Thermoplastic composite board, preparation method thereof, photovoltaic backboard and solar photovoltaic device

Abstract

The invention relates to a thermoplastic composite board, a preparation method thereof, a photovoltaic backboard and a solar photovoltaic device. The thermoplastic composite board comprises continuous fiber thermoplastic one-way prepreg tapes which are arranged in a stacked mode. The continuous fiber thermoplastic unidirectional prepreg tape comprises the following components in percentage by mass: 22%-59.9% of polyamide, 40%-70% of continuous glass fiber and 0.1%-8% of a functional aid, in two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extension directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction are mutually crossed. The thermoplastic composite board is good in aging resistance and weather resistance, not prone to cracking and environmentally friendly.

Description

Technical Field

[0001] The present application relates to the technical field of composite board materials, and in particular to a thermoplastic composite board material and a preparation method thereof, a photovoltaic backboard, and a solar photovoltaic device. Background Art

[0002] As the global demand for renewable energy continues to increase, solar photovoltaic power generation has been widely used as a clean and renewable energy technology. Photovoltaic backsheet is an important component of solar cell modules. Its main function is to protect solar cells from external environmental influences such as ultraviolet rays, moisture, temperature changes, etc. At the same time, photovoltaic backsheets also need to have good electrical insulation performance, aging resistance and mechanical strength.

[0003] At present, the commonly used photovoltaic backplanes on the market mainly include 3A backplanes, polyolefin co-extruded backplanes and fluorine-containing backplanes. Among them, the polyolefin co-extruded backplane is made of polyolefin materials through a co-extrusion process, and has the advantages of low cost and light weight, but its aging resistance and weather resistance are poor. The fluorine-containing backplane is made of fluorine-containing materials, such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc., which have excellent aging resistance and weather resistance, but the cost is high and it is not easy to recycle, causing certain pollution to the environment. The 3A backplane is composed of three layers of nylon (polyamide) 12 material. Although it has certain aging resistance and weather resistance, it is prone to cracking after long-term use. Summary of the invention

[0004] Based on this, the present application provides a thermoplastic composite sheet material having good aging resistance and weather resistance, not prone to cracking and environmentally friendly, and a preparation method thereof, a photovoltaic backplane, and a solar photovoltaic device.

[0005] In a first aspect of the present application, a thermoplastic composite plate is provided, comprising continuous fiber thermoplastic unidirectional prepreg tapes stacked in layers; in terms of mass percentage, the continuous fiber thermoplastic unidirectional prepreg tapes comprise:

[0006] Polyamide 22%~59.9%, continuous glass fiber 40%~70% and functional additives 0.1%~8%;

[0007] In two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extending directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction intersect each other.

[0008] In some embodiments, the angle between the first direction and the second direction is 60°~120°.

[0009] In some embodiments, the continuous glass fiber has at least one of the following characteristics:

[0010] (1) The diameter of the continuous glass fiber is 13 μm to 17 μm;

[0011] (2) The continuous glass fiber is an alkali-free glass fiber.

[0012] In some embodiments, the functional additives include one or more of a compatible toughening agent, a lubricant, an antioxidant, and an anti-ultraviolet additive;

[0013] Optionally, the continuous fiber thermoplastic unidirectional prepreg tape comprises, by mass percentage:

[0014] Polyamide 22%~59.9%, continuous glass fiber 40%~70%, compatible toughening agent 0%~5%, antioxidant 0.05%~1%, lubricant 0%~1% and anti-ultraviolet additive 0.05%~1%.

[0015] In some of the embodiments, the compatible toughening agent in the material of the continuous fiber thermoplastic unidirectional prepreg tape has one or more of the following characteristics, measured by mass percentage:

[0016] (1) In terms of mass percentage, the compatible toughening agent is 2% to 5%;

[0017] (2) The compatible toughening agent includes a copolymer of a polar monomer and a polymer elastomer;

[0018] Optionally, the polar monomer includes one or more of maleic anhydride and its derivatives, acrylate and its derivatives, and glycidyl methacrylate;

[0019] Optionally, the polymer elastomer includes one or more of polyolefins, ethylene-α-olefin copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, styrene-butadiene copolymers, polyethylene-polystyrene-polypropylene terpolymers, polyethylene-polypropylene-polybutene terpolymers, styrene-acrylonitrile copolymers and ethylene-acrylate copolymers.

[0020] In some embodiments, the functional auxiliary agent has one or more of the following characteristics:

[0021] (1) The lubricant includes one or more of polyethylene waxes, esters, metal soaps, stearic acid complex esters, amide waxes, montan waxes and bisphenol A epoxy resins;

[0022] (2) The antioxidant includes one or more of a copper salt antioxidant, a phosphate antioxidant, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphite antioxidant, a thioester antioxidant and a polymer antioxidant; optionally, the antioxidant is a copper salt antioxidant;

[0023] (3) The anti-ultraviolet auxiliary agent includes one or more of an ultraviolet absorber, a free radical scavenger and a light shielding agent; optionally, the anti-ultraviolet auxiliary agent includes one or more of UV312, UV329, UV234, UV360, 770, 944, 622 and S-EED;

[0024] (4) The polyamide includes one or more of PA46, PA6, PA66, PA56, PA610, PA612, PA1010, PA1012, PA11, PA12, PA1212, PA513, PA516, MXD6, PA4T, PA5T, PA6T, PA9T, PA10T and PA12T; optionally, the polyamide is one or more of PA1010, PA1012, PA11 and PA12, PA1212; further optionally, the polyamide is PA12.

[0025] In some embodiments, the thermoplastic composite sheet has one or more of the following features:

[0026] (1) The total number of layers of the continuous fiber thermoplastic unidirectional prepreg tape is 6 to 40 layers;

[0027] (2) The thickness of the thermoplastic composite sheet is 1 mm to 6 mm.

[0028] A second aspect of the present application provides a method for preparing a thermoplastic composite sheet, comprising the following steps:

[0029] Prepreg is prepared by mixing 22% to 59.9% of polyamide, 40% to 70% of continuous glass fiber and 0.1% to 8% of functional additives;

[0030] The prepreg is made into a continuous fiber thermoplastic unidirectional prepreg tape, so that the continuous glass fibers are oriented in the same direction;

[0031] Stacking and hot-pressing a plurality of the continuous fiber thermoplastic unidirectional prepreg tapes to prepare the thermoplastic composite sheet;

[0032] In two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extending directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction intersect each other.

[0033] A third aspect of the present application provides a photovoltaic back sheet, comprising the thermoplastic composite sheet described in the first aspect or the thermoplastic composite sheet prepared by the preparation method described in the second aspect.

[0034] A fourth aspect of the present application provides a solar photovoltaic device, comprising the photovoltaic backplane described in the third aspect.

[0035] After research, it was found that the main reason why traditional 3A backboards are prone to cracking is that traditional 3A backboards use chopped glass fiber reinforced polyamide resin, among which polyamide resin is mainly used to maintain the matrix morphology, and the chopped glass fibers are dispersed in the resin matrix in the form of dispersed phase. The linear expansion coefficient (CLTE) of the resin matrix is ​​large, and its size changes greatly with changes in ambient temperature. At the same time, the orientation of the chopped glass fibers is different during the processing process, resulting in a large difference in the linear expansion coefficient of the backboard in the horizontal and vertical directions. It has been in a state of uneven thermal fatigue shrinkage and creep in the horizontal and vertical directions for a long time, and is therefore prone to cracking.

[0036] Based on this, the present application introduces continuous glass fibers into the polyamide resin, wherein the continuous glass fibers are mainly used to maintain the matrix morphology. The glass fibers exist in the form of silicon-oxygen bonds connected by high bond energy, have a relatively stable structure, and have a low CLTE. They hardly change in size with changes in ambient temperature. At the same time, the continuous glass fibers in the two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes are cross-arranged to form an alternating stacked structure. The combination of the two can significantly reduce the dimensional change of the plate, thereby reducing the risk of stress cracking, making the composite plate less likely to crack, and is suitable for use as a photovoltaic backplane to protect solar cells from the influence of the external environment, including ultraviolet rays, moisture, temperature changes, etc., which is of great significance for promoting the development of solar photovoltaic power generation technology.

[0037] In addition, the above-mentioned thermoplastic composite sheet also has the following advantages:

[0038] (1) Good long-term weather resistance and chemical corrosion resistance, far superior to, for example, polyolefin co-extruded backsheets, etc. It is not easy to age during long-term use and can resist corrosion from various chemicals;

[0039] (2) Long service life: good weather resistance and chemical corrosion resistance greatly extend the service life, which can reach more than 30 years in some examples;

[0040] (3) It has high strength and rigidity and can withstand large external forces;

[0041] (4) Thermoplastic materials can be recycled to reduce environmental pollution;

[0042] (5) Compared with traditional fluorine-containing backsheets, the above-mentioned thermoplastic composite panels are lighter in weight, easier to install and transport, and have lower costs, less pollution, and higher cost-effectiveness. DETAILED DESCRIPTION

[0043] The following is a further detailed description of the thermoplastic composite sheet material and its preparation method, photovoltaic backsheet, and solar photovoltaic device of the present application in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0045] As used herein, "one or more" refers to any one, any two, or any two or more of the listed items.

[0046] In this application, "first aspect", "second aspect", "third aspect", "fourth aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0047] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0048] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0049] The percentage contents involved in this application, unless otherwise specified, refer to mass percentage for solid-liquid mixing and solid-solid mixing, and refer to volume percentage for liquid-liquid mixing.

[0050] The percentage concentrations mentioned in this application, unless otherwise specified, refer to the final concentration, which refers to the percentage of the added component in the system after the addition of the component.

[0051] The temperature parameters in this application, unless otherwise specified, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the accuracy range of instrument control.

[0052] Some examples of the present application provide a thermoplastic composite sheet, comprising continuous fiber thermoplastic unidirectional prepreg tapes stacked in layers; in terms of mass percentage, the continuous fiber thermoplastic unidirectional prepreg tapes include:

[0053] Polyamide 22%~59.9%, continuous glass fiber 40%~70% and functional additives 0.1%~8%;

[0054] In two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extending directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction intersect each other.

[0055] It can be understood that continuous glass fibers refer to continuous and uninterrupted glass fibers, and the corresponding length can be set according to the size of the plate. For example, the continuous glass fibers oriented along the first direction in the continuous fiber thermoplastic unidirectional prepreg tape are continuous and uninterrupted in the first direction.

[0056] Without limitation, within the scope of the present application, the material composition of each layer of continuous fiber thermoplastic unidirectional prepreg tape may be the same or different.

[0057] In some examples, the angle between the first direction and the second direction is 60°~120°. This facilitates sheet processing and enables the first sheet and the second sheet to restrict each other, thereby reducing cracking. Specifically, the angle between the first direction and the second direction includes, but is not limited to, 60°, 65°, 70°, 75°, 80°, 85°, 90°, 95°, 100°, 105°, 110°, 115°, 120° or a range between any two of the foregoing. Furthermore, the angle between the first direction and the second direction is 90°, that is, the continuous glass fibers in the two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes are arranged perpendicular to each other.

[0058] In some examples, the diameter of the continuous glass fiber is 13 μm to 17 μm. Reasonable control of the diameter of the continuous glass fiber can reduce the thermal expansion coefficient of the board and cracking while improving the strength and stiffness of the board. Specifically, the diameter of the continuous glass fiber includes but is not limited to: 13 μm, 13.5 μm, 14 μm, 14.5 μm, 15 μm, 15.5 μm, 16 μm, 16.5 μm, 17 μm or a range between any two of the foregoing.

[0059] In some examples, the continuous glass fibers are alkali-free glass fibers.

[0060] In some of the examples, the polyamide is nylon 12 (PA12). Nylon 12 can improve the low temperature resistance, chemical corrosion resistance and dimensional stability of the sheet.

[0061] Without limitation, the functional additives include one or more of a compatible toughening agent, a lubricant, an antioxidant, and an anti-ultraviolet (UV) additive. In some examples, the continuous fiber thermoplastic unidirectional prepreg tape includes, by mass percentage:

[0062] Polyamide 22%~59.9%, continuous glass fiber 40%~70%, compatible toughening agent 0%~5%, antioxidant 0.05%~1%, lubricant 0%~1% and anti-ultraviolet additive 0.05%~1%.

[0063] Among them, the introduction of antioxidants on the basis of polyamide and continuous glass fiber can effectively reduce the oxidation of materials during processing and use, and improve the stability of materials; the introduction of anti-ultraviolet additives can improve the anti-ultraviolet performance of materials and extend the service life of materials, thus further improving the weather resistance and chemical corrosion resistance of the board and extending the service life. In addition, the optional addition of lubricants can reduce the friction coefficient of materials, improve the processing performance of materials, and facilitate continuous production.

[0064] Specifically, the mass percentage of polyamide includes, but is not limited to, 22%, 23.5%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 59.9% or a range between any two of the foregoing.

[0065] Specifically, the mass percentage of continuous glass fibers includes, but is not limited to, 40%, 43%, 46.5%, 48%, 50%, 50.9%, 52%, 54.8%, 55%, 58.5%, 60%, 63.5%, 70%, or a range between any two of the foregoing.

[0066] Specifically, the mass percentage of the compatible toughening agent includes, but is not limited to, 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or a range between any two of the foregoing.

[0067] Specifically, the mass percentage of the antioxidant includes, but is not limited to, 0.05%, 0.1%, 0.2%, 0.5%, 0.7%, 1% or a range between any two of the foregoing.

[0068] Specifically, the mass percentage of the lubricant includes, but is not limited to, 0%, 0.05%, 0.1%, 0.2%, 0.5%, 0.7%, 1% or a range between any two of the foregoing.

[0069] Specifically, the mass percentage of the anti-ultraviolet additive includes, but is not limited to, 0.05%, 0.1%, 0.2%, 0.5%, 0.7%, 1% or a range between any two of the foregoing.

[0070] Furthermore, introducing a compatible toughening agent of appropriate proportion and type into the material of the continuous fiber thermoplastic unidirectional prepreg tape can improve the compatibility of materials such as polyamide and continuous glass fiber, which is beneficial to further enhance the toughness of the board and reduce cracking.

[0071] In some of the examples, the compatible toughening agent in the continuous fiber thermoplastic unidirectional prepreg tape is 2% to 5% by mass.

[0072] In some examples, the compatible toughening agent includes a copolymer of a polar monomer and a polymer elastomer. Further, the polar monomer includes one or more of maleic anhydride (MAH) and its derivatives, acrylates and their derivatives, and glycidyl methacrylate; the polymer elastomer includes one or more of polyolefin, ethylene-alpha olefin copolymer (POE), ethylene-propylene copolymer (EPR), ethylene-propylene-non-conjugated diene copolymer (EPDM), styrene-butadiene copolymer (SBS), polyethylene-polystyrene-polypropylene terpolymer, polyethylene-polypropylene-polybutene terpolymer, styrene-acrylonitrile copolymer, and ethylene-acrylate copolymer.

[0073] Without limitation, the compatible toughening agent may be one or more of GR216, N416, N493, MH5020, A560, 4170, AX4700, Royoltuf 527, 8900, 8840, PTW, SOG-03, CMG-5805L, etc.

[0074] In some examples, the compatible toughening agent includes one or more of POE-g-MAH, ethylene-acrylate-glyceryl methacrylate terpolymer, EPDM-g-MAH, ethylene-acrylate-maleic anhydride terpolymer, and POE-glyceryl methacrylate copolymer.

[0075] In addition, in some examples, the lubricant includes one or more of polyethylene waxes, esters, metal soaps, stearic acid complex esters, amide waxes, montan waxes, and bisphenol A epoxy resins. The esters may be low molecular weight esters with a molecular weight of less than 10,000, and the bisphenol A epoxy resin may be low viscosity bisphenol A epoxy resin with a viscosity of less than 1000 cps at 23°C.

[0076] In some of the examples, the antioxidant includes one or more of a copper salt antioxidant, a phosphate antioxidant, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphite antioxidant, a thioester antioxidant, and a polymer antioxidant. Further, the antioxidant is one or more of a copper salt antioxidant, a hindered phenol antioxidant, and a phosphite antioxidant. In some of the examples, the antioxidant is a copper salt antioxidant, or a combination of a hindered phenol antioxidant and a phosphite antioxidant.

[0077] In some examples, the anti-ultraviolet auxiliary agent includes one or more of an ultraviolet absorber, a free radical scavenger and a light shielding agent. Without limitation, the anti-ultraviolet auxiliary agent includes one or more of UV312, UV329, UV234, UV360, 770, 944, 622 and S-EED.

[0078] In some examples, the total number of layers of the continuous fiber thermoplastic unidirectional prepreg tape is 6 to 40. Specifically, the total number of layers includes but is not limited to: 6 layers, 8 layers, 10 layers, 12 layers, 16 layers, 18 layers, 20 layers, 22 layers, 24 layers, 27 layers, 30 layers, 32 layers, 35 layers, 37 layers, 40 layers, or a range between any two of the foregoing.

[0079] In some examples, the thickness of the thermoplastic composite sheet is 1 mm to 6 mm. Specifically, the thickness of the thermoplastic composite sheet includes, but is not limited to, 1 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm, 2.2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, or a range between any two of the foregoing.

[0080] In some other examples of the present application, a method for preparing a thermoplastic composite sheet is provided, comprising the following steps:

[0081] Prepreg is prepared by mixing 22% to 59.9% of polyamide, 40% to 70% of continuous glass fiber and 0.1% to 8% of functional additives;

[0082] The prepreg is made into a continuous fiber thermoplastic unidirectional prepreg tape, so that the continuous glass fibers are oriented in the same direction;

[0083] Stacking and hot-pressing a plurality of the continuous fiber thermoplastic unidirectional prepreg tapes to prepare the thermoplastic composite sheet;

[0084] In two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extending directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction intersect each other.

[0085] The above-mentioned preparation method adjusts the extension direction of the continuous glass fibers in the plate in the manner of preparing a unidirectional tape, so that the continuous glass fibers are oriented in the same direction, and then the continuous glass orientations in two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes are crossed by stacking. This can significantly reduce the dimensional change of the plate, reduce the risk of stress cracking, and make the composite plate less likely to crack.

[0086] Without limitation, the process of making the prepreg into a unidirectional tape can be carried out using a unidirectional tape preparation device, specifically, the unidirectional tape preparation device can be a melt impregnation pultruder; mixing can be carried out using, for example, a high-speed stirring device.

[0087] It can be understood that the thermoplastic composite sheet prepared by the above preparation method has similar schemes and advantages as the aforementioned thermoplastic composite sheet, which will not be described in detail here.

[0088] In some examples, the thickness of the continuous fiber thermoplastic unidirectional prepreg tape is 0.05 mm to 0.4 mm. Specifically, the thickness of the continuous fiber thermoplastic unidirectional prepreg tape includes but is not limited to: 0.05 mm, 0.075 mm, 0.11 mm, 0.15 mm, 0.18 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.35 mm, 0.4 mm or a range between any two of the foregoing.

[0089] In some examples, the temperature of hot pressing is 200° C. to 320° C. Specifically, the temperature of hot pressing includes, but is not limited to, 200° C., 210° C., 220° C., 230° C., 240° C., 250° C., 260° C., 270° C., 280° C., 290° C., 300° C., 310° C., 320° C., or a range between any two of the foregoing. Without limitation, hot pressing can be performed using a hot press.

[0090] In some other examples of the present application, a photovoltaic back sheet is provided, comprising the thermoplastic composite sheet as described above or the thermoplastic composite sheet prepared by the preparation method as described above.

[0091] Some other examples of the present application provide the use of the above photovoltaic backsheet in the preparation of solar photovoltaic cells.

[0092] In some other examples of the present application, a solar photovoltaic device is provided, comprising the photovoltaic backsheet as described above.

[0093] For experimental parameters not specified in the following specific embodiments, reference is made to the instructions given in the present application document, and reference may also be made to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by manufacturers.

[0094] The raw materials and reagents involved in the following specific examples can be obtained from commercial sources, or can be prepared by those skilled in the art according to known methods.

[0095] The "stacked at 90°" mentioned in the embodiments means that in two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the continuous glass fibers in the lower layer are oriented at 0°, and the continuous glass fibers in the upper layer are oriented at 90° to the lower layer.

[0096] The main raw materials involved in the embodiments and comparative examples are as follows:

[0097] Nylon 12, Wanhua Chemical, Wanamid L1000;

[0098] Compatible toughening agent, Mitsui Chemicals, MH5020, chemical name POE-g-MAH;

[0099] Compatible toughening agent, Arkema, France, 8900, chemical name ethylene-acrylate-methacrylate dehydrated glycerol terpolymer;

[0100] Compatible toughening agent, DuPont, USA, N416, chemical name EPDM-g-MAH;

[0101] Compatible toughening agent, Arkema, France, AX4700, chemical name ethylene-acrylate-maleic anhydride terpolymer;

[0102] Compatible toughening agent, Jiayirong, SOG-03, chemical name POE-methacrylate dehydrated glycerol copolymer;

[0103] Toughener, Dow Chemical, 8150, chemical name POE;

[0104] Antioxidant, Brueggemann, H3376, organic copper salt;

[0105] Antioxidant, Lionon, 1098, hindered phenol antioxidant;

[0106] Antioxidant, Lianlong, 168, phosphite antioxidant;

[0107] Lubricant, Clariant, LICOWAX E, montan wax;

[0108] Anti-UV additive, BASF, UV312, anti-UV additive;

[0109] Fiberglass, Taishan Fiberglass, EDR240-T835, continuous fiberglass.

[0110] Example 1

[0111] This embodiment is a method for preparing a photovoltaic backsheet, and the steps are as follows:

[0112] (1) Prepare the ingredients as follows:

[0113] PA12, Wanamid L1000: 50%;

[0114] Compatible toughening agent MH5020: 2%;

[0115] Antioxidant H3376: 0.5%;

[0116] Lubricant LICOWAX E: 0.5%;

[0117] Anti-UV additive UV312: 0.5%;

[0118] Continuous glass fiber EDR240-T835: 46.5% (alkali-free glass fiber with a diameter of 15μm).

[0119] (2) Mixing the ingredients evenly to obtain a prepreg;

[0120] (3) The unidirectional tape is made by melt impregnation pultrusion with a thickness of 0.3 mm.

[0121] (4) The unidirectional tapes were stacked at 90°, with a total of 10 layers, and hot pressed at a hot pressing temperature of 220°C to prepare a photovoltaic backsheet with a thickness of about 3 mm.

[0122] Example 2

[0123] This embodiment is a method for preparing a photovoltaic backsheet, and the steps are as follows:

[0124] (1) Prepare the ingredients as follows:

[0125] PA12, Wanamid L1000: 45%;

[0126] Compatible toughening agent 8900: 3%;

[0127] Antioxidant 1098: 0.3%;

[0128] Antioxidant 168: 0.2%;

[0129] Lubricant LICOWAX E: 0.1%;

[0130] Anti-UV additive UV312: 0.5%;

[0131] Continuous glass fiber EDR240-T835: 50.9% (alkali-free glass fiber with a diameter of 14μm).

[0132] (2) Mixing the ingredients evenly to obtain a prepreg;

[0133] (3) The unidirectional tape is made by melt impregnation pultrusion with a thickness of 0.18 mm.

[0134] (4) The unidirectional tapes were stacked at 90°, with a total of 12 layers, and hot pressed at a hot pressing temperature of 260°C to prepare a photovoltaic backsheet with a thickness of about 2.2 mm.

[0135] Example 3

[0136] This embodiment is a method for preparing a photovoltaic backsheet, and the steps are as follows:

[0137] (1) Prepare the ingredients as follows:

[0138] PA12, Wanamid L1000: 40%;

[0139] Compatible toughening agent N416: 4%;

[0140] Antioxidant H3376: 0.2%;

[0141] Lubricant LICOWAX E: 0.5%;

[0142] Anti-UV additive UV312: 0.5%;

[0143] Continuous glass fiber EDR240-T835: 54.8% (alkali-free glass fiber with a diameter of 16μm).

[0144] (2) Mixing the ingredients evenly to obtain a prepreg;

[0145] (3) The unidirectional tape is made by melt impregnation pultrusion with a thickness of 0.11 mm.

[0146] (4) The unidirectional tapes were stacked at 90°, with a total of 16 layers, and hot pressed at a hot pressing temperature of 280°C to prepare a photovoltaic backsheet with a thickness of about 1.8 mm.

[0147] Example 4

[0148] This embodiment is a method for preparing a photovoltaic backsheet, and the steps are as follows:

[0149] (1) Prepare the ingredients as follows:

[0150] PA12, Wanamid L1000: 35%;

[0151] Compatible toughening agent AX 4700: 5%;

[0152] Antioxidant 1098: 0.3%;

[0153] Antioxidant 168: 0.2%;

[0154] Lubricant LICOWAX E: 0.5%;

[0155] Anti-UV additive UV312: 0.5%;

[0156] Continuous glass fiber EDR240-T835: 58.5% (alkali-free glass fiber with a diameter of 17μm).

[0157] (2) Mixing the ingredients evenly to obtain a prepreg;

[0158] (3) The unidirectional tape is made by melt impregnation pultrusion machine with a thickness of 0.075 mm;

[0159] (4) The unidirectional tapes were stacked at 90°, with a total of 20 layers, and hot pressed at a hot pressing temperature of 300°C to prepare a photovoltaic backsheet with a thickness of about 1.5 mm.

[0160] Example 5

[0161] This embodiment is a method for preparing a photovoltaic backsheet, and the steps are as follows:

[0162] (1) Prepare the ingredients as follows:

[0163] PA12, Wanamid L1000: 23.5%;

[0164] Compatible toughening agent SOG-03: 5%;

[0165] Antioxidant 1098: 0.3%;

[0166] Antioxidant 168: 0.2%;

[0167] Lubricant LICOWAX E: 0.5%;

[0168] Anti-UV additive UV312: 0.5%;

[0169] Continuous glass fiber EDR240-T835: 70% (alkali-free glass fiber with a diameter of 16μm).

[0170] (2) Mixing the ingredients evenly to obtain a prepreg;

[0171] (3) The unidirectional tape is made by melt impregnation pultrusion machine with a thickness of 0.05 mm;

[0172] (4) The unidirectional tapes were stacked at 90°, with a total of 24 layers, and hot pressed at a hot pressing temperature of 320°C to prepare a photovoltaic backsheet with a thickness of about 1.2 mm.

[0173] Example 6

[0174] This embodiment is a method for preparing a photovoltaic backplane. The steps are the same as those of Embodiment 1, with the main difference being that no compatible toughening agent is used and PA12 is used to supplement 100%.

[0175] Example 7

[0176] This embodiment is a method for preparing a photovoltaic backplane. The steps are the same as those of Embodiment 1, with the main difference being that an equal amount of toughening agent 8150 is used to replace the compatible toughening agent MH5020 in Embodiment 1.

[0177] Comparative Example 1

[0178] The commercially available 3A backplane (produced by Isovolta, 3A backplane, all three layers are made of PA12, of which the middle layer is chopped glass fiber reinforced PA12) has a thickness of 3mm.

[0179] Comparative Example 2

[0180] The commercially available polyolefin co-extruded back sheet (produced by DSM, Co-extruded back sheet, all three layers are PP) has a thickness of 3 mm.

[0181] Comparative Example 3

[0182] The commercially available fluorine-containing back sheet (produced by Cybrid Company, TPT type back sheet, inner and outer layers are both PVDF, and the middle layer is PET) has a thickness of 3 mm.

[0183] Comparative Example 4

[0184] The nylon backboard (prepared according to Example 1, the matrix is ​​nylon 12 (L3001) single-layer extrusion, and the material is unreinforced PA12) has a thickness of 3 mm.

[0185] Comparative Example 5

[0186] The commercially available polyester back sheet (produced by Agfa, Monolayer back sheet, single-layer reinforced PET material) has a thickness of 3 mm.

[0187] Test example:

[0188] (1) Weathering test: The photovoltaic backsheet is placed in a UV aging box for accelerated aging test for 1000 hours.

[0189] (2) Chemical resistance test: The photovoltaic back panel is immersed in different chemical reagents, such as acid, alkali, and salt solutions, for 72 hours.

[0190] (3) Lightweight test: The percentage of weight reduction is measured based on a commercially available fluorinated backsheet.

[0191] (4) Life test: In accordance with the UL1703 standard, the photovoltaic backplane is tested for life by simulating the actual use environment.

[0192] (5) CLTE test: Use a thermal expansion coefficient tester to test the photovoltaic backplane.

[0193] (6) Cracking test: The photovoltaic back panel is subjected to a bending test.

[0194] (7) Strength test: A universal material testing machine is used to test the tensile strength and bending strength of the photovoltaic backsheet.

[0195] The test results are shown in Tables 1 and 2 below:

[0196] Table 1

[0197]

[0198] Table 2

[0199]

[0200] In addition, the photovoltaic backsheets of the embodiment and the comparative example were recycled, that is, the photovoltaic backsheets were crushed and then heated and melted, and the plastic components therein were recovered and reprocessed into other plastic products. The results are as follows:

[0201] Examples 1 to 7: Thermoplastic recycling can be achieved.

[0202] Comparative Example 1: The recyclability is good, but the performance after recycling is reduced.

[0203] Comparative Example 2: The recyclability is good, but the performance after recycling is reduced.

[0204] Comparative Example 3: Unable to recover by heating and melting.

[0205] Comparative Example 4: The recyclability is good, and the performance after recycling remains unchanged.

[0206] Comparative Example 5: The recyclability is good, but the performance after recycling is reduced.

[0207] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0208] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the patent application. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the content of the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A thermoplastic composite sheet, characterized in that: It includes continuous fiber thermoplastic unidirectional prepreg tapes arranged in layers; In terms of mass percentage, the continuous fiber thermoplastic unidirectional prepreg tape comprises: Polyamide 22%~59.9%, continuous glass fiber 40%~70% and functional additives 0.1%~8%; In two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extending directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction intersect each other.

2. The thermoplastic composite sheet according to claim 1, characterized in that: The angle between the first direction and the second direction is 60°~120°.

3. The thermoplastic composite sheet according to claim 1, characterized in that: The continuous glass fiber has at least one of the following characteristics: (1) The diameter of the continuous glass fiber is 13 μm to 17 μm; (2) The continuous glass fiber is an alkali-free glass fiber.

4. The thermoplastic composite sheet according to any one of claims 1 to 3, characterized in that: The functional additives include one or more of a compatible toughening agent, a lubricant, an antioxidant and an anti-ultraviolet additive; Optionally, the continuous fiber thermoplastic unidirectional prepreg tape comprises, by mass percentage: Polyamide 22%~59.9%, continuous glass fiber 40%~70%, compatible toughening agent 0%~5%, antioxidant 0.05%~1%, lubricant 0%~1% and anti-ultraviolet additive 0.05%~1%.

5. The thermoplastic composite sheet material according to claim 4, characterized in that: In terms of mass percentage, the compatible toughening agent in the material of the continuous fiber thermoplastic unidirectional prepreg tape has one or more of the following characteristics: (1) In terms of mass percentage, the compatible toughening agent is 2% to 5%; (2) The compatible toughening agent includes a copolymer of a polar monomer and a polymer elastomer; Optionally, the polar monomer includes one or more of maleic anhydride and its derivatives, acrylate and its derivatives, and glycidyl methacrylate; Optionally, the polymer elastomer includes one or more of polyolefins, ethylene-α-olefin copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, styrene-butadiene copolymers, polyethylene-polystyrene-polypropylene terpolymers, polyethylene-polypropylene-polybutene terpolymers, styrene-acrylonitrile copolymers and ethylene-acrylate copolymers.

6. The thermoplastic composite sheet material according to claim 4, characterized in that: The functional additive has one or more of the following characteristics: (1) The lubricant includes one or more of polyethylene waxes, esters, metal soaps, stearic acid complex esters, amide waxes, montan waxes and bisphenol A epoxy resins; (2) The antioxidant includes one or more of copper salt antioxidants, phosphate antioxidants, hindered phenol antioxidants, hindered amine antioxidants, phosphite antioxidants, thioester antioxidants and polymer antioxidants; optionally, the antioxidant is one or more of copper salt antioxidants, hindered phenol antioxidants and phosphite antioxidants; (3) The anti-ultraviolet additive includes one or more of an ultraviolet absorber, a free radical scavenger and a light shielding agent; optionally, the anti-ultraviolet additive includes one or more of UV312, UV329, UV234, UV360, 770, 944, 622 and S-EED; (4) The polyamide includes one or more of PA46, PA6, PA66, PA56, PA610, PA612, PA1010, PA1012, PA11, PA12, PA1212, PA513, PA516, MXD6, PA4T, PA5T, PA6T, PA9T, PA10T and PA12T; optionally, the polyamide is one or more of PA1010, PA1012, PA11, PA12 and PA1212; further optionally, the polyamide is PA12.

7. The thermoplastic composite sheet according to any one of claims 1 to 3 and 5 to 6, characterized in that: Has one or more of the following characteristics: (1) The total number of layers of the continuous fiber thermoplastic unidirectional prepreg tape is 6 to 40 layers; (2) The thickness of the thermoplastic composite sheet is 1 mm to 6 mm.

8. A method for preparing a thermoplastic composite sheet, characterized in that: The steps include: Prepreg is prepared by mixing 22% to 59.9% of polyamide, 40% to 70% of continuous glass fiber and 0.1% to 8% of functional additives; The prepreg is made into a continuous fiber thermoplastic unidirectional prepreg tape, so that the continuous glass fibers are oriented in the same direction; Stacking and hot-pressing a plurality of the continuous fiber thermoplastic unidirectional prepreg tapes to prepare the thermoplastic composite sheet; In two adjacent layers of continuous fiber thermoplastic unidirectional prepreg tapes, the extending directions of the continuous glass fibers are respectively a first direction and a second direction, and the first direction and the second direction intersect each other.

9. A photovoltaic backsheet, characterized in that: It comprises the thermoplastic composite sheet material according to any one of claims 1 to 7 or the thermoplastic composite sheet material prepared by the preparation method according to claim 8.

10. A solar photovoltaic device, characterized in that: Comprising the photovoltaic back panel as described in claim 9.

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