CN102157591B - Back panel of solar cell and preparation method thereof - Google Patents
Back panel of solar cell and preparation method thereof Download PDFInfo
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- CN102157591B CN102157591B CN201110004231A CN201110004231A CN102157591B CN 102157591 B CN102157591 B CN 102157591B CN 201110004231 A CN201110004231 A CN 201110004231A CN 201110004231 A CN201110004231 A CN 201110004231A CN 102157591 B CN102157591 B CN 102157591B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 37
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 36
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 28
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 28
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 21
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 21
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 12
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 10
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 230000004927 fusion Effects 0.000 claims abstract description 9
- 229920006254 polymer film Polymers 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 87
- 239000011347 resin Substances 0.000 claims description 87
- 239000002994 raw material Substances 0.000 claims description 33
- 239000003381 stabilizer Substances 0.000 claims description 29
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 21
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 15
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 235000010215 titanium dioxide Nutrition 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 15
- 235000014692 zinc oxide Nutrition 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000004611 light stabiliser Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000007766 curtain coating Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- YOCHOHIOBBCVFR-UHFFFAOYSA-N 3-tert-butyl-2,2-dimethyloctane Chemical compound CCCCCC(C(C)(C)C)C(C)(C)C YOCHOHIOBBCVFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 2
- 229920005372 Plexiglas® Polymers 0.000 claims 2
- 239000010410 layer Substances 0.000 abstract description 168
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 239000000853 adhesive Substances 0.000 abstract description 15
- 239000012790 adhesive layer Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 2
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract 2
- 239000005020 polyethylene terephthalate Substances 0.000 abstract 2
- 230000003014 reinforcing effect Effects 0.000 abstract 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 238000007731 hot pressing Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000004513 sizing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 229920002313 fluoropolymer Polymers 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 229920002620 polyvinyl fluoride Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CHJAYYWUZLWNSQ-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;ethene Chemical group C=C.FC(F)=C(F)Cl CHJAYYWUZLWNSQ-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a back panel of a solar cell and a preparation method thereof. The solar back panel is provided with three polymer film layers from top to bottom, namely an adhesive weatherable layer, an adhesive reinforcing layer and an adhesive moisture-retarding layer, wherein the adhesive weatherable layer is a PVDF(polyvinylidene fluoride)/EVA (ethylene vinyl acetate) alloy layer, the adhesive reinforcing layer is a PET (polyethylene terephthalate)/PMMA (polymethyl methacrylate) alloy layer, and the adhesive moisture-retarding layer is a PVDF/PVB (polyvinyl butyral) alloy layer. In the preparation method, a multi-layer melting and co-extrusion method is adopted for realizing interface-free fusion of the three film layers, and a composite film can achieve good dimensional stability by online high-temperature shaping. The structure of the back panel of the solar cell only comprises the three layers, an adhesive layer does not need to be used, the preparation process is simple, the steps of sizing and hot-pressing are omitted, and the production efficiency is high; and simultaneously, the back panel has excellent performances and is in line with the packaging requirements of the solar cell.
Description
Technical field
The invention belongs to the solar-energy photo-voltaic cell technical field, be specifically related to a kind of solar cell backboard and preparation method thereof.
Background technology
Solar cell backboard is a kind of important auxilliary material in the photovoltaic industry, and its high-end market is always by external monopolization.The back board structure of main flow is the TPT of European Isovolta company and the TPE of U.S. Madico company on the market; Wherein T is E.I.Du Pont Company
polyvinyl fluoride (PVF) film; P is PETG (PET) film, and E is ethylene-vinyl acetate copolymer (EVA) film.3M company is developing the backboard that THV (hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)-vinylidene) fluorine resin prepares the THV/PET/EVA structure always, is difficult to a bonding difficult problem to solve PVF; Also some u s company attempts adopting PVDF (Kynoar), ECTFE (ethene chlorotrifluoroethylene), ETFE (ethylene tetrafluoroethylene copolymer) to substitute PVF as back veneer material; But no matter be TPT, TPE; Or the backboard of other three-deckers; The method that lamination solidifies behind all necessary employing coated with adhesive between each layer is bonding, and technology relative complex, operation cycle length, adhesive layer thickness fluctuate easily, and can cause environmental pollution.
Along with the continuous development of solar cell industry, China has become the photovoltaic industry processing base of output first in the world at present, and the occupation rate of market of its dorsulum accounts for 1/3rd of the whole world, and domestic for this reason present backboard production has also got into the flourish phase.
CN101359695A (application number 200810079311.6) discloses a kind of solar cell backboard, and it comprises base material and Nai Hou layer, it is characterized in that, in the both sides of base material (1), has at least a side to be provided with weathering layer (2), is provided with Obstruct membrane (3) in a side of base material (1); The component and the parts by weight thereof that prepare said weathering layer are: 25～45 parts of fluorine resins, 1.5～3 parts of modified resin, 0.5～3 part of polymer filler, 0.1～1 part of inorganic filler, 50～70 parts of solvents.This has been invented and has adopted with the fluorine resin is that the coating of main component is applied to pet film (PET) surface, and the solvent in the coating that volatilizees again forms weather-proof fluoropolymer resin layer.Base material in this patent document (1) both sides are provided with in the technical scheme of weathering layer (2), though the bottom weathering layer has been avoided the binding agent between fluoropolymer resin layer and pet layer, fluorine resin paints needs repeatedly coating to avoid pin hole, complex process; Base material (1) one side is provided with in the technical scheme of weathering layer (2) in this patent document still need have binding agent between fluoropolymer resin layer and pet layer.
CN101615636A (application number 200910054994.4) provides a kind of solar panel that reduces the four-layer structure of tack coat; It is characterized in that; Comprise top-down weathering layer, first adhesive linkage, structure enhancement layer and bonding reflector; Said weathering layer is through the bonding said structure enhancement layer of said first adhesive linkage, the said structure enhancement layer said bonding reflector of fitting; The structure enhancement layer is a polyester layer, and bonding reflector is a polyolefin layer, and the thickness of polyester layer is 40～400 μ m; The thickness of polyolefin layer is 4～400 μ m, and weathering layer is the fluorine material layer, and thickness is 4～40 μ m; First adhesive linkage is a kind of in polyurethane glue-line, acrylic acid ester glue-line or the epoxy adhesive layer, and thickness is 1～30 μ m, and solar cell backboard of the present invention has only four-layer structure; Compare with five-layer structure commonly used, lacked the adhesive linkage between polyester layer and the polyolefin layer.This scheme still can't avoid top fluorine material layer and polyester layer still need adopt adhesive (first adhesive linkage) bonding.
CN101879808A (application number 201010207083.3) provides the adhesive method of a kind of fluoroplastic layer and polyester layer; Multi-layer co-extruded and curtain coating is applied on the polyester layer with fluoroplastic layer and tack coat or with fluoroplastic layer, transition zone and tack coat, thereby makes fluoroplastic layer and polyester layer bonding.Fluoroplastic layer can be a fluoroplastic layer arbitrarily, and thickness is any.Preferably, tack coat is the thin layer that the copolymer of ethene and polar resin forms, and transition zone is the polyacrylate plastic layer or contains the fluoroplastics of vinylidene and the mixture layer of polyacrylate plastics.This method adopts the fusion coextrusion processes to realize fluoroplastic layer and polyester-bonded, has simplified the preparation process of backboard, but between polyester layer and fluoroplastic layer, needs to add to extrude tack coat or transition zone.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of solar cell backboard and preparation method thereof is provided.
Technical scheme of the present invention is following:
Solar cell backboard is the method composite membrane-forming that is adopted the multilayered molten coextrusion by three polymer films, comprises top-down bonding weathering layer, bonding enhancement layer and the wet layer of bonding resistance.
Described bonding weathering layer is to be primary raw material with Kynoar (PVDF) resin and ethylene-vinyl acetate copolymer (EVA) resin; And add the mixed aid I that inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer and crosslinking agent are formed; And the plastic alloy alloy-layer that forms, wherein said Kynoar (PVDF) resin and ethylene-vinyl acetate copolymer (EVA) resin account for 60% of said bonding weathering layer weight at least.Preferably, described Kynoar (PVDF) resin and ethylene-vinyl acetate copolymer (EVA) resin account for the 70-90% of said bonding weathering layer weight.
PVDF is as the thermoplastic fluorine-containing plastics, with respect to PVF not only have more excellent weather resistance, block water, oxygen resistance, but also be suitable for simple method for melt processing film forming.Yet the surface energy of PVDF is relatively low, and adhesive property is very poor.The present invention adopts the method for blend to obtain alloy film according to PVDF and the good compatibility of EVA, and the EVA resin is dispersed in the PVDF matrix uniformly, improves the surface energy of PVDF, and the adhesive property of weathering layer is obviously improved.
Preferably, the weight ratio of described primary raw material PVDF resin and EVA resin is (50-90): (50-10); Preferably, (70-85): (30-15).The too high weather resistance that can influence this layer of EVA content, the too low cementability that then can reduce each layer with other.
Except mixing inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer, also add crosslinking agent in the described bonding weathering layer, it is crosslinked to make that EVA forms in follow-up battery pack process of assembling, thereby possesses good weather resistance.Crosslinking agent adopts the organic peroxide class; Can be selected from cumyl peroxide (DCP), benzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP), di-isopropylbenzene hydroperoxide, 2; In 5-dimethyl-2,5 di-t-butyl hexane peroxide any one or multiple.
Among the above-mentioned mixed aid I, the consumption of inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer, crosslinking agent accounts for 5-35%, 0.2-2%, 0.2-2%, the 0.2-2% of said bonding weathering layer weight respectively.The percentage sum of each composition is 100% in the bonding weathering layer.
The thickness of described bonding weathering layer can be any thickness as required, as long as be adapted to the range of work of coextrusion mould; Preferably, the thickness of described bonding weathering layer is the 5-50 micron.
Described bonding enhancement layer is to be primary raw material with PETG (PET) resin and polymethyl methacrylate (PMMA) resin; And add the mixed aid II that inorganic Chinese white, uvioresistant stabilizer and thermo oxidative aging stabilizer are formed; And the plastic alloy alloy-layer that forms, wherein said PETG (PET) resin and polymethyl methacrylate (PMMA) resin account for 70% of said bonding enhancement layer weight at least.Preferably, described PETG (PET) resin and polymethyl methacrylate (PMMA) resin account for the 70-90% of said bonding enhancement layer weight.
Since the adhesion of polyester resin and fluorinated and olefine kind resin all a little less than, therefore pure PET is difficult to and above-mentioned PVDF/EVA alloy-layer holds tightly together.The present invention adopts the method for blend to obtain alloy film according to compatibility good between PMMA and the PET.Owing to have good adhesiveness between PMMA and PVDF and the EVA, the PMMA that therefore is dispersed in the PET matrix can significantly improve the cementability between enhancement layer and above-mentioned weathering layer.
Preferably, the weight ratio of described primary raw material PET resin and PMMA resin is (60-90): (40-10) preferred, (65-80): (35-20).PMMA content is too high can to influence strengthening the property of this layer, the too low cementitiousness that then can reduce each layer with other.
Among the above-mentioned mixed aid II, the consumption of inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer accounts for 5-30%, 0.2-2%, the 0.2-2% of said bonding enhancement layer weight respectively.The percentage sum of each composition is 100% in the bonding enhancement layer.
The thickness of described bonding enhancement layer can be any thickness as required, as long as be adapted to the range of work of coextrusion mould; Preferably, the thickness of described bonding enhancement layer is the 50-400 micron.
The wet layer of described bonding resistance is to be primary raw material with Kynoar (PVDF) resin and polyvinyl butyral resin (PVB) resin; And add the mixed aid III that inorganic Chinese white, uvioresistant stabilizer and thermo oxidative aging stabilizer are formed; And the plastic alloy alloy-layer that forms, wherein said Kynoar (PVDF) resin and polyvinyl butyral resin (PVB) resin account for 60% of the wet layer of said bonding resistance weight at least.Preferably, described Kynoar (PVDF) resin and polyvinyl butyral resin (PVB) resin account for the 70-90% of the wet layer of said bonding resistance weight.
Because PVB self has very excellent weatherability, the moist and cementability of resistance; With the plastic alloy film that forms after the PVDF blend; Not only can improve the bonding force of PVDF, and better weather resistance ability and moisture barrier property can be provided as the bottom of solar cell backboard.
Preferably, the weight ratio of described primary raw material PVDF resin and PVB resin is (50-90): (50-10); Preferably, (60-80): (40-20).PVB content too high can influence the film forming processing characteristics of PVDF, the too low cementitiousness that then can reduce with middle enhancement layer.
Among the above-mentioned mixed aid III, the consumption of inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer accounts for 5-35%, 0.5-2.5%, the 0.5-2.5% of the wet layer of said bonding resistance weight respectively.The percentage sum of each composition is 100% in the wet layer of bonding resistance.
The thickness of the wet layer of described bonding resistance can be any thickness as required, as long as be adapted to the range of work of coextrusion mould; Preferably, the thickness of the wet layer of described bonding resistance is the 5-50 micron.
According to the present invention, above-described inorganic Chinese white is titanium white powder, barium sulfate, aluminium oxide, calcium carbonate, silicon dioxide or magnesium silicate; Preferably, described inorganic Chinese white is titanium white powder or barium sulfate.
According to the present invention, above-described uvioresistant stabilizer be among salicyl ester phenyl ester, Ultraviolet Absorber UV-P, ultra-violet absorber UV-O, ultra-violet absorber UV-9, ultraviolet absorbent UV-531, ultra-violet absorber UVP-327, ultra-violet absorber RMB, light stabilizer AM-101, light stabilizer GW-540, light stabilizer 744, the light stabilizer HPT any one or multiple; The uvioresistant stabilizer of being mentioned is on the market can buy auxiliary agent.
According to the present invention; Above-described thermo oxidative aging stabilizer adopts Hinered phenols antioxidant; Can select 2 for use, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four (β-(3; Three grades of butyl of 5--4-hydroxy phenyl) pentaerythritol ester, 2 propionic acid), any one or a few in 2 '-methylene-two-(the 4-methyl-6-tert butyl phenol).All but market is buied.
According to the present invention, the preparation method of described solar cell backboard, the method for employing multilayered molten coextrusion, step is following:
(1) will the bond primary raw material and the mixed aid I of weathering layer mixes; The primary raw material and the mixed aid II of bonding enhancement layer are mixed; The primary raw material and the mixed aid III of the wet layer of bonding resistance are mixed;
(2) each layer mixed material that above-mentioned steps (1) is made carries out fusion plastification simultaneously respectively, and the melt that plasticizing is good gets into the composite membrane that the coextrusion of curtain coating mould forms the fusion of no interface through distributor;
(3) three layers of composite membrane extruding from mould cool off after passing through online high-temperature shapings, rolling.Preferably, the temperature of said online high-temperature shaping is 100-200 ℃.Preferred, the temperature of said online high-temperature shaping is 130-180 ℃.
The temperature of the preferred described online high-temperature shaping of the present invention is between 100-200 ℃.Temperature is too low, can cause the crosslinked insufficient of bonding weathering layer EVA resin, thereby cause weather resistance to reduce; In addition, the too low stress of bonding enhancement layer that also can make of temperature can not fully discharge, thereby causes size instability in the follow-up use.The too high drawing-off performance that then can destroy each layer of temperature causes film rupture.
Preferably, the mixing described in the step (1) adopts homogenizer to carry out; Carry out three screw extruders that fusion plastification is to use respectively described in the step (2); Coextrusion described in the step (2) is to adopt have a distributor three-layer co-extruded to go out casting machine.The equipment that uses among the preparation method of the present invention is this field conventional equipment.
Beneficial effect of the present invention is:
Solar cell backboard of the present invention has only three-decker; Five layers or four-layer structure ratio with routine; Each interlayer need not to adopt any adhesive or tack coat; Solar cell backboard of the present invention adopts the preparation method of coextrusion can reach the excellent bonds of three interlayers, not only simplified greatly backboard moulding process, enhance productivity; Simultaneously, reach the fusion of no interface between each tunic of solar energy backboard, have good weatherability and, have excellent mechanical strength in addition, long service life the barrier of water, gas, ultraviolet.Solar cell backboard each item performance of the present invention meets the instructions for use of backboard, and is significant to the solar energy industry, is suitable for large-scale promotion application.
Description of drawings
Fig. 1 is the cutaway view of solar cell backboard of the present invention.Wherein, the 1st, the bonding weathering layer; The 2nd, the bonding enhancement layer; The 3rd, the wet layer of bonding resistance.
Embodiment
Through embodiment the present invention is described in detail below.It is important to point out that embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection range of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
The solar cell backboard structure is as shown in Figure 1.Wherein, 1 layer is the bonding weathering layer, and thickness is 25 microns; The weight ratio of primary raw material PVDF resin and EVA resin is 75: 25, accounts for 85% of bonding weathering layer total weight, adds the titanium white powder of mixed aid I:13% weight; The ultra-violet absorber UVP-327 of 0.5% weight; 2 of 1% weight, the di-isopropylbenzene hydroperoxide of 2 '-methylene-two-(4-methyl-6-tert butyl phenol) and 0.5% weight, said weight ratio is based on the weight meter of bonding weathering layer 1.2 layers are the bonding enhancement layer; Thickness is 250 microns, and primary raw material PET resin and PMMA weight resin ratio are 70: 30, accounts for 90% of bonding enhancement layer total weight; Add the titanium white powder of mixed aid II:8.5% weight; 2 of the ultra-violet absorber UVP-327 of 0.5% weight and 1% weight, 2 '-methylene-two-(4-methyl-6-tert butyl phenol), said weight ratio is based on the weight meter of bonding enhancement layer 2.3 layers are the wet layer of bonding resistance; Thickness is 40 microns, and the weight ratio of primary raw material PVDF resin and PVB resin is 75: 25, accounts for 82% of the wet layer of bonding resistance total weight; Add the titanium white powder of mixed aid III:16% weight; 2 of the ultra-violet absorber UVP-327 of 1% weight and 1% weight, 2 '-methylene-two-(4-methyl-6-tert butyl phenol), said weight ratio is based on the weight meter of the wet layer 3 of bonding resistance.
The preparation method, the method for employing multilayered molten coextrusion, step is following:
(1) adopts homogenizer, the primary raw material and the mixed aid I of bonding weathering layer mixed; The primary raw material and the mixed aid II of bonding enhancement layer are mixed; The primary raw material and the mixed aid III of the wet layer of bonding resistance are mixed;
(2) each layer mixed material that above-mentioned steps (1) is made adds three screw extruders simultaneously respectively and carries out fusion plastification, plastifies good melt and gets into the coextrusion of curtain coating mould through the three-layer co-extruded distributor that goes out casting machine that has distributor and form the composite membrane that no interface fuses;
(3) three layers of composite membrane extruding from mould through 150 ℃ online high-temperature shaping after cooling, rolling.
Embodiment 2
The solar cell backboard structure is as shown in Figure 1.Wherein, 1 layer is the bonding weathering layer, and thickness is 35 microns; The weight ratio of primary raw material PVDF resin and EVA resin is 70: 30, accounts for 80% of blend alloy layer total weight, adds the titanium white powder of 17% weight; The light stabilizer GW-540 of 1% weight; Two (3, three grades of butyl of the 5--4-hydroxy phenyl) thioethers of 1.2% weight and the oxidation diisopropylbenzene (DIPB) (DCP) of 0.8% weight, said weight is based on the weight meter of bonding weathering layer 1.2 layers are the bonding enhancement layer; Thickness is 180 microns, and primary raw material PET resin and PMMA weight resin ratio are 80: 20, account for 90% of blend alloy layer total weight; Add the titanium white powder of 8% weight; Two (3, three grades of butyl of 5--4-hydroxy phenyl) thioethers of the light stabilizer GW-540 of 1% weight and 1% weight, said weight is based on the weight meter of bonding enhancement layer 2.3 layers are the wet layer of bonding resistance; Thickness is 35 microns, and the weight ratio of primary raw material PVDF resin and PVB resin is 65: 35, accounts for 75% of blend alloy layer total weight; Add the titanium white powder of 23% weight; Two (3, three grades of butyl of 5--4-hydroxy phenyl) thioethers of the light stabilizer GW-540 of 1% weight and 1% weight, said weight is based on the weight meter of the wet layer 3 of bonding resistance.
The preparation method is with embodiment 1, and three layers of composite membrane that different is extrudes from the curtain coating mould are through cooling, rolling behind 160 ℃ the high-temperature shaping.
Embodiment 3
The solar cell backboard structure is as shown in Figure 1.Wherein, 1 layer is the bonding weathering layer, and thickness is 15 microns; The weight ratio of primary raw material PVDF resin and EVA resin is 90: 10, accounts for 91% of blend alloy layer total weight, adds the titanium white powder of 6% weight; The ultra-violet absorber UV-9 of 1.5% weight; 2 of 1.2% weight, the benzoyl peroxide (BPO) of three grades of butyl of 6--4-methylphenol and 0.3% weight, said weight is based on the weight meter of bonding weathering layer 1.2 layers are the bonding enhancement layer; Thickness is 300 microns, and primary raw material PET resin and PMMA weight resin ratio are 60: 40, account for 80% of blend alloy layer total weight; Add the titanium white powder of 17% weight; 2 of the ultra-violet absorber UV-9 of 1.5% weight and 1.5% weight, three grades of butyl of 6--4-methylphenol, said weight is based on the weight meter of bonding enhancement layer 2.3 layers are the wet layer of bonding resistance; Thickness is 25 microns, and the weight ratio of primary raw material PVDF resin and PVB resin is 80: 20, accounts for 80% of blend alloy layer total weight; Add the titanium white powder of 17% weight; 2 of the ultra-violet absorber UV-9 of 2% weight and 1% weight, three grades of butyl of 6--4-methylphenol, said weight is based on the weight meter of the wet layer 3 of bonding resistance.
The preparation method is with embodiment 1, and three layers of composite membrane that different is extrudes from the curtain coating mould are through cooling, rolling behind 180 ℃ the high-temperature shaping.
Embodiment 4
The solar cell backboard structure is as shown in Figure 1.Wherein, 1 layer is the bonding weathering layer, and thickness is 50 microns; The weight ratio of primary raw material PVDF resin and EVA resin is 60: 40, accounts for 70% of blend alloy layer total weight, adds the titanium white powder of 25% weight; The salicyl ester phenyl ester of 2% weight; Four (β-(3, three grades of butyl of the 5--4-hydroxy phenyl) propionic acid) pentaerythritol esters of 1.5% weight and the cumyl peroxide (DCP) of 1.5% weight, said weight are based on the weight meter of bonding weathering layer 1.2 layers are the bonding enhancement layer; Thickness is 280 microns, and primary raw material PET resin and PMMA weight resin ratio are 65: 35, account for 85% of blend alloy layer total weight; Add the titanium white powder of 13% weight; Four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid) pentaerythritol ester of the salicyl ester phenyl ester of 1% weight and 1% weight, said weight are based on the weight meter of bonding enhancement layer 2.3 layers are the wet layer of bonding resistance; Thickness is 45 microns, and the weight ratio of primary raw material PVDF resin and PVB resin is 65: 35, accounts for 70% of blend alloy layer total weight; Add the titanium white powder of 26% weight; Four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid) pentaerythritol ester of the salicyl ester phenyl ester of 2% weight and 2% weight, said weight are based on the weight meter of the wet layer 3 of bonding resistance.
The preparation method is with embodiment 1, and three layers of composite membrane that different is extrudes from the curtain coating mould are through cooling, rolling behind 130 ℃ the high-temperature shaping.
The solar cell backboard that embodiment 1,2,3,4 is made carries out Performance Detection, and testing result is as shown in table 1.Can know by data in the table, the adhesive property of backboard of the present invention is good, mechanical strength is high, ageing-resistant performance is good, resistance wet effective, dimensional stability good, satisfies the instructions for use of solar cell backboard fully.
Table 1
Claims (9)
1. a solar cell backboard is characterized in that it being the method composite membrane-forming that is adopted the multilayered molten coextrusion by three polymer films, comprises top-down bonding weathering layer, bonding enhancement layer and the wet layer of bonding resistance;
Described bonding weathering layer is to be primary raw material with Kynoar (PVDF) resin and ethylene-vinyl acetate copolymer (EVA) resin; And add the mixed aid I that inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer and crosslinking agent are formed; And the plastic alloy alloy-layer that forms, wherein Kynoar (PVDF) resin and ethylene-vinyl acetate copolymer (EVA) resin account for 60% of said bonding weathering layer weight at least; Polyvinylidene fluoride resin and ethylene-vinyl acetate copolymer resin weight ratio are (50-90): (50-10);
Described bonding enhancement layer is to be primary raw material with PETG (PET) resin and polymethyl methacrylate (PMMA) resin; And add the mixed aid II that inorganic Chinese white, uvioresistant stabilizer and thermo oxidative aging stabilizer are formed; And the plastic alloy alloy-layer that forms, wherein said PETG (PET) resin and polymethyl methacrylate (PMMA) resin account for 70% of said bonding enhancement layer weight at least; Pet resin and plexiglass weight ratio are (60-90): (40-10);
The wet layer of described bonding resistance is to be primary raw material with Kynoar (PVDF) resin and polyvinyl butyral resin (PVB) resin; And add the mixed aid III that inorganic Chinese white, uvioresistant stabilizer and thermo oxidative aging stabilizer are formed; And the plastic alloy alloy-layer that forms, wherein Kynoar (PVDF) resin and polyvinyl butyral resin (PVB) resin account for 60% of the wet layer of said bonding resistance weight at least; Polyvinylidene fluoride resin and polyvinyl butyral resin weight ratio are (50-90): (50-10).
2. solar cell backboard according to claim 1 is characterized in that, primary raw material polyvinylidene fluoride resin and ethylene-vinyl acetate copolymer resin weight ratio are (70-85) in the described bonding weathering layer: (30-15).
3. solar cell backboard according to claim 1 and 2 is characterized in that, primary raw material pet resin and plexiglass weight ratio are (65-80) in the described bonding enhancement layer: (35-20).
4. solar cell backboard according to claim 1 and 2 is characterized in that, primary raw material polyvinylidene fluoride resin and polyvinyl butyral resin weight ratio are (60-80) in the wet layer of described bonding resistance: (40-20).
5. solar cell backboard according to claim 1 and 2; It is characterized in that; Crosslinking agent is selected from cumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide or 2 in the described bonding weathering layer; One of 5-dimethyl-2,5 di-t-butyl hexane peroxide or combination.
6. according to claim 1 or 2 each described solar cell backboards, it is characterized in that described inorganic Chinese white is titanium white powder, barium sulfate, aluminium oxide, calcium carbonate, silicon dioxide or magnesium silicate;
Described uvioresistant stabilizer is one of salicyl ester phenyl ester, Ultraviolet Absorber UV-P, ultra-violet absorber UV-O, ultra-violet absorber UV-9, ultraviolet absorbent UV-531, ultra-violet absorber UVP-327, ultra-violet absorber RMB, light stabilizer AM-101, light stabilizer GW-540, light stabilizer 744, light stabilizer HPT or combination;
Described thermo oxidative aging stabilizer selects 2 for use; Three grades of butyl of 6--4-methylphenol, two (3; Three grades of butyl of 5--4-hydroxy phenyl) thioether, four (β-(3; Three grades of butyl of 5--4-hydroxy phenyl) pentaerythritol ester, 2 propionic acid), one of 2 '-methylene-two-(4-methyl-6-tert butyl phenol) or combination.
7. solar cell backboard according to claim 1 and 2; It is characterized in that; Among the mixed aid I of said bonding weathering layer, the consumption of inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer, crosslinking agent accounts for 5-35%, 0.2-2%, 0.2-2%, the 0.2-2% of said bonding weathering layer weight respectively.
8. solar cell backboard according to claim 1 and 2; It is characterized in that; Among the mixed aid III of the wet layer of said bonding resistance, the consumption of inorganic Chinese white, uvioresistant stabilizer, thermo oxidative aging stabilizer accounts for 5-35%, 0.5-2.5%, the 0.5-2.5% of the wet layer of said bonding resistance weight respectively.
9. the preparation method of each said solar cell backboard of claim 1-8 adopts the method for multilayered molten coextrusion, and step is following:
(1) will the bond primary raw material and the mixed aid I of weathering layer mixes; The primary raw material and the mixed aid II of bonding enhancement layer are mixed; The primary raw material and the mixed aid III of the wet layer of bonding resistance are mixed;
(2) each layer mixed material that step (1) is made carries out fusion plastification simultaneously respectively, plastifies good melt and gets into the composite membrane that the coextrusion of curtain coating mould forms the fusion of no interface through distributor;
(3) three layers of composite membrane extruding from mould cool off after passing through 100-200 ℃ of online high-temperature shaping, rolling.
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