Photovoltaic colored adhesive film as well as preparation method and application thereof

Abstract

The invention relates to a photovoltaic colored adhesive film as well as a preparation method and application thereof. The photovoltaic colored adhesive film comprises a first transparent layer, a colored middle layer and a second transparent layer which are sequentially stacked, the colored middle layer comprises the following components in parts by weight: 90-98 parts of a resin matrix A, 0.1-2 parts of a cross-linking agent A, 1-5 parts of a pigment and 0.1-1 part of a light stabilizer A, and the colored middle layer is subjected to pre-crosslinking treatment. According to the invention, the structural design is carried out on the photovoltaic colored adhesive film, the formula of the colored intermediate layer is improved, and the pre-crosslinking treatment is carried out, so that the photovoltaic colored adhesive film which can maintain the colored effect for a long time, is not easy to flow in the assembly laminating process and has good environment resistance is provided.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesive film, in particular to a color adhesive film for photovoltaic and a preparation method and application thereof. BACKGROUND

[0002] Building Integrated Photovoltaics (BIPV) is a technology that integrates solar components into buildings. In addition to power generation, BIPV components also need to have functions such as building materials and aesthetics, which is an inevitable trend of solar development. Colorization of photovoltaic components is one of the core technologies of BIPV.

[0003] However, color photovoltaic components are prone to damage, discoloration or fading, and it is difficult to maintain good color saturation and high power generation performance at the same time. In particular, when exposed to UV light, the color is prone to decomposition, discoloration or fading, affecting the appearance and performance of the component.

[0004] Currently, common color photovoltaic components are mainly realized by UV printing or screen printing on the front plate material (CN108242473A), but this method has high operation risk, is prone to damage, and is prone to wrinkles and size deformation during lamination. The prior art also attempts to use color-coated front plates (CN114350268A) or colored glaze glass (CN217173596U), but these methods still have defects such as uneven color, poor environmental reliability, and low overall light transmittance of the color front plate technology, resulting in significant loss of photovoltaic component power generation efficiency. Moreover, the existing color adhesive film for photovoltaic has a formula that the adhesive film is prone to flow during component lamination (temperature greater than 150°C), resulting in thinning of the component edges and inconsistent component colors, affecting the overall aesthetics and consistency of the component. In addition, the adhesive film still has deficiencies in weather resistance and durability, making it difficult to adapt to more severe environmental conditions, limiting its application in outdoor and other harsh environments.

[0005] CN209339502U discloses a color laminating device, which includes a front plate layer, a color adhesive layer, and a back plate layer. The color adhesive layer is arranged between the front plate layer and the back plate layer and is bonded to the front plate layer and the back plate layer, respectively. The color adhesive layer of this patent is located between the front plate layer and the back plate layer and does not directly contact the outside world, so it is not prone to discoloration and has a long service life. It can also be well bonded to the front plate layer and the back plate layer. However, this patent still has the problem of insufficient weather resistance and durability of the color laminating device.

[0006] CN118374235A discloses a three-layer composite photovoltaic packaging adhesive film, a preparation method thereof and a photovoltaic module. The patent uses an outer layer mixture as the upper and lower surface layer material, an intermediate layer mixture as the intermediate layer material, performs three-layer co-extrusion casting to obtain a co-extrusion adhesive film, and performs electron beam irradiation on the co-extrusion adhesive film. This method can ensure the adhesion between the adhesive film and the glass and the battery, while better avoiding the phenomenon of delamination of the intermediate layer four corners of the adhesive film during lamination, and the delamination and bubble phenomenon of the module after aging. However, the formulation and preparation process of the acrylate grafted ethylene-vinyl acetate copolymer still need to be further optimized.

[0007] Therefore, it has become an urgent problem to develop a colored adhesive film for photovoltaic applications that can persistently maintain color effects, is not prone to flow during module lamination, and has good environmental resistance. SUMMARY

[0008] To solve the above technical problems, the present application provides a colored adhesive film for photovoltaic applications, a preparation method thereof and applications. The colored adhesive film can persistently maintain color effects, is not prone to flow during module lamination, and has good environmental resistance.

[0009] To achieve this purpose, the present application adopts the following technical solutions:

[0010] In a first aspect, the present application provides a colored adhesive film for photovoltaic applications, which comprises a first transparent layer, a colored intermediate layer and a second transparent layer arranged in sequence.

[0011] The colored intermediate layer comprises the following components by weight: resin matrix A 90-98 parts, crosslinking agent A 0.1-2 parts, pigment 1-5 parts and light stabilizer A 0.1-1 part.

[0012] The colored intermediate layer is subjected to pre-crosslinking treatment.

[0013] For example, 90-98 parts can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts or 98 parts, etc.; 0.1-2 parts can be 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts or 2 parts, etc.; 1-5 parts can be 1 parts, 2 parts, 3 parts, 4 parts or 5 parts, etc.; 0.1-1 parts can be 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts or 1 parts, etc.

[0014] The present application provides a color film for photovoltaic devices, which can maintain color effect for a long time, is not easy to flow during lamination, and has good environmental resistance.

[0015] Preferably, the thickness of the first and second transparent layers is independently 50-150 μm, for example, 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm or 150 μm, etc.

[0016] Preferably, the melting point of the first and second transparent layers is independently 40-100℃, for example, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃ or 100℃, etc.

[0017] Preferably, the thickness of the color intermediate layer is 150-500 μm, for example, 150 μm, 200 μm, 300 μm, 400 μm or 500 μm, etc.

[0018] Preferably, the melting point of the color intermediate layer is 40-130℃, for example, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃ or 130℃, etc.

[0019] Preferably, the resin matrix A comprises a medium melting point resin matrix or a low melting point resin matrix.

[0020] Preferably, the melting point of the medium melting point resin matrix is 100-150℃, for example, 100℃, 110℃, 120℃, 130℃, 140℃ or 150℃, etc.

[0021] Preferably, the medium melting point resin matrix comprises any one or a combination of at least two of PE resin, EPPE resin or LDPE resin.

[0022] When the resin matrix A comprises a medium melting point resin matrix, the melting point of the color intermediate layer is 100-130℃, for example, 100℃, 110℃, 120℃ or 130℃, etc.

[0023] Preferably, the melting point of the low melting point resin matrix is less than 100℃, for example, 50℃, 60℃, 70℃, 80℃ or 90℃, etc.

[0024] Preferably, the low melting point resin matrix comprises any one or a combination of at least two of EVA resin, POE resin, EMMA resin or EBA resin.

[0025] When the resin matrix A comprises a low-melting-point resin matrix, the melting point of the colored intermediate layer is less than 100°C but greater than or equal to 40°C, for example, can be 40°C, 50°C, 60°C, 70°C, 80°C, or 90°C, etc.

[0026] In the present application, when the colored intermediate layer of the colored adhesive film for photovoltaic uses adopts a low-melting-point resin matrix or a medium-melting-point resin matrix, the melting point of the colored intermediate layer is lower than the lamination temperature of the module, and the colored intermediate layer melts and flows during the lamination process of the module, and needs to be pre-crosslinked.

[0027] However, the melting point of the high-melting-point resin matrix is greater than 150°C, and includes any one or a combination of at least two of PET resin, PC resin, or ETFE resin. When the colored intermediate layer comprises a high-melting-point resin matrix, the melting point of the colored intermediate layer is 250-260°C. When the colored intermediate layer of the colored adhesive film for photovoltaic uses adopts a high-melting-point resin matrix, the melting point of the colored intermediate layer is higher than the lamination temperature, and the colored intermediate layer does not melt during the lamination process, and does not need to be pre-crosslinked.

[0028] Preferably, the pigment comprises an organic pigment.

[0029] Preferably, the organic pigment comprises any one or a combination of at least two of azo pigment, phthalocyanine pigment, triarylmethane pigment, or polycyclic pigment.

[0030] Preferably, the colored intermediate layer further comprises a coupling agent A in an amount of 0.05-0.5 parts by weight, for example, can be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, or 0.5 parts, etc.

[0031] Preferably, the coupling agent A comprises any one or a combination of at least two of amino-based silane coupling agent, epoxy-based silane coupling agent, ethoxy-based silane coupling agent, or methacrylic acid-based silane coupling agent, and is further preferably an epoxy-based silane coupling agent.

[0032] Preferably, the epoxy-based silane coupling agent comprises 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and / or 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane.

[0033] The present application preferably uses an epoxy-based silane coupling agent, in particular 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane and / or 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, which has an epoxycyclohexane structure that is more stable under ultraviolet irradiation than the epoxypolypropylene structure of the commonly used KH-560 epoxy-based silane coupling agent, and is less likely to undergo chemical bond rupture or structural change, thereby further reducing the yellowing and discoloration of the adhesive film caused by chemical reaction.

[0034] Preferably, the first transparent layer and the second transparent layer each independently comprise the following components by weight: 90-98 parts of resin matrix B, 0.1-2 parts of crosslinking agent B, 0.05-0.5 parts of coupling agent B, 0.1-1 parts of light stabilizer B, and 0.1-1 parts of ultraviolet absorber.

[0035] Among them, 90-98 portions can be, for example, 90 portions, 91 portions, 92 portions, 93 portions, 94 portions, 95 portions, 96 portions, 97 portions, or 98 portions, etc.; 0.1-2 portions can be, for example, 0.1 portions, 0.2 portions, 0.4 portions, 0.6 portions, 0.6 portions, 0.8 portions, 1 portion, 1.2 portions, 1.4 portions, 1.5 portions, 1.6 portions, 1.8 portions, or 2 portions, etc.; 0.05-0.5 portions can be, for example, 0.05 portions, 0.1 portions, 0.2 portions, 0.3 portions, 0.4 portions, or 0.5 portions, etc.; 0.1-1 portion can be, for example, 0.1 portions, 0.2 portions, 0.4 portions, 0.5 portions, 0.6 portions, 0.8 portions, or 1 portion, etc.

[0036] The photovoltaic colored film provided by this invention adopts a three-layer structure design, including a first transparent layer, a colored intermediate layer and a second transparent layer stacked in sequence. The addition of an ultraviolet absorber to the transparent layer can effectively prevent the decomposition and fading of the colored intermediate layer by UV light, significantly improve the durability and stability of the color, and solve the problem of easy discoloration of existing colored films.

[0037] Preferably, the resin matrix B comprises EVA resin.

[0038] Preferably, crosslinking agent A and crosslinking agent B each independently comprise a primary crosslinking agent and / or a secondary crosslinking agent.

[0039] Preferably, the main crosslinking agent includes any one or a combination of at least two of peroxide ester crosslinking agents, peroxide ketal crosslinking agents, or dioxyperoxides.

[0040] Preferably, the crosslinking agent comprises any one or a combination of at least two of isocyanates, acrylates, or cyanates.

[0041] Preferably, the coupling agent B comprises any one or a combination of at least two of amino-based silane coupling agents, epoxy-based silane coupling agents, ethoxy-based silane coupling agents, or methacrylate-based silane coupling agents.

[0042] Preferably, light stabilizer A and light stabilizer B each independently comprise a phenolic light stabilizer.

[0043] Preferably, the ultraviolet absorber comprises 2,4-dimethacrylate-2,4-dimethacrylate.

[0044] Preferably, the first transparent layer and the second transparent layer further comprise an antioxidant 0.1-1 parts by weight and / or a polymerization inhibitor 0.1-1 parts by weight.

[0045] The 0.1-1 parts by weight may be, for example, 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts or 1 part, etc.

[0046] Preferably, the antioxidant comprises a phenolic antioxidant.

[0047] Preferably, the polymerization inhibitor comprises any one or a combination of at least two of a free radical polymerization inhibitor, a phenolic polymerization inhibitor, an ether polymerization inhibitor, a quinone polymerization inhibitor, an inorganic polymerization inhibitor or an aromatic amine polymerization inhibitor.

[0048] Preferably, the free radical polymerization inhibitor comprises any one or a combination of at least two of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate nitroxide, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl or 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl.

[0049] Preferably, the phenolic polymerization inhibitor comprises any one or a combination of at least two of hydroquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butyl-hydroquinone or 2-tert-butyl-hydroquinone.

[0050] Preferably, the quinone polymerization inhibitor comprises p-benzoquinone and / or methylhydroquinone.

[0051] Preferably, the inorganic polymerization inhibitor comprises any one or a combination of at least two of ferric chloride, cuprous chloride, copper sulfate, titanium trichloride, sodium sulfate or ammonium thiocyanate.

[0052] In a second aspect, the present application provides a method for preparing the colored adhesive film for photovoltaic as described in the first aspect, which comprises the following steps:

[0053] The components of the first transparent layer, the colored intermediate layer and the second transparent layer are mixed respectively, and the colored adhesive film for photovoltaic is obtained after molding.

[0054] Preferably, when the resin matrix A in the colored intermediate layer comprises a medium-melting-point resin matrix, the method for preparing the colored adhesive film for photovoltaic comprises the following steps:

[0055] (1) The components of the colored intermediate layer are mixed, and then cast molding is performed, and the colored intermediate layer is obtained after pre-crosslinking treatment.

[0056] (2) the premix of the components of the first transparent layer and the premix of the components of the second transparent layer are separately cast onto the two sides of the color intermediate layer to obtain the color adhesive film for photovoltaic.

[0057] Preferably, the temperature of the casting is 70-100℃, for example, it can be 70℃, 80℃, 90℃ or 100℃, etc.

[0058] Preferably, the pre-crosslinking treatment comprises electron beam irradiation treatment.

[0059] Preferably, the irradiation dose of the electron beam irradiation treatment is 10-60 kGy, for example, it can be 10 kGy, 20 kGy, 30 kGy, 40 kGy, 50 kGy or 60 kGy, etc.

[0060] Preferably, the crosslinking degree of the color intermediate layer after the pre-crosslinking treatment is 60-85%, for example, it can be 60%, 65%, 70%, 75%, 80% or 85%, etc.

[0061] Preferably, the temperature of the casting is 80-100℃, for example, it can be 80℃, 85℃, 90℃, 95℃ or 100℃, etc.

[0062] When the resin matrix A in the color intermediate layer of the present application comprises a medium-melting-point resin matrix (melting point is 100-150℃), the assembly lamination temperature is greater than the melting point of the medium-melting-point resin matrix, and the color intermediate layer will melt during lamination. Therefore, the present application adopts the process of casting the color intermediate layer in advance, then crosslinking treatment, so that the crosslinking degree of the color intermediate layer reaches 60-85%, and then casting the transparent layers on both sides of the color intermediate layer. The color intermediate layer will not flow during lamination, resulting in deformation of the adhesive film.

[0063] Preferably, when the resin matrix A in the color intermediate layer comprises a low-melting-point resin matrix, the preparation method of the color adhesive film for photovoltaic comprises the following steps:

[0064] The components of the first transparent layer, the color intermediate layer and the second transparent layer are mixed respectively, and the color adhesive film for photovoltaic is obtained by three-layer co-extrusion molding and pre-crosslinking treatment.

[0065] Preferably, the temperature of the three-layer co-extrusion molding is 80-100℃, for example, it can be 80℃, 85℃, 90℃, 95℃ or 100℃, etc.

[0066] Preferably, the pressure of the three-layer co-extrusion molding is 0.5-1 MPa, for example, it can be 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa or 1 MPa, etc.

[0067] Preferably, the pre-crosslinking treatment comprises electron beam irradiation treatment.

[0068] Preferably, the irradiation dose of the electron beam irradiation treatment is 10-30 kGy, for example, can be 10 kGy, 15 kGy, 20 kGy, 25 kGy or 30 kGy, etc.

[0069] Preferably, the crosslinking degree of the color intermediate layer after the pre-crosslinking treatment is 70-85%, for example, can be 70%, 75%, 80% or 85%, etc.

[0070] Preferably, the crosslinking degree of the first transparent layer and the second transparent layer after the pre-crosslinking treatment is each independently less than 5%, for example, can be 1%, 2%, 3%, 4% or 4.5%, etc.

[0071] When the resin matrix A in the color intermediate layer of the present application comprises a low-melting-point resin matrix (melting point less than 100℃), the assembly lamination temperature is greater than the melting point of the low-melting-point resin matrix, and the color intermediate layer will melt during lamination. Therefore, the present application adopts a process of three-layer co-extrusion molding and then pre-crosslinking, so that the color intermediate layer does not flow during lamination, causing the size of the adhesive film to deform, and the first transparent layer and the second transparent layer are added with a polymerization inhibitor or an antioxidant, so that they do not crosslink, ensuring that the transparent layer has good peel strength.

[0072] However, if the resin matrix A in the color intermediate layer comprises a high-melting-point resin matrix, the preparation method of the colored adhesive film for photovoltaic use comprises the following steps:

[0073] (1) After mixing the components of the color intermediate layer, cast molding is performed to obtain the color intermediate layer;

[0074] (2) The premix of the components of the first transparent layer and the premix of the components of the second transparent layer are separately coated onto both sides of the color intermediate layer to obtain the colored adhesive film for photovoltaic use.

[0075] If the resin matrix A in the color intermediate layer comprises a high-melting-point resin matrix (melting point > 150℃), the process of pre-casting the intermediate layer and then coating the transparent layer on both sides of the color intermediate layer is adopted. Since the melting point of the resin matrix A used is greater than the lamination temperature, the color intermediate layer will not flow during lamination, and the size of the adhesive film will not change, and it does not need to be pre-crosslinked.

[0076] In a third aspect, the present application provides a colored adhesive film for photovoltaic use in a photovoltaic assembly as described in the first aspect.

[0077] Compared with the prior art, the present application has at least the following beneficial effects:

[0078] (1) The photovoltaic color adhesive film provided by the present application has the advantages of persistent color effect, no easy flow in the component lamination process, and good environmental performance.

[0079] (2) The photovoltaic color adhesive film provided by the present application has the advantages of persistent color effect, no easy flow in the component lamination process, and good environmental performance.

[0080] (3) The photovoltaic color adhesive film provided by the present application has the advantages of persistent color effect, no easy flow in the component lamination process, and good environmental performance. The surface of the component after lamination is flat, without folds, concave-convex, and wave phenomena. DETAILED DESCRIPTION

[0081] In order to facilitate the understanding of the present application, the present application lists the following examples. It should be understood by those skilled in the art that the examples are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0082] In the following specific embodiments of the present application, the specific information of the materials used is as follows:

[0083] EVA resin: E282PV, purchased from Huanhua, melting point is 72℃;

[0084] LDPE resin: 18D, purchased from Daqing Petrochemical, melting point is 112℃;

[0085] Main crosslinking agent: t-butyl peroxy-2-ethylhexyl carbonate (TBEC), purchased from Arkema;

[0086] Co-catalyst: triallyl isocyanurate (TAIC), purchased from Hunan Minhe;

[0087] Coupling agent A: KH-570, purchased from Anhui Silicon Bao;

[0088] Coupling agent B: GX-171, purchased from Anhui Silicon Bao;

[0089] Pigment: Yellow HGR, purchased from Clariant;

[0090] UV absorber: UV531, purchased from Suqian Liansheng;

[0091] Antioxidant: antioxidant BHT, purchased from Suqian Liansheng;

[0092] Light stabilizer: light stabilizer 770, purchased from Suqian Liansheng.

[0093] Example 1

[0094] The embodiment provides a color adhesive film for photovoltaic and a preparation method thereof, the color adhesive film for photovoltaic comprises a first transparent layer, a color intermediate layer and a second transparent layer which are sequentially and layerwisely arranged, and the thicknesses are 100 microns, 350 microns and 100 microns respectively.

[0095] The color intermediate layer comprises the following components in parts by weight: EVA resin 95 parts, TBEC 0.7 part, TAIC 1 part, KH-570 0.3 part, pigment YellowHGR 3 parts and light stabilizer 770 0.2 part.

[0096] The melting point of the color intermediate layer is 75 DEG C.

[0097] The first transparent layer and the second transparent layer are the same in components and comprise the following components in parts by weight: EVA resin 95 parts, TBEC 0.5 part, TAIC 0.5 part, GX-171 0.3 part, light stabilizer 770 0.5 part, ultraviolet absorber UV531 0.5 part, antioxidant BHT 0.1 part.

[0098] The melting point of the first transparent layer and the second transparent layer is 60 DEG C.

[0099] The preparation method of the color adhesive film for photovoltaic comprises the following steps:

[0100] The components of the first transparent layer, the color intermediate layer and the second transparent layer are mixed respectively, and the color adhesive film for photovoltaic is obtained after three-layer co-extrusion molding (90 DEG C, 0.8 MPa) and pre-crosslinking treatment (electron beam irradiation treatment, 25 kGy), the pre-crosslinking degree of the color intermediate layer is 82%, and the pre-crosslinking degrees of the first transparent layer and the second transparent layer are 4.4%.

[0101] Embodiment 2

[0102] The embodiment provides a color adhesive film for photovoltaic and a preparation method thereof, the color adhesive film for photovoltaic comprises a first transparent layer, a color intermediate layer and a second transparent layer which are sequentially and layerwisely arranged, and the thicknesses are 100 microns, 350 microns and 100 microns respectively;

[0103] The color intermediate layer comprises the following components in parts by weight: LDPE resin 90 parts, TAIC 0.8 part, pigment YellowHGR 1 part and light stabilizer 770 0.5 part.

[0104] The melting point of the color intermediate layer is 120 DEG C.

[0105] The first transparent layer and the second transparent layer have the same components and include, by weight parts, EVA resin 90 parts, TBEC 0.3 parts, TAIC 0.1 part, GX-171 0.1 part, light stabilizer 770 0.1 part, ultraviolet absorber UV531 0.1 part, and antioxidant BHT 0.1 part.

[0106] The first transparent layer and the second transparent layer have a melting point of 60℃.

[0107] The preparation method of the colored adhesive film for photovoltaics includes the following steps:

[0108] The components of the first transparent layer, the colored intermediate layer, and the second transparent layer are mixed respectively, the colored intermediate layer is subjected to flow casting (90℃) and pre-crosslinking treatment (electron beam irradiation treatment, 50 kGy), the premix of the components of the first transparent layer and the premix of the components of the second transparent layer are respectively subjected to curtain coating (the temperature of curtain coating is 90℃) on both sides of the colored intermediate layer to obtain the colored adhesive film for photovoltaics, the crosslinking degree of the colored intermediate layer is 62%, and the crosslinking degree of the first transparent layer and the second transparent layer is 3.2%.

[0109] Example 3

[0110] The embodiment provides a colored adhesive film for photovoltaics and a preparation method thereof, the colored adhesive film for photovoltaics includes a first transparent layer, a colored intermediate layer, and a second transparent layer which are sequentially stacked and arranged, and the thicknesses are 100 μm, 350 μm, and 100 μm respectively.

[0111] The colored intermediate layer includes, by weight parts, EVA resin 98 parts, TBEC 1.5 parts, TAIC 0.5 part, KH-570 0.1 part, pigment YellowHGR 5 parts, and light stabilizer 770 1 part.

[0112] The colored intermediate layer has a melting point of 70℃.

[0113] The first transparent layer and the second transparent layer have the same components and include, by weight parts, EVA resin 98 parts, TBEC 1.5 parts, TAIC 0.5 part, GX-171 0.5 part, light stabilizer 770 0.8 part, ultraviolet absorber UV531 0.8 part, and antioxidant BHT 0.8 part.

[0114] The first transparent layer and the second transparent layer have a melting point of 70℃.

[0115] The preparation method of the colored adhesive film for photovoltaics includes the following steps:

[0116] The components of the first transparent layer, the color intermediate layer and the second transparent layer are mixed respectively, and the color adhesive film for photovoltaic is obtained after three-layer co-extrusion molding (90℃, 0.8 MPa), pre-crosslinking treatment (electron beam irradiation treatment, 25 kGy), the crosslinking degree of the color intermediate layer is 83%, and the crosslinking degree of the first transparent layer and the second transparent layer is 4.7%.

[0117] Example 4

[0118] The embodiment provides a color adhesive film for photovoltaic and a preparation method thereof, and the difference from the embodiment 1 is that the components of the first transparent layer and the second transparent layer do not include an ultraviolet absorber.

[0119] Example 5

[0120] The embodiment 5 provides a color adhesive film for photovoltaic and a preparation method thereof, and the difference from the embodiment 1 is that the coupling agent A in the color intermediate layer component is replaced by an equal amount of coupling agent KH560 (purchased from Anhui Silicon Bao).

[0121] Example 6

[0122] The embodiment 6 provides a color adhesive film for photovoltaic and a preparation method thereof, and the difference from the embodiment 1 is that the coupling agent A in the color intermediate layer component is replaced by an equal amount of coupling agent 6030 (purchased from Anhui Silicon Bao).

[0123] Comparative Example 1

[0124] The comparative example provides a color adhesive film for photovoltaic and a preparation method thereof, and the difference from the embodiment 1 is that the color adhesive film for photovoltaic is not subjected to pre-crosslinking treatment after three-layer co-extrusion molding.

[0125] Comparative Example 2

[0126] The comparative example provides a color adhesive film for photovoltaic and a preparation method thereof, and the difference from the embodiment 2 is that the color intermediate layer is not subjected to pre-crosslinking treatment after flow molding, but is directly subjected to film coating.

[0127] Comparative Example 3

[0128] The embodiment provides a color adhesive film for photovoltaic and a preparation method thereof, and the color adhesive film for photovoltaic includes a first transparent layer and a color intermediate layer, and the thicknesses are 200 μm, 350 μm in sequence.

[0129] The color intermediate layer includes the following components according to weight parts: 95 parts of EVA resin, 0.7 parts of main crosslinking agent, 1 part of auxiliary crosslinking agent, 0.3 parts of coupling agent A, 3 parts of pigment, and 0.2 parts of light stabilizer A.

[0130] The melting point of the color intermediate layer is 75℃.

[0131] The first transparent layer comprises, by weight parts: EVA resin 95 parts, main crosslinking agent 0.5 parts, auxiliary crosslinking agent 0.5 parts, coupling agent B 0.3 parts, light stabilizer B 0.5 parts, ultraviolet absorber 0.5 parts, antioxidant 0.1 parts.

[0132] The melting point of the first transparent layer is 60℃.

[0133] The preparation method of the color adhesive film for photovoltaic comprises the following steps:

[0134] The components of the first transparent layer and the color intermediate layer are respectively mixed, and then the color adhesive film for photovoltaic is obtained after double-layer co-extrusion molding (90℃, 0.8MPa), pre-crosslinking treatment (electron beam irradiation treatment, 25 kGy), the pre-crosslinking degree of the color intermediate layer is 82%, and the pre-crosslinking degree of the first transparent layer is 4.4%.

[0135] Comparative Example 4

[0136] The present comparative example provides a color adhesive film for photovoltaic and a preparation method thereof, comprising a first transparent layer, a color intermediate layer and a second transparent layer which are sequentially stacked from top to bottom, the thicknesses of the first transparent layer, the color intermediate layer and the second transparent layer are 50 μm, 450 μm and 50 μm respectively.

[0137] The color intermediate layer comprises, by weight parts: POE resin 80 parts, Permanent Orange HSL 20 parts, 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane 0.7 parts, triallyl cyanurate TAC 0.7 parts, coupling agent 6030 0.8 parts, antioxidant BHT 0.3 parts.

[0138] The melting point of the color intermediate layer is 75℃.

[0139] The components of the first transparent layer and the second transparent layer are the same, comprising, by weight parts: POE resin 100 parts, 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane 0.7 parts, triallyl cyanurate TAC 0.7 parts, coupling agent 6030 0.8 parts, antioxidant BHT 0.3 parts, ultraviolet absorber 531 0.5 parts.

[0140] The melting points of the first transparent layer and the second transparent layer are 75℃.

[0141] The raw materials of the color adhesive film layer and the transparent adhesive film layer are respectively mixed uniformly, and then plasticized by a co-extrusion casting machine and extruded and cast into a film by a T-shaped die, the processing temperature is set to 90℃, then shaped by three rollers, and then cooled at 20℃ to obtain the color adhesive film for photovoltaic.

[0142] Test method

[0143] The test method for the melting point of the resin matrix is to refer to GB / T 19466.3-2004 for testing;

[0144] The test method for the crosslinking degree of the adhesive film is to refer to GB / T 36965-2018 for testing;

[0145] The color adhesive film for photovoltaic provided by Examples 1-6 and Comparative Examples 1-4 is subjected to the following performance tests:

[0146] UV yellowing resistance: tested according to GB / T 36965-2018, the after UV 120 kWh is only 1.3-2.2.

[0147] Appearance: tested according to T / CPIA0004-2017, the lamination temperature is 145℃, and the lamination pressure is-50 kPa.

[0148] The test results are shown in Table 1 below:

[0149] Table 1

[0150]

[0151] From the test results, it can be seen that:

[0152] (1) From Examples 1 to 6, it can be seen that the color adhesive film for photovoltaic provided by the present application has excellent yellowing resistance, and the after UV 120 kWh is only 1.3-2.2, and the surface of the component after lamination is flat, without folds, unevenness, waves, etc.

[0153] (2) From Examples 1 and 4-6, it can be seen that by further introducing an ultraviolet absorber and a specific coupling agent into the first transparent layer and the second transparent layer, the present application can achieve better UV yellowing resistance.

[0154] (3) From Examples 1 and Comparative Examples 1-3, it can be seen that by using different film forming methods for different resin systems, and by designing the structure of the color adhesive film for photovoltaic, and by pre-crosslinking the color intermediate layer, the present application achieves the flatness of the appearance after lamination of the component.

[0155] (4) From Examples 1 and Comparative Example 4, it can be seen that the color adhesive film for photovoltaic provided by the present application has more excellent UV yellowing resistance and appearance of the component after lamination compared with the color adhesive film for photovoltaic provided by the prior art.

[0156] The applicant states that the above description is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and it should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily thought out by those skilled in the art, and all of them fall within the protection scope and disclosure scope of the present application.

Claims

1. A colored adhesive film for photovoltaic applications, characterized in that, The photovoltaic colored film includes a first transparent layer, a colored intermediate layer, and a second transparent layer stacked sequentially. The colored intermediate layer comprises the following components by weight: 90-98 parts of resin matrix A, 0.1-2 parts of crosslinking agent A, 1-5 parts of pigment, and 0.1-1 parts of light stabilizer A; The colored intermediate layer is pre-crosslinked.

2. The colored adhesive film for photovoltaic applications according to claim 1, characterized in that, The thickness of the first transparent layer and the second transparent layer are each independently 50-150 μm; Preferably, the melting points of the first transparent layer and the second transparent layer are each independently 40-100°C; Preferably, the thickness of the colored intermediate layer is 150-500 μm; Preferably, the melting point of the colored intermediate layer is 40-130℃.

3. The photovoltaic colored adhesive film according to claim 1 or 2, characterized in that, The resin matrix A includes a medium-melting-point resin matrix or a low-melting-point resin matrix; Preferably, the melting point of the medium-melting-point resin matrix is ​​100-150°C; Preferably, the medium-melting-point resin matrix includes any one or a combination of at least two of PE resin, EPPE resin, or LDPE resin; Preferably, the melting point of the low-melting-point resin matrix is ​​less than 100°C; Preferably, the low-melting-point resin matrix includes any one or a combination of at least two of EVA resin, POE resin, EMMA resin, or EBA resin.

4. The photovoltaic colored encapsulant film according to any one of claims 1-3, characterized in that, The pigments include organic pigments; Preferably, the organic pigment includes any one or a combination of at least two of azo pigments, phthalocyanine pigments, triarylmethane pigments, or polycyclic pigments.

5. The colored encapsulant film for photovoltaic applications according to any one of claims 1-4, characterized in that, The colored intermediate layer also includes 0.05-0.5 parts of coupling agent A by weight; Preferably, the coupling agent A comprises any one or a combination of at least two of amino-based silane coupling agents, epoxy-based silane coupling agents, ethoxy-based silane coupling agents, or methacrylate-based silane coupling agents, and more preferably an epoxy-based silane coupling agent; Preferably, the epoxy-based silane coupling agent includes 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and / or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

6. The colored encapsulant film for photovoltaic applications according to any one of claims 1-5, characterized in that, The first transparent layer and the second transparent layer each independently comprise the following components by weight: 90-98 parts of resin matrix B, 0.1-2 parts of crosslinking agent B, 0.05-0.5 parts of coupling agent B, 0.1-1 parts of light stabilizer B, and 0.1-1 parts of ultraviolet absorber; Preferably, the resin matrix B comprises EVA resin; Preferably, crosslinking agent A and crosslinking agent B each independently comprise a primary crosslinking agent and / or a co-crosslinking agent; Preferably, the main crosslinking agent includes any one or a combination of at least two of the following: peroxide ester crosslinking agents, peroxide ketal crosslinking agents, or dioxyperoxides; Preferably, the co-crosslinking agent comprises any one or a combination of at least two of isocyanates, acrylates, or cyanates; Preferably, the coupling agent B comprises any one or a combination of at least two of amino-based silane coupling agents, epoxy-based silane coupling agents, ethoxy-based silane coupling agents, or methacrylate-based silane coupling agents; Preferably, light stabilizer A and light stabilizer B each independently comprise a phenolic light stabilizer; Preferably, the ultraviolet absorber comprises 2,4-dimethacrylate-2,4-dimethacrylate; Preferably, the first transparent layer and the second transparent layer further include 0.1-1 parts by weight of antioxidant and / or 0.1-1 parts by weight of polymerization inhibitor; Preferably, the antioxidant includes phenolic antioxidants; Preferably, the polymerization inhibitor includes any one or a combination of at least two of the following: free radical polymerization inhibitors, phenolic polymerization inhibitors, ether polymerization inhibitors, quinone polymerization inhibitors, inorganic polymerization inhibitors, or aromatic amine polymerization inhibitors; Preferably, the free radical polymerization inhibitor comprises any one or a combination of at least two of the following: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate nitroxide free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxo free radical, or 4-oxo-2,2,6,6-tetramethylpiperidin-1-oxo free radical. Preferably, the phenolic polymerization inhibitor includes any one or a combination of at least two of hydroquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, or 2-tert-butylhydroquinone. Preferably, the quinone polymerization inhibitor includes p-benzoquinone and / or methylhydroquinone; Preferably, the inorganic polymerization inhibitor comprises any one or a combination of at least two of ferric chloride, cuprous chloride, copper sulfate, titanium trichloride, sodium sulfate, or ammonium thiocyanate.

7. A method for preparing a colored photovoltaic film as described in any one of claims 1-6, characterized in that, The method for preparing the photovoltaic colored adhesive film includes the following steps: The components of the first transparent layer, the colored intermediate layer, and the second transparent layer are mixed separately and then molded to obtain the colored encapsulant film for photovoltaic applications.

8. The method for preparing a colored photovoltaic film according to claim 7, characterized in that, When the resin matrix A in the colored intermediate layer includes a medium-melting-point resin matrix, the method for preparing the photovoltaic colored encapsulant film includes the following steps: (1) After mixing the components of the colored intermediate layer, the mixture is cast and then pre-crosslinked to obtain the colored intermediate layer; (2) The premix of the components of the first transparent layer and the premix of the components of the second transparent layer are respectively coated onto both sides of the colored intermediate layer to obtain the colored film for photovoltaic use; Preferably, the casting temperature is 70-100℃; Preferably, the pre-crosslinking treatment includes electron beam irradiation treatment; Preferably, the irradiation dose of the electron beam irradiation treatment is 10-60 kGy; Preferably, the degree of crosslinking of the pre-crosslinked colored intermediate layer is 60-85%; Preferably, the temperature of the coating is 80-100℃.

9. The method for preparing a colored photovoltaic film according to claim 7, characterized in that, When the resin matrix A in the colored intermediate layer includes a low-melting-point resin matrix, the method for preparing the photovoltaic colored encapsulant film includes the following steps: The components of the first transparent layer, the colored intermediate layer, and the second transparent layer are mixed separately, and then co-extruded and pre-crosslinked to obtain the photovoltaic colored film. Preferably, the temperature of the three-layer co-extrusion molding is 80-100℃; Preferably, the pressure of the three-layer co-extrusion molding is 0.5-1 MPa; Preferably, the pre-crosslinking treatment includes electron beam irradiation treatment; Preferably, the irradiation dose of the electron beam irradiation treatment is 10-30 kGy; Preferably, the degree of crosslinking of the pre-crosslinked colored intermediate layer is 70-85%; Preferably, after the pre-crosslinking treatment, the degree of crosslinking of the first transparent layer and the second transparent layer is independently less than 5%.

10. The application of a photovoltaic colored encapsulant film as described in any one of claims 1-6 in a photovoltaic module.

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