Composite adhesive film, photovoltaic module and laminated glass

Abstract

The invention relates to the technical field of adhesive films, and relates to a composite adhesive film, a photovoltaic module and laminated glass, the composite adhesive film comprises an oxygen barrier layer and an oxygen removal layer, the oxygen permeability of the oxygen barrier layer is less than or equal to 50cm < 3 > / (m < 2 >. 24h. 0.1 MPa); the oxygen removal layer comprises one or a combination of more than two of a first functional material, a second functional material and a third functional material; the first functional material is a polymer containing a carbon-carbon unsaturated double bond; the second functional material is a deoxidizing agent; the third functional material is a metal organic framework material. According to the invention, by adopting the specific functional additive and further optimizing the structure and composition of the adhesive film, the obtained composite adhesive film can effectively give consideration to the gas barrier property, reduce the adverse effect on the power attenuation of the photovoltaic module in the long-term service process, prevent the corrosion of a battery piece, stabilize the photoelectric conversion efficiency and prolong the life cycle of the photovoltaic module.

Description

Technical Field

[0001] This invention relates to the field of adhesive film technology, and more particularly to a composite adhesive film, a photovoltaic module, and laminated glass. Background Technology

[0002] With the increasing global demand for clean energy, photovoltaic (PV) power generation, as a mature and efficient renewable energy technology, has been widely adopted. As the core of a PV power generation system, the long-term stability and power generation efficiency of PV modules are crucial. Since PV modules are typically placed outdoors for extended periods, atmospheric moisture and oxygen continuously penetrate the module's interior, causing corrosion and oxidation of the cells (especially n-type cells), leading to a decline in photoelectric conversion performance and affecting the overall power output and lifespan of the module. Therefore, developing encapsulating films that effectively block moisture and oxygen is of great significance for improving the reliability of PV modules.

[0003] Currently, a common technical solution in the industry to address oxygen permeation is to incorporate a gas barrier layer into the photovoltaic encapsulation film. For example, some technologies use inorganic fillers such as montmorillonite added to polyolefin resins, utilizing the physical barrier and adsorption properties of the fillers to reduce the oxygen permeability of the film. However, this method has limited barrier effectiveness, and the addition of inorganic fillers may adversely affect other key properties of the film, such as light transmittance and toughness.

[0004] In fact, in addition to gas barrier properties, photovoltaic encapsulation films must also meet requirements such as high light transmittance. When designing encapsulation films, multiple factors must be considered simultaneously, especially the need to balance gas barrier properties and the ability to reduce the adverse effects on photovoltaic module power degradation during long-term service. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a composite encapsulating film, a photovoltaic module, and laminated glass, thereby resolving the issue that existing encapsulating films cannot simultaneously achieve gas barrier properties and reduce their adverse effects on photovoltaic module power degradation during long-term service.

[0006] Specifically, in a first aspect, the present invention provides a composite film comprising an oxygen barrier layer and an oxygen scavenging layer, wherein the oxygen barrier layer has an oxygen permeability of less than or equal to 50 cm⁻¹. 3 / (m 2 ·24h·0.1MPa); The oxygen removal layer includes one or more of the following: a first functional material, a second functional material, and a third functional material; The first functional material is a polymer containing carbon-carbon unsaturated double bonds; The second functional material is a deoxidizer; The third functional material is a metal-organic framework material.

[0007] According to the composite film provided by the present invention, the polymer containing carbon-carbon unsaturated double bonds is selected from one or more of the following: ethylene / methyl acrylate / cyclohexenyl methyl acrylate terpolymer (EMCM), ethylene / vinyl cyclohexene copolymer (EVCH), ethylene / cyclohexenyl methyl acrylate copolymer (ECMA), and cyclohexenyl methyl acrylate homopolymer (PCHMA). And / or, the deoxidizer is selected from one or a combination of two of the following: photosensitive dye deoxidizer, sulfite-based deoxidizer, and carbazide; preferably, the photosensitive dye deoxidizer is selected from photosensitive dye and / or singlet oxygen acceptor; the sulfite-based deoxidizer is selected from sodium dithionite and / or calcium hydroxide; And / or, the metal-organic framework material is selected from one or more combinations of ZIF-8, HKUST-1, UiO-66, UiO-67, Fe-BTC, Co-MOF-74, and ZIF-67.

[0008] According to the composite film provided by the present invention, the oxygen-removing layer comprises a host resin; each host resin is independently selected from one or more combinations of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

[0009] And / or, the oxygen barrier layer comprises an oxygen barrier resin, which is selected from one or more combinations of ethylene-vinyl alcohol copolymer (EVOH), polyamide (PA), polyvinylidene chloride (PVDC), and polyglycolic acid (PGA).

[0010] According to the composite film provided by the present invention, an adhesive layer is further included between the oxygen-removing layer and the oxygen-barrier layer; Preferably, the thickness of the oxygen barrier layer is 20~80μm; And / or, the thickness of the adhesive layer is 50~100μm; And / or, the thickness of the deoxygenation layer is 20~80μm.

[0011] According to the composite adhesive film provided by the present invention, the composite adhesive film sequentially comprises a first substrate layer, an oxygen barrier layer, an adhesive layer, an oxygen removal layer, and a second substrate layer; Preferably, the thickness of the oxygen barrier layer is 20~80μm; And / or, the thickness of the adhesive layer is 50~100μm; And / or, the thickness of the deoxygenation layer is 20~80μm; And / or, the basis weight of the first substrate layer in the composite film is 100~200 g / m².

[0012] And / or, the basis weight of the second matrix layer in the composite film is 100~200 g / m².

[0013] According to the composite film provided by the present invention, the first substrate layer, the adhesive layer, and the second substrate layer all include additives, which include one or a combination of two or more of the following: antipotential-induced degradation additives, initiators, co-crosslinking agents, silane coupling agents, ultraviolet absorbers, and light stabilizers. The oxygen barrier layer and the oxygen scavenging layer do not contain additives.

[0014] Preferably, the potential-induced decay additive is selected from one or more combinations of urea compounds, acrylate compounds, amide compounds, polyether polymers, crown ether compounds, metal phosphate salts, silicates, silicon dioxide, metal oxides, and metal hydroxides; According to the composite film provided by the present invention, the first matrix layer includes a first matrix resin, and the second matrix layer includes a second matrix resin; Preferably, the first matrix resin and the second matrix resin are each independently selected from one or more combinations of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

[0015] According to the composite film provided by the present invention, the adhesive layer comprises an adhesive resin; the adhesive resin is selected from one or more combinations of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

[0016] The present invention also provides a photovoltaic module, including an encapsulating film, wherein the encapsulating film includes at least one layer of composite film as described above.

[0017] Fourthly, the present invention also provides laminated glass, the laminated glass comprising at least two glass layers and a film disposed between adjacent glass layers, the film comprising at least one layer of composite adhesive film as described above.

[0018] This invention provides a composite film, a photovoltaic module, and laminated glass. By employing specific functional additives and further optimizing the structure and composition of the film, the resulting composite film can effectively balance gas barrier properties and reduce its adverse effects on the power degradation of the photovoltaic module during long-term service, prevent cell corrosion, stabilize photoelectric conversion efficiency, and extend the lifespan of the photovoltaic module. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0020] The endpoints and any values ​​of the ranges disclosed in this specification are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "specific implementation," or "some specific implementations," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0022] Specifically, in a specific embodiment of the present invention, a composite film is first provided, comprising: an oxygen barrier layer and an oxygen removal layer, wherein the oxygen permeability of the oxygen barrier layer is less than or equal to 50 cm⁻¹. 3 / (m 2 ·24h·0.1MPa); The oxygen removal layer includes one or more of the following: a first functional material, a second functional material, and a third functional material; The first functional material is a polymer containing carbon-carbon unsaturated double bonds; The second functional material is a deoxidizer; The third functional material is a metal-organic framework material.

[0023] This invention uses an oxygen permeability of less than or equal to 50 cm. 3 / (m 2 An oxygen barrier layer (0.1 MPa, 24h) provides physical protection, extending the oxygen transport path / time. An oxygen scavenging layer provides chemical protection; the added oxygen-scavenging material reacts with oxygen molecules, actively capturing and binding them. This invention utilizes a specifically composed oxygen barrier layer and an oxygen scavenging layer, working synergistically to achieve a multi-layered protective effect, further improving the long-term stability of photovoltaic modules.

[0024] In some specific embodiments of the present invention, the polymer containing carbon-carbon unsaturated double bonds is selected from one or more combinations of ethylene / methyl acrylate / cyclohexenyl methyl acrylate terpolymer, ethylene / vinylcyclohexene copolymer, ethylene / cyclohexenyl methyl acrylate copolymer, and cyclohexenyl methyl acrylate homopolymer. In some specific embodiments of the present invention, the deoxidizing agent is selected from one or a combination of two of photosensitive dye deoxidizing agents, sulfite-based deoxidizing agents, or carbazide; In some specific embodiments of the present invention, the metal-organic framework material is selected from one or more combinations of ZIF-8, HKUST-1, UiO-66, UiO-67, Fe-BTC, Co-MOF-74, and ZIF-67.

[0025] In some specific embodiments of the present invention, the oxygen barrier layer comprises an oxygen barrier resin, and the oxygen removal layer comprises a host resin.

[0026] In some specific embodiments of the present invention, the oxygen barrier resin is selected from ethylene-vinyl alcohol copolymer, polyamide, polyvinylidene chloride, and polyglycolic acid; In some specific embodiments of the present invention, each of the main resins is independently selected from one or more combinations of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

[0027] In some specific embodiments of the present invention, the first functional material is a polymer containing carbon-carbon unsaturated double bonds; the mass percentage of the first functional material in the oxygen-removing layer is less than 5%.

[0028] In some specific embodiments of the present invention, the second functional material is a deoxidizer; the mass percentage of the second functional material in the deoxidizing layer is less than 0.1%.

[0029] In some specific embodiments of the present invention, the third functional material is a metal-organic framework material; the mass percentage of the third functional material in the oxygen-removing layer is less than 0.1%.

[0030] In some specific embodiments of the present invention, an adhesive layer is further included between the oxygen removal layer and the oxygen barrier layer; Preferably, the thickness of the oxygen barrier layer is 20~80μm; Preferably, the thickness of the adhesive layer is 50~100μm; Preferably, the thickness of the deoxygenation layer is 20~80μm.

[0031] In some specific embodiments of the present invention, the composite film sequentially comprises a first substrate layer, an oxygen barrier layer, an adhesive layer, an oxygen removal layer, and a second substrate layer; Preferably, the thickness of the oxygen barrier layer is 20~80μm; Preferably, the thickness of the adhesive layer is 50~100μm; Preferably, the thickness of the deoxygenation layer is 20~80μm; Preferably, the basis weight of the first substrate layer in the composite film is 100~200 g / m².

[0032] Preferably, the basis weight of the second substrate layer in the composite film is 100~200 g / m².

[0033] As an example, the composite film mentioned above, which includes an oxygen barrier layer and an oxygen removal layer, can have a structure in which, in a first direction, a first substrate layer, an oxygen barrier layer, an adhesive layer, an oxygen removal layer, and a second substrate layer are sequentially stacked.

[0034] In some specific embodiments of the present invention, at least one of the first matrix layer, the adhesive layer, and the second matrix layer further includes an additive. The additive includes one or more of the following: antipotential-induced decay additives, initiators, co-crosslinking agents, silane coupling agents, ultraviolet absorbers, and light stabilizers. The oxygen barrier layer and the oxygen scavenging layer do not contain additives. The oxygen barrier layer has a high processing temperature and is not suitable for crosslinking additives. The oxygen scavenging layer contains active groups and is not suitable for various additives. In some specific embodiments of the present invention, the mass percentage of the antipotential-induced decay additive in the corresponding layer is 0.02~3%.

[0035] In some specific embodiments of the present invention, the initiator accounts for 0.1-3% of the mass in the corresponding layer.

[0036] In some specific embodiments of the present invention, the mass percentage of the crosslinking agent in the corresponding layer is 0.1-5%.

[0037] In some specific embodiments of the present invention, the mass percentage of the silane coupling agent in the corresponding layer is less than 3%.

[0038] In some specific embodiments of the present invention, the mass percentage of the ultraviolet absorber in the corresponding layer is 0-2%.

[0039] In some specific embodiments of the present invention, the mass percentage of the light stabilizer in the corresponding layer is 0.005~1%.

[0040] In some specific embodiments of the present invention, the first substrate layer comprises, by weight parts: 100 parts by weight of matrix resin; 0.1~3 parts by weight of initiator; 0.1~5 parts by weight of crosslinking agent; 0.01~3 parts by weight of silane coupling agent; 0-2 parts by weight of UV absorber; 0.005~1 parts by weight of light stabilizer; 0.02~3.0 parts by weight of antipotential-induced decay additive.

[0041] In some specific embodiments of the present invention, the second substrate layer comprises, by weight parts: 100 parts by weight of matrix resin; 0.1~3 parts by weight of initiator; 0.1~5 parts by weight of crosslinking agent; 0.01~3 parts by weight of silane coupling agent; 0-2 parts by weight of UV absorber; 0.005~1 parts by weight of light stabilizer; 0.02~3.0 parts by weight of antipotential-induced decay additive.

[0042] In some specific embodiments of the present invention, the adhesive layer comprises, by weight parts: 100 parts by weight of matrix resin; 0.1~3 parts by weight of initiator; 0.1~5 parts by weight of crosslinking agent; 0.01~3 parts by weight of silane coupling agent; 0-2 parts by weight of UV absorber; 0.005~1 parts by weight of light stabilizer; 0.02~3.0 parts by weight of antipotential-induced decay additive.

[0043] In some specific embodiments of the present invention, the deoxygenation layer comprises, by weight, the following: 100 parts by weight of the main resin; 0.01 to 5 parts by weight of the first functional material; In some specific embodiments of the present invention, the deoxygenation layer comprises, by weight, the following: 100 parts by weight of the main resin; 0.01~0.1 parts by weight of the second functional material; In some specific embodiments of the present invention, the deoxygenation layer comprises, by weight, the following: 100 parts by weight of the main resin; 0.01~0.1 parts by weight of a third functional material; In some specific embodiments of the present invention, the thickness of the oxygen barrier layer is 20~80μm. The oxygen barrier layer has a high degree of crystallinity. The oxygen barrier resin has an impact on the light transmittance and anti-PID properties of the composite film. By controlling the thickness of the oxygen barrier layer within the aforementioned range, the present invention can avoid the decrease in light transmittance caused by the presence of a certain amount of oxygen barrier resin.

[0044] In some specific embodiments of the present invention, the adhesive layer is 50~100μm.

[0045] In some specific embodiments of the present invention, the thickness of the oxygen-removing layer is 20~80μm. Since the oxygen barrier layer contains a certain amount of oxygen-removing material, this material affects the light transmittance and PID resistance of the composite film. By controlling the thickness of the oxygen barrier layer within the aforementioned range, the present invention can avoid the decrease in light transmittance caused by the presence of a certain amount of oxygen-removing material.

[0046] In some specific embodiments of the present invention, the potential-induced decay additive is selected from one or more combinations of urea compounds, acrylate compounds, amide compounds, polyether polymers, crown ether compounds, metal phosphate salts, silicates, silicon dioxide, metal oxides and metal hydroxides; In some specific embodiments of the present invention, the co-crosslinking agent includes one or more of triallyl isocyanurate, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate.

[0047] In some specific embodiments of the present invention, the initiator includes tert-butyl peroxycarbonate isopropyl ester, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxycarbonate-2-ethylhexyl ester, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-pentylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, etc. The following are one or more combinations of pentylperoxycyclohexane, 1,1-bis(tert-butylperoxycyclohexane), 2,2-bis(tert-butylperoxy)butane, tert-pentyl peroxyhexyl carbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-pentyl peroxycarbonate, tert-butyl peroxyhexanoate, azobisisobutyronitrile, azobisisopentanitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyramidine imidazoline hydrochloride, and azobisisobutyronitrile cyanoformamide.

[0048] In some specific embodiments of the present invention, the silane coupling agent includes one or a combination of two or more of the following double-bonded silane coupling agents: vinyltriethoxysilane, vinyltriisopropoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0049] In some specific embodiments of the present invention, the ultraviolet absorber includes benzophenones or benzotriazoles. The benzophenones are selected from one or more of 2-hydroxy-4-n-octyloxybenzophenone, 2,2-tetramethylenebis(3,1-benzoxazin-4-one), and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone in any proportion. The benzotriazoles are selected from one or more of 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-aminophenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-3',-5'-bis[1,1-dimethylphenyl])benzotriazole, 2-(2'-methyl-4'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, and 2-(2'-hydroxy-5-methylphenyl)-5-carboxylate benzotriazole.

[0050] In some specific embodiments of the present invention, the light stabilizer comprises one or more of the following: hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite, bis-2,2,6,6-tetramethylpiperidinol sebacate, bis-1-decyloxy-2,2,6,6-tetramethylpiperidin-4-ol sebacate, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, a polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, and a polymer of morpholine-2,4,6-trichloro-1,3,5-triazine.

[0051] In some specific embodiments of the present invention, the matrix resin in the first matrix layer includes a first matrix resin, and the matrix resin in the second matrix layer includes a second matrix resin.

[0052] Preferably, the first matrix resin and the second matrix resin are each independently selected from one or more combinations of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

[0053] In some specific embodiments of the present invention, the matrix resin in the adhesive layer includes an adhesive resin; the adhesive resin is selected from one or more of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

[0054] In a specific embodiment of the present invention, a photovoltaic module is also provided, including an encapsulating film, wherein the encapsulating film includes at least one layer of composite film as described above.

[0055] The composite encapsulant film provided in this application possesses excellent gas barrier properties and can effectively reduce the power degradation of photovoltaic modules during long-term service. Using it as an encapsulant film for photovoltaic modules can prevent cell corrosion, stabilize photoelectric conversion efficiency, and extend the lifespan of photovoltaic modules.

[0056] Preferably, the photovoltaic module is an n-type double-glass module; Preferably, the photovoltaic module is an n-type single-glass module; more preferably, the composite encapsulant film is used for backsheet encapsulation of the n-type single-glass module. Preferably, the composite film is used on both sides of the flexible component (lightweight component).

[0057] In a specific embodiment of the present invention, a laminated glass is also provided, the laminated glass comprising at least two glass layers and a film disposed between adjacent glass layers, the film comprising at least one layer of composite adhesive film as described above.

[0058] The composite film provided in this application has good sealing and barrier properties. Using it as a film in laminated glass can greatly improve the lamination and barrier properties of laminated glass.

[0059] In the embodiments provided in this specification, unless specific techniques or conditions are specified, the techniques or conditions described in the literature in this field, or the product instructions, shall be followed. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased from legitimate channels.

[0060] The following lists some of the raw materials used in the following embodiments of the present invention: Table 1

[0061] This embodiment also provides a method for preparing the above-mentioned composite film, which includes: Preparation of the first matrix layer: The antipotential-induced decay additive, initiator, co-crosslinking agent, silane coupling agent, ultraviolet absorber and light stabilizer are mixed in proportion and added to the resin to complete the mixing. The mixture is then cast and extruded into a film using a screw extruder.

[0062] Preparation of the second matrix layer: The antipotential-induced decay additive, initiator, crosslinking agent, silane coupling agent, ultraviolet absorber and light stabilizer are mixed according to the proportion and added to the resin to complete the mixing. The mixture is then cast and extruded into a film using a screw extruder.

[0063] Preparation of oxygen barrier layer: Its constituent raw materials are cast and extruded into a film using a screw extruder.

[0064] Adhesive layer: The antipotential-induced decay additive, initiator, co-crosslinking agent, silane coupling agent, ultraviolet absorber and light stabilizer are mixed according to the proportion and added to the resin to complete the mixing. The mixture is then cast and extruded into a film using a screw extruder.

[0065] Deoxygenated layer: Its constituent raw materials are mixed in a certain proportion and then cast into a film using a screw extruder.

[0066] Composite method: First, an oxygen barrier layer is cast and extruded, and then composited with the first substrate layer to prepare a double-layer composite film. Then, an oxygen removal layer is cast and extruded, and then composited with the second substrate layer to prepare a double-layer composite film. Finally, an adhesive layer is cast and extruded, and the two double-layer composite films are sequentially composited onto the adhesive layer to prepare a 5-layer composite film.

[0067] The composite film, photovoltaic module, and laminated glass of the present invention will be described in detail below with reference to specific implementation examples.

[0068] Examples 1-5 This embodiment provides a composite adhesive film, which has a five-layer structure stacked sequentially: a first substrate layer, an oxygen barrier layer, an adhesive layer, an oxygen scavenging layer, and a second substrate layer. The materials and structures of each layer are shown in the table below: Table 2

[0069] Example 6 This is essentially the same as Example 1, except that the first substrate layer is replaced with a first substrate layer having the following composition, wherein the basis weight of the composite film is 200 g / m³. 2 .

[0070] The composition of the first matrix layer, by weight, is as follows: 100 parts by weight of POE; 0.15 parts by weight of tert-butyl peroxycarbonate isopropyl ester; 1 part by weight of triallyl isocyanurate.

[0071] 1.5 parts by weight of vinyltriethoxysilane.

[0072] Example 7 This is essentially the same as Example 1, except that the second substrate layer is replaced with a second substrate layer having the following composition, wherein the basis weight of the composite film is 200 g / m³. 2 .

[0073] The composition of the second matrix layer, by weight, is as follows: 100 parts by weight of POE; 0.16 parts by weight of tert-butyl peroxycarbonate isopropyl ester; 0.8 parts by weight of triallyl isocyanurate; 1.5 parts by weight of vinyltriethoxysilane.

[0074] Example 8 It is basically the same as Example 1, except that the adhesive layer is replaced with an adhesive layer with the following composition, which has a thickness of 50 μm in the composite film.

[0075] The adhesive layer comprises the following parts by weight: 100 parts by weight of POE; 0.12 parts by weight of tert-butyl peroxycarbonate isopropyl ester; 0.18 parts by weight of triallyl isocyanurate; 1.5 parts by weight of vinyltriethoxysilane.

[0076] Example 9 It is basically the same as Example 1, except that the adhesive layer is replaced with an adhesive layer with the following composition, which has a thickness of 50 μm in the composite film.

[0077] The adhesive layer comprises the following parts by weight: 100 parts by weight of POE; 1.5 parts by weight of vinyltriethoxysilane.

[0078] Example 10 It is basically the same as Example 1, except that the adhesive layer is replaced with an adhesive layer with the following composition, which has a thickness of 50 μm in the composite film.

[0079] The adhesive layer comprises the following parts by weight: 100 parts by weight of POE; 1.5 parts by weight of vinyltriethoxysilane; 1.2 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone; 0.6 parts by weight of hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; 0.35 parts by weight of silicon dioxide.

[0080] Example 11 It is basically the same as Example 5, except that the deoxygenating layer is replaced with a deoxygenating layer with the following composition, which has a thickness of 80 μm in the composite film.

[0081] The composition of the deoxygenation layer, by weight, is as follows: 100 parts by weight of EVA; 0.01 parts by weight of EMCM; 0.05 parts by weight of carbazide.

[0082] Example 12 It is basically the same as Example 5, except that the deoxygenating layer is replaced with a deoxygenating layer with the following composition, which has a thickness of 80 μm in the composite film.

[0083] The composition of the deoxygenation layer, by weight, is as follows: 100 parts by weight of EVA; 1 part by weight of EMCM; 1 part by weight of PCHMA; 0.1 parts by weight of ZIF-67.

[0084] Example 13 It is basically the same as Example 5, except that the deoxygenating layer is replaced with a deoxygenating layer with the following composition, which has a thickness of 80 μm in the composite film.

[0085] The composition of the deoxygenation layer, by weight, is as follows: 100 parts by weight of EVA; 0.01 parts by weight of photosensitive dye deoxidizer; 0.01 parts by weight of ZIF-8; 0.01 parts by weight of ZIF-67.

[0086] Example 14 It is basically the same as Example 5, except that the deoxygenating layer is replaced with a deoxygenating layer with the following composition, which has a thickness of 80 μm in the composite film.

[0087] The composition of the deoxygenation layer, by weight, is as follows: 100 parts by weight of POE; 0.01 parts by weight of ECMA; 0.01 parts by weight of sulfite-based deoxidizer; 0.01 parts by weight of Co-MOF-74.

[0088] Examples 15-20 The process is basically the same as in Example 5, except that the oxygen barrier layer is replaced with an oxygen barrier layer with the following composition and structure, wherein each polymer in the oxygen barrier layer is selected from commonly used types in the art, and the total thickness and oxygen permeability of the oxygen barrier layer obtained by adjusting the thickness of each membrane layer meet the requirements in the table below.

[0089] Table 3

[0090] Comparative Example 1 A typical POE film has a basis weight of 500 g / m². 2 .

[0091] Comparative Example 2 A composite adhesive film, the structure of which is a three-layer composite film. Among them, First layer: Weight 200g / m 2 EVA film; Second layer: Weight 100g / m 2 EVOH membrane; Third layer: Weight 200g / m 2 EVA film.

[0092] Test case Oxygen transmission rate: The oxygen transmission rate of the photovoltaic encapsulation film was tested using an oxygen transmission rate tester (model: OX-TRAN 2 / 12 OTR), referring to the ASTM D3985 standard test method, and the test temperature was 23℃.

[0093] Power Attenuation: The composite encapsulating film is cut to the required size and laid up in the following order: photovoltaic backsheet (300μm thick), first encapsulating film layer (the composite encapsulating film prepared in the above embodiment), cell layer (N-type TOPCon solar cell, 130μm thick), second encapsulating film layer (the composite encapsulating film prepared in the above embodiment), and front glass layer (320μm thick). The layers are then placed in a laminator and vacuum-laminated at 150°C (vacuum degree of vacuum lamination is -0.09Mpa). The resulting photovoltaic module (N-type TOPCon solar cell) is then obtained. The attenuation data is measured after aging the finished photovoltaic module at 105°C and 95%RH for 144 hours.

[0094] The composite encapsulant used in a finished photovoltaic module is a composite encapsulant prepared in the same embodiment. The test results of the corresponding photovoltaic modules are shown in the table below, with the embodiment number corresponding to the composite encapsulant as the mark.

[0095] The test results are as follows: Table 4

[0096] Test results show that the combined use of oxygen barrier materials and oxygen removal materials can provide better protection for photovoltaic modules during long-term aging. In particular, optimization of the oxygen removal materials can further reduce the power degradation of photovoltaic modules.

[0097] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A composite adhesive film, characterized by, comprising an oxygen barrier layer and an oxygen scavenging layer, the oxygen barrier layer having an oxygen transmission rate of less than or equal to 50 cm 3 / m 2 ·24h·0.1MPa); The oxygen removal layer comprises one or a combination of two or more of a first functional material, a second functional material, and a third functional material; The first functional material is a polymer containing carbon-carbon unsaturated double bond; The second functional material is a deoxidizer; The third functional material is a metal organic framework material.

2. The composite adhesive film according to claim 1, wherein The polymer containing carbon-carbon unsaturated double bond is selected from one or a combination of two or more of ethylene / methyl acrylate / cyclohexenyl methyl acrylate terpolymer, ethylene / vinyl cyclohexene copolymer, ethylene / cyclohexenyl methyl acrylate copolymer, and cyclohexenyl methyl acrylate homopolymer; The deoxidizer is selected from one or a combination of two or more of a photosensitive dye deoxidizer, a sulfite deoxidizer, and carbazic acid hydrazide; The metal organic framework material is selected from one or a combination of two or more of ZIF-8, HKUST-1, UiO-66, UiO-67, Fe-BTC, Co-MOF-74, and ZIF-67.

3. The composite adhesive film according to claim 1, wherein The oxygen removal layer comprises a main resin; the main resin is selected from one or a combination of two or more of ethylene-vinyl acetate copolymer, metallocene catalyzed polyethylene, metallocene catalyzed ethylene-butene copolymer, metallocene catalyzed ethylene-octene copolymer, metallocene catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer; The oxygen barrier layer comprises an oxygen barrier resin selected from one or a combination of two or more of ethylene-vinyl alcohol copolymer, polyamide, polyvinylidene chloride, and polyglycolide.

4. The composite adhesive film according to any one of claims 1 to 3, characterized in that, The oxygen removal layer and the oxygen barrier layer further comprise a bonding layer; Preferably, the thickness of the oxygen barrier layer is 20-80 μm; The thickness of the bonding layer is 50-100 μm; The thickness of the oxygen removal layer is 20-80 μm.

5. The composite adhesive film according to any one of claims 1 to 3, characterized in that, The composite adhesive film comprises, in sequence, a first base layer, an oxygen barrier layer, a bonding layer, an oxygen removal layer, and a second base layer; Preferably, the thickness of the oxygen barrier layer is 20-80 μm; The thickness of the bonding layer is 50-100 μm; The thickness of the oxygen removal layer is 20-80 μm; The grammage of the first base layer in the composite adhesive film is 100-200 g / m²; The grammage of the second base layer in the composite adhesive film is 100-200 g / m².

6. The composite adhesive film of claim 5, wherein At least one of the first base layer, the bonding layer, and the second base layer further comprises an auxiliary agent selected from one or a combination of two or more of an electric potential-induced decay additive, an initiator, a co-crosslinking agent, a silane coupling agent, an ultraviolet absorber, and a light stabilizer; the oxygen barrier layer and the oxygen removal layer do not comprise the auxiliary agent; Preferably, the electric potential-induced decay additive is selected from one or a combination of two or more of urea compound, acrylate compound, amide compound, polyether polymer, crown ether compound, metal phosphate, silicate, silicon dioxide, metal oxide, and metal hydroxide.

7. The composite adhesive film according to claim 5 or 6, characterized in that, The first base layer comprises a first base resin, and the second base layer comprises a second base resin. Preferably, the first base resin and the second base resin are each independently selected from one or a combination of two or more of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

8. The composite adhesive film according to any one of claims 4 to 7, wherein The adhesive layer includes an adhesive resin; the adhesive resin is selected from one or a combination of two or more of ethylene-vinyl acetate copolymer, metallocene-catalyzed polyethylene, metallocene-catalyzed ethylene-butene copolymer, metallocene-catalyzed ethylene-octene copolymer, metallocene-catalyzed ethylene-pentene copolymer, ethylene-propylene copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer.

9. A photovoltaic module comprising an encapsulant film, characterized in that, The encapsulation film includes at least one composite film according to any one of claims 1-8.

10. A laminated glass, characterized by, The laminated glass includes at least two glass layers and a film disposed between adjacent glass layers, the film including at least one composite film according to any one of claims 1-8.

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