Upconversion complex masterbatch and preparation method thereof, resin composition containing same, encapsulation film, solar cell module and application thereof

Abstract

An upconversion complex masterbatch and a preparation method thereof, a resin composition containing the same, an encapsulation film, a solar cell module and an application thereof, belonging to the technical field of optoelectronic materials. The upconversion complex is obtained by surface modification of upconversion inorganic particles, then reacting with a multifunctional coupling agent, and then grafting with an ultraviolet cutoff agent. The upconversion complex is dispersed in a resin to obtain an upconversion complex masterbatch. The upconversion complex masterbatch can convert infrared light in sunlight into visible light that can be used by photovoltaic modules, thereby improving the utilization of infrared light by the modules; in addition, the ultraviolet cutoff agent is grafted with the upconversion inorganic particles, which reduces the migration of the ultraviolet cutoff agent in the film, and can protect ultraviolet-sensitive photovoltaic modules for a long time.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic materials, and in particular to an upconversion complex masterbatch and a preparation method thereof, as well as a resin composition containing the same, a packaging film, a solar cell module, and the application of the upconversion complex masterbatch in the field of photovoltaic cells. Background Art

[0002] Solar energy is one of the main renewable energy sources, with the characteristics of wide sources, clean and harmless, and sustainable. The energy of solar radiation is mainly concentrated between wavelengths of 0.15 and 4 microns. Within this wavelength range, it can be divided into three main regions, namely the ultraviolet region with a shorter wavelength, the infrared region with a longer wavelength, and the visible light region between the two. The energy of solar radiation is mainly distributed in the visible light region and the infrared region, the former accounting for 50% of the total solar radiation, the latter accounting for 43%, and the ultraviolet region accounting for only 7% of the energy. On the other hand, infrared radiation causes a significant increase in the operating temperature of the battery cell, thereby reducing the power generation. Generally speaking, for every 1°C increase in operating temperature, the output power decreases by 0.3% to 0.5%. A feasible solution is to add light conversion materials to the encapsulation film to convert the infrared light with the highest energy in sunlight into usable visible light; or to add light cutoff materials to the photovoltaic film to filter part of the ultraviolet light, thereby protecting the battery components while improving the stability of the photovoltaic module's photoelectric conversion efficiency.

[0003] The light conversion materials reported so far (CN114854316A, CN116478633A) mainly include pure organic fluorescent pigments, inorganic metal oxide phosphors, organic-inorganic composite photoluminescent materials, and fluorescent quantum dots, most of which convert ultraviolet light into visible light (CN114958215A, CN117431022A, CN117247362B, CN116769466A). Although there are some upconversion luminescent photovoltaic films (CN106566435A), the upconversion luminescent particles are directly added to the photovoltaic encapsulation film without modification (CN115566081B). In addition, some photovoltaic modules, such as heterojunction battery modules, are sensitive to ultraviolet light and usually add unmodified ultraviolet cutoff materials (CN117757383A, CN114854331A). During long-term outdoor use, the cutoff films obtained by these physical mixtures are prone to ultraviolet cutoff agents precipitating from the films or migrating and diffusing between different layers of films, which to a certain extent affects the efficiency and stability of photovoltaic modules and reduces the utilization rate of light. Summary of the invention

[0004] In view of the above factors, in order to improve the poor stability of upconversion light-converting materials and ultraviolet absorption materials in existing photovoltaic modules, the technical solution of the present invention is to provide an upconversion complex masterbatch and a resin composition containing the same and a preparation method thereof. Specifically, the upconversion complex is obtained by surface modification of upconversion inorganic particles, then reacting with a multifunctional coupling agent, and then grafting with an ultraviolet cut-off agent. The upconversion complex has good compatibility with olefin-based resins (such as vinyl resins) and can be dispersed in olefin-based resins to obtain upconversion complex masterbatch. The upconversion complex masterbatch in the present invention can convert infrared light in sunlight into visible light that can be used by photovoltaic modules, thereby improving the utilization rate of infrared light by the modules; in addition, the ultraviolet cut-off agent is grafted with solid particles, which reduces the migration of the ultraviolet cut-off agent in the film and protects ultraviolet-sensitive photovoltaic modules for a long time.

[0005] The present invention first provides an upconversion complex masterbatch, wherein the upconversion complex masterbatch is prepared by surface modification of upconversion inorganic particles, reaction with a multifunctional coupling agent, and then grafting with an ultraviolet cutoff agent to obtain an upconversion complex of the ultraviolet cutoff agent grafted upconversion inorganic particles, which is dispersed in a resin to obtain the upconversion complex masterbatch.

[0006] Furthermore, the resin is an olefin-based resin, including vinyl resin and propylene-based resin. In order to avoid agglomeration between these complexes due to electrostatic effects and to avoid uneven dispersion of complex particles in the vinyl resin during extrusion processing, the complex of the ultraviolet cutoff agent grafted upconversion particles is pre-dispersed in the vinyl resin to form a masterbatch of a certain concentration.

[0007] Furthermore, the up-conversion inorganic particles are doped fluorine-containing compound particles.

[0008] Furthermore, the up-conversion inorganic particles are calcium fluoride, or magnesium fluoride, or barium fluoride, or sodium yttrium tetrafluoride, or sodium gadolinium tetrafluoride, or yttrium fluoride doped with one or more of manganese ions, yttrium ions, ytterbium ions, erbium ions, holmium ions, cerium ions, thulium ions, praseodymium ions, iridium ions, and gallium ions.

[0009] Furthermore, calcium fluoride and / or magnesium fluoride and / or barium fluoride doped with ytterbium ions and / or erbium ions and / or holmium ions are preferred.

[0010] Further, the multifunctional coupling agent is selected from one or more of methyl silicate, ethyl orthosilicate, propyl orthosilicate, isopropyl silicate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, diethylenetriaminopropyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, n-butylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl-3-aminopropyl)methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

[0011] Furthermore, one or more of ethyl orthosilicate, isopropyl silicate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-diethylaminopropyltrimethoxysilane are preferred.

[0012] Furthermore, the UV cut-off agent is selected from one or more of substituted triazine UV cut-off agents, benzophenone UV cut-off agents, salicylate UV cut-off agents, benzotriazole UV cut-off agents, and substituted acrylonitrile UV cut-off agents, and the UV cut-off agent contains one or more of vinyl, acrylic, methacrylic, acryloxy, methacryloyloxy, carboxyl, epoxy, acyl chloride, and isocyanate functional groups.

[0013] Furthermore, the UV cut-off agent is preferably 3-benzoyl-4-hydroxybenzoic acid (CAS 106782-33-6), 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionyl chloride (CAS 84268-35-9), 4-(4,6-bis(2-hydroxyphenyl)-1,3,5-triazine-2-yl)benzoic acid (CAS 1262725-25-6), 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid (CAS 84268-36-0), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (CAS 96478-09-0), 2-(4-benzoyl-3-hydroxyphenoxy)ethyl 2-acrylate (CAS 16432-81-8), 2-(2'-hydroxy-3'-allyl-5'-methylphenyl)-2H-benzotriazole (CAS 2170-39-0).

[0014] Among them, CAS (Chemical Abstracts Service) represents the chemical substance registration number, also known as the substance digital identification number.

[0015] Furthermore, the reaction temperature required for the preparation of the upconversion complex is in the range of 40 to 150° C., and the reaction time is 0.5 to 10 hours.

[0016] The solvent required for the above reaction is preferably chloroform, dichloromethane, acetonitrile, ethanol, methanol, n-butanol, benzene, toluene, xylene, chlorobenzene, acetone, butanone, dimethyl sulfoxide, N, N-dimethylformamide, water, dioxane, tetrahydrofuran, ethyl acetate, ether, isopropyl ether, carbon tetrachloride, ethyl bromide, cyclohexane, any one or a mixture of at least two of hexane, and further, preferably dichloromethane, acetonitrile, butanone, ethyl acetate, isopropyl ether or more. The solvent required for the reaction can better disperse the up-conversion inorganic particles, dissolve the coupling agent, ultraviolet cut-off agent, and catalyst added during the preparation process, and can also be easily separated from the reaction product on the other hand.

[0017] Further, the number average molecular weight of the olefin-based resin is 50,000 to 400,000 g / mol, preferably 80,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, or 350,000 g / mol; the vinyl resin is preferably polyethylene, or a copolymer of ethylene and 1-butene, or a copolymer of ethylene and 1-octene, or a copolymer of ethylene and one or more of propylene, vinyl acetate, acrylic acid, maleic anhydride, and glycidyl methacrylate.

[0018] Furthermore, the vinyl resin is preferably one or more of ethylene and vinyl acetate copolymer, ethylene and 1-butene copolymer, and ethylene and 1-octene copolymer.

[0019] Furthermore, the mass fraction of the upconversion complex in the upconversion complex masterbatch is 0.5% to 15%, for example, it can be 1.0%, 2.0%, 5.0%, 8.0%, 10.0%, 12.0%, 13.0%, and the mass fraction of the olefin-based resin is 85% to 99.5%, for example, it can be 88%, 90%, 92%, 95%, 98%.

[0020] The present invention also provides a method for preparing the above-mentioned upconversion complex masterbatch, comprising surface-modifying the upconversion inorganic particles, reacting with a multifunctional coupling agent, and then grafting with an ultraviolet cutoff agent to obtain an upconversion complex of the ultraviolet cutoff agent-grafted upconversion particles, dispersing the upconversion complex in a resin, and obtaining an upconversion complex masterbatch.

[0021] The present invention also provides a resin composition, which comprises 82% to 99.8% (for example, 85%, 88%, 90%, 92%, 95%) of vinyl resin, 0.02% to 9.7% (for example, 0.5%, 0.8%, 1.0%, 5.0%, 8.0%) of upconversion complex masterbatch and 0.02% to 11% (for example, 0.5%, 0.8%, 1.0%, 5.0%, 8.0%, 10%) of auxiliary agent, wherein the upconversion complex masterbatch is the aforementioned upconversion complex masterbatch.

[0022] Furthermore, the auxiliary agent is a mixture of one or more of an initiator, a cross-linking agent, a coupling agent, an antioxidant, and a stabilizer.

[0023] Further, the weight percentage of the initiator is 0.005% to 5% (for example, it can be 0.005%, 0.08%, 0.1%, 0.5%, 2%, 3%, 5%), and / or the weight percentage of the cross-linking agent is 0.005% to 5% (for example, it can be 0.005%, 0.08%, 0.1%, 0.5%, 3%, 4%, 5%), and / or the weight percentage of the coupling agent is 0.005% to 5% (for example, it can be 0.005%, 0.08%, 0.1%, 0.5%, 1%, 2%, 5%), and / or the weight percentage of the antioxidant is 0.005% to 5% (for example, it can be 0.005%, 0.08%, 0.1%, 0.5%, 1%, 4%, 5%), and / or the weight percentage of the stabilizer is 0.005% to 5% (for example, it can be 0.005%, 0.08%, 0.1%, 0.5%, 1%, 3%, 5%).

[0024] According to another aspect of the present invention, there is also provided an encapsulation film, which is a film-like material formed by mixing the aforementioned resin composition, melt blending, extruding by an extruder, and cast embossing. The encapsulation film composition is a single-layer structure or a multi-layer structure, and the material of at least one layer in the encapsulation film includes an upconversion complex masterbatch.

[0025] According to another aspect of the present invention, a solar cell assembly is provided, comprising a first glass plate or an organic back plate, a rear encapsulation film, a cell array, a front encapsulation film, and a second glass plate arranged in sequence; wherein at least one of the front encapsulation film and the rear encapsulation film is made of the aforementioned encapsulation film; wherein the cell array can be any one of PERC (Passivated Emitter Rear Cell), TOPCon (Tunnel Oxide Passivated Contact), HJT (Heterojunction with Intrinsic Thin-film), and BC (Back Contact) cells.

[0026] The present invention also provides an application of an up-conversion complex masterbatch in a solar cell module, including improving the utilization of infrared light by the solar cell module, reducing the migration of the ultraviolet cut-off agent in the packaging film, and protecting the ultraviolet-sensitive solar cell module.

[0027] In summary, the upconversion complex provided by the present invention is obtained by surface modification of upconversion inorganic particles, then reacting with a multifunctional coupling agent, and then grafting with a UV cutoff agent. The upconversion complex has good compatibility with olefin-based resins, such as vinyl resins, and can be dispersed in vinyl resins to obtain upconversion complex masterbatches. The upconversion complex masterbatch in the present invention can convert infrared light in sunlight into visible light that can be used by photovoltaic modules, thereby improving the utilization rate of infrared light by the modules and also reducing the temperature of the modules; in addition, the UV cutoff agent is grafted with the upconversion inorganic particles, which reduces the migration of the UV cutoff agent in the film and protects UV-sensitive photovoltaic modules for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 Schematic diagram of the structure of a double-glass solar cell assembly according to an embodiment of the present invention.

[0030] Figure 2 Schematic diagram of the structure of a single-glass solar cell assembly according to an embodiment of the present invention.

[0031] Figure 3This is the infrared spectrum of the silane-coated BaF2:Yb,Er solid prepared in Example 1.

[0032] Figure 4 This is the infrared spectrum of the aminosilane-modified BaF2:Yb,Er solid prepared in Example 1.

[0033] Figure 5 This is the infrared spectrum of the benzophenone-based UV cutoff agent grafted silane-coated BaF2:Yb,Er solid prepared in Example 1.

[0034] Explanation of reference numerals: 25, organic backplane; 24, first glass plate; 23, rear encapsulation film; 22, battery cell array; 21, front encapsulation film; 20, second glass plate. DETAILED DESCRIPTION

[0035] In order to better illustrate the purpose, technical scheme and advantages of the present invention, the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. The test methods used in the embodiments of the present invention are conventional methods unless otherwise specified; the materials, reagents, etc. used in the embodiments of the present invention can be obtained from commercial channels unless otherwise specified.

[0036] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0037] As described in the background technology section, the energy of solar radiation is mainly distributed in the visible light region and the infrared region, with the former accounting for 50% of the total solar radiation and the latter accounting for 43%. On the other hand, infrared radiation causes a significant increase in the operating temperature of the battery cell, thereby reducing the power generation. Generally speaking, for every 1°C increase in operating temperature, the output power decreases by 0.3% to 0.5%. A feasible solution is to add light conversion materials to the encapsulation film to convert the infrared light with the highest energy in sunlight into usable visible light. Although there are some upconversion luminescent photovoltaic films, the upconversion luminescent particles are not modified and directly added to the photovoltaic encapsulation film.

[0038] In addition, some photovoltaic modules (solar cell modules), such as heterojunction cell modules, are sensitive to ultraviolet light. One feasible way is to add light-cutoff materials to the photovoltaic film, thereby protecting the photovoltaic module while improving the stability of the photovoltaic module's photoelectric conversion efficiency. However, if unmodified ultraviolet cutoff materials are added, these physically mixed ultraviolet cutoff films are prone to ultraviolet cutoff agents precipitating from the film or migrating and diffusing between different layers of the film during long-term outdoor use, which to a certain extent affects the efficiency stability of the photovoltaic module.

[0039] In order to improve the above-mentioned deficiencies, the present invention provides an upconversion complex, which is obtained by surface modification of upconversion inorganic particles, then reacting with a multifunctional coupling agent, and then grafting with a UV cutoff agent. The upconversion complex has good compatibility with olefin-based resins and can be dispersed in olefin-based resins to obtain upconversion complex masterbatches. The upconversion complex masterbatch in the present invention can convert infrared light in sunlight into visible light that can be used by photovoltaic modules, improve the utilization of infrared light by the modules, and also reduce the temperature of the modules. In addition, the UV cutoff agent is grafted with the upconversion inorganic particles, which reduces the migration of the UV cutoff agent in the film and protects UV-sensitive photovoltaic modules for a long time.

[0040] According to one aspect of the present invention, an upconversion complex masterbatch is provided. In the present invention, the upconversion complex masterbatch is prepared by surface modification of upconversion inorganic particles, then reacting with a multifunctional coupling agent, then grafting with an ultraviolet cutoff agent to obtain an upconversion complex, and finally dispersing it into a resin. The resin is an olefin-based resin, and the olefin-based resin can be, for example, a vinyl resin.

[0041] Furthermore, the up-conversion inorganic particles are calcium fluoride, or magnesium fluoride, or barium fluoride, or sodium yttrium tetrafluoride, or sodium gadolinium tetrafluoride, or yttrium fluoride doped with one or more of manganese ions, yttrium ions, ytterbium ions, erbium ions, holmium ions, cerium ions, thulium ions, praseodymium ions, iridium ions, and gallium ions.

[0042] Furthermore, calcium fluoride and / or magnesium fluoride and / or barium fluoride doped with ytterbium ions and / or erbium ions and / or holmium ions are preferred.

[0043] Further, the multifunctional coupling agent is selected from one or more of methyl silicate, ethyl orthosilicate, propyl orthosilicate, isopropyl silicate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, diethylenetriaminopropyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, n-butylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl-3-aminopropyl)methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

[0044] Furthermore, one or more of ethyl orthosilicate, isopropyl silicate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-diethylaminopropyltrimethoxysilane are preferred.

[0045] Furthermore, the UV cut-off agent is selected from one or more of substituted triazine UV cut-off agents, benzophenone UV cut-off agents, salicylate UV cut-off agents, benzotriazole UV cut-off agents, and substituted acrylonitrile UV cut-off agents, and the UV cut-off agent contains one or more of vinyl, acrylic, methacrylic, acryloxy, methacryloyloxy, carboxyl, epoxy, acyl chloride, and isocyanate functional groups.

[0046] Further, 3-benzoyl-4-hydroxybenzoic acid (CAS 106782-33-6), 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionyl chloride (CAS 84268-35-9), 4-(4,6-bis(2-hydroxyphenyl)-1,3,5-triazin-2-yl)benzoic acid (CAS 1262725-25-6), 3-(2-benzotriazolyl)-4-hydroxy-5-tert-butylbenzenepropionic acid (CAS 84268-36-0), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (CAS 96478-09-0), 2-(4-benzoyl-3-hydroxyphenoxy)ethyl 2-acrylate (CAS 16432-81-8), 2-(2'-hydroxy-3'-allyl-5'-methylphenyl)-2H-benzotriazole (CAS 2170-39-0).

[0047] Furthermore, the reaction temperature required in the preparation process of the up-conversion complex is in the range of 40 to 150° C., the reaction time is 0.5 to 10 hours, and the solvent required for the reaction is chloroform, dichloromethane, acetonitrile, ethanol, methanol, n-butanol, benzene, toluene, xylene, chlorobenzene, acetone, butanone, dimethyl sulfoxide, N,N-dimethylformamide, water, dioxane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, ether, isopropyl ether, carbon tetrachloride, ethyl bromide, cyclohexane, hexane, any one or a mixture of at least two thereof, and further, preferably one or more of dichloromethane, acetonitrile, butanone, ethyl acetate, and isopropyl ether.

[0048] Furthermore, the number average molecular weight of the vinyl resin is 50,000 to 400,000 g / mol, preferably polyethylene, or a copolymer of ethylene and 1-butene, or a copolymer of ethylene and 1-octene, or a copolymer of ethylene and one or more of propylene, vinyl acetate, acrylic acid, maleic anhydride, and glycidyl methacrylate.

[0049] Furthermore, the vinyl resin is preferably one or more of ethylene and vinyl acetate copolymer, ethylene and 1-butene copolymer, and ethylene and 1-octene copolymer, that is, EVA (ethylene and vinyl acetate copolymer, Ethylene Vinyl Acetate Copolymer) and / or POE (Poly Olefin Elastomer) commonly used in the industry.

[0050] Furthermore, in the upconversion complex masterbatch, the mass fraction of the upconversion complex is between 0.5% and 15%, and the mass fraction of the vinyl resin is between 85% and 99.5%.

[0051] The present invention also provides a resin composition, which comprises 82% to 99.8% of vinyl resin, 0.02% to 9.7% of upconversion complex masterbatch and 0.02% to 11% of auxiliary agent, wherein the upconversion complex masterbatch is the above-mentioned upconversion complex masterbatch.

[0052] Furthermore, the auxiliary agent is a mixture of one or more of an initiator, a cross-linking agent, a coupling agent, an antioxidant, and a stabilizer.

[0053] Furthermore, the weight percentage of the initiator is 0.005% to 5%, and / or the weight percentage of the cross-linking agent is 0.005% to 5%, and / or the weight percentage of the coupling agent is 0.005% to 5%, and / or the weight percentage of the antioxidant is 0.005% to 5%, and / or the weight percentage of the stabilizer is 0.005% to 5%.

[0054] Furthermore, the initiator is selected from any one of peroxide initiators, azo initiators, and redox initiators, or a combination of at least two of them.

[0055] Furthermore, the initiator is preferably selected from any one or a combination of at least two of di-tert-butyl peroxide diisopropylbenzene, 2,5-di-tert-butyl peroxide-2,5-methylhexane, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, tert-butyl peroxide 2-ethylhexyl carbonate, tert-amyl peroxide 2-ethylhexyl carbonate or dibenzoyl peroxide.

[0056] Furthermore, the crosslinking agent is a molecule having multiple unsaturated olefin groups, which can promote polymer crosslinking to achieve a higher degree of crosslinking.

[0057] Furthermore, the crosslinking agent is preferably selected from any one or a combination of at least two of triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanate, trimethylolpropane methacrylate, ethoxylated pentaerythritol tetraacrylate or ethoxylated trimethylolpropane triacrylate.

[0058] Furthermore, the coupling agent is selected from any one of vinyl silane coupling agents, chloroalkyl silane coupling agents, aminoalkyl silane coupling agents, methacryloyloxyalkyl silane coupling agents, sulfur-containing hydrocarbon silane coupling agents or quaternary aminoalkyl silane coupling agents, or a combination of at least two thereof.

[0059] Furthermore, the coupling agent is preferably selected from one or more of vinyl triisopropoxy silane, methacryloxypropyl trimethoxy silane, 3-aminopropyl trimethoxy silane, N-(2-aminoethyl-3-aminopropyl) trimethoxy silane, diethylene triamino propyl trimethoxy silane, 3-diethylamino propyl trimethoxy silane, n-butylamino propyl trimethoxy silane, 3-aminopropyl methyl diethoxy silane, N-(2-aminoethyl-3-aminopropyl) methyl dimethoxy silane, 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl triethoxy silane, and 3-mercaptopropyl methyl dimethoxy silane.

[0060] Furthermore, the light stabilizer is selected from piperidine light stabilizers.

[0061] Furthermore, the piperidine photostabilizer is selected from any one of tetramethyl piperidinol, pentamethyl piperidinol, bis(2,2,6,6-tetramethyl-4-piperidinol) sebacate, 2,2,6,6-tetramethyl-4-piperidinyl stearate or bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate or a combination of at least two thereof.

[0062] According to another aspect of the present invention, there is also provided a solar cell assembly, such as Figure 1 and Figure 2 As shown, the solar cell assembly includes a first glass plate 24 or an organic back plate 25, a rear encapsulation film 23, a cell array 22, a front encapsulation film 21 and a second glass plate 20 arranged in sequence; wherein at least one of the front encapsulation film 21 and the rear encapsulation film 23 uses the aforementioned encapsulation film. The cell array 23 may be any one of PERC, TOPCon, HJT, and BC cells.

[0063] The present invention is further described in detail below in conjunction with specific examples. The raw materials used in the following examples are all commercially available products, and these examples cannot be construed as limiting the scope of protection claimed by the present invention.

[0064] Example 1

[0065]

[0066] Preparation of upconversion complex: add 10 g of BaF2:Yb,Er particles with an average particle size of 5 μm to the reactor, add 500 ml of ethanol, ultrasonically treat for 10 minutes, add 16 g of ethyl orthosilicate dropwise under stirring, then adjust the solution pH to 10 with ammonia water, stir and react at 30 degrees Celsius for 24 hours, then wash and filter with anhydrous ethanol until the solution is neutral, and finally disperse the product in 50 ml of anhydrous ethanol to obtain a silane-coated BaF2:Yb,Er ethanol suspension. Figure 3 The infrared spectrum of silane-coated BaF2:Yb,Er particles is shown.

[0067] 200 ml of anhydrous toluene was added to the silane-coated BaF2:Yb,Er ethanol suspension, and 15 g of 3-aminopropyltrimethoxysilane was added dropwise under stirring, and the mixture was reacted at 110 degrees Celsius for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol, and the residue was dispersed in 500 ml of anhydrous toluene and ultrasonicated for 5 minutes to obtain an aminosilane-modified BaF2:Yb,Er toluene suspension. Figure 4 The infrared spectrum of aminosilane-modified BaF2:Yb,Er particles is shown. The infrared spectrum at 3400 cm -1 The stretching vibration at 790 cm-1 comes from the amino group in the modified silane. -1 and 1080cm -1 The signal at comes from the strong absorption of siloxane (-Si-O-Si-). In addition, no absorption peak of 3-aminopropyltrimethoxysilane was found in the spectrum.

[0068] 21 g of 3-benzoyl-4-hydroxybenzoic acid was added to the aminosilane-modified BaF2:Yb,Er toluene suspension, and the mixture was reacted at 110°C for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol. The residue was dispersed in 500 ml of anhydrous ethanol and ultrasonicated for 5 minutes. The solution was then concentrated to 50 ml to obtain a UV cutoff-modified BaF2:Yb,Er ethanol suspension UPUV-1 (i.e., an upconversion complex). Figure 5 The infrared spectrum of BaF2:Yb,Er particles modified with benzophenone UV cutoff agent is shown, and no characteristic absorption peak of 3-benzoyl-4-hydroxybenzoic acid is found in the spectrum.

[0069] Preparation of masterbatch: The upconversion complex UPUV-1 and EVA resin were fully mixed in a mass ratio of 5:95, vacuum dried in an oven at 60°C for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare 5% concentration upconversion complex masterbatch 1.

[0070] Film preparation: Weigh 15 parts of up-conversion complex EVA masterbatch 1, 85 parts of Sailbon EVA resin, 0.51 parts of tert-butyl peroxycarbonate-2-ethylhexyl ester, 0.53 parts of triallyl isocyanurate, 0.25 parts of vinyl triisopropoxysilane, 0.32 parts of 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, and 0.43 parts of 4,4'-thiobis(3-methyl-6-tert-butylphenol), and place them in a mixing kettle for stirring and mixing. The mixed materials are extruded into a film using a single-screw extruder, and after embossing, pulling, and winding, a rolled packaging film is obtained with a film thickness of 0.38 mm; the above parts are all weight parts.

[0071] Production of solar cell modules: stacking in the order of the first glass plate 24 (photovoltaic glass), the rear encapsulation film 23, the welded cell array 22, the front encapsulation film 21, and the second glass plate 20 (photovoltaic glass), and then laminating with a vacuum laminator at a lamination temperature of 145°C for 18 minutes, and sealing the edges after cooling to obtain a solar cell module.

[0072] Example 2

[0073]

[0074] Preparation of upconversion complex: Add 4.5 g of CaF2:Yb,Ho particles with an average particle size of 5 μm to the reactor, add 500 ml of ethanol, ultrasonically treat for 10 minutes, add 15 g of ethyl orthosilicate dropwise under stirring, and then adjust the solution pH to 10 with ammonia water. Stir the reaction at 30 degrees Celsius for 24 hours, then wash and filter with anhydrous ethanol until the solution is neutral, and finally disperse the product in 50 ml of anhydrous ethanol to obtain a silane-coated CaF2:Yb,Ho ethanol suspension.

[0075] 200 ml of anhydrous toluene was added to the silane-coated CaF2:Yb,Ho ethanol suspension, and 16 g of 3-aminopropyltriethoxysilane was added dropwise under stirring, and the mixture was reacted at 110°C for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol, and the residue was dispersed in 500 ml of anhydrous toluene and ultrasonicated for 5 minutes to obtain an aminosilane-modified CaF2:Yb,Ho toluene suspension.

[0076] To the aminosilane-modified CaF2:Yb,Ho toluene suspension, 26 g of 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionyl chloride was added, and the mixture was reacted at 110°C for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol. The residue was dispersed in 500 ml of anhydrous ethanol and ultrasonicated for 5 minutes. The solution was then concentrated to 50 ml to obtain a UV cutoff agent-modified CaF2:Yb,Ho ethanol suspension UPUV-2 (i.e., upconversion complex).

[0077] Preparation of masterbatch: The upconversion complex UPUV-2 and POE resin were fully mixed in a mass ratio of 5:95, vacuum dried in an oven at 60°C for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare 5% concentration upconversion complex masterbatch 2.

[0078] Film preparation: Weigh 15 parts of up-conversion complex masterbatch 2, 50 parts of POE8660 resin, 35 parts of POE8669 resin, 0.51 parts of tert-butyl peroxycarbonate-2-ethylhexyl ester, 0.53 parts of triallyl isocyanurate, 0.25 parts of vinyl triisopropoxysilane, 0.32 parts of 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, and 0.43 parts of 4,4'-thiobis(3-methyl-6-tert-butylphenol), and place them in a mixing kettle for stirring and mixing. The mixed materials are extruded into a film using a single screw extruder, and after embossing, pulling, and winding, a rolled packaging film is obtained with a film thickness of 0.38 mm; the above parts are all weight parts.

[0079] The manufacturing process of the solar cell assembly is the same as that of Example 1.

[0080] Example 3

[0081]

[0082] Preparation of upconversion complex: 10 g of CaF2:Yb,Er particles with an average particle size of 5 μm were added to the reactor, 500 ml of ethanol was added, ultrasonic treatment was performed for 10 minutes, heating was performed under stirring for azeotropy for 6 hours, and then concentrated to 50 ml to obtain an activated CaF2:Yb,Er ethanol suspension.

[0083] 200 ml of anhydrous toluene was added to the CaF2:Yb,Er ethanol suspension, and 16 g of 3-aminopropyltrimethoxysilane was added dropwise under stirring, and the mixture was reacted at 110 degrees Celsius for 12 hours. The mixture was then washed and filtered three times with anhydrous ethanol, and the residue was dispersed in 500 ml of anhydrous toluene and ultrasonicated for 5 minutes to obtain an aminosilane-modified CaF2:Yb,Er toluene suspension.

[0084] To the aforementioned aminosilane-modified CaF2:Yb,Er toluene suspension, 33 g of 4-(4,6-bis(2-hydroxyphenyl)-1,3,5-triazine-2-yl)benzoic acid was added, and the mixture was reacted at 110°C for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol, and the residue was dispersed in 500 ml of anhydrous ethanol. The mixture was ultrasonicated for 5 minutes, and the solution was concentrated to 50 ml to obtain a UV cutoff agent-modified CaF2:Yb,Er ethanol suspension UPUV-3 (i.e., upconversion complex).

[0085] Preparation of masterbatch: The upconversion complex UPUV-3 and POE resin were fully mixed in a mass ratio of 5:95, vacuum dried in an oven at 60°C for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare 5% concentration upconversion complex masterbatch 3.

[0086] Film preparation: Weigh 15 parts of up-conversion complex masterbatch 3, 50 parts of POE8660 resin, 35 parts of POE8669 resin, 0.51 parts of tert-butyl peroxycarbonate-2-ethylhexyl ester, 0.53 parts of triallyl isocyanurate, 0.25 parts of vinyl triisopropoxysilane, 0.32 parts of 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, and 0.43 parts of 4,4'-thiobis(3-methyl-6-tert-butylphenol), and place them in a mixing kettle for stirring and mixing. The mixed materials are extruded into a film using a single screw extruder, and after embossing, pulling, and winding, a rolled packaging film is obtained with a film thickness of 0.38 mm; the above parts are all weight parts.

[0087] The manufacturing process of the solar cell assembly is the same as that of Example 1.

[0088] Example 4

[0089]

[0090] Preparation of upconversion complex: add 10 g of BaF2:Yb,Ho particles with an average particle size of 3 μm to the reactor, add 220 ml of ethanol, ultrasonically treat for 10 minutes, heat under stirring for azeotropy for 6 hours, and then concentrate to 50 ml to obtain an activated BaF2:Yb,Ho ethanol suspension.

[0091] 130 ml of anhydrous toluene was added to the BaF2:Yb,Ho ethanol suspension, and 7 g of 3-aminopropyltriethoxysilane was added dropwise under stirring, and the mixture was reacted at 110°C for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol, and the residue was dispersed in 240 ml of anhydrous toluene and ultrasonicated for 5 minutes to obtain a toluene suspension of BaF2:Yb,Ho modified with aminosilane.

[0092] 10 g of 3-benzoyl-4-hydroxybenzoic acid was added to the aminosilane-modified BaF2:Yb,Ho toluene suspension, and the mixture was reacted at 110°C for 24 hours. The mixture was then washed and filtered three times with anhydrous ethanol. The residue was dispersed in 300 ml of anhydrous ethanol and ultrasonicated for 5 minutes. The solution was then concentrated to 50 ml to obtain a UV cutoff agent-modified BaF2:Yb,Ho ethanol suspension UPUV-4 (i.e., upconversion complex).

[0093] Preparation of masterbatch: The upconversion complex UPUV-4 and POE resin were fully mixed in a mass ratio of 5:95, vacuum dried in an oven at 50°C for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare 5% concentration upconversion complex masterbatch 4.

[0094] Film preparation: Weigh 15 parts of up-conversion complex masterbatch 4, 50 parts of POE8660 resin, 35 parts of POE8669 resin, 0.51 parts of tert-butyl peroxycarbonate-2-ethylhexyl ester, 0.53 parts of triallyl isocyanurate, 0.25 parts of vinyl triisopropoxysilane, 0.32 parts of 3,5-di-tert-butyl-4-hydroxy-benzoic acid hexadecyl ester, and 0.43 parts of 4,4'-thiobis(3-methyl-6-tert-butylphenol), and place them in a mixing kettle for stirring and mixing. The mixed materials are extruded into a film using a single screw extruder, and after embossing, pulling, and winding, a rolled packaging film is obtained with a film thickness of 0.38 mm; the above parts are all weight parts.

[0095] The manufacturing process of the solar cell assembly is the same as that of Example 1.

[0096] Comparative Example 1

[0097] Preparation of masterbatch: 10 g of BaF2:Yb,Er particles with an average particle size of 5 μm, 21 g of 3-benzoyl-4-hydroxybenzoic acid and 589 g of EVA resin (i.e., the upconversion inorganic particles and the UV cut-off agent are mixed with the EVA resin in a mass ratio of 5:95), dried in a vacuum oven at 60°C for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare a 5% concentration upconversion UV cut-off agent masterbatch 5.

[0098] The process of making the adhesive film and the solar cell assembly is the same as that in Example 1.

[0099] Comparative example 2.

[0100] Preparation of masterbatch: 4.5 g of CaF2:Yb,Ho particles with an average particle size of 5 μm, 26 g of 3-(3-(2H-benzo[d][1,2,3]triazol-2-yl)-5-(tert-butyl)-4-hydroxyphenyl)propionyl chloride and 579.5 g of POE resin were fully mixed, vacuum dried in an oven at 60°C for 24 hours, and granulated at 85°C by a twin-screw extruder to prepare 5% concentration of up-conversion UV cutoff agent masterbatch 6.

[0101] The process of making the adhesive film and the solar cell assembly is the same as that in Example 2.

[0102] Comparative Example 3

[0103] Preparation of masterbatch: 10 g of CaF2:Yb,Er particles with an average particle size of 5 μm, 33 g of 4-(4,6-bis(2-hydroxyphenyl)-1,3,5-triazine-2-yl)benzoic acid and 817 g of POE resin (i.e., the up-conversion inorganic particles and the UV cut-off agent are mixed with the POE resin in a mass ratio of 5:95), dried in a vacuum oven at 60°C for 24 hours, and granulated at 85°C by a twin-screw extruder to prepare a 5% concentration up-conversion UV cut-off agent masterbatch 7.

[0104] The process of making the adhesive film and the solar cell assembly is the same as that in Example 3.

[0105] Comparative Example 4

[0106] Preparation of masterbatch: 10 g of BaF2:Yb,Ho particles with an average particle size of 3 μm, 10 g of 3-benzoyl-4-hydroxybenzoic acid and 380 g of POE resin (i.e., the upconversion inorganic particles and the UV cutoff agent are mixed with the POE resin in a mass ratio of 5:95), dried in a vacuum oven at 50°C for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare a 5% concentration upconversion complex masterbatch 8.

[0107] The process of making the adhesive film and the solar cell assembly is the same as that of Example 4.

[0108] Comparative Example 5

[0109] Masterbatch preparation: 10 g of 3-benzoyl-4-hydroxybenzoic acid and POE resin were fully mixed in a mass ratio of 5:95, dried in an oven at 50°C under vacuum for 24 hours, and granulated at 85°C using a twin-screw extruder to prepare a 5% concentration masterbatch 9.

[0110] The process of making the adhesive film and the solar cell assembly is the same as that of Comparative Example 4.

[0111] Performance Test:

[0112] Light transmittance test: The cast film was hot-pressed at 150°C for 18 minutes to obtain a laminated film sample, and the light transmittance was tested according to the test method provided in GB / T29848-2018.

[0113] Solar cell module power test: Prepare test samples in accordance with the standard of GB / T29848-2018, and conduct photovoltaic module current and voltage tests, the unit is W.

[0114] UV cut-off agent migration test: Prepare test samples according to the standard of GB / T29848-2018, such as Figure 2 As shown, the packaging is carried out by combining a glass plate and an organic backplane. The upper side of the cell array with a length of 182 mm and a width of 92 mm adopts the film sample in the embodiment or the comparative example, and the back side adopts a 400 um thick ordinary high-transmittance EVA film sample. The test sample is subjected to a high-temperature migration test (temperature is 120°C), taken out after 96 hours, the backplane is cut open with a prop, and the back film at the middle of the long side of the cell array and 5 mm away from the edge of the cell array is removed. The content of the UV cutoff agent is measured. If the mass content of the UV cutoff agent reaches 30% of the same type of UV cutoff agent in the front film, it is considered that the UV cutoff agent has migrated from the front film to the back film. See Table 1 for the data test results.

[0115] Table 1 Data test results

[0116]

[0117] In the above test, Comparative Examples 1, 2, 3, 4, and 5 did not coat the upconversion inorganic particles with silane or perform an activation treatment, nor did they perform a complex treatment between the ultraviolet cutoff agent and the upconversion inorganic particles, or did not add upconversion inorganic particles, serving as blank control groups; Examples 1 and 2 used a method of coating the upconversion inorganic particles with silane, then modifying the difunctional silane, and finally complexing the ultraviolet cutoff agent; Examples 3 and 4 used a method of activating the upconversion inorganic particles, then modifying the difunctional silane, and finally complexing the ultraviolet cutoff agent.

[0118] The test results reflect the advantages of the upconversion complex very well. The transmittance of Examples 1-4 in the visible light region and the light transmittance in the ultraviolet light region are basically consistent with the comparative example, indicating that the grafting treatment of the ultraviolet cutoff agent with the upconversion inorganic particles has limited effect on the transmittance of the film. Compared with Comparative Examples 1-5, after high-temperature aging treatment, there is no phenomenon of ultraviolet cutoff agent migration in Examples 1-4, indicating that the complexation treatment of the ultraviolet cutoff agent with the upconversion inorganic particles can slow down the migration of the ultraviolet cutoff agent to a limited extent. In addition, the component power of Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, 4 is higher than that of Comparative Example 5, indicating that the upconversion material can produce positive gain on the component power.

[0119] Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It should be particularly noted that all similar replacements and modifications are obvious to those skilled in the art, and they all fall within the scope of protection of the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

Claims

1. An upconversion complex masterbatch, characterized in that: The upconversion complex masterbatch is obtained by surface-modifying upconversion inorganic particles, reacting with a multifunctional coupling agent, grafting with an ultraviolet cutoff agent to obtain an upconversion complex, and finally dispersing the upconversion complex in a resin; wherein the upconversion inorganic particles are doped fluorine-containing compound particles.

2. The upconversion complex masterbatch according to claim 1, characterized in that: The resin is an olefin-based resin.

3. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: The up-conversion inorganic particles are calcium fluoride, or magnesium fluoride, or barium fluoride, or sodium yttrium tetrafluoride, or sodium gadolinium tetrafluoride, or yttrium fluoride doped with one or more of manganese ions, yttrium ions, ytterbium ions, erbium ions, holmium ions, cerium ions, thulium ions, praseodymium ions, iridium ions, and gallium ions.

4. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: The multifunctional coupling agent is selected from one or more of methyl silicate, ethyl orthosilicate, propyl orthosilicate, isopropyl silicate, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, diethylenetriaminopropyltrimethoxysilane, 3-diethylaminopropyltrimethoxysilane, n-butylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl-3-aminopropyl)methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane.

5. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: The UV cut-off agent is selected from one or more of substituted triazine UV cut-off agents, benzophenone UV cut-off agents, salicylate UV cut-off agents, benzotriazole UV cut-off agents, and substituted acrylonitrile UV cut-off agents, and the UV cut-off agent contains one or more of vinyl, acrylic, methacrylic, carboxyl, epoxy, acyl chloride, and isocyanate functional groups.

6. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: In the reaction process of preparing the up-conversion complex, the reaction temperature ranges from 40 to 150° C. and the reaction time is from 0.5 to 10 hours.

7. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: In the reaction process of preparing the up-conversion complex, the required solvent is any one of chloroform, dichloromethane, acetonitrile, ethanol, methanol, n-butanol, benzene, toluene, xylene, chlorobenzene, acetone, butanone, dimethyl sulfoxide, N,N-dimethylformamide, water, dioxane, tetrahydrofuran, ethyl acetate, ether, isopropyl ether, carbon tetrachloride, ethyl bromide, cyclohexane, and hexane, or a mixture of at least two of them.

8. The upconversion complex masterbatch according to claim 2, characterized in that: The number average molecular weight of the olefin-based resin is 50,000 to 400,000 g / mol, and the olefin-based resin is polyethylene, or a copolymer of ethylene and 1-butene, or a copolymer of ethylene and 1-octene, or a copolymer of ethylene and one or more of propylene, vinyl acetate, acrylic acid, maleic anhydride, and glycidyl methacrylate.

9. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: The mass fraction of the up-conversion complex in the up-conversion complex masterbatch is 0.5% to 15%, and the mass fraction of the resin is 85% to 99.5%.

10. The upconversion complex masterbatch according to claim 1 or 2, characterized in that: The surface modification of the up-conversion inorganic particles includes: the up-conversion inorganic particles are coated or activated by silane.

11. A method for preparing an upconversion complex masterbatch according to any one of claims 1 to 10, comprising: The upconversion inorganic particles are surface-modified by silane coating or activation treatment, then reacted with a multifunctional coupling agent, and then grafted with an ultraviolet cutoff agent to obtain an upconversion complex of the upconversion inorganic particles grafted with the ultraviolet cutoff agent, and the upconversion complex is dispersed in a resin to obtain the upconversion complex masterbatch.

12. A resin composition, characterized in that The resin composition comprises 82% to 99.8% of vinyl resin, 0.02% to 9.7% of upconversion complex masterbatch and 0.02% to 11% of auxiliary agent, wherein the upconversion complex masterbatch is the upconversion complex masterbatch according to any one of claims 1 to 10.

13. The resin composition according to claim 12, characterized in that The auxiliary agent is a mixture of one or more of an initiator, a cross-linking agent, a coupling agent, an antioxidant, and a stabilizer; the weight percentage of the initiator is 0.005% to 5%, and / or the weight percentage of the cross-linking agent is 0.005% to 5%, and / or the weight percentage of the coupling agent is 0.005% to 5%, and / or the weight percentage of the antioxidant is 0.005% to 5%, and / or the weight percentage of the stabilizer is 0.005% to 5%.

14. A packaging film, characterized in that: The encapsulation film is a single-layer structure or a multi-layer structure, and the material of at least one layer of the encapsulation film comprises the resin composition according to claim 12 or 13.

15. A solar cell module, characterized in that: The solar cell assembly comprises an organic backplane (25) or a first glass plate (24), a rear encapsulation film (23), a cell array (22), a front encapsulation film (21) and a second glass plate (20) stacked in sequence, wherein the front encapsulation film (21) and / or the rear encapsulation film (23) are the encapsulation films according to claim 14.

16. Use of the upconversion complex masterbatch according to any one of claims 1 to 10 in a solar cell module, comprising improving the utilization of infrared light by the solar cell module, reducing the migration of the UV cutoff agent in the packaging film, and protecting the UV-sensitive solar cell module.

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