CN115837783A - Composite solar cell back plate with high weather resistance and preparation method thereof - Google Patents
Composite solar cell back plate with high weather resistance and preparation method thereof Download PDFInfo
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- CN115837783A CN115837783A CN202111659983.6A CN202111659983A CN115837783A CN 115837783 A CN115837783 A CN 115837783A CN 202111659983 A CN202111659983 A CN 202111659983A CN 115837783 A CN115837783 A CN 115837783A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the technical field of IPC 08, in particular to a composite solar cell back plate with high weather resistance and a preparation method thereof. The solar cell back plate is structurally characterized in that a PO inner layer, a polyester supporting layer and a PO outer layer are sequentially stacked. The composite solar cell back plate with high weather resistance provided by the invention has both processing performance and weather resistance; through optimizing the PET structural layer and the adhesive, the moisture and heat resistance, UV resistance, cooking resistance, high and low temperature cycle resistance, low water vapor permeability and other properties of the photovoltaic back plate are improved, the defects of bubbling, delaminating, cracking, yellowing and the like easily occurring in the conventional solar cell back plate under severe conditions are overcome, the back plate has mechanical strength and chemical stability, and the use requirements of the photovoltaic module under various working environments can be met.
Description
Technical Field
The invention relates to the technical field of IPC 08, in particular to a composite solar cell back plate with high weather resistance and a preparation method thereof.
Background
In the existing photovoltaic back plate structure, when a PET layer and other layers are bonded through an adhesive, the problem that both the bonding property and the processability are difficult to be considered is solved; the photovoltaic back plate has high water vapor transmission rate and is difficult to play a long-acting role under severe conditions such as tide, heat, insolation and the like.
Chinese patent CN104559080 discloses a thermoplastic polyester polyethylene composition and application thereof, wherein polyethylene terephthalate is used as thermoplastic resin, and reacts with polyethylene, maleic anhydride graft modified ethylene-vinyl acetate copolymer, antioxidant 1010 and antioxidant 168 to obtain a material applied to a solar cell backboard, the shrinkage rate of the obtained material is reduced, and the mechanical property is improved; chinese patent CN108075006 discloses a solar cell back plate with a multilayer structure, wherein a first polyethylene layer, a first adhesive resin layer, a polyester layer, a second adhesive resin layer and a second polyethylene layer are compounded, and the solar cell back plate with the multilayer structure is obtained through tape casting compounding and electron beam radiation crosslinking, so that the heat resistance of the back plate is improved; chinese patent CN205395342 discloses a high-water-resistance high-reflection solar cell back panel and a solar cell module comprising the same, wherein a back panel structure with low cost and good water resistance is formed by co-extrusion of a resin film layer, a water-resistance layer and a weather-resistant layer. However, the above prior art still does not solve the technical problems of heat resistance, water resistance, ultraviolet aging resistance and the like of the photovoltaic back panel; the obtained photovoltaic back plate cannot meet the use requirement of severe outdoor conditions, and the application of the photovoltaic module is limited.
Aiming at the problems, the PET structural layer and the adhesive of the solar cell backboard are optimized in multiple ways, so that the moisture and heat resistance, UV resistance, steaming resistance, high and low temperature cycle resistance, low water vapor transmittance and other properties of the photovoltaic backboard are improved.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a composite type solar cell back sheet with high weatherability. The solar cell back plate is structurally characterized in that a PO inner layer, a polyester supporting layer and a PO outer layer are sequentially stacked.
In some preferred embodiments, the thickness ratio of the inner PO layer, the polyester support layer and the outer PO layer is (1-8): (10-36): (0.5-10).
Further preferably, the thickness ratio of the PO inner layer, the polyester support layer and the PO outer layer is (1-5): (15-30): (1-5).
In some preferred embodiments, the raw materials of the PO inner layer include: PE base stock, anti-UV agent, antioxidant and auxiliary agent A.
Further preferably, the raw materials of the PO inner layer include: based on the total mass of the PO inner layer, 94-99% of PE base material, 0.2-2% of anti-UV agent, 0.1-2% of antioxidant and 0-5% of auxiliary agent A.
In some preferred embodiments, the raw materials of the polyester support layer include: polyester base stock, filler, toughening agent, hydrolysis resistant agent, anti-UV agent, antioxidant and auxiliary agent B.
Further preferably, the raw materials of the polyester support layer comprise: based on the total mass of the polyester supporting layer, 80-99% of polyester base material, 1-15% of filler, 0.5-5% of toughening agent, 0.1-2% of hydrolysis resistant agent, 0.1-1.5% of anti-UV agent, 0-2% of antioxidant and 0-3% of auxiliary agent B.
In some preferred embodiments, the raw material of the PO outer layer comprises: polyolefin mixture, anti-UV agent, filler, antioxidant and auxiliary agent C.
Further preferably, the raw material of the PO outer layer includes: based on the total mass of the PO outer layer, 85-98% of the polyolefin mixture, 0.1-2% of the anti-UV agent, 1-10% of the filler, 0.1-2% of the antioxidant and 0-1.5% of the auxiliary agent C.
In some preferred embodiments, the PE base stock has a melt flow rate of 2 to 10g/10min, a tensile yield strength of 15 to 40MPa, and an elongation at break of 400 to 800%.
Further preferably, the melt flow rate of the PE base material is 5g/10min, the tensile yield strength is 27MPa, and the elongation at break is 650%; in particular Dow HDPE 05962B.
In some preferred embodiments, the anti-UV agent comprises one or a combination of more of hindered amines, benzophenones, benzotriazoles, triazines, acrylonitriles, oxamides, organo nickel species.
Further preferably, the anti-UV agent is a hindered amine, and examples of the hindered amine include, but are not limited to, combinations of one or more of GW-480, GW-622, GW-944, GW-540, tinuvin 770, UV-3853, UV-3346, and UV-3529.
Even more preferably, the anti-UV agent is UV-3529 and/or UV-3853, both of which are derived from U.S. cyanogen specialty Chemicals.
In some preferred embodiments, the antioxidant comprises one or a combination of hindered phenols, thioether esters, phosphite esters, thiols, or the like.
More preferably, the antioxidant is hindered phenol and thioether ester, and the mass ratio of the hindered phenol to the thioether ester is (0.5-2.5): 1.
examples of the hindered phenol include at least one of antioxidant 1010, antioxidant 1076, antioxidant 1098, and antioxidant 1024.
Examples of thioether esters include the antioxidant DLTP and/or the antioxidant DSTP.
In some preferred embodiments, the adjuvant A comprises a combination of one or more of PS-g-EGMA, PP-g-ST, ABS-g-MAH, PE-g-ST, PP-g-MAH, PE-g-MAH.
In some preferred embodiments, the polyester base is PET and/or TPEE, further preferably TPEE.
In some preferred embodiments, the TPEE (thermoplastic polyester elastomer) has a melt flow rate of 2 to 15g/10min, a tensile modulus of 15 to 35MPa and an elongation at break > 200%.
Further preferably, the polyester base stock is TPEE, the melt flow rate of the polyester base stock is 5g/10min, the tensile modulus is 240MPa, and the elongation at break is 300 percent; in particular to United states Dupont TPEE HTR8425 NC010.
In some preferred embodiments, the filler comprises a combination of one or more of titanium dioxide, calcium carbonate, calcined kaolin, talc, wollastonite, hollow glass microspheres.
Further preferably, the filler is titanium dioxide. The titanium dioxide is nano-scale titanium dioxide produced by a gas phase method, and the specific surface area of the nano-scale titanium dioxide is 30-60m 2 (iv)/g, average particle diameter of 15-30nm.
In some preferred embodiments, the toughening agent is preferably an ethylene copolymer, such as dupont Elvaloy4170.
In some preferred embodiments, the anti-hydrolysis agent comprises a carbodiimide, specifically N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, CAS number 2162-74-5.
In some preferred embodiments, the auxiliary agent B includes a coupling agent, which is a combination of one or more of a silane coupling agent, a titanate coupling agent, and a rare earth coupling agent.
Further preferably, the coupling agent is preferably a titanate coupling agent, such as TC-131.
In some preferred embodiments, the polyolefin blend comprises at least 2 of PP, PE, EPDM, POE, OBC.
Further preferably, the polyolefin blend comprises PP (polypropylene), PE (polyethylene) and POE (polyethylene octene co-elastomer); the weight ratio of PP, PE and POE is (1-4): (2.5-6): (0.5-3)
In some preferred embodiments, the coagent C includes a radical scavenger and a radical quencher; the radical scavenger is preferably a hindered amine, such as BASFTinuvin123; the radical quencher is preferably an organic complex of nickel, such as calla 1084.
The photovoltaic back plate is positioned on the back of the solar cell and constructs an outermost protective barrier for the photovoltaic module, and the environmental tolerance of the photovoltaic back plate directly influences the service life of the module. The existing photovoltaic back plate can not meet the long-term stable use in humid, sultry environment and illumination condition, on one hand, the problems of degradation and aging of the back plate material are easy to occur in severe environment, and the physical and mechanical properties of the product are deteriorated; on the other hand, although the composite layer structure is adopted, a performance complementary effect can be formed to a certain degree, when the composite layers are connected through a glue medium, the glue layer is affected by water vapor and temperature, the bonding strength cannot be maintained, and the problems of falling, cracking and the like easily occur to the glue layer.
The applicant finds that through a great deal of research, a polyester base material with a melt flow rate of 2-15g/10min, a tensile modulus of 15-35MPa and an elongation at break of more than 200% is used as a base material of a middle supporting layer of a back plate, the aging resistance of the photovoltaic back plate can be remarkably improved under the combined action of nano titanium dioxide with a specific surface area of 30-60m2/g and an average particle size of 15-30nm, the obtained back plate still has high mechanical strength after high-low temperature cyclic treatment, probably because the degradation activity of polyethylene glycol terephthalate under the formula system is inhibited, a carbon-carbon molecular main chain is protected by polar molecules under the participation of an alkaline small molecular auxiliary agent, and meanwhile, inorganic particles with specific specifications are uniformly dispersed in a polymer space three-dimensional structure, so that moisture, acidic components and the like are inhibited from penetrating into the back plate structure to cause violent erosion on the material, the resistance of the back plate to environmental change is improved, the weather resistance of the back plate is improved, the crack and the yellowing defect is not easily caused under the conditions of humidity, high temperature, sun and the service life is prolonged.
The invention provides a preparation method of a composite solar cell back plate with high weather resistance, which comprises the step of sequentially laminating and bonding a PO inner layer, a polyester supporting layer and a PO outer layer by using an adhesive to obtain a finished back plate product.
In some preferred embodiments, the adhesive comprises a combination of one or more of a polyurethane adhesive, an epoxy adhesive, an acrylate adhesive, a silicone adhesive.
Further preferably, the adhesive is a polyurethane adhesive; still more preferably a polyether polyurethane adhesive.
In some preferred embodiments, the raw materials of the polyether polyurethane adhesive comprise, by weight, 50-70 parts of polyglycol, 30-54 parts of diisocyanate, 0.1-2 parts of catalyst, 2-15 parts of chain extender, 0-5 parts of rheological additive and 4-66 parts of solvent.
Preferably, the polyglycol comprises at least one of polypropylene oxide dihydric alcohol and polyethylene oxide dihydric alcohol.
Preferably, the polyglycol has an average molecular weight of 400 to 4000.
More preferably, the weight ratio of the polyglycol is 1: the polyoxypropylene diol and the polyoxyethylene diol of (2-5).
Preferably, the chain extender comprises one or more of 1, 4-butanediol, dipropylene glycol, diethylene glycol and 1, 2-propanediol.
Further preferably, the chain extender is 1, 4-butanediol and dipropylene glycol; the weight ratio of the 1, 4-butanediol to the dipropylene glycol is (0.5-3): 1.
preferably, the diisocyanate is a diisocyanate commonly used in the art, such as TDI, MDI, HDI, IPDI.
By adopting the reaction of the specific polyester base material and the auxiliary agent, the compactness degree of the space structure of the TPEE structural layer can be improved, the mechanical property and the weather resistance of the back plate are optimized, but the technical problems that the bonding strength of the TPEE structural layer and the adhesive is poor, the middle polyester supporting layer is easy to separate from the upper layer and the lower layer, and all functional layers of the back plate cannot fully play roles are derived. The applicant further researches and discovers that the polyether polyurethane adhesive can promote the polyester supporting layer to form effective bonding with the PO inner/outer layer, and the hydrolysis resistance of the material is improved. It is unexpectedly found that the reaction activity of the polyglycol with the average molecular weight of 400-4000 and diisocyanate is higher, and the weight ratio of the polyglycol to the diisocyanate is (0.5-3): 1, 4-butanediol and dipropylene glycol are used as chain extenders, polyurethane generated by reaction can effectively permeate into a composite layer structure of the back plate, bonding sites in the composite material structure are increased to form a mechanical interlocking effect, and the back plate forms a tight and firm connection effect of a PO inner layer, a polyester supporting layer and a PO outer layer under the action of an adhesive with high curing strength. Meanwhile, when the weight ratio of the polyglycol is 1: and (2) when the polypropylene oxide dihydric alcohol and the polyethylene oxide dihydric alcohol are used, the water resistance and the aging resistance of the adhesive in the back plate structure are obviously improved, and the combined action of the TPEE structural layer with optimized performance is matched, so that the structural change of a high/low temperature layer, the change of the internal structure of the photovoltaic back plate in a high-temperature high-humidity environment and under the illumination condition are inhibited, the humidity and heat resistance and the boiling resistance of the photovoltaic back plate are improved, and the photovoltaic module is endowed with excellent processing performance and long service life.
Has the beneficial effects that:
the composite solar cell back plate with high weather resistance provided by the invention has both processing performance and weather resistance; through optimizing the PET structural layer and the adhesive, the moisture and heat resistance, UV resistance, cooking resistance, high and low temperature cycle resistance, low water vapor permeability and other properties of the photovoltaic back plate are improved, the defects of bubbling, delaminating, cracking, yellowing and the like easily occurring in the conventional solar cell back plate under severe conditions are overcome, the back plate has mechanical strength and chemical stability, and the use requirements of the photovoltaic module under various working environments can be met.
Detailed Description
Example 1.
The embodiment provides a composite solar cell backboard with high weather resistance, which structurally comprises a PO inner layer, a polyester supporting layer and a PO outer layer which are sequentially stacked.
The thicknesses of the PO inner layer, the polyester support layer and the PO outer layer are respectively 30 micrometers, 200 micrometers and 40 micrometers.
The PO inner layer comprises the following raw materials: based on the total mass of the PO inner layer, 96.5 percent of PE base material, 1 percent of anti-UV agent, 1 percent of antioxidant and 1.5 percent of auxiliary agent A.
The polyester support layer comprises the following raw materials: calculated by the total mass of the polyester supporting layer, 85.7 percent of polyester base material, 8 percent of filler, 2.5 percent of toughening agent, 1 percent of hydrolysis resistant agent, 0.6 percent of anti-UV agent, 1.2 percent of antioxidant and 1 percent of auxiliary agent B.
The PO outer layer comprises the following raw materials: based on the total mass of the PO outer layer, 90.6% of the polyolefin mixture, 0.8% of the UV resistant agent, 6% of the filler, 1% of the antioxidant and 1.6% of the auxiliary agent C.
The melt flow rate of the PE base material is 5g/10min, the tensile yield strength is 27MPa, and the elongation at break is 650%; in particular Dow HDPE 05962B.
The anti-UV agent is hindered amine, specifically UV-3529 and UV-3853 with the weight ratio of 2.
The antioxidant is hindered phenol and thioether ester, and the mass ratio of the hindered phenol to the thioether ester is 1.4:1.
the hindered phenol is specifically an antioxidant 235; the thioether ester is antioxidant DSTP.
The auxiliary agent A is PS-g-EGMA which is sourced from Nippon oil and fat Co.
The polyester base material is TPEE, the melt flow rate of the TPEE is 5g/10min, the tensile modulus is 240MPa, and the elongation at break is 300%; in particular to United states Dupont TPEE HTR8425 NC010.
The filler is nano-scale titanium dioxide produced by a gas phase method, and the specific surface area of the nano-scale titanium dioxide is 50m 2 (iv)/g, average particle size 21nm; specifically, degussa AEROXIDE P25.
The toughening agent is an ethylene copolymer, the melt flow rate is 8g/10min, and the toughening agent is specifically DuPont Elvaloy4170 in the United states.
The anti-hydrolysis agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, and the CAS number is 2162-74-5.
The assistant B is a coupling agent, in particular to a titanate coupling agent TC-131.
The polyolefin mixture comprises PP, PE and POE; the weight ratio of PP, PE and POE is 3:4:2.
the PE has a melt index of 8g/10min and a tensile yield strength of 10.3MPa; in particular Dupont LDPE 0098S LE.
The melt index of the PP is 8.7g/10min, and the flexural modulus is 1500MPa; in particular, malaysia CIPC
PP-2301。
The POE has a melt index of 0.5g/10min and a tensile strength of 35kN/m; in particular to American Exxon Mobil POE 5061.
The auxiliary agent C is a free radical scavenger and a free radical quencher with the weight ratio of 1; the free radical scavenger is a hindered amine compound, specifically BASFTinuvin123; the free radical quencher is an organic complex of nickel, specifically calla 1084.
In a second aspect of this embodiment, a method for preparing a composite solar cell back sheet with high weather resistance is provided, in which an adhesive is used to sequentially laminate and bond an inner PO layer, a polyester support layer, and an outer PO layer (the coating thickness of the adhesive is 10 μm), and the PO layer is placed at 60 ℃ for 3 hours to be shaped, so as to obtain a back sheet finished product.
The adhesive is a polyurethane adhesive, in particular a polyether polyurethane adhesive; the polyether polyurethane adhesive comprises the following raw materials, by weight, 64 parts of polyglycol, 40 parts of diisocyanate, 0.1 part of catalyst, 8 parts of chain extender, 1 part of rheological additive and 20 parts of solvent.
The weight ratio of the polyglycol is 1:3 of polyoxypropylene diol and polyoxyethylene diol.
The average molecular weight of the polyoxypropylene diol is 2000, and the polyoxypropylene diol is from Nanjing Yamameshan Shiyashi company.
The polyoxyethylene glycol has an average molecular weight of 1000 and is sourced from Nanjing Yao Shishan chemical company.
The diisocyanate is TDI (toluene diisocyanate) and IPDI (isophorone diisocyanate); the weight ratio of TDI to IPDI was 1.
The chain extender is 1, 4-butanediol and dipropylene glycol; the weight ratio of 1, 4-butanediol to dipropylene glycol is 2:1.
the rheological aid has a viscosity of 2900mPa.s (25 ℃), and is sourced from Rohm and Haas RM-2020.
The catalyst is stannous octoate, and the CAS number is 301-10-0.
The solvent is ethyl acetate.
The preparation steps of the polyether adhesive are as follows: mixing the raw materials except the diisocyanate according to the formula amount, and uniformly stirring at 800rpm to obtain a material A; before use, diisocyanate is added into the material A and is uniformly mixed to obtain the polyether adhesive.
Example 2.
The embodiment provides a composite solar cell backboard with high weather resistance, which structurally comprises a PO inner layer, a polyester supporting layer and a PO outer layer which are sequentially stacked.
The thicknesses of the PO inner layer, the polyester support layer and the PO outer layer are respectively 30 micrometers, 200 micrometers and 40 micrometers.
The PO inner layer comprises the following raw materials: based on the total mass of the PO inner layer, 98 percent of PE base material, 0.2 percent of anti-UV agent, 0.8 percent of antioxidant and 1 percent of auxiliary agent A.
The polyester support layer comprises the following raw materials: the polyester support layer comprises, by mass, 86% of a polyester base material, 5% of a filler, 3% of a toughening agent, 1.2% of an anti-hydrolysis agent, 0.4% of an anti-UV agent, 1.4% of an antioxidant and 2% of an auxiliary agent B.
The PO outer layer comprises the following raw materials: based on the total mass of the PO outer layer, 88% of the polyolefin mixture, 1.4% of the UV resistant agent, 9% of the filler, 0.5% of the antioxidant and 1.1% of the auxiliary agent C.
The melt flow rate of the PE base material is 5g/10min, the tensile yield strength is 27MPa, and the elongation at break is 650%; in particular Dow HDPE 05962B.
The anti-UV agent is hindered amine, specifically UV-3529 and UV-3853 with the weight ratio of 2.
The antioxidant is hindered phenols and thioether esters, and the mass ratio of the hindered phenols to the thioether esters is 1.4:1.
the hindered phenol is antioxidant 235; the thioether ester is antioxidant DSTP.
The auxiliary agent A is PS-g-EGMA which is sourced from Nippon oil and fat Co.
The melt flow rate of the polyester base material is 5g/10min, the tensile modulus is 240MPa, and the elongation at break is 300%; in particular to Dupont TPEE HTR8425 NC010 in the United states.
The filler is nano-scale titanium dioxide produced by a gas phase method, and the specific surface area of the nano-scale titanium dioxide is 50m 2 (ii)/g, average particle diameter of 21nm; specifically, degussa AEROXIDE P25.
The toughening agent is an ethylene copolymer, the melt flow rate is 8g/10min, and the toughening agent is specifically DuPont Elvaloy4170 in the United states.
The anti-hydrolysis agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, and the CAS number is 2162-74-5.
The assistant B is a coupling agent, in particular to a titanate coupling agent TC-131.
The polyolefin mixture comprises PP, PE and POE; the weight ratio of PP, PE and POE is 3:4:2.
the PE has a melt index of 8g/10min and a tensile yield strength of 10.3MPa; in particular Dupont LDPE 0098S LE.
The melt index of the PP is 8.7g/10min, and the flexural modulus is 1500MPa; in particular, malaysia CIPC
PP-2301。
The POE has a melt index of 0.5g/10min and a tensile strength of 35kN/m; in particular to American Exxon Mobil POE 5061.
The auxiliary agent C is a free radical scavenger and a free radical quencher with the weight ratio of 1; the free radical scavenger is a hindered amine compound, specifically BASFTinuvin123; the free radical quencher is an organic complex of nickel, specifically calla 1084.
In a second aspect of this embodiment, a method for preparing a composite solar cell back sheet with high weatherability is provided, in which an adhesive is used to sequentially laminate and bond an inner PO layer, a polyester support layer, and an outer PO layer (the coating thickness of the adhesive is 10 μm), and the PO layer is left at 60 ℃ for 3 hours to shape, so as to obtain a back sheet finished product.
The adhesive is a polyurethane adhesive, in particular a polyether polyurethane adhesive; the polyether polyurethane adhesive comprises the following raw materials, by weight, 64 parts of polyglycol, 40 parts of diisocyanate, 0.1 part of catalyst, 8 parts of chain extender, 1 part of rheological additive and 20 parts of solvent.
The weight ratio of the polyglycol is 1:3 of polyoxypropylene diol and polyoxyethylene diol.
The average molecular weight of the polyoxypropylene diol is 2000, and the polyoxypropylene diol is from Nanjing Yamameshan Shiyashi company.
The polyoxyethylene glycol has an average molecular weight of 1000 and is sourced from Nanjing Yao Shishan chemical company.
The diisocyanate is TDI (toluene diisocyanate) and IPDI (isophorone diisocyanate); the weight ratio of TDI to IPDI was 1.
The chain extender is 1, 4-butanediol and dipropylene glycol; the weight ratio of 1, 4-butanediol to dipropylene glycol is 2:1.
the rheology aid was 2900mPa.s (25 ℃), and was derived from Rohm and Haas RM-2020.
The catalyst is stannous octoate, and the CAS number is 301-10-0.
The solvent is ethyl acetate.
The preparation method of the polyether adhesive polyester polyol comprises the following steps: mixing the raw materials except the diisocyanate according to the formula amount, and uniformly stirring at 800rpm to obtain a material A; before use, diisocyanate is added into the material A and is uniformly mixed to obtain the polyether adhesive.
Example 3.
The embodiment provides a composite solar cell backboard with high weather resistance, which structurally comprises a PO inner layer, a polyester supporting layer and a PO outer layer which are sequentially stacked.
The thicknesses of the PO inner layer, the polyester support layer and the PO outer layer are respectively 30 mu m,240 mu m and 30 mu m.
The PO inner layer comprises the following raw materials: based on the total mass of the PO inner layer, 96.5 percent of PE base material, 1 percent of anti-UV agent, 1 percent of antioxidant and 1.5 percent of auxiliary agent A.
The raw materials of the polyester support layer comprise: calculated by the total mass of the polyester supporting layer, 85.7% of polyester base material, 8% of filler, 2.5% of toughening agent, 1% of hydrolysis resistant agent, 0.6% of UV resistant agent, 1.2% of antioxidant and 1% of auxiliary agent B.
The PO outer layer comprises the following raw materials: based on the total mass of the PO outer layer, 90.6 percent of the polyolefin mixture, 0.8 percent of the anti-UV agent, 6 percent of the filler, 1 percent of the antioxidant and 1.6 percent of the auxiliary agent C.
The melt flow rate of the PE base material is 5g/10min, the tensile yield strength is 27MPa, and the elongation at break is 650%; in particular Dow HDPE 05962B.
The anti-UV agent is hindered amine, specifically UV-3529 and UV-3853 with the weight ratio of 2.
The antioxidant is hindered phenol and thioether ester, and the mass ratio of the hindered phenol to the thioether ester is 1.4:1.
the hindered phenol is antioxidant 235; the thioether ester is antioxidant DSTP.
The auxiliary agent A is PS-g-EGMA, and is from Nippon oil and fat Co.
The melt flow rate of the polyester base material is 5g/10min, the tensile modulus is 240MPa, and the elongation at break is 300%; in particular to United states Dupont TPEE HTR8425 NC010.
The filler is nano-scale titanium dioxide produced by a gas phase method, and the specific surface area of the nano-scale titanium dioxide is 50m 2 (ii)/g, average particle diameter of 21nm; specifically, degussa AEROXIDE P25.
The toughening agent is an ethylene copolymer, the melt flow rate is 8g/10min, and the toughening agent is specifically DuPont Elvaloy4170 in the United states.
The anti-hydrolysis agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, and the CAS number is 2162-74-5.
The assistant B is a coupling agent, in particular to a titanate coupling agent TC-131.
The polyolefin mixture comprises PP, PE and POE; the weight ratio of PP, PE and POE is 2.5:5:1.5.
the PE has a melt index of 8g/10min and a tensile yield strength of 10.3MPa; in particular Dupont LDPE 0098S LE.
The PP has a melt index of 8.7g/10min and a flexural modulus of 1500MPa; in particular CIPC in malaysia
PP-2301。
The POE has a melt index of 0.5g/10min and a tensile strength of 35kN/m; in particular to American Exxon Mobil POE 5061.
The auxiliary agent C is a free radical scavenger and a free radical quencher with the weight ratio of 1; the free radical scavenger is a hindered amine compound, specifically BASFTinuvin123; the free radical quencher is an organic complex of nickel, specifically calla 1084.
In a second aspect of this embodiment, a method for preparing a composite solar cell back sheet with high weather resistance is provided, in which an adhesive is used to sequentially laminate and bond an inner PO layer, a polyester support layer, and an outer PO layer (the coating thickness of the adhesive is 10 μm), and the PO layer is placed at 60 ℃ for 3 hours to be shaped, so as to obtain a back sheet finished product.
The adhesive is a polyurethane adhesive, in particular a polyether polyurethane adhesive; the polyether polyurethane adhesive comprises the following raw materials, by weight, 64 parts of polyglycol, 40 parts of diisocyanate, 0.1 part of catalyst, 8 parts of chain extender, 1 part of rheological additive and 20 parts of solvent.
The weight ratio of the polyglycol is 1:3 of polyoxypropylene diol and polyoxyethylene diol.
The average molecular weight of the polyoxypropylene diol is 2000, and the polyoxypropylene diol is from Nanjing Yamameshan Shiyashi company.
The polyoxyethylene glycol has an average molecular weight of 1000 and is sourced from Nanjing Yao Shishan chemical company.
The diisocyanate is TDI (toluene diisocyanate) and IPDI (isophorone diisocyanate); the weight ratio of TDI to IPDI was 1.
The chain extender is 1, 4-butanediol and dipropylene glycol; the weight ratio of 1, 4-butanediol to dipropylene glycol is 2:1.
the rheological aid has a viscosity of 2900mPa.s (25 ℃), and is sourced from Rohm and Haas RM-2020.
The catalyst is stannous octoate, and the CAS number is 301-10-0.
The solvent is ethyl acetate.
The preparation steps of the polyether adhesive polyester polyol are as follows: mixing the raw materials except the diisocyanate according to the formula amount, and uniformly stirring at 800rpm to obtain a material A; before use, diisocyanate is added into the material A and is uniformly mixed to obtain the polyether adhesive.
Example 4.
The embodiment provides a composite solar cell backboard with high weather resistance, which structurally comprises a PO inner layer, a polyester supporting layer and a PO outer layer which are sequentially stacked.
The thicknesses of the PO inner layer, the polyester support layer and the PO outer layer are respectively 30 micrometers, 200 micrometers and 40 micrometers.
The PO inner layer comprises the following raw materials: based on the total mass of the PO inner layer, 96.5 percent of PE base material, 1 percent of anti-UV agent, 1 percent of antioxidant and 1.5 percent of auxiliary agent A.
The raw materials of the polyester support layer comprise: calculated by the total mass of the polyester supporting layer, 85.7 percent of polyester base material, 8 percent of filler, 2.5 percent of toughening agent, 1 percent of hydrolysis resistant agent, 0.6 percent of anti-UV agent, 1.2 percent of antioxidant and 1 percent of auxiliary agent B.
The PO outer layer comprises the following raw materials: based on the total mass of the PO outer layer, 90.6 percent of the polyolefin mixture, 0.8 percent of the anti-UV agent, 6 percent of the filler, 1 percent of the antioxidant and 1.6 percent of the auxiliary agent C.
The melt flow rate of the PE base material is 5g/10min, the tensile yield strength is 27MPa, and the elongation at break is 650%; in particular Dow HDPE 05962B.
The anti-UV agent is hindered amine, specifically UV-3529 and UV-3853 with the weight ratio of 2.
The antioxidant is hindered phenol and thioether ester, and the mass ratio of the hindered phenol to the thioether ester is 1.4:1.
the hindered phenol is specifically an antioxidant 235; the thioether ester is an antioxidant DSTP.
The auxiliary agent A is PS-g-EGMA which is sourced from Nippon oil and fat Co.
The melt flow rate of the polyester base material is 5g/10min, the tensile modulus is 240MPa, and the elongation at break is 300%; in particular to United states Dupont TPEE HTR8425 NC010.
The filler is nano-scale titanium dioxide produced by a gas phase method, and the specific surface area of the nano-scale titanium dioxide is 50m 2 (ii)/g, average particle diameter of 21nm; in particular, degussa AEROXIDE P25
The toughening agent is an ethylene copolymer, the melt flow rate is 8g/10min, and the toughening agent is specifically DuPont Elvaloy4170 in the United states.
The anti-hydrolysis agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, and the CAS number is 2162-74-5.
The assistant B is a coupling agent, in particular to a titanate coupling agent TC-131.
The polyolefin mixture comprises PP, PE and POE; the weight ratio of PP, PE and POE is 5:1:4.
the PE has a melt index of 8g/10min and a tensile yield strength of 10.3MPa; in particular U.S. Dupont LDPE 0098S LE.
The PP has a melt index of 8.7g/10min and a flexural modulus of 1500MPa; in particular, malaysia CIPC
PP-2301。
The POE has a melt index of 0.5g/10min and a tensile strength of 35kN/m; in particular to American Exxon Mobil POE 5061.
The auxiliary agent C is a free radical scavenger and a free radical quencher with the weight ratio of 1; the free radical scavenger is a hindered amine compound, specifically BASFTinuvin123; the free radical quencher is an organic complex of nickel, specifically calla 1084.
In a second aspect of this embodiment, a method for preparing a composite solar cell back sheet with high weather resistance is provided, in which an adhesive is used to sequentially laminate and bond an inner PO layer, a polyester support layer, and an outer PO layer (the coating thickness of the adhesive is 10 μm), and the PO layer is placed at 60 ℃ for 3 hours to be shaped, so as to obtain a back sheet finished product.
The adhesive is a polyurethane adhesive, in particular a polyether polyurethane adhesive; the polyether polyurethane adhesive comprises the following raw materials, by weight, 64 parts of polyglycol, 40 parts of diisocyanate, 0.1 part of catalyst, 8 parts of chain extender, 1 part of rheological additive and 20 parts of solvent.
The weight ratio of the polyglycol is 1:3 of polyoxypropylene diol and polyoxyethylene diol.
The average molecular weight of the polyoxypropylene diol is 2000, and the polyoxypropylene diol is from Nanjing Yamameshan Shiyashi company.
The polyoxyethylene glycol has an average molecular weight of 1000 and is sourced from Nanjing Yamamoto petrochemical company.
The diisocyanate is TDI (toluene diisocyanate) and IPDI (isophorone diisocyanate); the weight ratio of TDI to IPDI was 1.
The chain extender is 1, 4-butanediol and dipropylene glycol; the weight ratio of 1, 4-butanediol to dipropylene glycol is 2:1.
the rheological aid has a viscosity of 2900mPa.s (25 ℃), and is sourced from Rohm and Haas RM-2020.
The catalyst is stannous octoate, and the CAS number is 301-10-0.
The solvent is ethyl acetate.
The preparation method of the polyether adhesive polyester polyol comprises the following steps: mixing the raw materials except the diisocyanate according to the formula amount, and uniformly stirring at 800rpm to obtain a material A; before use, diisocyanate is added into the material A and is uniformly mixed to obtain the polyether adhesive.
Example 5.
The embodiment provides a composite solar cell backboard with high weather resistance, which structurally comprises a PO inner layer, a polyester supporting layer and a PO outer layer which are sequentially stacked.
The thicknesses of the PO inner layer, the polyester support layer and the PO outer layer are respectively 30 micrometers, 200 micrometers and 40 micrometers.
The PO inner layer comprises the following raw materials: based on the total mass of the PO inner layer, 96.5 percent of PE base material, 1 percent of anti-UV agent, 1 percent of antioxidant and 1.5 percent of auxiliary agent A.
The raw materials of the polyester support layer comprise: calculated by the total mass of the polyester supporting layer, 85.7% of polyester base material, 8% of filler, 2.5% of toughening agent, 1% of hydrolysis resistant agent, 0.6% of UV resistant agent, 1.2% of antioxidant and 1% of auxiliary agent B.
The PO outer layer comprises the following raw materials: based on the total mass of the PO outer layer, 90.6 percent of the polyolefin mixture, 0.8 percent of the anti-UV agent, 6 percent of the filler, 1 percent of the antioxidant and 1.6 percent of the auxiliary agent C.
The melt flow rate of the PE base material is 5g/10min, the tensile yield strength is 27MPa, and the elongation at break is 650%; in particular Dow HDPE 05962B.
The anti-UV agent is hindered amine, specifically UV-3529 and UV-3853 with the weight ratio of 2.
The antioxidant is hindered phenol and thioether ester, and the mass ratio of the hindered phenol to the thioether ester is 1.4:1.
the hindered phenol is antioxidant 235; the thioether ester is antioxidant DSTP.
The auxiliary agent A is PS-g-EGMA, and is from Nippon oil and fat Co.
The melt flow rate of the polyester base material is 5g/10min, the tensile modulus is 240MPa, and the elongation at break is 300%; in particular to Dupont TPEE HTR8425 NC010 in the United states.
The filler is nano-scale titanium dioxide produced by a gas phase method, and the specific surface area of the nano-scale titanium dioxide is 50m 2 (ii)/g, average particle diameter of 21nm; in particular toIs Degussa AEROXIDE P25
The toughening agent is an ethylene copolymer, the melt flow rate is 8g/10min, and the toughening agent is specifically DuPont Elvaloy4170 in the United states.
The anti-hydrolysis agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, and the CAS number is 2162-74-5.
The assistant B is a coupling agent, in particular to a titanate coupling agent TC-131.
The polyolefin mixture comprises PP, PE and POE; the weight ratio of PP, PE and POE is 3:4:2.
the PE has a melt index of 8g/10min and a tensile yield strength of 10.3MPa; in particular Dupont LDPE 0098S LE.
The melt index of the PP is 8.7g/10min, and the flexural modulus is 1500MPa; in particular, malaysia CIPC
PP-2301。
The POE has a melt index of 0.5g/10min and a tensile strength of 35kN/m; in particular to American Exxon Mobil POE 5061.
The auxiliary agent C is a free radical scavenger and a free radical quencher with the weight ratio of 1; the free radical scavenger is a hindered amine compound, specifically BASFTinuvin123; the free radical quencher is an organic complex of nickel, specifically calla 1084.
In a second aspect of this embodiment, a method for preparing a composite solar cell back sheet with high weather resistance is provided, in which an adhesive is used to sequentially laminate and bond an inner PO layer, a polyester support layer, and an outer PO layer (the coating thickness of the adhesive is 10 μm), and the PO layer is placed at 60 ℃ for 3 hours to be shaped, so as to obtain a back sheet finished product.
The adhesive is a polyurethane adhesive, in particular a polyether polyurethane adhesive; the polyether polyurethane adhesive comprises the following raw materials, by weight, 64 parts of polyglycol, 40 parts of diisocyanate, 0.1 part of catalyst, 8 parts of chain extender, 1 part of rheological additive and 20 parts of solvent.
The weight ratio of the polyglycol is 1:1 of polyoxypropylene diol and polyoxyethylene diol.
The average molecular weight of the polyoxypropylene diol is 2000, and the polyoxypropylene diol is from Nanjing Yamameshan Shiyashi company.
The polyoxyethylene glycol has an average molecular weight of 1000 and is sourced from Nanjing Yao Shishan chemical company.
The diisocyanate is TDI (toluene diisocyanate) and IPDI (isophorone diisocyanate); the weight ratio of TDI to IPDI was 1.
The chain extender is 1, 4-butanediol.
The rheological aid has a viscosity of 2900mPa.s (25 ℃), and is sourced from Rohm and Haas RM-2020.
The catalyst is stannous octoate, and the CAS number is 301-10-0.
The solvent is ethyl acetate.
The preparation steps of the polyether adhesive polyester polyol are as follows: mixing the raw materials except the diisocyanate according to the formula amount, and uniformly stirring at 800rpm to obtain a material A; before use, diisocyanate is added into the material A and is uniformly mixed to obtain the polyether adhesive.
Performance test method
1. Cold and hot cycle test
The temperature resistance of the solar cell back sheets provided in examples 1 to 5 is tested by referring to GB/T31034 2014;
the test conditions are-40 ℃ to 85 ℃,6 h/period and 400 periods.
15 parallel samples were set for each set of examples, and the number M of samples exhibiting delamination, blistering, discoloration, cracking, and tacky adhesive layer after cooling and heating cycles was observed and recorded in Table 1.
UV testing
The solar cell back sheets provided in examples 1 to 5 were tested for UV resistance with reference to GB/T31034 2014; the test conditions were 60 kWh.m -2 72h; the initial value and retention k1 of the elongation at break of the solar cell backsheet were recorded in table 1.
3. Constant moist Heat test
The solar cell back sheets provided in examples 1 to 5 were tested for wet and heat resistance with reference to GB/T31034 2014; the test conditions were 85 ℃,85% r.h.,3000h; the initial value and retention k2 of the elongation at break of the solar cell backsheet were recorded in table 1.
4. Tensile strength
The solar cell backsheet provided in examples 1-5 was tested for tensile strength with reference to ISO 1184, recorded in table 1.
Performance test data
TABLE 1 Performance test results
Claims (10)
1. The composite solar cell backboard with high weather resistance is characterized in that the solar cell backboard is structurally characterized in that a PO inner layer, a polyester supporting layer and a PO outer layer are sequentially laminated.
2. The composite solar cell backsheet as claimed in claim 1, wherein the thickness ratio of the PO inner layer, the polyester support layer and the PO outer layer is (1-8): (10-36): (0.5-10).
3. The composite solar cell back sheet with high weather resistance as claimed in claim 1 or 2, wherein the raw materials of the polyester support layer comprise: polyester base stock, filler, toughening agent, hydrolysis resistant agent, anti-UV agent, antioxidant and auxiliary agent B.
4. The composite type solar cell back sheet with high weatherability as claimed in any one of claims 1-3, wherein the raw materials of the PO inner layer comprise: PE base stock, anti-UV agent, antioxidant and auxiliary agent A.
5. The composite type solar cell back sheet with high weatherability as claimed in any one of claims 1-4, wherein the raw materials of the PO outer layer comprise: polyolefin mixture, anti-UV agent, filler, antioxidant and auxiliary agent C.
6. The composite solar cell back sheet according to claim 4, wherein the PE base material has a melt flow rate of 2-10g/10min, a tensile yield strength of 15-40MPa, and an elongation at break of 400-800%.
7. The composite solar cell back sheet according to claim 4, wherein the anti-UV agent comprises one or more of hindered amines, benzophenones, benzotriazoles, triazines, acrylonitriles, oxalamides, and organo-nickel.
8. The composite solar cell back sheet according to claim 4, wherein the antioxidant comprises one or more of hindered phenols, thioether esters, phosphite esters, and thiols.
9. The composite solar cell back sheet according to claim 3, wherein the polyester base material has a melt flow rate of 2-15g/10min, a tensile modulus of 15-35MPa, and an elongation at break of > 200%.
10. The preparation method of the composite solar cell back sheet with high weather resistance according to any one of claims 1 to 9, wherein the solar photovoltaic back sheet is prepared by sequentially laminating and bonding an inner layer of PO, a polyester support layer and an outer layer of PO by using an adhesive to obtain a finished back sheet.
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