Flame-retardant black packaging adhesive film as well as preparation method and application thereof

Abstract

The invention provides a flame-retardant black packaging adhesive film and a preparation method and application thereof.The flame-retardant black packaging adhesive film comprises a first black adhesive film layer, a white flame-retardant reflecting layer and a second black adhesive film layer which are arranged in a stacked mode, and through the stacked structure design, the obtained flame-retardant black packaging adhesive film is good and lasting in adhesive force and good in flame-retardant effect. The prepared solar photovoltaic module has the characteristics of excellent flame retardancy, high reflectivity and the like, and can ensure that the appearance of the module is all black, so that the prepared solar photovoltaic module is good in appearance and has relatively high power.

Description

Technical Field

[0001] This invention relates to the field of adhesive film technology, and in particular to a flame-retardant black encapsulating adhesive film, its preparation method, and its application. Background Technology

[0002] With the continuous development of new energy sources and the increasing demand for urban energy conservation, emission reduction, and green environmental protection, building-integrated photovoltaics (BIPV) is gradually becoming a future trend in the photovoltaic market. BIPV combines photovoltaic modules with buildings, applying them to rooftops, exterior walls, and other building surfaces. It places high demands on the photovoltaic modules, which must not only meet the functional requirements of photovoltaic power generation but also take into account the basic functional requirements of the building.

[0003] Currently, in order to match the style of buildings, most double-glass modules on the market use black encapsulating film to meet the aesthetic requirements of buildings. However, the requirements for photovoltaic modules to be used in building materials are high. First of all, they need to meet the safety requirements of building materials such as fire resistance and flame retardancy. The fire resistance and flame retardancy of the encapsulating film itself is relatively weak.

[0004] Therefore, developing an encapsulant film with both good appearance and good flame-retardant properties is particularly important for the fire safety of photovoltaic modules. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a flame-retardant black encapsulating film, its preparation method, and its application. The flame-retardant black encapsulating film possesses excellent flame-retardant properties, good adhesion, and high infrared reflectivity. Furthermore, during the lamination process, neither the black film layer nor the white flame-retardant reflective layer exhibits problems such as flow, overflow, overturning, or wrinkling. This ensures that the resulting component has an all-black appearance and further improves the component's efficiency.

[0006] To achieve this objective, the present invention adopts the following technical solution: In a first aspect, the present invention provides a flame-retardant black encapsulating film, the flame-retardant black encapsulating film comprising a first black encapsulating film layer, a white flame-retardant reflective layer and a second black encapsulating film layer stacked together.

[0007] The flame-retardant black encapsulating film provided by this invention has a "sandwich structure," comprising a first black encapsulating film layer, a white flame-retardant reflective layer, and a second black encapsulating film layer stacked together. On one hand, by placing the first and second black encapsulating film layers on opposite sides, the resulting flame-retardant black encapsulating film is ensured to have durable and good adhesion while maintaining the overall black appearance of the module, resulting in a good-looking module with transparent and easy-to-clean excess adhesive. On the other hand, by placing the white flame-retardant reflective layer in the middle, it not only provides the encapsulating film with high flame-retardant properties, solving the problem of the film being flammable but not fireproof, but also has good reflectivity, especially high infrared reflectivity, which can further improve the power of the module. Ultimately, the solar cell module containing the flame-retardant black encapsulating film provided by this invention can meet the basic requirements of photovoltaic modules while also satisfying the aesthetic requirements of building materials and the fire-retardant safety requirements.

[0008] Preferably, the thickness of the first black adhesive film layer and the second black adhesive film layer are each independently 200-500 μm, for example, 200 μm, 300 μm, 400 μm or 500 μm.

[0009] Preferably, the thickness of the white flame-retardant reflective layer is 50-300 μm, for example, it can be 50 μm, 100 μm, 150 μm, 200 μm, 250 μm or 300 μm.

[0010] Preferably, the first black adhesive film layer and the second black adhesive film layer are each independently an EVA black adhesive film layer, a POE black adhesive film layer, an EAA black adhesive film layer, an EEA black adhesive film layer, an EMMA black adhesive film layer, a PEMA black adhesive film layer, an EBA black adhesive film layer, a PVB black adhesive film layer, or a PU black adhesive film layer, preferably an EVA black adhesive film layer or a POE black adhesive film layer.

[0011] Preferably, the white flame-retardant reflective layer is an EVA white flame-retardant reflective layer, a POE white flame-retardant reflective layer, an EAA white flame-retardant reflective layer, an EEA white flame-retardant reflective layer, an EMMA white flame-retardant reflective layer, a PEMA white flame-retardant reflective layer, an EBA white flame-retardant reflective layer, a PVB white flame-retardant reflective layer, or a PU white flame-retardant reflective layer, and more preferably an EVA white flame-retardant reflective layer or a POE white flame-retardant reflective layer.

[0012] Preferably, the raw materials for preparing the first black adhesive film layer and the second black adhesive film layer each independently include 80-98 parts of matrix resin A, 8-20 parts of black reflective filler, 0.2-2 parts of main crosslinking agent A, 0.2-1 parts of co-crosslinking agent A and 0.1-2 parts of silane coupling agent A.

[0013] Among them, 80-98 portions can be, for example, 80 portions, 82 portions, 84 portions, 86 portions, 88 portions, 90 portions, 92 portions, 94 portions, 96 portions, 98 portions, etc.; 8-20 portions can be, for example, 8 portions, 10 portions, 12 portions, 14 portions, 16 portions, 18 portions, 20 portions, etc.; 0.2-2 portions can be, for example, 0.2 portions, 0.4 portions, 0.6 portions, 0.8 portions, 1 portion, 1.2 portions, 1.4 portions, 1.6 portions, 1.8 portions, 2 portions, etc.; 0.2-1 portion can be, for example, 0.2 portions, 0.3 portions, 0.4 portions, 0.5 portions, 0.6 portions, 0.7 portions, 0.8 portions, 0.9 portions, 1 portion, etc.; 0.1-2 portions can be, for example, 0.2 portions, 0.4 portions, 0.6 portions, 0.8 portions, 1 portion, 1.2 portions, 1.4 portions, 1.6 portions, 1.8 portions, etc.

[0014] Preferably, the raw materials for preparing the white flame-retardant reflective layer include 60-90 parts of matrix resin B, 8-20 parts of white reflective filler, 0.2-2 parts of main crosslinking agent B, 0.2-1 parts of co-crosslinking agent B, 0.1-2 parts of silane coupling agent B, and 5-30 parts of flame-retardant filler.

[0015] Among them, 60-90 portions can be, for example, 40 portions, 42 portions, 44 portions, 46 portions, 48 ​​portions, 80 portions, 82 portions, 84 portions, 86 portions, 88 portions, 90 portions, etc.; 8-20 portions can be, for example, 8 portions, 10 portions, 12 portions, 14 portions, 16 portions, 18 portions, 20 portions, etc.; 0.2-2 portions can be, for example, 0.2 portions, 0.4 portions, 0.6 portions, 0.8 portions, 1 portion, 1 portion, etc. 0.2 portions, 1.4 portions, 1.6 portions, 1.8 portions, 2 portions, etc.; 0.2-1 portions, for example, 0.2 portions, 0.3 portions, 0.4 portions, 0.5 portions, 0.6 portions, 0.7 portions, 0.8 portions, 0.9 portions, 1 portion, etc.; 0.1-2 portions, for example, 0.2 portions, 0.4 portions, 0.6 portions, 0.8 portions, 1 portion, 1.2 portions, 1.4 portions, 1.6 portions, 1.8 portions, etc.

[0016] Preferably, the white flame-retardant reflective layer is a white flame-retardant reflective layer with a reflectivity of ≥50% in the 730-1400 nm wavelength band (e.g., it can be 50%, 60%, 70%, 80% or 90%).

[0017] Preferably, the matrix resin A and matrix resin B each independently comprise any one of ethylene-vinyl acetate copolymer (EVA), ethylene-α-olefin copolymer (POE), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), ethyl methacrylate copolymer (PEMA), ethylene-butyl acrylate copolymer (EBA), polyvinyl butyral (PVB), or polyurethane (PU), preferably ethylene-vinyl acetate copolymer or ethylene-α-olefin copolymer.

[0018] Preferably, the main crosslinking agent A and the main crosslinking agent B each independently comprise a peroxide-based crosslinking agent.

[0019] Preferably, the peroxide-based crosslinking agent comprises any one or a combination of at least two of the following: 2-ethylhexyl carbonate tert-butyl peroxide, 2-ethylhexyl carbonate tert-pentyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, 3,5,5-trimethylhexanoate tert-butyl peroxide, di(4-methylbenzoyl)peroxide, benzoyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, tert-butylperoxycarbonate-2-ethylhexyl, butyl-4,4-bis(tert-butylperoxy)valerate, dicumyl peroxide, or α,α′-bis(tert-butylperoxy)-1,3-diisopropylbenzene.

[0020] Preferably, the co-crosslinking agent A and co-crosslinking agent B each independently comprise an acrylate crosslinking agent and / or an isocyanurate crosslinking agent.

[0021] Preferably, the acrylate crosslinking agent includes any one or a combination of at least two of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, or ethoxylated pentaerythritol tetraacrylate.

[0022] Preferably, the isocyanurate crosslinking agent includes triallyl isocyanurate.

[0023] Preferably, silane coupling agent A and silane coupling agent B each independently comprise a combination of alkane coupling agent monomers and silane coupling agent oligomers.

[0024] Preferably, the mass ratio of the silane coupling agent monomer to the silane coupling agent oligomer is 1:(0.2-0.8), for example, it can be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, etc.

[0025] Preferably, the silane coupling agent monomer comprises any one or a combination of at least two of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(methacryloylchloro)propyltrimethoxysilane, or 3-(methacryloyloxy)propyltrimethoxysilane.

[0026] Preferably, the number average molecular weight of the silane coupling agent oligomer is 100-5000, for example, it can be 150, 200, 300, 400, 600, 800, 1000, 2000, 3000, 4000, 4500, etc.

[0027] Preferably, the silane coupling agent oligomer includes any one or a combination of at least two of vinyltrimethoxysilane oligomers, vinyltriethoxysilane oligomers, vinyltri(β-methoxyethoxy)silane oligomers, or 3-(methacryloyloxy)propyltrimethoxysilane oligomers.

[0028] Preferably, the black reflective filler includes any one or a combination of at least two of carbon black, iron oxide black, manganese iron black, titanium iron black, copper chromium black, perylene oxide, dioxazine, isoindoline, or indolinone ring.

[0029] Preferably, the white reflective filler comprises any one or a combination of at least two of the following: titanium dioxide, zirconium oxide, calcium carbonate, mica, talc, zinc barium white, ceramic microspheres, aluminum hydroxide, or glass microspheres.

[0030] Preferably, the flame-retardant filler is any one or a combination of at least two of inorganic flame retardants, bromine-based flame retardants, and phosphorus-based flame retardants.

[0031] Preferably, the raw materials of the first black adhesive film layer, the second black adhesive film layer and the white flame-retardant reflective layer, by weight, each independently include 0.05-5.4 parts of light stabilizer, for example, 0.05 parts, 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.4 parts, etc.

[0032] Preferably, the light stabilizer includes an ultraviolet absorber and / or other light stabilizers.

[0033] Preferably, the light stabilizer comprises 0.01-0.4 parts by weight of ultraviolet absorber, such as 0.01 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, etc.

[0034] Preferably, the ultraviolet absorber comprises any one or a combination of at least two of the following: bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6,pentamethylpiperidinyl) sebacate, polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or poly{[6[(1,1,3,3-tetramethylbutyl)amino]]1,3,5-triazine 2,4[(2,2,6,6,tetramethylpiperidinyl)imino]1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}.

[0035] Preferably, the light stabilizer comprises 0.05-5 parts by weight of other light stabilizers.

[0036] Preferably, the other light stabilizers include 2,2'-tetramethylenebis(3,1-benzoxazin-4-one), 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2(2'-hydroxy-5'-aminophenyl)benzotriazole, bisphenol A bis(salicylic acid), 2(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2(2'-methyl-4'-hydroxyphenyl)benzotriazole, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, 2(2'-hydroxy-5-methylphenyl)benzotriazole, 2(2'-hydroxy-5-methylphenyl)-5-carboxylate butyl benzotriazole, 2-hydroxy-4- Alkoxybenzophenone, 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, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine, and 2,4-dichloro-6-(1,1,3,3-tetramethyl) The polymer of 1,3,5-triazine (methylbutyl)amino, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine and 2,4-dichloro-6-(4-morpholinyl)1,3,5-triazine, or N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine and tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite, or any combination of at least two of these polymers.

[0037] In a second aspect, the present invention provides a method for preparing a flame-retardant black encapsulating film according to the first aspect, the method comprising: The raw materials of the first black adhesive film layer, the white flame-retardant reflective layer and the second black adhesive film layer are mixed and co-extruded in multiple layers, and then pre-crosslinked by irradiation to obtain the flame-retardant black encapsulation film.

[0038] Preferably, the equipment for multi-layer co-extrusion is a co-extrusion casting machine.

[0039] Preferably, the raw materials for the first black adhesive film layer, the white flame-retardant reflective layer, and the second black adhesive film layer are melted in the three single-screw extruders of the co-extrusion casting machine.

[0040] Preferably, the melting temperatures of the raw materials for the first black adhesive film layer and the second black adhesive film layer are each independently 55-100℃, for example, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, etc.

[0041] In this invention, when the raw materials for the first and second black adhesive film layers are melted using a single-screw extruder, the temperatures of each zone of the single-screw extruder are independently set as follows: Zone I 55-80℃, Zone II 60-85℃, Zone III 70-100℃, Zone IV 75-100℃, Zone V 75-100℃, Zone VI 80-100℃, and the die head temperature is 95-105℃.

[0042] Among them, 55-80℃ can be, for example, 55℃, 60℃, 65℃, 70℃, 75℃ or 80℃, etc.; 65-85℃ can be, for example, 65℃, 70℃, 75℃, 80℃ or 85℃, etc.; 70-100℃ can be, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃, etc.; 75-100℃ can be, for example, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃, etc.; 80-100℃ can be, for example, 80℃, 85℃, 90℃, 95℃ or 100℃, etc.; 95-105℃ can be, for example, 95℃, 96℃, 98℃, 100℃, 102℃, 104℃ or 105℃, etc.

[0043] Preferably, the melting temperature of the raw material for the white flame-retardant reflective layer is 60-110℃, for example, it can be 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 100℃, etc.

[0044] In this invention, when the raw material for the white flame-retardant reflective layer is melted using a single-screw extruder, the temperatures of each zone of the single-screw extruder are set as follows: Zone I 60-80℃, Zone II 65-85℃, Zone III 70-100℃, Zone IV 85-100℃, Zone V 90-100℃, Zone VI 95-100℃, and the die head temperature is 95-105℃.

[0045] Among them, 60-80℃ can be, for example, 60℃, 65℃, 70℃, 75℃ or 80℃, 65-85℃ can be, for example, 65℃, 70℃, 75℃, 80℃ or 85℃, 70-100℃ can be, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or 100℃, 85-100℃ can be, for example, 85℃, 90℃, 95℃ or 100℃, 90-100℃ can be, for example, 90℃, 95℃ or 100℃, 95-100℃ can be, for example, 95℃, 96℃, 98℃ or 100℃, 95-105℃ can be, for example, 95℃, 96℃, 98℃, 100℃, 102℃, 104℃ or 105℃, etc.

[0046] Preferably, the irradiation dose is 1-50 kGy, for example, it can be 1 kGy, 2 kGy, 4 kGy, 6 kGy, 8 kGy, 10 kGy, 20 kGy, 25 kGy, 30 kGy, 35 kGy, 40 kGy, 45 kGy, etc.

[0047] In this invention, the radiation used for the pre-crosslinking irradiation includes beta rays (electron beams), gamma rays (electromagnetic waves), X-rays (electromagnetic waves), alpha rays (fast helium nuclei), or neutron rays (uncharged particle streams); more preferably, beta rays are generated by a low-energy radiation device with an intensity of less than 5 MeV. After irradiation of the matrix resin, free radicals are generated, and these free radicals react with adjacent carbon chains containing free radicals or double bonds to produce a crosslinking reaction.

[0048] Thirdly, the present invention provides an application of the flame-retardant black encapsulating film as described in the first aspect in photovoltaic modules or decorative glass.

[0049] Preferably, the photovoltaic module includes a single-glass module or a double-glass module.

[0050] Fourthly, the present invention provides a solar photovoltaic module, the solar photovoltaic module comprising a front panel, a transparent film layer, solar cells, a flame-retardant black encapsulating film as described in the first aspect, and a back panel stacked together.

[0051] Preferably, the backplate is glass, KPf backplate, PPf backplate or CPC backplate.

[0052] Compared with the prior art, the present invention has at least the following beneficial effects: (1) The flame-retardant black encapsulating film provided by the present invention has a three-layer structure, including a first black encapsulating film layer, a white flame-retardant reflective layer and a second black encapsulating film layer stacked together. Through the above-mentioned stacked structure design, the resulting flame-retardant black encapsulating film has the characteristics of long-lasting and good adhesion, and can ensure the all-black appearance of the component. The resulting component has a good appearance and the excess adhesive is transparent and easy to clean. At the same time, it also has the characteristics of high flame retardancy and high reflectivity, which can effectively solve the problem of existing conventional encapsulating films being flammable and not fireproof, and improve the power of the component.

[0053] (2) The flame-retardant black encapsulating film provided by the present invention has a reflectivity of 63-77% in the near-infrared band 730-1400 nm, an initial adhesion force of 116-145 N / cm, a tensile strength of 14-17 MPa, an elongation at break of 527-734%, and a burning time of 557-643 s. Attached Figure Description

[0054] Figure 1 A cross-sectional structural diagram of the flame-retardant black encapsulating film provided by the present invention; Among them, 1-first black adhesive film layer, 2-white flame-retardant reflective layer, 3-second black adhesive film layer. Detailed Implementation

[0055] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0056] The specific information of the materials used in the following specific embodiments of the present invention is as follows: Ethylene-vinyl acetate copolymer (EVA): Purchased from Hanwha's 282; Ethylene-α-olefin copolymer (POE): purchased from Dow 8660; Black reflective filler: purchased from BASFPaliogen L0086; White reflective filler: titanium dioxide; Main crosslinking agent: tert-butyl percarbonate-2-ethylhexyl ester (TBEC); Co-crosslinking agent: Triallyl isocyanurate (TAIC); Silane coupling agent monomer: vinyltrimethoxysilane; Silane coupling agent oligomers: vinyltrimethoxysilane oligomers; UV absorber: UV944; Other light stabilizers: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; Flame-retardant filler: Decabromodiphenyl ethane combined with antimony trioxide bromide flame retardant.

[0057] Example 1 Example 1 provides a flame-retardant black encapsulating film and its preparation method, the cross-sectional structure of which is as follows: Figure 1 As shown, it includes a first black adhesive film layer 1, a white flame-retardant reflective layer 2, and a second black adhesive film layer 3, which are stacked together. The first black adhesive film layer 1 and the second black adhesive film layer 3 are both 200 μm thick and are both EVA black adhesive film layers. The raw materials for preparation include 88 parts of ethylene-vinyl acetate copolymer, 10 parts of black reflective filler, 0.8 parts of main crosslinking agent, 0.6 parts of co-crosslinking agent, 0.6 parts of silane coupling agent monomer, 0.3 parts of silane coupling agent oligomer, 0.4 parts of ultraviolet absorber and 0.3 parts of other light stabilizers.

[0058] The white flame-retardant reflective layer 2 has a thickness of 100 μm and is an EVA white flame-retardant reflective layer. The raw materials for its preparation include 75 parts of ethylene-vinyl acetate copolymer, 10 parts of white reflective filler, 0.8 parts of main crosslinking agent, 0.6 parts of co-crosslinking agent, 0.6 parts of silane coupling agent monomer, 0.3 parts of silane coupling agent oligomer, 0.4 parts of ultraviolet absorber, 0.3 parts of other light stabilizers, and 15 parts of flame-retardant filler.

[0059] The preparation method includes: The raw materials for the first black adhesive film layer, the second black adhesive film layer, and the white flame-retardant reflective layer are respectively fed into the three single-screw extruders of the co-extrusion casting machine for melting. When melting the raw materials for the first and second black adhesive film layers using the single-screw extruders, the temperatures of each zone of the single-screw extruder are independently set as follows: Zone I 70℃, Zone II 75℃, Zone III 85℃, Zone IV 90℃, Zone V 95℃, Zone VI 100℃, and the die head temperature is 100℃. When melting the raw material for the white flame-retardant reflective layer using the single-screw extruders, the temperatures of each zone of the single-screw extruder are set as follows: Zone I 70℃, Zone II 75℃, Zone III 85℃, Zone IV 90℃, Zone V 95℃, Zone VI 100℃, and the die head temperature is 100℃. After melting, the material is conveyed to the co-extrusion die. The distributor at the die inlet distributes the molten black film layer to the upper and lower layers, and the molten white flame-retardant reflective layer to the middle layer. The materials are then conveyed to the same co-extrusion die outlet to converge for multi-layer co-extrusion. After that, the material is irradiated and pre-crosslinked with an irradiation device at a dose of 30 kGy to obtain the flame-retardant high-reflective black film.

[0060] Example 2 Example 2 provides a flame-retardant black encapsulating film and its preparation method. The difference from Example 1 is that the thickness of the first black film layer 1 and the second black film layer 3 is 300 μm, both of which are EVA black film layers, and the thickness of the white flame-retardant reflective layer is 200 μm.

[0061] Example 3 Example 3 provides a flame-retardant black encapsulating film and its preparation method, which differs from Example 1 in that: the EVA (ethylene-vinyl acetate copolymer) in the first black film layer, the second black film layer and the white flame-retardant reflective layer are replaced with POE (ethylene-1-octene copolymer) in equal amounts.

[0062] Example 4 Example 4 provides a flame-retardant black encapsulating film and its preparation method. The difference from Example 3 is that the thickness of the first black film layer and the second black film layer is 300 μm, both are POE black film layers, and the thickness of the white flame-retardant reflective layer is 200 μm.

[0063] Comparative Example 1 This comparative example provides a three-layer high-reflectivity black adhesive film and its preparation method, comprising a first black adhesive film layer, a white reflective layer and a second black adhesive film layer stacked together. The difference from Example 1 is as follows: The raw materials for preparing the white reflective layer include 75 parts of ethylene-vinyl acetate copolymer, 10 parts of white reflective filler, 0.8 parts of main crosslinking agent, 0.6 parts of co-crosslinking agent, 0.6 parts of silane coupling agent monomer, 0.3 parts of silane coupling agent oligomer, 0.4 parts of ultraviolet absorber, and 0.3 parts of other light stabilizers.

[0064] Comparative Example 2 This comparative example provides a three-layer high-reflectivity black adhesive film and its preparation method, comprising a first black adhesive film layer, a white reflective layer and a second black adhesive film layer stacked together. The difference from Example 3 is that: The raw materials for preparing the first and second black adhesive film layers include 88 parts of ethylene-1-octene copolymer, 10 parts of black reflective filler, 0.8 parts of main crosslinking agent, 0.6 parts of co-crosslinking agent, 0.6 parts of silane coupling agent monomer, 0.3 parts of silane coupling agent oligomer, 0.4 parts of ultraviolet absorber, and 0.3 parts of other light stabilizers.

[0065] The raw materials for preparing the white reflective layer include 75 parts of ethylene-1-octene copolymer, 10 parts of white reflective filler, 0.8 parts of main crosslinking agent, 0.6 parts of co-crosslinking agent, 0.6 parts of silane coupling agent monomer, 0.3 parts of silane coupling agent oligomer, 0.4 parts of ultraviolet absorber, and 0.3 parts of other light stabilizers.

[0066] Performance testing: (1) Appearance: Visually inspect whether the thickness of the adhesive film is uniform and whether there are defects such as excess adhesive, insufficient adhesive, and bubbles. If none of the above defects are found, the appearance is judged to be good. (2) Reflectance: Tested using an ultraviolet spectrophotometer, in accordance with the test standard GB29848; (3) Initial adhesion: tested using a universal testing machine according to the GB29848 method; (4) Tensile strength and elongation at break: tested using a universal testing machine according to the method of GB / T 1040.1-2006; (5) Burning time: The test shall be conducted in accordance with GB / T 5169.16-2017 "Fire Hazard Tests for Electrical and Electronic Products - Part 16: Test Flame 50W - Horizontal and Vertical Flame Test Method".

[0067] The flame-retardant black encapsulating films provided in Examples 1-4 and Comparative Example 1 were tested according to the above test methods. The test results are shown in Table 1. Table 1 According to the data in Table 1: (1) As can be seen from Examples 1-4, the flame-retardant black encapsulating film provided by the present invention has the characteristics of long-lasting and good adhesion, and can ensure the all-black appearance of the component. The resulting component has uniform thickness, good appearance, and transparent and easy-to-clean excess adhesive. At the same time, it also has the characteristics of high flame retardancy and high reflectivity, which can effectively solve the problem of existing conventional adhesive films being flammable and not fireproof. The reflectivity is 63-77%, the initial adhesion is 116-145 N / cm, the tensile strength is 14-17 MPa, the elongation at break is 527-734%, and the burning time is 557-643 s.

[0068] (2) As can be seen from Examples 1 and 3 and Comparative Examples 1-2, the present invention adds a flame retardant to the white flame retardant high reflective layer, so that the flame retardant high reflective black film has good flame retardant properties; and the basic properties of the film, such as peel strength and tensile properties, can still maintain good performance.

[0069] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A flame-retardant black encapsulating film, characterized in that, The flame-retardant black encapsulating film comprises a first black film layer, a white flame-retardant reflective layer, and a second black film layer, which are stacked together.

2. The flame-retardant black encapsulating film according to claim 1, characterized in that, The thickness of the first black adhesive film layer and the second black adhesive film layer are each independently 200-500 μm; Preferably, the thickness of the white flame-retardant reflective layer is 50-300 μm.

3. The flame-retardant black encapsulating film according to claim 1 or 2, characterized in that, The first black adhesive film layer and the second black adhesive film layer are each independently an EVA black adhesive film layer, a POE black adhesive film layer, an EAA black adhesive film layer, an EEA black adhesive film layer, an EMMA black adhesive film layer, a PEMA black adhesive film layer, an EBA black adhesive film layer, a PVB black adhesive film layer or a PU black adhesive film layer, preferably an EVA black adhesive film layer or a POE black adhesive film layer. Preferably, the white flame-retardant reflective layer is an EVA white flame-retardant reflective layer, a POE white flame-retardant reflective layer, an EAA white flame-retardant reflective layer, an EEA white flame-retardant reflective layer, an EMMA white flame-retardant reflective layer, a PEMA white flame-retardant reflective layer, an EBA white flame-retardant reflective layer, a PVB white flame-retardant reflective layer, or a PU white flame-retardant reflective layer, and more preferably an EVA white flame-retardant reflective layer or a POE white flame-retardant reflective layer. Preferably, the raw materials for preparing the first black adhesive film layer and the second black adhesive film layer each independently include 80-98 parts of matrix resin A, 8-20 parts of black reflective filler, 0.2-2 parts of main crosslinking agent A, 0.2-1 parts of co-crosslinking agent A and 0.1-2 parts of silane coupling agent A; Preferably, the raw materials for preparing the white flame-retardant reflective layer include 60-90 parts of matrix resin B, 8-20 parts of white reflective filler, 0.2-2 parts of main crosslinking agent B, 0.2-1 parts of co-crosslinking agent B, 0.1-2 parts of silane coupling agent B, and 5-30 parts of flame-retardant filler.

4. The flame-retardant black encapsulating film according to any one of claims 1-3, characterized in that, The white flame-retardant reflective layer is a white flame-retardant reflective layer with a reflectivity of ≥50% in the 730-1400 nm wavelength band.

5. The flame-retardant black encapsulating film according to claim 3, characterized in that, The matrix resin A and matrix resin B each independently include any one of ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethyl-methacrylate copolymer, ethylene-butyl acrylate copolymer, polyvinyl butyral, or polyurethane, preferably ethylene-vinyl acetate copolymer or ethylene-α-olefin copolymer. Preferably, the main crosslinking agent A and the main crosslinking agent B each independently comprise a peroxide-based crosslinking agent; Preferably, the peroxide-based crosslinking agent comprises any one or a combination of at least two of the following: 2-ethylhexyl carbonate tert-butyl peroxide, 2-ethylhexyl carbonate tert-pentyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, 3,5,5-trimethylhexanoate tert-butyl peroxide, di(4-methylbenzoyl)peroxide, benzoyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, tert-butylperoxycarbonate-2-ethylhexyl, butyl-4,4-bis(tert-butylperoxy)valerate, dicumyl peroxide, or α,α′-bis(tert-butylperoxy)-1,3-diisopropylbenzene. Preferably, the co-crosslinking agent A and co-crosslinking agent B each independently comprise an acrylate crosslinking agent and / or an isocyanurate crosslinking agent; Preferably, the acrylate crosslinking agent includes any one or a combination of at least two of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, or ethoxylated pentaerythritol tetraacrylate; Preferably, the isocyanurate crosslinking agent includes triallyl isocyanurate; Preferably, silane coupling agent A and silane coupling agent B each independently comprise a combination of silane coupling agent monomer and silane coupling agent oligomer; Preferably, the mass ratio of the silane coupling agent monomer to the silane coupling agent oligomer is 1:(0.2-0.8); Preferably, the silane coupling agent monomer comprises any one or a combination of at least two of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(methacryloylchloro)propyltrimethoxysilane, or 3-(methacryloyloxy)propyltrimethoxysilane. Preferably, the number average molecular weight of the silane coupling agent oligomer is 100-5000; Preferably, the silane coupling agent oligomer includes any one or a combination of at least two of vinyltrimethoxysilane oligomer, vinyltriethoxysilane oligomer, vinyltri(β-methoxyethoxy)silane oligomer or 3-(methacryloyloxy)propyltrimethoxysilane oligomer; Preferably, the black reflective filler includes any one or a combination of at least two of carbon black, iron oxide black, manganese iron black, titanium iron black, copper chromium black, perylene series, dioxazine, isoindoline or indolinone ring; Preferably, the white reflective filler comprises any one or a combination of at least two of the following: titanium dioxide, zirconium oxide, calcium carbonate, mica, talc, zinc barium white, ceramic microspheres, aluminum hydroxide, or glass microspheres. Preferably, the flame-retardant filler is any one or a combination of at least two of inorganic flame retardants, bromine-based flame retardants, and phosphorus-based flame retardants.

6. The flame-retardant black encapsulating film according to claim 3, characterized in that, The raw materials of the first black adhesive film layer, the second black adhesive film layer and the white flame-retardant reflective layer, by weight, each independently include 0.05-5.4 parts of light stabilizer; Preferably, the light stabilizer includes an ultraviolet absorber and / or other light stabilizers; Preferably, the light stabilizer comprises 0.01-0.4 parts by weight of ultraviolet absorber; Preferably, the ultraviolet absorber comprises any one or a combination of at least two of the following: bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6,pentamethylpiperidinyl) sebacate, polysuccinate (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or poly{[6[(1,1,3,3-tetramethylbutyl)amino]]1,3,5-triazine 2,4[(2,2,6,6,tetramethylpiperidinyl)imino]1,6-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}. Preferably, the light stabilizer comprises 0.05-5 parts by weight of other light stabilizers; Preferably, the other light stabilizers include 2,2'-tetramethylenebis(3,1-benzoxazin-4-one), 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2(2'-hydroxy-5'-aminophenyl)benzotriazole, bisphenol A bis(salicylic acid), 2(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2(2'-methyl-4'-hydroxyphenyl)benzotriazole, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, 2(2'-hydroxy-5-methylphenyl)benzotriazole, 2(2'-hydroxy-5-methylphenyl)-5-carboxylate butyl benzotriazole, 2-hydroxy-4- Alkoxybenzophenone, 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, a polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine, and 2,4-dichloro-6-(1,1,3,3-tetramethyl) The polymer of 1,3,5-triazine (methylbutyl)amino, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine and 2,4-dichloro-6-(4-morpholinyl)1,3,5-triazine, or N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,6-hexanediamine and tris(1,2,2,6,6-pentamethyl-4-piperidinyl)phosphite, or any combination of at least two of these polymers.

7. A method for preparing a flame-retardant black encapsulating film as described in any one of claims 1-6, characterized in that, The preparation method includes: The raw materials of the first black adhesive film layer, the white flame-retardant reflective layer and the second black adhesive film layer are mixed and co-extruded in multiple layers, and then pre-crosslinked by irradiation to obtain the flame-retardant black encapsulation film.

8. The method for preparing the flame-retardant black encapsulating film according to claim 7, wherein the multilayer co-extrusion equipment is a co-extrusion casting machine; Preferably, the raw materials for the first black adhesive film layer, the white flame-retardant reflective layer, and the second black adhesive film layer are melted in the three single-screw extruders of the co-extrusion casting machine; Preferably, the melting temperatures of the raw materials for the first black adhesive film layer and the second black adhesive film layer are each independently 55-100°C; Preferably, the melting temperature of the raw material for the white flame-retardant reflective layer is 60-110℃; Preferably, the irradiation dose is 1-50 kGy.

9. The application of a flame-retardant black encapsulating film as described in any one of claims 1-6 in photovoltaic modules or decorative glass.

10. A solar photovoltaic module, characterized in that, The solar photovoltaic module includes a front panel, a transparent film layer, solar cells, a flame-retardant black encapsulating film as described in any one of claims 1-6, and a back panel, all stacked together.

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