acid composition solution without bubbles and without layering.

[0264] (3) The polyamic acid composition solution obtained in step (2) is directly sprayed onto the surface of the solar cell array under the conditions of 0.3 MPa and spray valve running speed of 100 mm / s. After standing and waiting for the solution to be evenly distributed and reach a semi-cured state, the coating is cured by setting parameters such as baking temperature of 250℃ and baking time of 120 minutes until it is completely cured.

[0265] (4) Repeat step (3) to perform multiple spraying and curing operations, so that the thickness of the obtained second polyimide layer reaches 100 μm.

[0266] (5) Using a cerium dioxide target, cerium oxide was sputtered on the surface of the obtained second polyimide layer at a speed of 1 Å / s at room temperature by magnetron sputtering to obtain a cerium oxide-containing ultraviolet protection layer with a thickness of 68.18 nm.

[0267] The refractive index of the cerium oxide sputtered layer in the obtained protective reinforcement film m3 was compared with that of the standard database, and the result was 2.20.

[0268] (UV resistance test)

[0269] The obtained protective reinforcement film m3 was subjected to an ultraviolet radiation resistance test.

[0270] First, before ultraviolet irradiation, the transmittance of the protective reinforcement film m3 was measured and used as the transmittance before ultraviolet irradiation. Then, the protective reinforcement film m3 was irradiated with ultraviolet light with wavelengths of 115–400 nm at a power density of 27 mW / cm². -2 Irradiate for 30 hours, then measure the transmittance after ultraviolet irradiation.

[0271] The transmittance (solid line) and transmittance (dashed line) of the protective reinforcement film m3 before ultraviolet irradiation are shown in the figure. Figure 5 middle.

[0272] according to Figure 5 It can be seen that the transmittance of the protective enhancement film m3 did not decrease significantly after ultraviolet irradiation, which indicates that the protective enhancement film m3 can achieve ultraviolet protection function.

[0273] (Atomic Oxygen Exposure Test)

[0274] An atomic oxygen exposure test was conducted on the protective reinforcement membrane m3.

[0275] The protective reinforcement film m3 and the control film (pure polyimide resin film) were respectively subjected to high-speed atomic oxygen irradiation at 2.5 × 10⁻⁶. 20 atoms cm -2 After irradiation with the specified dose, the mass loss of the protective reinforcement film m3 was 0.12 wt%, while that of the control film (pure polyimide resin film) was 10.9 wt%. This result indicates that the atomic resistance of the protective reinforcement film m3 is significantly improved, and its atomic resistance is superior to that of the protective reinforcement film m1 (mass loss 1.5 wt%).

[0276] (Anti-reflective and anti-reflective properties)

[0277] In this embodiment, the thickness d of the ultraviolet protection layer serving as the surface layer in the protective enhancement film m3 is 68.18 nm, and the refractive index n is 2.20. This protective enhancement film m3 has an anti-reflection effect for light with a wavelength of approximately 600.00 nm (k = 0) and an anti-reflection effect for light with a wavelength of approximately 300.00 nm (k = 1). Therefore, it can improve the utilization rate of light with a wavelength of around 600.00 nm required by the solar cell and reduce the heat accumulation caused by light with a wavelength of around 300.00 nm.

[0278] As used herein, the terms “comprising,” “including,” “containing,” “having,” or any other variation thereof are intended to cover non-exclusive inclusion. For example, a method, article, or apparatus that includes a list of features is not necessarily limited to those features, but may include other features not expressly listed or inherent to the aforementioned method, article, or apparatus. Furthermore, unless expressly stated to the contrary, “or” means inclusive or, not exclusive, or. For example, condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0279] Furthermore, the articles “a” or “an” indicate a single kind or a broad class comprising multiple kinds. In this document, any limiting meaning does not necessarily exclude its common and customary meaning in some embodiments.

[0280] Finally, it should be understood that the above description of the embodiments and examples is illustrative in all respects and does not constitute a limitation of the present invention. Those skilled in the art can make various improvements without departing from the spirit of the present invention without creative effort. The scope of the present invention is defined by the claims, not by the above embodiments or examples. Furthermore, the scope of the present invention includes all modifications within the meaning and scope equivalent to the claims.

[0281] Industrial availability

[0282] The protective enhancement film disclosed herein can enhance the transmission performance of light in the desired light transmission band or the reflection performance of light in the desired light reflection band while achieving ultraviolet protection and atomic oxygen protection. Therefore, it is suitable for use as a film for optoelectronic devices in spacecraft, and is particularly suitable for surface protection of solar cells, space solar cell arrays, etc. in spacecraft.

Claims

1. A protective and reinforcing film for the protection and reinforcement of the surface of spacecraft optoelectronic devices, comprising a transparent polyimide resin, a siloxane compound, and an ultraviolet absorber. wherein The protective reinforcement film has a first polyimide layer comprising the polyimide resin, the siloxane compound, and the ultraviolet absorber, and an atomic oxygen protective layer comprising an atomic oxygen protective agent, wherein the thickness of the outermost atomic oxygen protective layer is 1 / 4 of the wavelength of the incident light in the desired anti-transmittance band in the medium of the layer or an odd multiple thereof, or 1 / 2 of the wavelength of the incident light in the desired anti-reflection band in the medium of the layer or an integer multiple thereof. The siloxane compound is selected from aminopropylheptyl-cage-polysemi-siloxane, trisilylphenyl-cage-polysemi-siloxane, N-[(heptaisobutylcage-polysemi-siloxane)propyl]3,5-diaminobenzamide, trisilanol isobutylcage-polysemi-siloxane, trans-cyclohexanediol hepyl-cage-polysemi-siloxane, 1,2-propanediol isobutylcage-polysemi-siloxane, aminopropylheptyl-cage-polysemi-siloxane. At least one of the following: semisiloxane, N-phenylamino cage-type silsesquioxane, acryloylisobutyl cage-type silsesquioxane, allyl cage-type siloxane, isooctyl ester cage-type polysilsesquioxane, octaisobutyl cage-type polysilsesquioxane, tetramethylammonium cage-type polysilsesquioxane, tetrasilane cage-type polysilsesquioxane, trisilyl isooctyl cage-type polysilsesquioxane, and trisilyl phenyl cage-type polysilsesquioxane. The polyimide resin is obtained by reacting a dianhydride monomer and a diamine monomer in an organic solvent to obtain a polyamic acid solution, followed by imidization of the polyamic acid. The dianhydride monomer is at least one selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride. The diamine monomer is selected from at least one of 2,2'-di(trifluoromethyl)diaminobiphenyl, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(3-(trifluoromethyl)aniline), 1,4-bis(2-trifluoromethyl4-aminophenoxy)benzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

2. The protective reinforcing film as described in claim 1, characterized in that, The ultraviolet absorber is at least one selected from 2,(2-hydroxy-5-methylphenyl)benzotriazole, hexamethylphosphoric triamine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, and nano-cerium oxide.

3. The protective reinforcement film of claim 1, wherein The atomic oxygen protectant is selected from at least one of titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, and indium tin oxide.

4. The protective reinforcement film of claim 1, wherein When the protective reinforcing film is a protective antireflective film, and the thickness of the outermost layer of the protective reinforcing film is set as d, the thickness d of the outermost layer satisfies the following formula (1): (Formula 1) Where λ is the desired wavelength for enhanced light transmission or the optimized wavelength for peak device performance, n is the refractive index of the outermost layer, and k is a natural number.

5. The protective reinforcement film of claim 1, wherein When the protective reinforcing film is a protective anti-reflective film, and the thickness of the outermost layer of the protective reinforcing film is set as d, the thickness d of the outermost layer satisfies the following formula (2): (Formula 2) Where λ1 is the desired wavelength for enhanced reflection or the optimized wavelength for peak device performance, n is the refractive index of the outermost layer, and k is a natural number greater than 1.

6. A method for manufacturing a protective reinforcing film, comprising the method for manufacturing the protective reinforcing film according to any one of claims 1 to 5, including: A transparent first polyimide layer is formed by adhering a composition comprising a dianhydride monomer, a diamine monomer, the siloxane compound, and the ultraviolet absorber to the surface of a spacecraft optoelectronic device and then curing it. An atomic oxygen protective layer containing an atomic oxygen protective agent is formed on the first polyimide layer by a dry process. The siloxane compound is selected from aminopropylheptyl-cage-polysemi-siloxane, trisilylphenyl-cage-polysemi-siloxane, N-[(heptaisobutylcage-polysemi-siloxane)propyl]3,5-diaminobenzamide, trisilanol isobutylcage-polysemi-siloxane, trans-cyclohexanediol hepyl-cage-polysemi-siloxane, 1,2-propanediol isobutylcage-polysemi-siloxane, aminopropylheptyl-cage-polysemi-siloxane. At least one of the following: semisiloxane, N-phenylamino cage-type silsesquioxane, acryloylisobutyl cage-type silsesquioxane, allyl cage-type siloxane, isooctyl ester cage-type polysilsesquioxane, octaisobutyl cage-type polysilsesquioxane, tetramethylammonium cage-type polysilsesquioxane, tetrasilane cage-type polysilsesquioxane, trisilyl isooctyl cage-type polysilsesquioxane, and trisilyl phenyl cage-type polysilsesquioxane. The dianhydride monomer is at least one selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride. The diamine monomer is selected from at least one of 2,2'-di(trifluoromethyl)diaminobiphenyl, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))bis(3-(trifluoromethyl)aniline), 1,4-bis(2-trifluoromethyl4-aminophenoxy)benzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

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