Protective reinforced film and preparation method thereof

Abstract

The invention provides a protection enhancement film capable of simultaneously realizing ultraviolet protection and atomic oxygen protection and enhancing the transmission performance of light in a required light transmission enhancement wave band or the reflection performance of light in a required reflection enhancement wave band, and a preparation method of the protection enhancement film. The protective reinforcing film contains a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from the group consisting of an ultraviolet absorbent and an ultraviolet cut-off agent, and has at least one layer. Wherein the thickness of the outermost layer is 1 / 4 or odd times of the wavelength of incident light of a required light transmission enhancing wave band in the layer of medium, or 1 / 2 or integer times of the wavelength of incident light of a required light reflection enhancing wave band in the layer of medium. The protective reinforced film is suitable for being used as a film for a spacecraft photoelectric device.

Description

Technical Field

[0001] The present disclosure relates to the fields of material engineering technology and aerospace technology, and particularly to a protective enhanced film for spacecraft optoelectronic devices and a preparation method thereof. Background Art

[0002] Due to the foldable volume advantage and excellent mechanical properties, various flexible aerospace devices 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 are exposed to long-term strong ultraviolet radiation and high-energy atomic oxygen attacks, so flexible encapsulation materials are required to protect the devices. Transparent flexible surface coating materials, such as tetrafluoroethylene, polyimide, and polyethylene, have been widely used in frontier fields such as flexible solar cells due to their excellent light transmittance in the initial stage.

[0003] It should be noted that at present, the surface coating materials of various aerospace devices can often only protect against one or more types of attacks, such as protecting against ultraviolet rays or atomic oxygen, and cannot enhance the performance of the protected devices. For example, while protecting, it is impossible to enhance the light utilization rate of solar cells or reduce the photo-thermal accumulation of devices.

[0004] Therefore, a protective enhanced film technology for spacecraft optoelectronic devices that can simultaneously achieve ultraviolet protection and atomic oxygen protection, and enhance the transmission performance or reflection performance of light in the required light band is needed. Summary of the Invention

[0005] In view of the above technical problems existing in the prior art, the purpose of the present disclosure is to provide a protective enhanced film that can be used for spacecraft optoelectronic devices and can simultaneously achieve ultraviolet protection and atomic oxygen protection, and enhance the transmission performance of light in the required light transmission band or the reflection performance of light in the required light reflection band.

[0006] The purpose of the present disclosure is also to provide a manufacturing method of the above protective enhanced film.

[0007] The present disclosure includes the following technical solutions.

[0008] [1] A protective enhanced film, which comprises a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from an ultraviolet absorber or an ultraviolet blocker,

[0009] wherein, the above protective enhanced film has at least one layer, and the thickness of the outermost layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the required light transmission band in this layer medium, or 1 / 2 and its integer multiples of the wavelength of the incident light in the required light reflection band in this layer medium.

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

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

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

[0013] A first polyimide layer containing the above polyimide resin, the above siloxane compound, and the above ultraviolet absorber, and

[0014] A second polyimide layer containing the above polyimide resin and the above siloxane compound.

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

[0016] A first polyimide layer containing the above polyimide resin, the above siloxane compound, and the above ultraviolet absorber, and

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

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

[0019] A second polyimide layer containing the above polyimide resin and the above siloxane compound, and

[0020] An ultraviolet protection layer containing the above ultraviolet cutoff agent.

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

[0022] The above siloxane compound is at least one selected from hexamethyldisiloxane, a siloxane containing at least one group selected from vinyl, propenyl, amino, phenyl, hydroxyl, and carboxyl groups, and aminopropylheptyl-cage polyhemisiloxane, trisilylphenylcage polysiloxane, N-[(heptaisobutylcage polysiloxane)propyl]3,5-diaminobenzamide, trisilanol isobutylcage polyhemisiloxane, trans-cyclohexanediol heptyl-cage polyhedral oligomeric silsesquioxane, 1,2-propanediol isobutylcage polyhemisiloxane, aminopropylheptyl-cage polyhemisiloxane, N-phenylaminocage polyhedral oligomeric silsesquioxane, acryloyl isobutylcage polyhedral oligomeric silsesquioxane, allyl cage polysiloxane, isooctyl ester cage polyhedral oligomeric silsesquioxane, octaisobutyl cage polyhedral oligomeric silsesquioxane, tetramethylammonium cage polyhedral oligomeric silsesquioxane, tetrasilane cage polyhedral oligomeric silsesquioxane, trisilanol isooctyl cage polyhedral oligomeric silsesquioxane, and trisilanol phenyl cage polyhedral oligomeric silsesquioxane;

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

[0024] The above ultraviolet ray cutoff agent is at least one selected from titanium dioxide, aluminum oxide, cerium oxide, zinc oxide, and indium tin oxide.

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

[0026] [8] The protective enhanced film as described in [1], wherein when the protective enhanced film is a protective and antireflective film, and the thickness of the outermost layer of the protective enhanced film is set as d, the thickness d of the outermost layer satisfies the following formula (1):

[0027]

[0028] where λ is the Anti-reflection desired light wavelength or the optimized wavelength of the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number.

[0029] [9] The protective enhanced film as described in [1], wherein when the protective enhanced film is a protective and antireflective film, and the thickness of the outermost layer of the protective enhanced film is set as d, the thickness d of the outermost layer further satisfies the following formula (2):

[0030]

[0031] where λ1 is the High reflection desired light wavelength or the optimized wavelength of the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number greater than or equal to 1.

[0032]

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

[0033]

[11] A manufacturing method of a protective enhanced film, which includes:

[0034] After attaching a composition containing a dianhydride monomer, a diamine monomer, a siloxane compound, and an ultraviolet absorber to the surface of a spacecraft optoelectronic device, curing is performed to form a first polyimide layer, and

[0035] Optionally, a composition containing a dianhydride monomer, a diamine monomer, and a siloxane compound is attached to the above-mentioned first polyimide layer and then cured to form a second polyimide layer; or an atomic oxygen protection layer containing an atomic oxygen protector is formed on the above-mentioned first polyimide layer by a dry process.

[0036]

[12] A method for manufacturing a protective enhanced film, which includes:

[0037] After attaching a composition containing a dianhydride monomer, a diamine monomer, and a siloxane compound to the surface of a spacecraft optoelectronic device, curing is performed to form a second polyimide layer, and

[0038] A composition containing a dianhydride monomer, a diamine monomer, a siloxane compound, and an ultraviolet absorber is attached to the above-mentioned second polyimide layer and then cured to form a first polyimide layer; or an ultraviolet protection layer containing an ultraviolet cutoff agent is formed on the above-mentioned second polyimide layer by a dry process.

[0039]

[13] The method for manufacturing a protective enhanced film according to the above

[11] or

[12] , wherein,

[0040] The above-mentioned dianhydride monomer is at least one selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride;

[0041] The above-mentioned diamine monomer is at least one selected from 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-trifluoromethyl-4-aminophenoxy)benzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane;

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

[0043] Advantageous Effects

[0044] According to the present disclosure, a protective enhanced film can be provided, which can be used for spacecraft optoelectronic devices and can simultaneously achieve ultraviolet protection and atomic oxygen protection, as well as enhance the light transmission performance of the desired light transmittance band or the light reflection performance of the desired light reflection band.

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

[0046] Figure 1 Photograph of the protective enhanced film of Example 1 of the present invention;

[0047] Figure 2 Transmittance of the protective enhanced film of Example 1 of the present invention before (solid line) and after (dashed line) ultraviolet irradiation;

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

[0049] Figure 4 Transmittance of the protective enhanced film of Example 2 of the present invention before (solid line) and after (dashed line) atomic oxygen irradiation;

[0050] Figure 5 Transmittance of the protective enhanced film of Example 3 of the present invention before (solid line) and after (dashed line) ultraviolet irradiation. Detailed implementation manners

[0051] The meanings of the following terms in the present disclosure are as follows.

[0052] In the present disclosure, "film" includes a single-layer film and a laminated film formed by laminating multiple layers.

[0053] In the present disclosure, a "protective enhanced film" refers to a film having ultraviolet protection and atomic oxygen protection properties, and at the same time having enhanced light transmission performance for the desired light transmission band or enhanced light reflection performance for the desired light reflection band; a "protective antireflection film" refers to a film having ultraviolet protection and atomic oxygen protection properties, and at the same time having enhanced light transmission performance for the desired light transmission band; a "protective reflection film" refers to a film having ultraviolet protection and atomic oxygen protection properties, and at the same time having enhanced light reflection performance for the desired light reflection band.

[0054] The "~" representing a numerical range means including the numerical values described before and after it as the lower limit value and the upper limit value. In the numerical ranges described hierarchically in the present disclosure, the upper limit value or the lower limit value described in one numerical range can also be replaced with the upper limit value or the lower limit value of other hierarchically described numerical ranges. In addition, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range can also be replaced with the values shown in the examples.

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

[0056] The protective enhanced film of the present disclosure comprises a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from an ultraviolet absorber or an ultraviolet blocker. Among them, the above protective enhanced film has at least one layer, and the thickness of the outermost layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the required light-transmitting band in this layer of medium, or 1 / 2 and its integer multiples of the wavelength of the incident light in the required light-reflecting band in this layer of medium.

[0057] In the protective enhanced film of the present disclosure, the polyimide resin is a flexible transparent resin, which has excellent high and low temperature resistance, mechanical properties, insulation properties, space radiation resistance, and flame-retardant self-extinguishing characteristics, and is applied as a substrate to optoelectronic devices on spacecraft. A siloxane compound is contained in the polyimide resin. By introducing silicon atoms (or silicon-containing groups) into the polyimide molecular structure, since silicon atoms can react with atomic oxygen to form a passivation layer, the polyimide is given anti-atomic oxygen performance, thereby improving the anti-atomic oxygen performance of the polyimide film. In addition, the protective enhanced film improves its anti-ultraviolet performance by containing an anti-ultraviolet compound selected from an ultraviolet absorber or an ultraviolet blocker.

[0058] The protective enhanced film of the present disclosure has at least one layer. For example, the protective enhanced film can be a single-layer film or a laminated film formed by laminating multiple layers. When the protective enhanced film is a single-layer film, the outermost layer of the protective enhanced film is the protective enhanced film itself. When the protective enhanced film is a laminated film, the outermost layer is the outermost surface layer of the protective enhanced film.

[0059] In the protective enhanced film of the present disclosure, the thickness of the outermost layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the required light-transmitting band in this layer of medium. Specifically, when the wavelength of the incident light in a specific light band (for example, 400-750 nm) in vacuum is denoted as λ and the refractive index of the film medium is denoted as n, the wavelength of the incident light in the film medium is λ n is λ / n. By making the thickness of the film (the outermost layer in the case of a laminated film) 1 / 4 and its odd multiples of the wavelength of the incident light in the film medium λ n it is possible to increase the light transmittance of the above incident light in the film, thereby enhancing the utilization rate of light with a wavelength of λ, that is, realizing the function of increasing transmittance and reducing reflection. At the same time, for light with a wavelength that is 1 / 2 and its integer multiples of the wavelength of the above incident light λ, the film (the outermost layer in the case of a laminated film) can enhance the reflectivity of this light, realizing the function of increasing reflection and reducing transmittance, thereby reducing the heat accumulation on the optoelectronic device caused by this light.

[0060] Through the above composition, the protective enhancement film of the present disclosure can achieve ultraviolet protection and atomic oxygen protection, as well as enhance the light transmission performance of the light in the required light transmittance enhancement band or the light reflection performance of the light in the required light reflection enhancement band. Therefore, when used in spacecraft optoelectronic devices, it can provide ultraviolet protection and atomic oxygen protection for the spacecraft optoelectronic devices, and can enhance the light utilization rate of the spacecraft optoelectronic devices such as solar cells, as well as reduce the photo-thermal accumulation caused by specific light rays, which is beneficial to extending the service life of the optoelectronic devices.

[0061] The following shows preferred embodiments to illustrate the protective enhancement film of the present disclosure. This is intended to illustrate the present invention rather than limit the present invention. The protective enhancement film of the present invention is not limited to the following embodiments.

[0062] [First Embodiment]

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

[0064] The above protective enhancement film 1 has a single-layer first polyimide layer, and the thickness of the first polyimide layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the required light transmittance enhancement band in the medium of this layer, or 1 / 2 and its integer multiples of the wavelength of the incident light in the required light reflection enhancement band in the medium of this layer.

[0065] (First Polyimide Layer)

[0066] The first polyimide layer contains a polyimide resin, a siloxane compound, and an ultraviolet absorber.

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

[0068] The polyimide resin in the present invention can be obtained by mixing a dianhydride monomer and a diamine monomer in an organic solvent to react to obtain a polyamic acid solution, and then subjecting the polyamic acid to imidization 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 - 1.2), preferably 1:(0.9 - 1.1), and particularly preferably 1:1.

[0069] As the above-mentioned dianhydride monomers, for example, 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, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[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 dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 5,5'-(1,4-phenylene)bis(hexahydro-4,7-methanoisobenzofuran-1,3-dione) and other aliphatic or alicyclic tetracarboxylic dianhydrides; pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyl diphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diophthalic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalic acid) dianhydride, m-phenylene-bis(triphenyl phthalic acid) dianhydride, bis(triphenyl phthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenyl phthalic acid)-4,4'-diphenyl methane dianhydride and other aromatic tetracarboxylic dianhydrides, etc.From the perspective of easily obtaining a polyimide resin with excellent flexibility, it is preferable to use an aliphatic or alicyclic tetracarboxylic dianhydride. From the perspective of easily obtaining a polyimide resin with excellent heat resistance, it is preferable to use an aromatic tetracarboxylic dianhydride. 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, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride or pyromellitic dianhydride is particularly preferred.

[0070] As the above diamine monomers, for example, 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-trifluoromethyl-4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenylmethane, 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-ethane-1,1-diyl)]bis(aniline), 4,4'-[1,4-phenylenebis(1-methyl-ethane-1,1-diyl)]bis(aniline), 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzanilide, o-tolidine sulfone, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 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’ - dicarboxylate, 4,4” - diamino - p - terphenyl, N,N’ - bis(4 - aminobenzoyl) - p - phenylene diamine, bis[4 - (4 - aminophenoxy)phenyl]ketone, 4 - aminophenyl - 4 - aminobenzoate, [1,1’ - biphenyl] - 4,4’ - diyl bis(4 - aminobenzoate), etc. In some preferred embodiments, the diamine monomer 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’ - diyl bis(oxy))bis(3 - (trifluoromethyl)aniline), 1,4 - bis(2 - trifluoromethyl - 4 - aminophenoxy)benzene, 2,2 - bis[4 - (4 - aminophenoxy)phenyl] - 1,1,1,3,3,3 - hexafluoropropane, and 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 above - mentioned siloxane compound, it is preferable to use at least one of hexamethyldisiloxane, a siloxane containing at least one group selected from vinyl, propenyl, amino, phenyl, hydroxyl, and carboxyl groups, and a cage - type siloxane.

[0072] As the cage - type siloxane, for example, aminopropylheptyl - silsesquioxane, trisilylphenylcage - type siloxane, N - [(heptaisobutylcage - type silsesquioxane)propyl]3,5 - diaminobenzamide, trisilanol isobutylcage - type siloxane, trans - cyclohexanediol heptyl - silsesquicage - type siloxane, 1,2 - propanediol isobutylcage - type siloxane, aminopropylheptyl - silsesquioxane, N - phenylaminocage - type sesquisiloxane, acryloyl isobutylcage - type sesquisiloxane, allyl cage - type siloxane, isooctyl ester - silsesquicage - type siloxane, octaisobutylcage - type silsesquioxane, tetramethylammonium - cage - type silsesquioxane, tetrasilane cage - type silsesquioxane, trisilanol isooctylcage - type silsesquioxane, trisilanol phenylcage - type silsesquioxane, etc. can be cited.

[0073] As the siloxane containing at least one group selected from vinyl, propenyl, amino, phenyl, hydroxyl, and carboxyl groups, for example, methacryloyloxypropyl siloxane, allyloxypropyl siloxane, dodecylbenzene siloxane, etc. can be cited.

[0074] It is further preferable to use hexamethyldisiloxane, trisilylphenylcage - type siloxane, or a siloxane containing at least one group selected from vinyl, phenyl, and hydroxyl groups as the above - mentioned siloxane compound.

[0075] The above-mentioned silicone compound can be used alone or in combination of two or more.

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

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

[0078] In the first polyimide layer, the content of the above-mentioned ultraviolet absorber is not particularly limited as long as a protective enhanced film with ultraviolet protection performance can be obtained. In some preferred embodiments, relative to 100% by weight of the polyimide resin, the content of the ultraviolet absorber is 0.1 to 10% by weight, preferably 0.3 to 8% by weight, more preferably 0.5 to 5% by weight. 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 enhanced film 1 has a first polyimide layer as a single layer. Therefore, the first polyimide layer is the outermost layer of the protective enhanced film 1. In this embodiment, the thickness of the first polyimide layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the medium of this layer in the desired light transmittance increasing band.

[0081] In some preferred embodiments, when the protective enhancement film 1 is a protective antireflection film, when 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 wavelength of the desired increased transmitted light or the optimized wavelength of the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number and preferably 0.

[0084] By having the above-mentioned first polyimide layer, the protective enhancement film 1 can achieve the antireflection performance for incident light with a wavelength of λ, thereby improving the utilization rate of the incident light.

[0085] In some preferred embodiments, when the protective enhancement film 1 is a protective reflection-enhancing film, when 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 wavelength of the desired High reflection light wavelength or the optimized wavelength of the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number greater than or equal to 1.

[0088] By having the above-mentioned first polyimide layer, the protective enhancement film 1 can achieve the reflection-enhancing performance for incident light with a wavelength of λ1, thereby being able to prevent the photo-thermal accumulation caused by the incident light.

[0089] The thickness of the first polyimide layer in the protective enhancement film 1 can be adjusted, for example, by controlling the coating thickness and number of times of the coating solution as described in the following manufacturing method.

[0090] (Manufacturing method of the protective enhancement film 1)

[0091] Next, the manufacturing method of the protective enhancement film 1 in the present embodiment will be described.

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

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

[0094] In some preferred embodiments, the protective enhancement 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, and stir evenly to obtain a siloxane solution;

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

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

[0098] (4) Drop the siloxane solution containing an ultraviolet absorber obtained in step (3) into the polyamic acid solution containing an ultraviolet absorber at an injection rate of 2 - 10 mL / min for mixing reaction, and then let it stand for 24 - 48 hours to obtain a polyamic acid composition solution;

[0099] (5) Attach the obtained polyamic acid composition solution to the surface of the optoelectronic device of the spacecraft, let it stand until the solution is evenly distributed to reach a semi-cured state, and then cure it to obtain a first polyimide layer.

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

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

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

[0103] In the above manufacturing method, in step (5), the above "adhesion" is preferably spraying, spin coating, direct coating, casting or additive manufacturing. When the device is small, the spin coating process is preferably used; when the device is large or has an irregular curved surface, the spraying process is preferably used. When the spraying process is used for adhesion, it is preferably carried out under the conditions of 0.2 - 0.5 Mpa and a spray valve running speed of 50 - 200 mm / s, and particularly preferably carried out under the conditions of 0.3 Mpa and a spray valve running 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] (Function and effect)

[0106] The protective enhancement film 1 of the present embodiment has the first polyimide layer as described above, which is a transparent and flexible coating, capable of achieving ultraviolet protection and atomic oxygen protection, as well as enhancing the light transmission performance of the light in the desired light transmission band or the light reflection performance of the light in the desired light reflection band, suitable for application on the surfaces of various spacecraft optoelectronic devices such as flexible, rigid, and irregular curved surfaces, capable of providing ultraviolet protection and atomic oxygen protection for spacecraft optoelectronic devices, and capable of enhancing the light utilization rate of spacecraft optoelectronic devices such as solar cells, and reducing the photo-thermal accumulation caused by specific light rays.

[0107] [Second Embodiment]

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

[0109] There is no particular limitation on the lamination order of the first polyimide layer and the second polyimide layer in the protective enhancement film 2. For example, the base layer can be the first polyimide layer, and the second polyimide layer can be further laminated thereon as the outermost layer, or the base layer can be the second polyimide layer, and the first polyimide layer can be further laminated thereon as the outermost layer. Note that regardless of the lamination order, the outermost layer of the protective enhancement film 2 satisfies that the thickness is 1 / 4 and its odd multiples of the wavelength of the incident light in the desired light transmission band in this layer medium, or 1 / 2 and its integer multiples of the wavelength of the incident light in the desired light reflection band in this layer medium.

[0110] Next, the morphology of the protective enhancement film 2 with the second polyimide layer as the base layer and the first polyimide layer as the outermost layer will be described.

[0111] (First Polyimide Layer)

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

[0113] For the sake of simplicity, the repeated description of the first polyimide layer is omitted.

[0114] (Second polyimide layer)

[0115] The second polyimide layer is a base layer directly formed on the surface of the optoelectronic device of the spacecraft, and contains a polyimide resin and a 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 above first embodiment, 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 above first embodiment, 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 as the base layer, as long as the thickness of the second polyimide layer does not affect the object of the present invention.

[0120] The thickness of the second polyimide layer may 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 reinforcement film 2 can be adjusted, for example, by controlling the coating thickness and number of times of the coating solution as described in the following manufacturing method.

[0122] (Manufacturing method of the protective reinforcement film 2)

[0123] Next, the manufacturing method of the protective reinforcement film 2 in the present embodiment will be described.

[0124] The manufacturing method of the protective reinforcement film 2 includes: attaching a composition containing a dianhydride monomer, a diamine monomer, and a siloxane compound to the surface of the optoelectronic device of the spacecraft and then curing it to form a second polyimide layer, and attaching a composition containing a dianhydride monomer, a diamine monomer, a siloxane compound, and an ultraviolet absorber to the above 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 the preferred forms are also the same.

[0126] In addition, the first polyimide layer in this embodiment can be manufactured by 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 diamine monomer in a polar organic solvent at a molar ratio of 1:(0.9 - 1.2) to obtain a polyamic acid solution; add 0 - 30% by weight of the siloxane compound relative to the weight of the polyamic acid to the polar organic solvent, and stir evenly to obtain a siloxane solution;

[0129] (2) Drop the siloxane solution obtained in step (1) into the polyamic acid solution at an injection rate of 2 - 10 mL / min for mixing and reaction, and then let it stand for 24 - 48 hours to obtain a siloxane-containing polyamic acid composition solution;

[0130] (3) Attach the above-obtained siloxane-containing polyamic acid composition solution to the surface of the spacecraft optoelectronic device, let it stand until the solution is evenly distributed to reach a semi-cured state, and then cure it to obtain the second polyimide layer.

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

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

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

[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] (Function and effect)

[0136] The protective enhanced film 2 of this embodiment has a second polyimide layer as the base layer and a first polyimide layer as the outermost layer. Both the first polyimide layer and the second polyimide layer are transparent and flexible coatings. Among them, the first polyimide layer can achieve ultraviolet protection and atomic oxygen protection, and enhance the light transmission performance of light in the required light transmission enhancement band or the light reflection performance of light in the required light reflection enhancement band. The second polyimide layer can achieve atomic oxygen protection. When the protective enhanced film 2 is applied on the surface of a spacecraft optoelectronic device, it can protect the spacecraft optoelectronic device from ultraviolet rays and atomic oxygen, and can enhance the light utilization rate of the spacecraft optoelectronic device such as a solar cell, and reduce the photo-thermal accumulation caused by specific light rays.

[0137] It should be noted that the form of the protective enhanced film 2 having a second polyimide layer as the base layer and a first polyimide layer as the outermost layer has been described above. However, those of ordinary skill in the art can make appropriate combinations and changes based on the content disclosed in this article, and can easily obtain a protective enhanced film 2 having a first polyimide layer as the base layer and a second polyimide layer as the outermost layer.

[0138] [Third Embodiment]

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

[0140] There is no particular limitation on the lamination order of the first polyimide layer and the atomic oxygen protection layer in the protective enhanced film 3. For example, the base layer can be the first polyimide layer, and the atomic oxygen protection layer as the outermost layer can be further laminated thereon. Or the base layer can be the atomic oxygen protection layer, and the first polyimide layer as the outermost layer can be further laminated thereon. Note that regardless of the lamination order, the outermost layer of the protective enhanced film 3 satisfies that the thickness is 1 / 4 and its odd multiples of the wavelength of the incident light in the required light transmission enhancement band in this layer medium, or 1 / 2 and its integer multiples of the wavelength of the incident light in the required light reflection enhancement band in this layer medium.

[0141] Next, the form of the protective enhanced film 3 having a first polyimide layer as the base layer and an atomic oxygen protection layer as the outermost layer will be described.

[0142] (First Polyimide Layer)

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

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

[0145] (Atomic oxygen protection layer)

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

[0147] As the atomic oxygen protection agent, at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, and indium tin oxide is preferably used, and titanium dioxide, silicon dioxide, or cerium oxide is more preferably used.

[0148] In some preferred embodiments, the atomic oxygen protection layer is formed on the first polyimide layer by a dry process. As the dry process, physical vapor deposition (hereinafter also referred to as "PVD method"), chemical vapor deposition (hereinafter also referred to as "CVD method"), etc. can be cited.

[0149] As the PVD method, vacuum evaporation, sputtering, ion plating, pulsed laser deposition, etc. can be cited, and any one of these methods can be used. As the sputtering method, any one of DC sputtering, RF sputtering, magnetron sputtering, single (multi)-target sputtering, and hybrid target sputtering can be used. From the aspects of excellent productivity, wide industrial use, and obtaining a film with high adhesion to the first polyimide layer with a very dense and uniform film thickness, the sputtering method is preferred, and the magnetron sputtering method is particularly preferred.

[0150] As the CVD method, plasma CVD, thermal CVD, catalytic CVD, etc. can be cited, and any one of these methods can be used. Among them, from the aspects of excellent productivity, wide industrial use, and obtaining a film with high adhesion to the first polyimide layer with a very dense and uniform film thickness, the plasma CVD method is preferred.

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

[0152] As described above, the protective enhancement film 3 has an atomic oxygen protection layer as the outermost layer. In this embodiment, the thickness of the atomic oxygen protection layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the medium of this layer in the required light transmittance increasing wavelength band, or 1 / 2 and its integer multiples of the wavelength of the incident light in the medium of this layer in the required light reflectance increasing wavelength band.

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

[0154]

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

[0156] The protective enhanced film 3 can achieve the antireflection performance for incident light with a wavelength of λ by having the above-mentioned atomic oxygen protective layer, thereby improving the utilization rate of the incident light.

[0157] In some preferred embodiments, when the protective enhanced film 3 is a protective antireflection film, when the thickness of the atomic oxygen protective layer is set to d, the thickness d of the atomic oxygen protective layer satisfies the following formula (2):

[0158]

[0159] where λ1 is the High reflection optimization wavelength of the required optical wavelength or the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number of 1 or more.

[0160] The protective enhanced film 3 can achieve the antireflection performance for incident light with a wavelength of λ1 by having the above-mentioned atomic oxygen protective layer, thereby being able to prevent the photoinduced heat accumulation caused by the incident light.

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

[0162] (Manufacturing method of the protective enhanced film 3)

[0163] Next, the manufacturing method of the protective enhanced film 3 in the present embodiment will be described.

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

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

[0166] In addition, the first polyimide layer in the present embodiment can be manufactured by the same manufacturing steps as the first polyimide layer in the first embodiment.

[0167] As the atomic oxygen protectant used for forming the atomic oxygen protective layer, at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, and indium tin oxide is preferably used, and more preferably titanium dioxide, silicon dioxide, or cerium oxide.

[0168] In some preferred embodiments, as the dry process for forming the atomic oxygen protection layer, the PVD method is preferred, the sputtering method is more preferred, and any one of DC sputtering, RF sputtering, magnetron sputtering, single (multi)-target sputtering, and hybrid target sputtering is further preferred, and the magnetron sputtering method is particularly preferred.

[0169] When forming the atomic oxygen protection layer on the first polyimide layer by the magnetron sputtering method, the thickness of the atomic oxygen protection layer is regulated by controlling the magnetron sputtering time.

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

[0171] (Function and effect)

[0172] The protection enhancement film 3 of the present embodiment has a first polyimide layer as the 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. Among them, the first polyimide layer can achieve ultraviolet protection and atomic oxygen protection, and while the atomic oxygen protection layer realizes atomic oxygen protection, it can also enhance the light transmission performance of the light in the desired light transmittance increasing band or the light reflection performance of the light in the desired light reflectance increasing band. When the protection 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 the spacecraft optoelectronic device such as a solar cell, and reduce the photo-thermal accumulation caused by specific light.

[0173] It should be noted that the form of the protection enhancement film 3 having a first polyimide layer as the base layer and an atomic oxygen protection layer as the outermost layer has been described above. However, those of ordinary skill in the art can make appropriate combinations and changes according to the content disclosed herein, and can easily obtain a protection enhancement film 3 having an atomic oxygen protection layer as the base layer and a first polyimide layer as the outermost layer.

[0174] [Fourth Embodiment]

[0175] The protection enhancement film 4 of the fourth embodiment has: a second polyimide layer containing a polyimide resin and a siloxane compound, and an ultraviolet protection layer containing an ultraviolet ray blocker.

[0176] There is no particular limitation on the stacking order of the second polyimide layer and the ultraviolet protection layer in the protection enhancement film 4. For example, the base layer can be the second polyimide layer, and the ultraviolet protection layer as the outermost layer can be further stacked thereon, or the base layer can be the ultraviolet protection layer, and the second polyimide layer as the outermost layer can be further stacked thereon. Note that regardless of the stacking order, the outermost layer of the protection enhancement film 4 satisfies that the thickness is 1 / 4 and its odd multiples of the wavelength of the incident light in the required light transmittance increasing wavelength band in this layer of medium, or 1 / 2 and its integer multiples of the wavelength of the incident light in the required light reflectance increasing wavelength band.

[0177] Next, the morphology of the protection enhancement film 4 having the second polyimide layer as the base layer and the ultraviolet protection layer as the outermost layer will be described.

[0178] (Second polyimide layer)

[0179] The second polyimide layer has the same constitution as the second polyimide layer in the protection enhancement film 2 described in the above second embodiment. There is no particular limitation on the thickness of the second polyimide layer as long as the thickness of the second polyimide layer does not affect the object of the present invention.

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

[0181] (Ultraviolet protection layer)

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

[0183] As the ultraviolet ray blocking agent, it is preferably at least one selected from titanium dioxide, aluminum oxide, cerium oxide, zinc oxide, and indium tin oxide, and more preferably titanium dioxide, zinc oxide, or cerium oxide.

[0184] In some preferred embodiments, the ultraviolet protection layer is formed on the second polyimide layer by a dry method. As the dry method, physical vapor deposition (hereinafter also referred to as "PVD method"), chemical vapor deposition (hereinafter also referred to as "CVD method"), etc. can be cited.

[0185] As the PVD method, vacuum evaporation method, sputtering method, ion plating method, pulsed laser deposition, etc. can be cited, and any one of the methods can be used. As the sputtering method, any one of DC sputtering, RF sputtering, magnetron sputtering, single (multi)-target sputtering, and hybrid target sputtering can be used. From the aspects of excellent productivity, wide industrial use, and at the same time obtaining a film with high adhesion to the second polyimide layer with a very dense and uniform film thickness, the sputtering method is preferred, and the magnetron sputtering method is particularly preferred.

[0186] As the CVD method, examples include plasma CVD method, thermal CVD method, catalytic CVD method, etc., and any one of these methods can be used. Among them, considering the aspects of excellent productivity, wide industrial use, and obtaining a film with high adhesion to the second polyimide layer with a very dense and uniform film thickness, the plasma CVD method is preferred.

[0187] (Thickness of the ultraviolet protection layer)

[0188] As described above, the protection enhancement film 4 has an ultraviolet protection layer as the outermost layer. In the present embodiment, the thickness of the ultraviolet protection layer is 1 / 4 and its odd multiples of the wavelength of the incident light in the medium of this layer in the required light transmittance increasing wavelength band, or 1 / 2 and its integer multiples of the wavelength of the incident light in the medium of this layer in the required light reflectance increasing wavelength band.

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

[0190]

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

[0192] By having the above ultraviolet protection layer, the protection enhancement film 4 can achieve the antireflection performance for the incident light with a wavelength of λ, thereby improving the utilization rate of this incident light.

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

[0194]

[0195] Where λ1 is the required High reflection light wavelength or the optimized wavelength of the device peak performance, n is the refractive index of the outermost layer, and k is a natural number of 1 or more.

[0196] By having the above ultraviolet protection layer, the protection enhancement film 4 can achieve the reflection enhancement performance for the incident light with a wavelength of λ1, thereby being able to prevent the photoinduced thermal accumulation caused by this incident light.

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

[0198] (Manufacturing method of the protection enhancement film 4)

[0199] Next, a method for manufacturing the protective enhanced film 4 in this embodiment will be described.

[0200] The manufacturing method of the protective enhanced film 4 includes: attaching a composition containing a dianhydride monomer, a diamine monomer, and a siloxane compound onto the surface of a spacecraft optoelectronic device and then curing to form a second polyimide layer, and forming an ultraviolet protection layer containing an ultraviolet absorber on the above-mentioned second polyimide layer by a dry process.

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

[0202] In addition, the second polyimide layer in this embodiment can be manufactured by the same manufacturing steps as the second polyimide layer in the second embodiment.

[0203] As the ultraviolet absorber used for forming the ultraviolet protection layer, at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, zinc oxide, and indium tin oxide is preferably used, and titanium dioxide, zinc oxide, or cerium oxide is more preferably used.

[0204] In some preferred embodiments, as the dry process used for forming the ultraviolet protection layer, the PVD method is preferred, the sputtering method is more preferred, and any one of DC sputtering, RF sputtering, magnetron sputtering, single (multi)-target sputtering, and hybrid target sputtering is further preferred, and the magnetron sputtering method is particularly preferred.

[0205] When forming the ultraviolet protection layer on the second polyimide layer by the magnetron sputtering method, the thickness of the ultraviolet protection layer is controlled by controlling the magnetron sputtering time.

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

[0207] (Function and effect)

[0208] The protective enhanced film 4 of this embodiment has a second polyimide layer as the base layer and an ultraviolet protection layer as the outermost layer. The second polyimide layer is a transparent and flexible coating, and the ultraviolet protection layer is a transparent layer. Among them, the second polyimide layer can achieve atomic oxygen protection, and the ultraviolet protection layer can enhance the light transmission performance of the light in the required light transmission enhancement band or the light reflection performance of the light in the required light reflection enhancement band while achieving ultraviolet protection. When the protective enhanced film 4 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 the spacecraft optoelectronic device such as a solar cell, and reduce the light-induced heat accumulation caused by specific light rays.

[0209] It should be noted that the morphology of the protective enhancement film 4 having a second polyimide layer as the base layer and an ultraviolet protection layer as the outermost layer has been described above. However, those of ordinary skill in the art can make appropriate combinations and changes based on the content disclosed herein, and can easily obtain a protective enhancement film 4 having an ultraviolet protection layer as the base layer and a second polyimide layer as the outermost layer.

[0210] [Use]

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

[0212] [Examples]

[0213] The following further illustrates the composition and advantages of the present invention through examples. However, it should be understood that the following examples are only illustrative of the implementation of the present invention and are not intended to limit the protection scope of the present invention.

[0214] [Example 1]

[0215] A protective enhancement film m1 having a structure with a first polyimide layer containing a polyimide resin, a siloxane compound, and an ultraviolet absorber is manufactured through the following steps.

[0216] (1) 100 g of a mixture of cyclobutane tetracarboxylic dianhydride as the dianhydride unit and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane as the diamine unit (the molar percentage of the dianhydride unit to the diamine unit is 1:1) is dissolved in 566.6 g of DMAc to obtain a polyamic acid solution; in addition, 25 g of trisilanol phenylsiloxane as the siloxane compound is added to 100 g of DMAc and stirred evenly to obtain a siloxane solution;

[0217] (2) 2 g of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole as the ultraviolet absorber is dissolved in 5 g of DMAc and uniformly dispersed by ultrasonic stirring to obtain an ultraviolet absorber-containing solution;

[0218] (3) The ultraviolet absorber-containing solution obtained in step (2) is slowly dropped into the polyamic acid solution and the siloxane solution obtained in step (1) to obtain a polyamic acid solution containing an ultraviolet absorber and a siloxane solution containing an ultraviolet absorber;

[0219] (4) The silicone solution containing the ultraviolet absorber obtained in step (3) was dropped into the polyamic acid solution containing the ultraviolet absorber at an injection rate of 5 mL / min for mixing reaction, and then left standing for 48 hours to obtain a polyamic acid composition solution without bubbles and layering;

[0220] (5) The polyamic acid composition solution obtained in step (4) was directly sprayed on the surface of the solar cell array under the conditions of 0.3 Mpa and a spray valve operation speed of 100 mm / s. After standing and waiting for the solution to be evenly distributed to reach the semi-cured state, parameters such as a film baking temperature of 250 °C and a film baking time of 120 minutes were set to cure the coating film, and finally until it was completely cured;

[0221] (6) The spraying and curing operations in step (5) were repeated multiple times so that the thickness of the finally obtained protective enhanced film m1 reached 29.92 μm.

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

[0223] In addition, the obtained protective enhanced film m1 was a transparent flexible film, as shown in the photo in Figure 1 .

[0224] (Ultraviolet irradiation resistance test)

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

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

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

[0228] According to Figure 2 it can be seen that after ultraviolet irradiation, the transmittance of the protective enhanced film m1 did not decrease significantly, indicating that the protective enhanced film m1 can achieve the ultraviolet protection function.

[0229] (Atomic oxygen exposure test)

[0230] The protective enhanced film m1 and the comparative film (pure polyimide resin film) were respectively subjected to high-speed atomic oxygen irradiation. At a rate of 2.5×10 20 atoms cm -2After irradiation with a dose of, the mass loss of the protective enhanced film m1 is only 1.5 wt%, while the mass loss of the comparative film (pure polyimide resin film) is 10.9 wt%. This result indicates that the atomic resistance of the protective enhanced film m1 has been significantly improved.

[0231] (Antireflection performance and reflection enhancement performance)

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

[0233] [Reference Example]

[0234] In the reference example, except for not adding 2-[2-hydroxy-3,5-bis(1,1-dimethylpropylphenyl)]-2H-benzotriazole as an ultraviolet absorber, the same procedures as in Example 1 were carried out. Specifically, a silicon-containing polyimide film as a reference example was manufactured through the following steps.

[0235] (1) 100 g 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 (the molar percentage of the dianhydride unit to the diamine unit is 1:1) was dissolved in 566.6 g of DMAc to obtain a polyamic acid solution; in addition, 25 g of trisilanol phenylsiloxane as a siloxane compound was added to 100 g of DMAc and stirred evenly to obtain a siloxane solution;

[0236] (2) The siloxane solution obtained in step (1) was added dropwise to the polyamic acid solution at an injection rate of 5 ml / min for mixing reaction, and then left standing for 48 hours to obtain a polyamic acid composition solution;

[0237] (3) Under the conditions of 0.3 Mpa and a spray valve operating speed of 100 mm / s, the polyamic acid composition solution obtained in step (2) was directly sprayed on the surface of the solar cell array. After standing and waiting for the solution to be evenly distributed to reach a semi-cured state, parameters such as a film baking temperature of 250 °C and a film baking time of 120 minutes were set to cure the coating film, and finally until it was completely cured;

[0238] (4) The spraying and curing operations in step (3) were repeated multiple times to make the thickness of the finally obtained protective enhanced film m1 reach 30.5 μm.

[0239] (Ultraviolet irradiation resistance test)

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

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

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

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

[0244] [Example 2]

[0245] A protective enhanced film m2 having a structure including a first polyimide layer containing a polyimide resin, a siloxane compound, and an ultraviolet absorber, and an atomic oxygen protection layer of the present invention was manufactured through the following steps.

[0246] (1) 100 g of a mixture of cyclobutane tetracarboxylic dianhydride as the dianhydride unit and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane as the diamine unit (the molar percentage of the dianhydride unit to the diamine unit is 1:1) was dissolved in 566.6 g of DMAc to obtain a polyamic acid solution. Additionally, 25 g of hexamethyldisiloxane as the siloxane compound was added to 100 g of DMAc and stirred evenly to obtain a siloxane solution;

[0247] (2) 2 g of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole as the ultraviolet absorber was dissolved in 5 g of DMAc and uniformly dispersed by ultrasonic stirring to obtain an ultraviolet absorber-containing solution;

[0248] (3) The ultraviolet absorber-containing solution obtained in step (2) was slowly dropped into the polyamic acid solution and the siloxane solution obtained in step (1) to obtain an ultraviolet absorber-containing polyamic acid solution and an ultraviolet absorber-containing siloxane solution;

[0249] (4) The silicone solution containing the ultraviolet absorber obtained in step (3) was dropped into the polyamic acid solution containing the ultraviolet absorber at an injection rate of 5 mL / min for mixing reaction, and then left standing for 48 hours to obtain a polyamic acid composition solution without bubbles and layering.

[0250] (5) The polyamic acid composition solution obtained in step (4) was directly sprayed onto the surface of the solar cell array under the conditions of 0.3 Mpa and a spray valve running speed of 100 mm / s. After standing and waiting for the solution to be evenly distributed and reach the semi-cured state, parameters such as a baking film temperature of 250 °C and a baking film time of 120 minutes were set to cure the coating film, and finally until it was completely cured.

[0251] (6) Steps (5) were repeated for multiple spraying and curing operations so that the thickness of the obtained first polyimide layer reached 30.50 μm.

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

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

[0254] (Atomic oxygen exposure test)

[0255] The protective enhanced film m2 and the comparative film (pure polyimide resin film) were respectively subjected to high-speed atomic oxygen irradiation. After irradiation at a dose of 2.5×10 20 atoms cm -2 , the mass loss of the protective enhanced film m2 was 0.8 wt%, while the mass loss of the comparative film (pure polyimide resin film) was 10.9 wt%. This result shows that the atomic oxygen resistance of the protective enhanced film m2 has been significantly improved, and it has more excellent atomic oxygen resistance compared to the protective enhanced film m1 (mass loss 1.5 wt%).

[0256] In addition, the transmittance of the protective enhanced 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 Figure 4 .

[0257] According to Figure 4 it can be seen that after atomic oxygen irradiation, the transmittance of the protective enhanced film m2 has not decreased significantly, which indicates that the protective enhanced film m2 can achieve the atomic oxygen irradiation function.

[0258] (Anti-reflection performance and anti-reflection performance)

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

[0260] [Embodiment 3]

[0261] The protection-enhanced film m3 of the present invention having a structure including a second polyimide layer containing a polyimide resin and a siloxane compound and an ultraviolet protection layer is manufactured through the following steps.

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

[0263] (2) The siloxane solution obtained in step (1) is dropped into the polyamic acid solution at an injection rate of 5 ml / min for mixing reaction, and then left standing for 48 hours to obtain a polyamic acid composition solution without bubbles and without stratification.

[0264] (3) The polyamic acid composition solution obtained in step (2) is directly sprayed on the surface of the solar cell array under the conditions of 0.3 Mpa and a spray valve operation speed of 100 mm / s. After leaving it standing until the solution is evenly distributed and reaches a semi-cured state, parameters such as a film baking temperature of 250°C and a film baking time of 120 minutes are set to cure the coating film, and finally until it is completely cured.

[0265] (4) The spraying and curing operations in step (3) are repeated multiple times so that the thickness of the obtained second polyimide layer reaches 100 μm.

[0266] (5) Cerium oxide is sputtered on the surface of the obtained second polyimide layer at a speed of 1 angstrom per second at room temperature by magnetron sputtering using a cerium oxide target to obtain an ultraviolet protection layer containing cerium oxide with a thickness of 68.18 nm.

[0267] The refractive index of the cerium oxide sputtering layer in the obtained protection-enhanced film m3 is compared with the standard database, and the result is 2.20.

[0268] (Ultraviolet irradiation resistance test)

[0269] Perform an ultraviolet irradiation resistance test on the obtained protective enhanced film m3.

[0270] First, before performing ultraviolet irradiation, measure the transmittance of the protective enhanced film m3 and use it as the transmittance before ultraviolet irradiation; then, irradiate the protective enhanced film m3 with ultraviolet light having a wavelength of 115 - 400 nm at a power density of 27 mW / cm² -2 for 30 hours, and then measure the transmittance after ultraviolet irradiation.

[0271] Show the transmittance before ultraviolet irradiation (solid line) and the transmittance after ultraviolet irradiation (dashed line) of the protective enhanced film m3 in Figure 5 it.

[0272] According to Figure 5 it can be seen that after ultraviolet irradiation, the transmittance of the protective enhanced film m3 does not decrease significantly, indicating that the protective enhanced film m3 can achieve the ultraviolet protection function.

[0273] (Atomic oxygen exposure test)

[0274] Perform an atomic oxygen exposure test on the protective enhanced film m3.

[0275] Perform high-speed atomic oxygen irradiation on the protective enhanced film m3 and the comparison film (pure polyimide resin film) respectively. After irradiation with a dose of 2.5×10²¹ atoms / cm², the mass loss of the protective enhanced film m3 is 0.12 wt%, while the mass loss of the comparison film (pure polyimide resin film) is 10.9 wt%. This result shows that the atomic oxygen resistance of the protective enhanced film m3 has been significantly improved, and it is more excellent in atomic oxygen resistance than the protective enhanced film m1 (mass loss 1.5 wt%). 20 atoms cm² -2

[0276] (Antireflection performance and reflection enhancement performance)

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

[0278] As used herein, the terms "comprise", "comprising", "include", "including", "having" or any other variation thereof are intended to cover non-exclusive inclusion. For example, a method, article, or apparatus that comprises a series of features is not necessarily limited to those features, but may include other features not expressly listed or inherent to the above method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or rather than an exclusive or. For example, condition A or B is satisfied by any of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0279] In addition, the article "a" or "an" denotes a class or a broad category that includes multiple classes. In this document, any defined meaning does not necessarily exclude the ordinary and customary meaning in some embodiments.

[0280] Finally, it should be understood that the descriptions of the above embodiments and examples are illustrative in all aspects and do not constitute a limitation on the present invention. Those of ordinary skill in the art can make various improvements without creative work within the scope of the spirit of the present invention. The scope of the present invention is represented by the claims, rather than by the above embodiments or examples. In addition, the scope of the present invention includes all changes within the meaning and scope equivalent to the claims.

[0281] Industrial availability

[0282] The protective enhanced film of the present disclosure can enhance the light transmission performance of the desired light transmittance band or the light reflection performance of the desired light reflection band while achieving ultraviolet protection and atomic oxygen protection, and thus is suitable for use as a film for spacecraft optoelectronic devices, particularly suitable for use as a film for surface protection of solar cells, space solar cell arrays, etc. of spacecraft.

Claims

1. A protective enhanced film, which comprises a polyimide resin, a siloxane compound, and an anti-ultraviolet compound selected from an ultraviolet absorber or an ultraviolet blocker. Among them, The protective enhanced 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 medium of this layer and its odd multiples, or 1 / 2 of the wavelength of the incident light in the medium of this layer and its integer multiples for the desired light transmittance enhancement band, or for the desired light reflectance enhancement band.

2. The enhanced protection film according to claim 1, characterized in that, The protective enhanced film has: A first polyimide layer containing the polyimide resin, the siloxane compound, and the ultraviolet absorber.

3. The enhanced protection film according to claim 1, characterized in that, The protective enhanced film has: A first polyimide layer containing the polyimide resin, the siloxane compound, and the ultraviolet absorber, and a second polyimide layer containing the polyimide resin and the siloxane compound.

4. The protective enhanced film according to claim 1, wherein, The protective enhanced film has: A first polyimide layer containing the polyimide resin, the siloxane compound, and the ultraviolet absorber, and an atomic oxygen protection layer containing an atomic oxygen protector.

5. The enhanced protection film according to claim 1, wherein The protective enhanced film has: A second polyimide layer containing the polyimide resin and the siloxane compound, and an ultraviolet protection layer containing the ultraviolet blocker.

6. The protective enhanced film according to any one of claims 1 to 5, wherein the siloxane compound is at least one selected from hexamethyldisiloxane, siloxanes containing at least one group among vinyl, propenyl, amino, phenyl, hydroxyl, and carboxyl groups, and aminopropylheptyl-cage poly(silsesquioxane), trisilylphenylcage poly(siloxane), N-[(heptaisobutylcage poly(silsesquioxane))propyl]-3,5-diaminobenzamide, trisilanol isobutylcage poly(silsesquioxane), trans-cyclohexanediol heptyl-cage poly(silsesquioxane), 1,2-propanediol isobutylcage poly(silsesquioxane), aminopropylheptyl-cage poly(silsesquioxane), N-phenylaminocage poly(silsesquioxane), acryloyl isobutylcage poly(silsesquioxane), allyl cage poly(siloxane), isooctyl ester cage poly(silsesquioxane), octaisobutyl cage poly(silsesquioxane), tetramethylammonium cage poly(silsesquioxane), tetrasilane cage poly(silsesquioxane), trisilanol isooctyl cage poly(silsesquioxane), and trisilanol phenyl cage poly(silsesquioxane); the ultraviolet absorber is at least one selected from 2-(2-hydroxy-5-methylphenyl)benzotriazole, hexamethylphosphoric triamide, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, and nano-cerium oxide; the ultraviolet blocker is at least one selected from titanium dioxide, aluminum oxide, cerium oxide, zinc oxide, and indium tin oxide; 7. The protective enhanced film according to claim 4, wherein, the atomic oxygen protector is at least one selected from titanium dioxide, silicon dioxide, aluminum oxide, cerium oxide, and indium tin oxide; 8. The protective enhanced film according to claim 1, wherein, When the protective enhanced film is a protective light-transmitting film, when the thickness of the outermost layer of the protective enhanced film is set as d, the thickness d of this outermost layer satisfies the following formula (1): where λ is the desired Light transmittance enhancement optical wavelength or the optimized wavelength for the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number.

9. The protective enhanced film according to claim 1, wherein When the protective enhanced film is a protective light-reflecting film, when the thickness of the outermost layer of the protective enhanced film is set as d, the thickness d of this outermost layer satisfies the following formula (2): where λ1 is the desired Light reflectance enhancement optical wavelength or the optimized wavelength for the peak performance of the device, n is the refractive index of the outermost layer, and k is a natural number greater than 1.

10. The protective enhanced film according to any one of claims 1 to 5, characterized in that, The protective and enhancing film is used for the protection and enhancement of the surface of spacecraft optoelectronic devices.

11. A method for manufacturing a protective and enhancing film, comprising: After attaching a composition containing a dianhydride monomer, a diamine monomer, the siloxane compound, and the ultraviolet absorber to the surface of a spacecraft optoelectronic device, curing is performed to form a first polyimide layer, and Optionally, a composition containing a dianhydride monomer, a diamine monomer, and the siloxane compound is attached to the first polyimide layer, and then curing is performed to form a second polyimide layer; or an atomic oxygen protection layer containing an atomic oxygen protector is formed on the first polyimide layer by a dry process.

12. A method for manufacturing a protective and enhancing film, comprising: After attaching a composition containing a dianhydride monomer, a diamine monomer, and the siloxane compound to the surface of a spacecraft optoelectronic device, curing is performed to form a second polyimide layer, and A composition containing a dianhydride monomer, a diamine monomer, the siloxane compound, and the ultraviolet absorber is attached to the second polyimide layer, and then curing is performed to form a first polyimide layer; or an ultraviolet protection layer containing an ultraviolet cutoff agent is formed on the second polyimide layer by a dry process.

13. The method for manufacturing a protective and enhancing film according to claim 11 or 12, wherein The dianhydride monomer is at least one selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, and pyromellitic dianhydride; The diamine monomer is at least one selected from 2,2'-bis(trifluoromethyl)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-trifluoromethyl-4-aminophenoxy)benzene, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

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