CN103280479A - Novel fluoride-free multilayer coextrusion solar cell back plate and preparation method thereof - Google Patents
Novel fluoride-free multilayer coextrusion solar cell back plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a solar cell assembly, in particular to a novel fluoride-free multilayer coextrusion solar cell back plate and a preparation method thereof. The back plate mainly comprises three layers; a weather-proof layer is formed by modified PA (Poly A) and has a thickness of 25mu. m; a structural reinforcing layer is formed by modified PET (polyethylene glycol terephthalate) and has a thickness of 300mu. m; and a bonding layer is formed by modified PA and has a thickness of 25mu. m. The preparation method comprises the following steps of: firstly, modifying PA and PET; and then carrying out three-layer coextrusion on the weather-proof layer, the structural reinforcing layer and the bonding layer by a multilayer coextrusion device. The solar cell back plate disclosed by the invention, which does not use fluorine-containing resin and is prepared by adopting a processing manner of three-layer coextrusion, does not need to use an adhesive; the PA and the PET are modified; an APA structure obtained by coextrusion has higher mechanical property; adhesion performance between the layers is excellent; weather resistance and hydrolytic resistance capacity are greatly improved; and the service life of a solar cell is ensured.
Description
Technical field
The present invention relates to solar module, particularly multi-layer co-extruded solar cell backboard of a kind of novel free-floride and preparation method thereof.
Background technology
2012, after Tokyo Electric Power's Fukushima first nuclear power plant accident, various circles of society thought deeply the development problem of regenerative resource again.Solar energy is as a kind of cleaning, non-pollution of renewable energy, being subject to people's attention all the more.Solar battery back film is positioned at the back side of solar panel, and the battery sheet is played protection and supporting role, requires to have certain insulating properties, water preventing ability, resistance to ag(e)ing etc.At present, main flow notacoria product mainly comprises: the compound notacoria of (1) gluing, and at the compound fluorine film in PET polyester film two sides or EVA glued membrane, three-decker, common have structures such as TPT, TPE, KPK, KPE.(2) application type backboard film is at PET polyester film coated on both sides fluororesin, drying film-forming.Along with the development of technology and the pressure of cost, solar battery back film has experienced from the development course of the fluorine-containing notacoria of two-sided fluorine-containing notacoria-single face-floride-free notacoria, the cost of two fluorine backboards is the most expensive, but solar module in use, ultraviolet ray in the sunlight is via after toughened glass, battery sheet and the EVA glued membrane, really shine the also few of solar energy back plate surface, so as in traditional two-sided fluorine-containing backboard with the inreal value that embodies him of the fluorine face of EVA lamination, performance surplus.Use the most Kynoar that adopt of fluorine material comparatively widely in the market, discover Kynoar in the process of processing film forming, local temperature is too high, causes degraded, produces a large amount of HF gas, can cause the human body calcium loss after being absorbed by the body.Simultaneously the surface wettability of Kynoar is very poor, when unprocessed and other plastic basis material be difficult to bonding.Therefore develop a kind of free-floride, have good insulation performance, water preventing ability, ageing-resistant performance excellence, process simple new type solar energy notacoria and have very significant meaning.
" a kind of floride-free solar cell backboard and preparation method thereof " disclosed among patent CN 102642360 A, its backboard mainly is made up of adhesive linkage (composition epoxide-resin glue, polyamide glue, organic silica gel or acrylic resin heavier a kind of), base layer (modified poly ethylene), need in the preparation process to use a large amount of organic solvents to prepare adhesive linkage, during manufacturing cost, contaminative is strong.
Polyamide is a kind of linearity and thermoplastic polycondensation polymer, have that the transparency is good, hot formability is good, mechanical performance is excellent, case hardness is big, wear-resisting and lubrification and higher characteristics such as impact property are arranged, and the C=O in the strand and NH group have certain polarity, can well be bonded together with the polymeric material of polarity, improve deflection and the hot strength of composite membrane.Patent of the present invention adopts multi-layer co-extruded device to prepare a kind of novel floride-free solar energy backboard, the APA structure, and wherein A is acylamide polymer, P is polybutylene terephthalate (PBT).
Summary of the invention
In order to overcome existing technical deficiency, the invention provides multi-layer co-extruded solar cell backboard of a kind of novel free-floride and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: the multi-layer co-extruded solar cell backboard of a kind of novel free-floride, ground floor is weathering layer, the second layer is the structure enhancement layer, and the 3rd layer is adhesive linkage, and described weathering layer is modification PA, thick 25um, wherein modification PA is by 100 parts PA6, PA66, PA11, PA1012 or PA12,5 ~ 10 parts of ultraviolet light screeners, 1 ~ 10 part of ultraviolet absorber, 0.5 ~ 1 part of antioxidant, and 1 ~ 10 part of modified poly resin I is formed; Described structure enhancement layer is modified PET, thick 300um, and wherein modified PET is by 70 ~ 80 parts PET, 5 ~ 10 parts ultraviolet light screener, 1 ~ 5 part hydrolysis-resisting agent, 10 ~ 15 parts of alkali-free glass fibers are formed; Described tack coat is modification PA, thick 25um, and wherein modification PA is by 80 ~ 90 parts PA6, PA66, PA11, PA1012 or PA12, and 10 ~ 20 parts TPO copolymer is formed.
According to another embodiment of the invention, comprise that further described ultraviolet light screener is the TiO through surface modification
2, ZnO or ZnS.
According to another embodiment of the invention, comprise that further described ultraviolet absorber is the benzophenone class, benzotriazole replaces the fine class of propylene or triazines.
According to another embodiment of the invention, comprise that further described antioxidant is aromatic amine or hindered phenol.
According to another embodiment of the invention, comprise that further described fluoropolymer resin I is the modifier of TPO.
According to another embodiment of the invention, comprise that further described water repellent agent is polycarbodiimide.
According to another embodiment of the invention, comprise that further described alkali-free glass fiber surface through silane coupled processing, has good compatibility with PET.
According to another embodiment of the invention, the copolymer that further comprises described TPO is a kind of or two kinds of blends in ethylene ethyl acrylate copolymer (EEA), EMA anhydride copolymer (EMA), ethylene vinyl acetate copolymer (EVA), the ethylene-methacrylic acid copolymer (EMAA, EAA) etc.
The present invention further comprises the preparation method of the multi-layer co-extruded solar cell backboard of novel free-floride, earlier PA and PET are carried out modification, the back is carried out weathering layer and enhancement layer, adhesive linkage by multi-layer co-extruded device three-layer co-extruded, prepares the multi-layer co-extruded solar cell backboard of novel free-floride.
The invention has the beneficial effects as follows, do not use fluorine resin, the solar cell backboard that adopts three-layer co-extruded processing mode to prepare, do not need to use adhesive, PA and PET are carried out modification, the APA structure that coextrusion obtains has better mechanical property, and adhesive property excellence, weatherability and anti-hydrolysis ability between layer and the layer are greatly improved, and have guaranteed the useful life of solar cell.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
The solar energy back board structure schematic diagram that Fig. 1 prepares for embodiment 1;
The ESEM picture of the solar cell backboard section that Fig. 2 prepares for embodiment 1;
Wherein, 1, weathering layer, 2, the structure enhancement layer, 3, adhesive linkage.
Embodiment
As shown in Figure 1 and Figure 2, the multi-layer co-extruded solar cell backboard of a kind of novel free-floride, ground floor is weathering layer 1, the second layer is structure enhancement layer 2, the 3rd layer is adhesive linkage 3, described weathering layer 1 is modification PA, thick 25um, and wherein modification PA is by 100 parts PA6, PA66, PA11, PA1012 or PA12,5 ~ 10 parts of ultraviolet light screeners, 1 ~ 10 part of ultraviolet absorber, 0.5 ~ 1 part of antioxidant, and 1 ~ 10 part of modified poly resin I is formed; Described structure enhancement layer 2 is modified PET, thick 300um, and wherein modified PET is by 70 ~ 80 parts PET, 5 ~ 10 parts ultraviolet light screener, 1 ~ 5 part hydrolysis-resisting agent, 10 ~ 15 parts of alkali-free glass fibers are formed; Described tack coat 3 is modification PA, thick 25um, and wherein modification PA is by 80 ~ 90 parts PA6, PA66, PA11, PA1012 or PA12, and 10 ~ 20 parts TPO copolymer is formed.
Described ultraviolet light screener comprises the TiO through surface modification
2, ZnO, ZnS, mainly be in order to improve the uvioresistant effect of PA, prevent that the PA macromolecular chain from degrading, material aging.TiO
2, ZnO, ZnS etc., effective acting time is long, has good chemical stability and thermal stability, nontoxic, nonirritant, and chemical reaction does not take place with other auxiliary agent, and through surface modification, good dispersion in resin matrix, be difficult for reuniting, as R706, the R902 etc. of Du Pont's production.The ultraviolet light screener that adopts in weathering layer 1 and the structure enhancement layer 2 is similar, and wherein the PET of structure enhancement layer 2 modifications also can adopt the R420 of Sha Haliben production etc.
Described ultraviolet absorber is the benzophenone class, and benzotriazole replaces the fine class of propylene or triazines.As, UV-P, UV-O, UV-9, UV-531 etc.
Described antioxidant is aromatic amine or hindered phenol, as antioxidant 1010 etc., mainly is to prevent PA in the course of processing because the too high strand thermal oxidative degradation that causes of temperature.
Described fluoropolymer resin I is the modifier of TPO, can reduce the water absorption of PA significantly, improves the hydrolytic resistance of its film, as HD900P, PC-33C, TRD-428P etc.
Described water repellent agent is polycarbodiimide, good with the compatibility of polyester, under hot conditions, to the macromolecular chain repairing effect of polyester, play the effect that prevents and reduce the macromolecular chain degraded, effectively keep high molecular molecular weight, keep the physical and mechanical properties of material.As Stabaxol l of Lay mattress chemistry etc.
Described alkali-free glass fiber surface has good compatibility through silane coupled processing with PET, as the 988A of megalith etc., plays the effect of enhancing.
The copolymer of described TPO is a kind of or two kinds of blends in ethylene ethyl acrylate copolymer (EEA), EMA anhydride copolymer (EMA), ethylene vinyl acetate copolymer (EVA), the ethylene-methacrylic acid copolymer (EMAA, EAA) etc.
The preparation method of the multi-layer co-extruded solar cell backboard of a kind of novel free-floride: earlier PA and PET are carried out modification, the back is carried out weathering layer and enhancement layer, adhesive linkage by multi-layer co-extruded device three-layer co-extruded, prepares the multi-layer co-extruded solar cell backboard of novel free-floride.
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
With 100 parts of PA6(UBE 1013B), 5 parts of titanium dioxide (Ti-Pure R902), 1 part of UV-P, 0.5 part of antioxidant 1010 and 5 parts of modified poly resin HD900P mix, batch mixing is added in the double screw extruder, stand-by behind the extruding pelletization, be designated as 1#, extruder temperature is set at: 170 ℃, and 200 ℃, 230 ℃, 245 ℃, 245 ℃, 240 ℃.
With 100 parts of PET(Yizheng Fiber Optical plant BG80), 5 parts of titanium dioxide (Ti-Pure R960) and 1 part of polycarbodiimide (Lay mattress chemistry Stabaxol l) mix, batch mixing is added in the double screw extruder, alkali-free glass fiber (megalith 988A) adds at the spout of the 3rd section heating place, and granulation is stand-by then, is designated as 2#, extruder temperature is set at: 200,230,240,245,250,240.
With 80 parts of PA6(UBE 1013B), 20 parts of EAA(LG-DOWs 1040) mix, batch mixing is added in the double screw extruder, extruding pelletization is stand-by, is designated as 3#, extruder temperature is set at: 170,200,230,245,250,240.
Above-mentioned three kinds of particle 1# through the modification granulation, 2#, 3# join corresponding 1# respectively, 2#, three single screw extrusion machines of 3#, extrusion temperature is respectively 180 ℃ of 1#, 200 ℃, 220 ℃, 240 ℃; 190 ℃ of 2#, 220 ℃, 230 ℃, 245 ℃; 180 ℃ of 3#, 200 ℃, 220 ℃, 240 ℃, three kinds of melts converge the temperature of die head through separately runner to the die lip place of triple extrusion die head: 260 ℃, and 255 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 255 ℃, 260 ℃, three layers thickness is controlled by the extrusion capacity of three kinds of materials, and the ratio of extrusion capacity is 1:12:1, and the film of extruding is through the casting roller cooling and shaping, baking oven heat treatment is cut edge, and rolling obtains three-layer co-extruded solar battery back film.
Embodiment 2
100 parts of PA12(are won wound Degussa E40-S3), 5 parts of titanium dioxide (Sha Haliben R420), 1 part of UV-P, 0.5 part of antioxidant 1010 and 5 parts of modified poly resin HD900P mix, batch mixing is added in the double screw extruder, stand-by behind the extruding pelletization, be designated as 1#, extruder temperature is set at: 170 ℃, and 190 ℃, 220 ℃, 240 ℃, 240 ℃, 230 ℃.
With 100 parts of PET(Yizheng Fiber Optical plant BG80), 5 parts of titanium dioxide (Ti-Pure R960) and 1 part of polycarbodiimide (Lay mattress chemistry Stabaxol l) mix, batch mixing is added in the double screw extruder, alkali-free glass fiber (megalith 988A) adds at the spout of the 3rd section heating place, and granulation is stand-by then, is designated as 2#, extruder temperature is set at: 200 ℃, 230 ℃, 240 ℃, 245 ℃, 250 ℃, 240 ℃.
80 parts of PA12(are won wound Degussa E40-S3), 20 parts of EMA(Dupont 1125AC) mix, batch mixing is added in the double screw extruder, extruding pelletization is stand-by, is designated as 3#, extruder temperature is set at: 170 ℃, and 190 ℃, 220 ℃, 240 ℃, 240 ℃, 230 ℃.
Above-mentioned three kinds of particle 1# through the modification granulation, 2#, 3# join corresponding 1# respectively, 2#, three single screw extrusion machines of 3#, extrusion temperature is respectively 170 ℃ of 1#, 190 ℃, 220 ℃, 240 ℃; 190 ℃ of 2#, 220 ℃, 230 ℃, 245 ℃; 170 ℃ of 3#, 190 ℃, 220 ℃, 240 ℃, three kinds of melts converge the temperature of die head through separately runner to the die lip place of triple extrusion die head: 260 ℃, and 255 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 255 ℃, 260 ℃, three layers thickness is controlled by the extrusion capacity of three kinds of materials, and the ratio of extrusion capacity is 1:12:1, and the film of extruding is through the casting roller cooling and shaping, baking oven heat treatment is cut edge, and rolling obtains three-layer co-extruded solar battery back film.
Embodiment 3
With 100 parts of PA11(France A Kema 5161MAC), 5 parts of titanium dioxide (Ti-Pure R350), 1 part of UV-P, 0.5 part of antioxidant 1010 and 5 parts of modified poly resin HD900P mix, batch mixing is added in the double screw extruder, stand-by behind the extruding pelletization, be designated as 1#, extruder temperature is set at: 180 ℃, and 210 ℃, 230 ℃, 245 ℃, 245 ℃, 240 ℃.
With 100 parts of PET(Yizheng Fiber Optical plant BG80), 5 parts of titanium dioxide (Ti-Pure R960) and 1 part of polycarbodiimide (Lay mattress chemistry Stabaxol l) mix, batch mixing is added in the double screw extruder, alkali-free glass fiber (megalith 988A) adds at the spout of the 3rd section heating place, and granulation is stand-by then, is designated as 2#, extruder temperature is set at: 200 ℃, 230 ℃, 240 ℃, 245 ℃, 250 ℃, 240 ℃.
With 80 parts of PA11(France A Kema 5161MAC), 20 parts of organic 14-2 in EVA(Beijing) mix, batch mixing is added in the double screw extruder, extruding pelletization is stand-by, is designated as 3#, extruder temperature is set at: 180 ℃, and 210 ℃, 230 ℃, 245 ℃, 245 ℃, 240 ℃.
Above-mentioned three kinds of particle 1# through the modification granulation, 2#, 3# join corresponding 1# respectively, 2#, three single screw extrusion machines of 3#, extrusion temperature is respectively 180 ℃ of 1#, 200 ℃, 220 ℃, 240 ℃; 190 ℃ of 2#, 220 ℃, 230 ℃, 245 ℃; 180 ℃ of 3#, 200 ℃, 220 ℃, 240 ℃, three kinds of melts converge the temperature of die head through separately runner to the die lip place of triple extrusion die head: 260 ℃, and 255 ℃, 250 ℃, 250 ℃, 250 ℃, 250 ℃, 255 ℃, 260 ℃, three layers thickness is controlled by the extrusion capacity of three kinds of materials, and the ratio of extrusion capacity is 1:12:1, and the film of extruding is through the casting roller cooling and shaping, baking oven heat treatment is cut edge, and rolling obtains three-layer co-extruded solar battery back film.
The solar energy backboard that embodiment 1 ~ 3 prepares carries out Mechanics Performance Testing, hydrothermal aging test, ultraviolet test and lamination experiment.Hot strength and elongation at break are according to ASTM D882 standard testing; The ultraviolet ageing test condition, UVA+UVB wherein UVB accounts for 10%, irradiation power 0.68W/m2, total irradiation 60kwh; Aberration behind the test predose changes; The hydrothermal aging condition is: 85 ℃ of temperature, humidity 85% is observed the xanthochromia situation behind the 2000h, have or not delamination.The lamination experiment is backboard and EVA glued membrane lamination, test peeling force between the two.The result tests as following table:
In sum, it only is preferred embodiment of the present invention, be not to limit scope of the invention process, all equalizations of doing according to the described shape of claim scope of the present invention, structure, feature and spirit change and modify, and all should be included in the claim scope of the present invention.
The present invention does not use fluorine resin, the solar cell backboard that adopts three-layer co-extruded processing mode to prepare, do not need to use adhesive, PA and PET are carried out modification, the APA structure that coextrusion obtains has better mechanical property, adhesive property excellence, weatherability and anti-hydrolysis ability between layer and the layer are greatly improved, guaranteed the useful life of solar cell, and the preparation method is simple, serialization is produced fast, cost declines to a great extent, and has extraordinary application prospect.
Claims (9)
1. multi-layer co-extruded solar cell backboard of novel free-floride, ground floor is weathering layer (1), and the second layer is structure enhancement layer (2), and the 3rd layer is adhesive linkage (3), it is characterized in that, described weathering layer (1) is modification PA, thick 25um, and wherein modification PA is by 100 parts PA6, PA66, PA11, PA1012 or PA12,5 ~ 10 parts of ultraviolet light screeners, 1 ~ 10 part of ultraviolet absorber, 0.5 ~ 1 part of antioxidant, and 1 ~ 10 part of modified poly resin I is formed; Described structure enhancement layer (2) is modified PET, thick 300um, and wherein modified PET is by 70 ~ 80 parts PET, 5 ~ 10 parts ultraviolet light screener, 1 ~ 5 part hydrolysis-resisting agent, 10 ~ 15 parts of alkali-free glass fibers are formed; Described adhesive linkage (3) is modification PA, thick 25um, and wherein modification PA is by 80 ~ 90 parts PA6, PA66, PA11, PA1012 or PA12, and 10 ~ 20 parts TPO copolymer is formed.
2. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1 is characterized in that, described ultraviolet light screener is the TiO through surface modification
2, ZnO or ZnS.
3. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1 is characterized in that, described ultraviolet absorber is the benzophenone class, and benzotriazole replaces the fine class of propylene or triazines.
4. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1 is characterized in that, described antioxidant is aromatic amine or hindered phenol.
5. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1 is characterized in that, described fluoropolymer resin I is the modifier of TPO.
6. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1 is characterized in that, described water repellent agent is polycarbodiimide.
7. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1 is characterized in that, described alkali-free glass fiber surface has compatibility through silane coupled processing with PET.
8. the multi-layer co-extruded solar cell backboard of novel free-floride according to claim 1, it is characterized in that the copolymer of described TPO is a kind of or two kinds of blends in ethylene ethyl acrylate copolymer, EMA anhydride copolymer, ethylene vinyl acetate copolymer, the ethylene-methacrylic acid copolymer etc.
9. preparation method according to the multi-layer co-extruded solar cell backboard of the described novel free-floride of claim 1-8, it is characterized in that, earlier PA and PET are carried out modification, the back is carried out weathering layer and enhancement layer, adhesive linkage by multi-layer co-extruded device three-layer co-extruded, prepares the multi-layer co-extruded solar cell backboard of novel free-floride.
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| CN103589148A (en) * | 2013-11-21 | 2014-02-19 | 常州回天新材料有限公司 | Preparation method of heat-conducting and insulation solar cell back plate |
| CN105633184A (en) * | 2016-03-09 | 2016-06-01 | 中利腾晖光伏科技有限公司 | Environment-friendly solar component, solar power generation system and photovoltaic power station |
| CN106558629A (en) * | 2015-09-17 | 2017-04-05 | 中电电气(上海)太阳能科技有限公司 | A kind of environment protection solar cell component and laminating method |
| CN107254156A (en) * | 2017-06-09 | 2017-10-17 | 江苏东昇光伏科技有限公司 | A kind of preparation method of the floride-free backboard of solar cell |
| CN109473498A (en) * | 2018-11-15 | 2019-03-15 | 苏州赛伍应用技术股份有限公司 | Integrated backboard of a kind of encapsulation and preparation method thereof |
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| CN111211189A (en) * | 2018-11-20 | 2020-05-29 | 杭州永信洋光电材料有限公司 | Solar backboard and solar cell module comprising same |
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| CN103589148A (en) * | 2013-11-21 | 2014-02-19 | 常州回天新材料有限公司 | Preparation method of heat-conducting and insulation solar cell back plate |
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| CN109994565A (en) * | 2017-12-28 | 2019-07-09 | 宁波长阳科技股份有限公司 | Solar energy backboard membrane and preparation method thereof |
| CN109473498A (en) * | 2018-11-15 | 2019-03-15 | 苏州赛伍应用技术股份有限公司 | Integrated backboard of a kind of encapsulation and preparation method thereof |
| CN109473498B (en) * | 2018-11-15 | 2021-01-05 | 苏州赛伍应用技术股份有限公司 | Packaging integrated backboard and preparation method thereof |
| CN111211189A (en) * | 2018-11-20 | 2020-05-29 | 杭州永信洋光电材料有限公司 | Solar backboard and solar cell module comprising same |
| CN117264248A (en) * | 2023-11-21 | 2023-12-22 | 天津瑞盛包装材料有限公司 | Preparation method of high-temperature-resistant environment-friendly CPET sheet |
| CN117264248B (en) * | 2023-11-21 | 2024-02-06 | 天津瑞盛包装材料有限公司 | Preparation method of high-temperature-resistant environment-friendly CPET sheet |
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