CA2673018A1 - Backing sheet for photovoltaic modules and method for repairing same - Google Patents
Backing sheet for photovoltaic modules and method for repairing same Download PDFInfo
- Publication number
- CA2673018A1 CA2673018A1 CA002673018A CA2673018A CA2673018A1 CA 2673018 A1 CA2673018 A1 CA 2673018A1 CA 002673018 A CA002673018 A CA 002673018A CA 2673018 A CA2673018 A CA 2673018A CA 2673018 A1 CA2673018 A1 CA 2673018A1
- Authority
- CA
- Canada
- Prior art keywords
- backing sheet
- layer
- polyester
- fluorocopolymer
- sputtered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 229920000728 polyester Polymers 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 34
- 238000009472 formulation Methods 0.000 claims description 23
- -1 alkyl vinyl ethers Chemical class 0.000 claims description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 19
- 229920000515 polycarbonate Polymers 0.000 claims description 18
- 239000004417 polycarbonate Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229920002313 fluoropolymer Polymers 0.000 claims description 12
- 239000004811 fluoropolymer Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920000554 ionomer Polymers 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000004971 Cross linker Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229920001897 terpolymer Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920004439 Aclar® Polymers 0.000 claims description 6
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000008439 repair process Effects 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 6
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims 3
- 239000012860 organic pigment Substances 0.000 claims 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 3
- 239000013078 crystal Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 13
- 239000008393 encapsulating agent Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 43
- 229920002620 polyvinyl fluoride Polymers 0.000 description 31
- 238000000576 coating method Methods 0.000 description 30
- 239000005038 ethylene vinyl acetate Substances 0.000 description 22
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 21
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 239000000049 pigment Substances 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 229920001780 ECTFE Polymers 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229940113088 dimethylacetamide Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000012669 liquid formulation Substances 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- ODACNRQBNVVGAI-UHFFFAOYSA-N 5-[2-chloroethyl(2-fluoroethyl)amino]-6-methyl-1h-pyrimidine-2,4-dione Chemical compound CC=1NC(=O)NC(=O)C=1N(CCF)CCCl ODACNRQBNVVGAI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical group CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- H01L31/0216—
-
- H01L31/049—
-
- 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
Landscapes
- Laminated Bodies (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention provides a protective backing sheet for photovoltaic modules. The backing sheets of the current invention possess excellent weather resistance, heat resistance, color retention, adhesion between layers and encapsulant, and scratch resistance. The backing sheet can minimize the deterioration in the performance of the solar module due to moisture permeation. It also can achieve desirable photoelectric conversion efficiency over a long period of time. Additionally the described backing sheet, or alternately referred to backskin, can be made in an aesthetically pleasing form.
Description
BACKING SHEET FOR PHOTOVOLTAIC MODULES AND METHOD FOR
REPAIRING SAME
Background of the Invention Field of the Invention [0001] The present invention relates to photovoltaic modules. More specifically the present invention related to the protective backing sheets.
Description of Related Art [0002] Solar energy utilized by photovoltaic modules is among the most promising alternatives to the fossil fuel that is being exhausted this century. However, production and installation of the photovoltaic modules remains an expensive process.
Typical photovoltaic modules consist of glass or flexible transparent front sheet, solar cells, encapsulant, protective backing sheet, a protective seal which covers the edges of the module, and a perimeter frame made of aluminum which covers the seal. As illustrated in Figure 1, a front sheet 10, backing sheet 20 and encapsulant 30 and 30' are designed to protect array of cells 40 from weather agents, humidity, mechanical loads and impacts. Also, they provide electrical isolation for people's safety and loss of current.
Protective backing sheets 20 are intended to improve the lifecycle and efficiency of the photovoltaic modules, thus reducing the cost per watt of the photovoltaic electricity.
While the front sheet 10 and encapsulant 30 and 30' must be transparent for high light transmission, the backing sheet must have high opacity for aesthetical purposes and high reflectivity for functional purposes. Light and thin solar cell modules are desirable for a number of reasons including weight reduction, especially for architectural (building integrated PV) and space applications, as well as military applications (incorporated into the soldier outfit, etc). Additionally light and thin modules contribute to cost reduction.
Also reduction in quantity of consumed materials makes the technology "greener", thus saving more natural resources.
REPAIRING SAME
Background of the Invention Field of the Invention [0001] The present invention relates to photovoltaic modules. More specifically the present invention related to the protective backing sheets.
Description of Related Art [0002] Solar energy utilized by photovoltaic modules is among the most promising alternatives to the fossil fuel that is being exhausted this century. However, production and installation of the photovoltaic modules remains an expensive process.
Typical photovoltaic modules consist of glass or flexible transparent front sheet, solar cells, encapsulant, protective backing sheet, a protective seal which covers the edges of the module, and a perimeter frame made of aluminum which covers the seal. As illustrated in Figure 1, a front sheet 10, backing sheet 20 and encapsulant 30 and 30' are designed to protect array of cells 40 from weather agents, humidity, mechanical loads and impacts. Also, they provide electrical isolation for people's safety and loss of current.
Protective backing sheets 20 are intended to improve the lifecycle and efficiency of the photovoltaic modules, thus reducing the cost per watt of the photovoltaic electricity.
While the front sheet 10 and encapsulant 30 and 30' must be transparent for high light transmission, the backing sheet must have high opacity for aesthetical purposes and high reflectivity for functional purposes. Light and thin solar cell modules are desirable for a number of reasons including weight reduction, especially for architectural (building integrated PV) and space applications, as well as military applications (incorporated into the soldier outfit, etc). Additionally light and thin modules contribute to cost reduction.
Also reduction in quantity of consumed materials makes the technology "greener", thus saving more natural resources.
[0003] On means to manufacture light and thin solar cells is to incorporate light and thin backing sheets. The backside covering material however, must also have some moisture resistance to prevent permeation of moisture vapor and water, which can cause rusting in underlying parts such as the photovoltaic element, wire, and electrodes, and damage solar cells. In addition, backing sheets should provide electric isolation, mechanical protection, some UV stability, adherence to the encapsulant and ability to attach output leads.
[0004] Currently used protective backing sheets are typically laminates.
Figure 2 provides an illustration of a typical laminate backing sheet 20. The laminate consists of films of polyvinylfluorides 22, which is most commonly Tedlar , polyesters (PET) 24, and copolymers of ethylene vinyl acetate (EVA) 26 as key components. The EVA
layer 26 bonds with the encapsulant layer 30 in the module and serves as a dielectric layer and has good moisture barrier properties. It is dimensionally stable. White EVA
allows significant power boost. The polyester layer 24 is very tough, has excellent dielectric properties, is dimensionally stable, and also has good moisture barrier properties. The polyvinylfluoride layer 22 serves as a very weatherable layer.
Figure 2 provides an illustration of a typical laminate backing sheet 20. The laminate consists of films of polyvinylfluorides 22, which is most commonly Tedlar , polyesters (PET) 24, and copolymers of ethylene vinyl acetate (EVA) 26 as key components. The EVA
layer 26 bonds with the encapsulant layer 30 in the module and serves as a dielectric layer and has good moisture barrier properties. It is dimensionally stable. White EVA
allows significant power boost. The polyester layer 24 is very tough, has excellent dielectric properties, is dimensionally stable, and also has good moisture barrier properties. The polyvinylfluoride layer 22 serves as a very weatherable layer.
[0005] Even though these films have met performance standards in the required tests and during actual use, they exhibit certain limitations such as high cost and limited availability of the Tedlar films. Another drawback of prior art materials such as PVF
(Tedlar(g), ECTFE (Halar ) and other fluoropolymers, is that such materials cannot be processed at ambient or moderately elevated temperatures. For example, PVF
film is produced by a casting process from dispersion, using high boiling solvents (usually dimethyl acetamide for oriented Tedlar and propylene carbonate for Tedlar SP). The boiling point of dimethyl acetamide is 164-166 C and the boiling point of propylene carbonate is 200 C. The dispersion must be processed at 160 C and 90% of solvent content or greater to ensure adequate film formation. Higher temperatures are unacceptable due to PVF resin thermal instability: its fusion and decomposition temperatures are so close, that PVF can decompose during the baking. As a result, there is always a residual solvent in Tedlar film. DuPont reports that residual amounts of dimethyl acetamide (DMAC) ranging from 0.05 to 1.0 wt% will be present in all oriented Tedlar PVF films.
(Tedlar(g), ECTFE (Halar ) and other fluoropolymers, is that such materials cannot be processed at ambient or moderately elevated temperatures. For example, PVF
film is produced by a casting process from dispersion, using high boiling solvents (usually dimethyl acetamide for oriented Tedlar and propylene carbonate for Tedlar SP). The boiling point of dimethyl acetamide is 164-166 C and the boiling point of propylene carbonate is 200 C. The dispersion must be processed at 160 C and 90% of solvent content or greater to ensure adequate film formation. Higher temperatures are unacceptable due to PVF resin thermal instability: its fusion and decomposition temperatures are so close, that PVF can decompose during the baking. As a result, there is always a residual solvent in Tedlar film. DuPont reports that residual amounts of dimethyl acetamide (DMAC) ranging from 0.05 to 1.0 wt% will be present in all oriented Tedlar PVF films.
[0006] Alternatively, ECTFE (Halar ) films are produced by melt extrusion at 350 C-375 C. As a result, they cannot be easily compounded with pigments, clays, etc.
and are also expensive.
and are also expensive.
[0007] U.S. Pat. No. 5,741,370 suggests that manufacturing and module mounting costs could be reduced by using, as the backskin material, a thermoplastic olefin comprising a combination of two different ionomers, e.g., a sodium ionomer and a zinc ionomer, with that combination being described as producing a synergistic effect which improves the water vapor barrier property of the backskin material over and above the barrier property of either of the individual ionomer components. Also, the patent discloses use of an ionomer encapsulant with the dual ionomer backskin.
[0008] However, National Renewable Energy Laboratory (NREL) reports that ionomer resins contain free and bound methacrylic acid, which requires using stainless steel tooling during melt processing, thus increasing the manufacturing costs.
PVMaT
Improvements in the Solarex Photovoltaic Module Manufacturing Technology Annual Subcontract Report May 5, 1998 - April 30, 1999, National Renewable Energy Laboratory, January 2000 = NREL/SR-520-27643.
Summary of the Invention [0009] The present invention provides a protective backing sheet for photovoltaic modules. The backing sheets of the current invention possess excellent weather resistance, heat resistance, color retention, adhesion between layers and encapsulant, and scratch resistance. The backing sheet can minimize the deterioration in the performance of the solar module due to moisture permeation. It also can achieve desirable photoelectric conversion efficiency over a long period of time. Additionally the described backing sheet, or alternately referred to backskin, can be made in an aesthetically pleasing form.
PVMaT
Improvements in the Solarex Photovoltaic Module Manufacturing Technology Annual Subcontract Report May 5, 1998 - April 30, 1999, National Renewable Energy Laboratory, January 2000 = NREL/SR-520-27643.
Summary of the Invention [0009] The present invention provides a protective backing sheet for photovoltaic modules. The backing sheets of the current invention possess excellent weather resistance, heat resistance, color retention, adhesion between layers and encapsulant, and scratch resistance. The backing sheet can minimize the deterioration in the performance of the solar module due to moisture permeation. It also can achieve desirable photoelectric conversion efficiency over a long period of time. Additionally the described backing sheet, or alternately referred to backskin, can be made in an aesthetically pleasing form.
[0010] The backing sheets of the present invention are produced by utilizing liquid coatings application technology, followed by lamination with EVA, and can be tailored according to the application requirements. Furthermore, advantages of solar cell modules utilizing the described backskin material include a significant reduction in manufacturing costs.
[0011] The liquid coatings formulations used in the backskins overcome one or more of the deficiencies of the prior art backskins. The backskin can be made thinner than currently available backskins. The backing materials include more readily available materials which can be processed at ambient or moderately elevated temperatures. These liquid coatings can be applied directly on the second layer of laminate, thus eliminating the need for an adhesive. Additionally, they can be easily compounded with additives such as pigments, clays, etc.
[0012] In one aspect, a backing sheet for a photovoltaic module is described having a layer comprising an organic solvent soluble, crosslinkable amorphous fluoropolymers. The fluoropolymer may be a fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers, including alkyl vinyl ethers with reactive OH
functionality. The backing sheet can include a crosslinking agent mixed with the flourocopolymer.
functionality. The backing sheet can include a crosslinking agent mixed with the flourocopolymer.
[0013] The backing sheet may also include additional layers, such as a polyester layer. For another example, the backing sheet of may also include an EVA
layer. Other optional additional layers may include one or of coextruded polyester with EVA, polycarbonate, polyolefin, polyurethane, liquid crystal polymer, aclar, aluminum, of sputtered aluminum oxide polyester, sputtered silicon oxide or silicon nitride polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon oxide or silicon nitride polycarbonate [0014] The fluorocopolymer layer of the backing sheet can be applied to the polyester layer, or other type of layer with or without an adhesive. Also, it can be applied as a single layer or multiple layers. In one embodiment, the fluorocopolymer layer has a thickness of less than 1 mil. In another aspect, the fluorocopolymer has a layer that is greater than lmil. In another embodiment, the backing sheet includes silica.
layer. Other optional additional layers may include one or of coextruded polyester with EVA, polycarbonate, polyolefin, polyurethane, liquid crystal polymer, aclar, aluminum, of sputtered aluminum oxide polyester, sputtered silicon oxide or silicon nitride polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon oxide or silicon nitride polycarbonate [0014] The fluorocopolymer layer of the backing sheet can be applied to the polyester layer, or other type of layer with or without an adhesive. Also, it can be applied as a single layer or multiple layers. In one embodiment, the fluorocopolymer layer has a thickness of less than 1 mil. In another aspect, the fluorocopolymer has a layer that is greater than lmil. In another embodiment, the backing sheet includes silica.
[0015] In another aspect of the invention, a backing sheet for a photovoltaic module is described. The backing sheet has a layer comprising a copolymer of tetrafluoroethylene (TFE) and hydrocarbon olefins with reactive OH
functionality. The backing sheet may further include a crosslinking agent mixed with the flourocopolymer.
In one embodiment the fluorocopolymer layer has a thickness of less than I
mil. In another embodiment, the fluorocopolymer layer has a thickness of greater than lmil. In another embodiment, the backing sheet also has an ionomer layer.
functionality. The backing sheet may further include a crosslinking agent mixed with the flourocopolymer.
In one embodiment the fluorocopolymer layer has a thickness of less than I
mil. In another embodiment, the fluorocopolymer layer has a thickness of greater than lmil. In another embodiment, the backing sheet also has an ionomer layer.
[0016] The fluorocopolymer may be or include a terpolymer of one or more fluoromonomers. In one embodiment the terpolymer comprises vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
[0017] Again, the backing sheet may also include additional layers, such as a polyester layer. The fluorocopolymer layer may be applied to the polyester layer with or without adhesive. The fluorocopolymer layer may be applied as a single layer or as a combination of clear and pigmented multiple layers. The polyester film can be additionally corona or chemically treated to improve adhesion. The backing sheet of may also include an EVA layer. In another embodiment the backing sheet contains silica.
Other optional additional layers may include one or of polycarbonate, coextruded polyester with EVA, polyolefin, polyurethane, liquid crystal polymer, aclar, aluminum, of CA 02673018 20oPCT/US2008/001351 sputtered aluminum oxide polyester, sputtered silicon oxide or silicon nitride polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon oxide or silicon nitride polycarbonate, sputtered aluminum oxide Lumiflon , sputtered aluminum oxide Zeffle , sputtered silicon oxide or silicon nitride Lumiflon, sputtered silicon oxide or silicon nitride Zeffle.
Other optional additional layers may include one or of polycarbonate, coextruded polyester with EVA, polyolefin, polyurethane, liquid crystal polymer, aclar, aluminum, of CA 02673018 20oPCT/US2008/001351 sputtered aluminum oxide polyester, sputtered silicon oxide or silicon nitride polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon oxide or silicon nitride polycarbonate, sputtered aluminum oxide Lumiflon , sputtered aluminum oxide Zeffle , sputtered silicon oxide or silicon nitride Lumiflon, sputtered silicon oxide or silicon nitride Zeffle.
[0018] In another aspect, a method of repairing the backing sheet of a photovoltaic module is provided. The method includes the step of applying a formulation comprising an amorphous fluorocopolymer of chlorotrifluoroethylene (CTFE) with one or more alkyl vinyl ethers, including alkyl vinyl ethers with reactive OH
functionality to an area on the backing sheet in need of repair. In one embodiment the formulation is applied to the backing sheet at ambient temperature or moderately elevated temperature.
In another embodiment, the formulation is comprised of a first and second component that are placed in a twin-chamber syringe equipped with static mixer and applied through an applicator attached to the syringe.
functionality to an area on the backing sheet in need of repair. In one embodiment the formulation is applied to the backing sheet at ambient temperature or moderately elevated temperature.
In another embodiment, the formulation is comprised of a first and second component that are placed in a twin-chamber syringe equipped with static mixer and applied through an applicator attached to the syringe.
[0019] In one embodiment the first component of the formulation is comprised of a mixture of a crosslinker and a solvent, and the second component is comprised of a mixture of a solvent and a fluorocopolymer.
Brief Description of the Drawings [0020] For a better understanding of the present invention, reference may be made to the accompanying drawings.
Brief Description of the Drawings [0020] For a better understanding of the present invention, reference may be made to the accompanying drawings.
[0021] FIG. 1 represents an expanded view of the components of a typical photovoltaic module.
[0022] FIG. 2 represents one embodiment of the typical backing sheet.
[0023] FIG. 3 is a graph showing tensile strength as a function of exposure to "Damp Heat" for Lumiflon-based back sheet as compared to Tedlar-based back sheet.
[0024] FIG. 4 is a graph showing elongation at break as a function of exposure to "Damp Heat" for Lumiflon-based back sheet as compared to Tedlar-based back sheet.
[0025] FIG. 5 is a graph showing UV stability of Lumiflon-based back sheet as compared to Tedlar-based back sheet.
[0026] FIG. 6 illustrates an example of an applicator used with the patch kit.
Detailed Description [0027] The present invention provides a protective backing sheet for photovoltaic modules. In one embodiment, the backing sheets are produced by utilizing liquid coatings application technology. In the preferred embodiment the liquid coating application is followed by lamination with EVA. The process can be tailored according to the application requirements.
Detailed Description [0027] The present invention provides a protective backing sheet for photovoltaic modules. In one embodiment, the backing sheets are produced by utilizing liquid coatings application technology. In the preferred embodiment the liquid coating application is followed by lamination with EVA. The process can be tailored according to the application requirements.
[0028] In another embodiment, an encapsulating material is provided. The encapsulating material has excellent weather resistance, heat resistance, and UV stability, adhesion to backing material and to other components of solar module, electrical isolation and excellent color retention without yellowing. The described encapsulating material is applied by spraying, thus eliminating vacuum lamination process at elevated temperatures and reducing the manufacturing costs.
[0029] In another aspect methods for quick and easy repair of torn or otherwise damaged backskin are provided using a "patch kit". The method and patch kit allow for fast application of aesthetically pleasing, robust coating over scratched backing sheet without using extreme temperatures and pressures. Also, such "patch kit"
allows for fast and efficient repair "in-situ". The coating of the patch kit applied in accordance with the method of the present invention meet all the requirements of IEC 60664-1, IEC
61730, IEC 1646, and ASTM F 1249. In the preferred embodiment of this aspect of the invention, the "patching" formulation is applied by using a twin-chamber syringe equipped with static mixer and applicator.
allows for fast and efficient repair "in-situ". The coating of the patch kit applied in accordance with the method of the present invention meet all the requirements of IEC 60664-1, IEC
61730, IEC 1646, and ASTM F 1249. In the preferred embodiment of this aspect of the invention, the "patching" formulation is applied by using a twin-chamber syringe equipped with static mixer and applicator.
[0030] The liquid coatings formulations used in the present invention can be applied at ambient temperature or moderately elevated temperature. The primary component of the liquid coatings formulations are fluoropolymers, and preferably organic solvent soluble or water dispersible, crosslinkable amorphous fluoropolymers.
[0031] Preferred components of coatings include fluorocopolymers with the following structure :
H H
I I I I H H
3Tt) C C C
I I b I ~ c a OR H Q
H H
I I I I H H
3Tt) C C C
I I b I ~ c a OR H Q
[0032] OH
F H H H
4T) I I I I I H I ()b I a H O c I CH2 [0033] OH
F H H H
4T) I I I I I H I ()b I a H O c I CH2 [0033] OH
[0034] and F F H F
I ~ I I I
-c c I A IZ
~
~
I ~ I I I
-c c I A IZ
~
~
[0035] o H
[0036] Fluoropolymers that can be utilized in the liquid formulations include, but is not limited to, Lumiflon (Asahi Glass) and Zeffle (Daikin). Other materials include FluoroPelTM and FluoroThane TM (Cytonix Corporation), FluoroLinkTM Polymer Modifiers (Solvay Solexis). Additional components in the liquid coating formulations include crosslinking agents, catalysts, solvents, and optionally, fillers and inorganic materials such as boron nitride (Zyp Coatings).
[0037] One particularly preferred fluoropolymer is Lumiflon , developed by Asahi Glass in 1982. Lumiflon is an amorphous fluorocopolymer of chlorotrifluoroethylene (CTFE) with several specific alkyl vinyl ethers (VE).
[0038] A combination of the alkyl vinyl ether monomers and hydroxyl groups provides the polymer with significant properties, such as solubility, compatibility to pigment, crosslinking reactivity, adhesiveness to the substrate, hardness and flexibility.
[0039] Another preferred fluoropolymer is Zeffle resins (Daikin), which are copolymers of tetrafluoroethylene (TFE) and hydrocarbon olefins that are organic solvent soluble. More particularly, Zeffle is a solvent-based, copolymer of tetrafluoroethylene and hydrocarbon olefins with reactive OH functionality formulated for use as a base resin in high performance paints and coatings.
[0040] In another embodiment, the fluoropolymer is a terpolymer. The terpolymer may contain one or more different fluoromonomers. For one example, the terpolymer contains vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
DyneonTM THV is one such terpolymer and provides a combination of performance advantages, such as low processing temperature, ability to bond to elastomers and hydrocarbon-based plastics, flexibility and optical clarity. As a clear film it can be used as a front sheet to replace glass. The addition of pigment provides a film that can be used as a backing sheet for a photovoltaic module.
DyneonTM THV is one such terpolymer and provides a combination of performance advantages, such as low processing temperature, ability to bond to elastomers and hydrocarbon-based plastics, flexibility and optical clarity. As a clear film it can be used as a front sheet to replace glass. The addition of pigment provides a film that can be used as a backing sheet for a photovoltaic module.
[0041] Organic solvents which may be used in this invention for the formation of the liquid coating formulations include but are not limited to organic solvents such as methyl ethyl ketone (MEK), acetone, methyl isobutyl ketone (MIBK), toluene, xylene, methanol, isopropanol, ethanol, heptane, ethyl acetate, isopropyl acetate, n-butyl acetate, n-butyl alcohol or mixtures thereof. Preferred solvents include xylene, cyclohexanone and methyl ethyl ketone (MEK). The appropriate solvent is one in which all components dissolve and one in which the boiling point is low enough to minimize or remove the presence of residual solvent in the coating.
[0042] Optional pigments and fillers which may be used in this invention for the formation of the protective coatings include but are not limited to titanium dioxide, carbon black, Perylene pigments, pigments, dyes, mica, polyamide powders, boron nitride, zinc oxide, aluminum oxide, silica, UV absorbers, corrosion inhibitors, and desiccants. One preferred pigment is titanium dioxide Ti-Pure R-105(DuPont).
One preferred hydrophobically modified silica is Cab-o-sil TS 720 (Cabot).
Pigments, UV
absorbers and corrosion inhibitors function to impart opacity and weatherability.
Orgasol Ultrafine is a preferred polyamide powders (Arkema Inc) and can be included for gloss reduction. Carbon black, pigments and dyes can be included to alter the color of the backing sheet. Mica can be included to impart flame retardancy. Boron nitride, aluminum nitride, and/or aluminum oxide can be included to improve thermal conductivity. Cloisite Nanoclays (Southern Clay Products), 3MTM Glass Bubbles and desiccants are preferably included to improve moisture barrier properties.
Silica and/or boron nitride can be included to improve dielectric properties. Silica may also be included to reduce gloss and to impart flame retardancy [0043] Crosslinking agents are preferably used in the formation of the protective coatings include to obtain organic solvent insoluble, tack-free film.
Preferred crosslinking agents include but are not limited to DuPont Tyzor organic titanates, silanes, isocyanates, and melamine. Aliphatic isocyanates are preferred to ensure weatherability as these films are typically intended for over 30 years use outdoor.
One preferred hydrophobically modified silica is Cab-o-sil TS 720 (Cabot).
Pigments, UV
absorbers and corrosion inhibitors function to impart opacity and weatherability.
Orgasol Ultrafine is a preferred polyamide powders (Arkema Inc) and can be included for gloss reduction. Carbon black, pigments and dyes can be included to alter the color of the backing sheet. Mica can be included to impart flame retardancy. Boron nitride, aluminum nitride, and/or aluminum oxide can be included to improve thermal conductivity. Cloisite Nanoclays (Southern Clay Products), 3MTM Glass Bubbles and desiccants are preferably included to improve moisture barrier properties.
Silica and/or boron nitride can be included to improve dielectric properties. Silica may also be included to reduce gloss and to impart flame retardancy [0043] Crosslinking agents are preferably used in the formation of the protective coatings include to obtain organic solvent insoluble, tack-free film.
Preferred crosslinking agents include but are not limited to DuPont Tyzor organic titanates, silanes, isocyanates, and melamine. Aliphatic isocyanates are preferred to ensure weatherability as these films are typically intended for over 30 years use outdoor.
[0044] For one example, liquid formulations for Lumiflon -based coatings compositions can be prepared by mixing a Lumiflon solution, pigment, crosslinker and a catalyst. Tin dibutyl dilaureate, is used to accelerate the crosslinking reaction between Lumiflon (polyol) and isocyanate in an organic solvent. Such compositions are prepared by mixing preferably 3 to 80, and even more preferably around 46 parts by weight of Lumiflori solution, 5 to 60 (more preferably around 17) parts by weight of pigment, and 20 to 80 (more preferably around 32) parts by weight of organic solvent (a mixture of MEK and xylene or cyclohexanone).
[0045] The backing sheet may also include additional layers. The additional layers may be applied to the fluorocopolymer layer with or without adhesive.
The optional additional layers may include, for example, one or of polyester, EVA, polycarbonate, polyolefins, polyurethanes, acrylics, polyimides, polyamides, ' liquid crystal polymer, aclar, aluminum, of sputtered aluminum oxide polyester, sputtered silicon oxide or silicon nitride polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon oxide or silicon nitride polycarbonate, clear fluoropolymers and clear fluorocopolymers, coextruded layer of a polymers such as polyester and EVA, and polybutadiene.
The optional additional layers may include, for example, one or of polyester, EVA, polycarbonate, polyolefins, polyurethanes, acrylics, polyimides, polyamides, ' liquid crystal polymer, aclar, aluminum, of sputtered aluminum oxide polyester, sputtered silicon oxide or silicon nitride polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon oxide or silicon nitride polycarbonate, clear fluoropolymers and clear fluorocopolymers, coextruded layer of a polymers such as polyester and EVA, and polybutadiene.
[0046] Example 1.
[0047] Example 1 illustrates the preparation of a Lumiflori -based protective backing sheet according to the present invention. Lumiflon used in this example is LF
200 grade, obtained from Asahi Glass as a 60% solution in xylene (200g).
Pigment used in this example is Ti-Pure R-105, obtained from DuPont (76.2g). The crosslinker is Desmodur N3300, obtained from Bayer (21.4g). The pigment is mixed with Lumiflon solution using high shear mixer, followed by solvent and the crosslinker addition.
200 grade, obtained from Asahi Glass as a 60% solution in xylene (200g).
Pigment used in this example is Ti-Pure R-105, obtained from DuPont (76.2g). The crosslinker is Desmodur N3300, obtained from Bayer (21.4g). The pigment is mixed with Lumiflon solution using high shear mixer, followed by solvent and the crosslinker addition.
[0048] The formulation is then applied. The liquid formulation is transferred from the pan to the film by applicator roll and metered off by Mayer Rod to obtain the desired coating weight. The coating is applied directly on a Mylar (DuPont) (5mil) polyester film. No adhesive is required and in this example none is used. The coating is applied at a coating weight of 10 - 120 g/mZ, preferably 30-90 g/m2, and more preferably 30 -45 g/m2.
CA 02673018 20oPCT/US2008/001351 [0049] The dry coating consists of 60-65% by weight of Lumiflon and 35% by weight of pigment. In this example, the polyester film coated with Lumiflori -based formulation is laminated with EVA (vinyl acetate content 4%) using polyester-urethane laminating adhesive. The laminate is then vacuum laminated with an EVA
encapsulant and module.
CA 02673018 20oPCT/US2008/001351 [0049] The dry coating consists of 60-65% by weight of Lumiflon and 35% by weight of pigment. In this example, the polyester film coated with Lumiflori -based formulation is laminated with EVA (vinyl acetate content 4%) using polyester-urethane laminating adhesive. The laminate is then vacuum laminated with an EVA
encapsulant and module.
[0050] Table 1 show the properties of Lumiflon and Zeffle based protective backing sheets as compared to a backing sheet prepared with Tedlar SP.
[0051] Table 1 Thickness Water Vapor g/(100in2 = Partial Thickness Voltage Sample of outer Transmission day) 100F Discharge m max, VDC
layer pm Test 100% RH Test Tedlar SP 25.4 IEC 60994-1, 178 ASTM F1249 0.195 820 /Polyester/EVA IEC 61730 Lumiflon / 12.7 IEC 60994-1, 165 ASTM F 1249 0.174 860 Polyester/EVA IEC 61730 Zeffle /Polyester 12.7 IEC 60994-1, 165 ASTM F1249 0.143 860 [0052] Table 2 show the properties of Lumiflori based protective backing sheets as compared to a backing sheet prepared with oriented Tedlar .
layer pm Test 100% RH Test Tedlar SP 25.4 IEC 60994-1, 178 ASTM F1249 0.195 820 /Polyester/EVA IEC 61730 Lumiflon / 12.7 IEC 60994-1, 165 ASTM F 1249 0.174 860 Polyester/EVA IEC 61730 Zeffle /Polyester 12.7 IEC 60994-1, 165 ASTM F1249 0.143 860 [0052] Table 2 show the properties of Lumiflori based protective backing sheets as compared to a backing sheet prepared with oriented Tedlar .
[0053] Table 2 Thickness Water Vapor g/(100in2 = Partial Thickness Voltage Sample of outer Transmission day) 100F Discharge m max, VDC
layer m Test 100% RH Test Tedlar IEC 60994-1, 267 ASTM F 1249 0.12 1020 /Polyester/EVA 38 IEC 61730 Lumiflon / IEC 60994-1, 241 ASTM F 1249 0.12 1015 Polyester/EVA 13 IEC 61730 [0054] The results illustrate that Lumiflon and Zeffle -based coatings at a 0.5mil thickness demonstrate superior barrier properties (lower moisture permeability and higher voltage resistance) than non-oriented Tedlar SP at a thickness of lmil, which is twice the thickness of the Lumiflon and Zeffle layers. Additionally, the Lumiflon based backing sheets are more cost-effective than the Tedlar based backing sheets.
layer m Test 100% RH Test Tedlar IEC 60994-1, 267 ASTM F 1249 0.12 1020 /Polyester/EVA 38 IEC 61730 Lumiflon / IEC 60994-1, 241 ASTM F 1249 0.12 1015 Polyester/EVA 13 IEC 61730 [0054] The results illustrate that Lumiflon and Zeffle -based coatings at a 0.5mil thickness demonstrate superior barrier properties (lower moisture permeability and higher voltage resistance) than non-oriented Tedlar SP at a thickness of lmil, which is twice the thickness of the Lumiflon and Zeffle layers. Additionally, the Lumiflon based backing sheets are more cost-effective than the Tedlar based backing sheets.
[0055] Table 3 illustrates the weatherability of Lumiflon based protective backing sheets as compared to a backing sheet prepared with oriented Tedlar .
Samples were placed into an environmental chamber at conditions of 85 C and 85%
Relative Humidity ("Damp Heat") for 2000 hrs. The weatherability of the outer layer was estimated by measuring adhesion between outer layer and polyester, tensile strength and elongation at break as a function of exposure to "Damp Heat" according to ASTM
98 peel adhesion test, ASTM D 3359 cross cut tape adhesion test, and ASTM
D882. The following abbreviations in Table 3 apply: TB is tear bond; 5B = 0% of coating removed;
4B = less than 5% of coating removed; 3B = 5-15 % of coating removed; 2B = 15-35% of coating removed; 1B = 35-65% of coating removed; and OB = greater than 65% of coating removed.
Samples were placed into an environmental chamber at conditions of 85 C and 85%
Relative Humidity ("Damp Heat") for 2000 hrs. The weatherability of the outer layer was estimated by measuring adhesion between outer layer and polyester, tensile strength and elongation at break as a function of exposure to "Damp Heat" according to ASTM
98 peel adhesion test, ASTM D 3359 cross cut tape adhesion test, and ASTM
D882. The following abbreviations in Table 3 apply: TB is tear bond; 5B = 0% of coating removed;
4B = less than 5% of coating removed; 3B = 5-15 % of coating removed; 2B = 15-35% of coating removed; 1B = 35-65% of coating removed; and OB = greater than 65% of coating removed.
[0056] Table 3 HOURS
OUTER LAYER
edlar 38 m B TB TB TB
umiflon 13 m 5B 5B 5B 4B
OUTER LAYER
edlar 38 m B TB TB TB
umiflon 13 m 5B 5B 5B 4B
[0057] As illustrated in Table 3, the weatherability of thin Lumiflon -based back sheet is comparable to one of oriented Tedlar -based back sheet.
[0058] Figures 3 and 4 show that the tensile strength and elongation at break of Lumiflon -based back sheet depreciates much less than those of Tedlar -based back sheet as a function of exposure to "Damp Heat".
[0059] To evaluate UV stability, samples were placed into the Atlas ci 4000 Xenon Weather-Ometer, equipped with Xenon Arc Lamp for duration of 4600 hrs, measuring L*a*b* regularly. b*-value represents "yellowing" of the material.
As is represented in Figure 5, UV stability of Lumiflon -based back sheet is comparable to Tedlar -based back sheet.
As is represented in Figure 5, UV stability of Lumiflon -based back sheet is comparable to Tedlar -based back sheet.
[0060] Example 2 100611 Example 2 illustrates the preparation of an alternate embodiment of a Lumiflon -based protective backing sheet according to the present invention.
Lumiflon used in Example 2 is LF 200 grade, obtained from Asahi Glass as a 60% solution in xylene (150g). Pigment used in this example is Ti-Pure R-105, obtained from DuPont (57g). Hydrophobically modified silica used in this example is Cab-o-sil TS-720 (lOg) obtained from Cabot. The crosslinker used is Desmodur N3300, obtained from Bayer (16 g). The catalyst used in this example is dibutyl tin dilaureate (0.15 g of 0.1%solution in MEK) obtained from Aldrich. The pigment and silica are mixed with Lumiflon solution using high shear mixer, followed by solvent, crosslinker and catalyst addition.
[0062] The formulation is then applied. The liquid formulation is transferred from the pan to the film by applicator roll and metered off by Mayer Rod to obtain the desired coating weight. The coating is applied directly on a Mylar (DuPont) (5mil) polyester film. No adhesive is required and in this example none is used. The coating is applied at a coating weight of 10 - 120 g/m2, preferably 30-90 g/m2, and more preferably 30 -45 g/m2.
[0063] Table 4.
Thickness g/(100in2 Water Vapor Voltage Thickness of outer = day) Partial Sample Transmission max, m layer m 100F Discharge Test Test VDC
100% RH
Lumiflon IEC 60994-1, 241 ASTM F 1249 0.12 1015 /Polyester/EVA 13 IEC 61730 Lumiflon silica/ IEC 60994-1, 241 ASTM F 1249 0.12 1060 Polyester/EVA 13 IEC 61730 [0064] As illustrated in Table 4, Example 2, which includes the addition of silica, results in 45 V (max permissible voltage) increase over the Lumiflon based back sheet without silica, and in 40V increase over Tedlar based back sheet.
[0065] Example 3 [0066] Example 3 illustrates the preparation of another embodiment of the present invention; a Lumiflon -based "patch kit" formulation.
[0067] The Lumiflon based patch kit formulation is preferably prepared from a formulation comprising 2 separate components: A and B.
[0068] Component A comprises of a mixture of a crosslinker (Isocyanate Desmodur N3300 (2.5g, Bayer)) and a solvent (in this Example, xylene).
[0069] Component B is comprised of a mixture of a solvent, pigment and a fluorocopolymer. In this Example Component B is prepared as follows. A
dispersing agent (Disperbyk 111 (0.25g, BYK- Chemie)) is mixed with xylene, 14.1 g of Lumiflori LF 200, pigment Ti-Pure R101 (IOg, DuPont), Orgasol 2002D (4.7 g, Arkema Inc) and a mixture of coloring agents (Microlith Blue, Microlith Yellow, Microlith Brown and Orasol Black). Different coloring agents can be added to match the color of the torn backing sheet.
[0070] In use, components A and B are placed into a twin-chamber syringe equipped with static mixer. The formulation is applied over damaged piece of backing sheet by using an applicator. One such applicator is available from Brandywine Associates and is illustrated in Figure 6 where 50 is the mixer, 52 is an applicator tip, and 54 is the applied patch kit formulation. However, any type of applicator, such as a brush, may be used to apply the formulation.
[0071] The patch kit is compatible with many backing sheets, such as those prepared of prior art materials such as Tedlar /Polyester/EVA or backing sheet made in accordance with the present invention. The applied formulation to a Tedlar based backing sheet was subjected to partial discharge test. The results of this test are summarized in Table 5.
[0072] Table 5. Results of Partial Discharge Test Outer layer Partial Laminate Thickness mil Voltage max, VDC
thickness mil Discharge Test Tedlar /Polyester/EVA 10.5 1.5 IEC 60994-1, 1020 Tedlar /Polyester/EVA IEC 60994-1, 10.5 1.5 1020 patched IEC 61730 [0073] Additionally, this formulation demonstrated excellent adhesion to underlying layers of the backing sheet material, namely, 5B, by cross- cut tape test ASTM
D 3359-97.
[0074] There will be various modifications, adjustments, and applications of the disclosed invention that will be apparent to those of skill in the art, and the present application is intended to cover such embodiments. Although the present invention has been described in the context of certain preferred embodiments, it is intended that the full scope of these be measured by reference to the scope of the following claims.
[0075] The disclosures of various publications, patents and patent applications that are cited herein are incorporated by reference in their entireties.
Lumiflon used in Example 2 is LF 200 grade, obtained from Asahi Glass as a 60% solution in xylene (150g). Pigment used in this example is Ti-Pure R-105, obtained from DuPont (57g). Hydrophobically modified silica used in this example is Cab-o-sil TS-720 (lOg) obtained from Cabot. The crosslinker used is Desmodur N3300, obtained from Bayer (16 g). The catalyst used in this example is dibutyl tin dilaureate (0.15 g of 0.1%solution in MEK) obtained from Aldrich. The pigment and silica are mixed with Lumiflon solution using high shear mixer, followed by solvent, crosslinker and catalyst addition.
[0062] The formulation is then applied. The liquid formulation is transferred from the pan to the film by applicator roll and metered off by Mayer Rod to obtain the desired coating weight. The coating is applied directly on a Mylar (DuPont) (5mil) polyester film. No adhesive is required and in this example none is used. The coating is applied at a coating weight of 10 - 120 g/m2, preferably 30-90 g/m2, and more preferably 30 -45 g/m2.
[0063] Table 4.
Thickness g/(100in2 Water Vapor Voltage Thickness of outer = day) Partial Sample Transmission max, m layer m 100F Discharge Test Test VDC
100% RH
Lumiflon IEC 60994-1, 241 ASTM F 1249 0.12 1015 /Polyester/EVA 13 IEC 61730 Lumiflon silica/ IEC 60994-1, 241 ASTM F 1249 0.12 1060 Polyester/EVA 13 IEC 61730 [0064] As illustrated in Table 4, Example 2, which includes the addition of silica, results in 45 V (max permissible voltage) increase over the Lumiflon based back sheet without silica, and in 40V increase over Tedlar based back sheet.
[0065] Example 3 [0066] Example 3 illustrates the preparation of another embodiment of the present invention; a Lumiflon -based "patch kit" formulation.
[0067] The Lumiflon based patch kit formulation is preferably prepared from a formulation comprising 2 separate components: A and B.
[0068] Component A comprises of a mixture of a crosslinker (Isocyanate Desmodur N3300 (2.5g, Bayer)) and a solvent (in this Example, xylene).
[0069] Component B is comprised of a mixture of a solvent, pigment and a fluorocopolymer. In this Example Component B is prepared as follows. A
dispersing agent (Disperbyk 111 (0.25g, BYK- Chemie)) is mixed with xylene, 14.1 g of Lumiflori LF 200, pigment Ti-Pure R101 (IOg, DuPont), Orgasol 2002D (4.7 g, Arkema Inc) and a mixture of coloring agents (Microlith Blue, Microlith Yellow, Microlith Brown and Orasol Black). Different coloring agents can be added to match the color of the torn backing sheet.
[0070] In use, components A and B are placed into a twin-chamber syringe equipped with static mixer. The formulation is applied over damaged piece of backing sheet by using an applicator. One such applicator is available from Brandywine Associates and is illustrated in Figure 6 where 50 is the mixer, 52 is an applicator tip, and 54 is the applied patch kit formulation. However, any type of applicator, such as a brush, may be used to apply the formulation.
[0071] The patch kit is compatible with many backing sheets, such as those prepared of prior art materials such as Tedlar /Polyester/EVA or backing sheet made in accordance with the present invention. The applied formulation to a Tedlar based backing sheet was subjected to partial discharge test. The results of this test are summarized in Table 5.
[0072] Table 5. Results of Partial Discharge Test Outer layer Partial Laminate Thickness mil Voltage max, VDC
thickness mil Discharge Test Tedlar /Polyester/EVA 10.5 1.5 IEC 60994-1, 1020 Tedlar /Polyester/EVA IEC 60994-1, 10.5 1.5 1020 patched IEC 61730 [0073] Additionally, this formulation demonstrated excellent adhesion to underlying layers of the backing sheet material, namely, 5B, by cross- cut tape test ASTM
D 3359-97.
[0074] There will be various modifications, adjustments, and applications of the disclosed invention that will be apparent to those of skill in the art, and the present application is intended to cover such embodiments. Although the present invention has been described in the context of certain preferred embodiments, it is intended that the full scope of these be measured by reference to the scope of the following claims.
[0075] The disclosures of various publications, patents and patent applications that are cited herein are incorporated by reference in their entireties.
Claims (22)
1. A backing sheet for a photovoltaic module comprising:
a layer comprising an organic solvent soluble and/or water dispersible, crosslinkable amorphous fluoropolymers.
a layer comprising an organic solvent soluble and/or water dispersible, crosslinkable amorphous fluoropolymers.
2. The backing sheet of claim 1 where the fluoropolymer is a fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers.
3. The backing sheet of claim 2 further comprising a crosslinking agent mixed with the flourocopolymer.
4. The backing sheet of claim 3 further comprising a layer comprising one or more of polyester, polycarbonate, polyolefin, polyurethane, a liquid. crystal polymer, aclar, aluminum, sputtered aluminum oxide polyester, sputtered silicon dioxide polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon dioxide polycarbonate.
5. The backing sheet of claim 4 wherein the layer comprising the crosslinking agent mixes with the flourocopolymer is applied to the polyester layer without adhesive.
6. The backing sheet of claim 5 further comprising an EVA layer.
7. The backing sheet of claim 6 wherein the fluorocopolymer layer has a thickness of less than 1mil.
8. The backing sheet of claim 6 wherein the fluorocopolymer layer has a thickness of greater than 1mil.
9. The backing sheet of claim 4 further comprising silica, titanium oxide, aluminum oxide, zinc oxide, beryllium oxide, mica, clays, boron nitride, aluminum nitride, titanium nitride, carbon black, and/or organic pigments.
10. A backing sheet for a photovoltaic module comprising:
a layer comprising a copolymer of tetrafluoroethylene (TFE) and hydrocarbon olefins with reactive OH functionality.
a layer comprising a copolymer of tetrafluoroethylene (TFE) and hydrocarbon olefins with reactive OH functionality.
11. The backing sheet of claim 10 further comprising a crosslinking agent mixed with the flourocopolymer.
12. The backing sheet of claim 11 further comprising a layer comprising one or more of polyester, polycarbonate, polyolefin, polyurethane, liquid crystal polymer, aclar, aluminum, of sputtered aluminum oxide polyester, sputtered silicon dioxide polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon dioxide polycarbonate.
13. The backing sheet of claim 11 wherein the layer comprising the crosslinking agent mixes with the flourocopolymer is applied to the polyester layer without adhesive.
14. The backing sheet of claim 13 further comprising an EVA layer.
15. The backing sheet of claim 13 further comprising an ionomer layer.
16. The backing sheet of claim 12 further comprising a layer of a fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers.
17. The backing sheet of claim 13 wherein the fluorocopolymer layer has a thickness of less than 1mil.
18. The backing sheet of claim 13 wherein the fluorocopolymer layer has a thickness of greater than 1mil.
19. The backing sheet of claim 11 further comprising one or more of silica, titanium oxide, aluminum oxide, zinc oxide, beryllium oxide, mica, clays, boron nitride, aluminum nitride, titanium nitride, carbon black, and organic pigments.
20. A backing sheet for a photovoltaic module comprising:
a layer comprising a terpolymer of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
a layer comprising a terpolymer of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
21. The backing sheet of claim 20 further comprising a layer comprising one or more of polyester, polycarbonate, polyolefin, polyurethane, liquid crystal polymer, aclar, aluminum, of sputtered aluminum oxide polyester, sputtered silicon dioxide polyester, sputtered aluminum oxide polycarbonate, and sputtered silicon dioxide polycarbonate.
22. The backing sheet of claim 21 further comprising an EVA layer.
24. The backing sheet of claim 21 further comprising an ionomer layer.
25. The backing sheet of claim 21 further comprising a layer of fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers.
26. The backing sheet of claim 25 wherein the fluorocopolymer layer has a thickness of less than 1mil.
27. The backing sheet of claim 25 wherein the fluorocopolymer layer has a thickness of greater than 1mil.
28. The backing sheet of claim 20 further comprising silica, titanium oxide, aluminum oxide, zinc oxide, beryllium oxide, mica, clays, boron nitride, aluminum nitride, titanium nitride, carbon black, and/or organic pigments.
29. A method of repairing the backing sheet of a photovoltaic module comprising:
applying a formulation comprising an amorphous fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers to an area on the backing sheet in need of repair.
30. The method of repairing the backing sheet of claim 29 wherein the formulation is comprised of two components, wherein the first component is comprised of a mixture of a crosslinker and a solvent, and the second component is comprised of a mixture of a solvent and a fluorocopolymer.
31. The method of claim 29 wherein the formulation is applied to the backing sheet at ambient temperature or moderately elevated temperature.
32. The method of claim 29 wherein the formulation is applied to the backing sheet at ambient temperature or moderately elevated temperature by spraying.
33. The method of claim 30 wherein the first and second components are placed in a twin-chamber syringe equipped with static mixer and applied through an applicator and/or brush attached to the syringe.
24. The backing sheet of claim 21 further comprising an ionomer layer.
25. The backing sheet of claim 21 further comprising a layer of fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers.
26. The backing sheet of claim 25 wherein the fluorocopolymer layer has a thickness of less than 1mil.
27. The backing sheet of claim 25 wherein the fluorocopolymer layer has a thickness of greater than 1mil.
28. The backing sheet of claim 20 further comprising silica, titanium oxide, aluminum oxide, zinc oxide, beryllium oxide, mica, clays, boron nitride, aluminum nitride, titanium nitride, carbon black, and/or organic pigments.
29. A method of repairing the backing sheet of a photovoltaic module comprising:
applying a formulation comprising an amorphous fluorocopolymer of chlorotrifluoroethylene (CTFE) and one or more alkyl vinyl ethers to an area on the backing sheet in need of repair.
30. The method of repairing the backing sheet of claim 29 wherein the formulation is comprised of two components, wherein the first component is comprised of a mixture of a crosslinker and a solvent, and the second component is comprised of a mixture of a solvent and a fluorocopolymer.
31. The method of claim 29 wherein the formulation is applied to the backing sheet at ambient temperature or moderately elevated temperature.
32. The method of claim 29 wherein the formulation is applied to the backing sheet at ambient temperature or moderately elevated temperature by spraying.
33. The method of claim 30 wherein the first and second components are placed in a twin-chamber syringe equipped with static mixer and applied through an applicator and/or brush attached to the syringe.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US90198207P | 2007-02-16 | 2007-02-16 | |
US60/901,982 | 2007-02-16 | ||
US12/011,962 | 2008-01-30 | ||
US12/011,962 US20080264484A1 (en) | 2007-02-16 | 2008-01-30 | Backing sheet for photovoltaic modules and method for repairing same |
PCT/US2008/001351 WO2008143719A2 (en) | 2007-02-16 | 2008-02-01 | Backing sheet for photovoltaic modules and method for repairing same |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2673018A1 true CA2673018A1 (en) | 2008-11-27 |
Family
ID=41091652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002673018A Abandoned CA2673018A1 (en) | 2007-02-16 | 2008-02-01 | Backing sheet for photovoltaic modules and method for repairing same |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP2121311A4 (en) |
JP (1) | JP2010519742A (en) |
KR (2) | KR101388381B1 (en) |
CN (1) | CN101605657B (en) |
AU (1) | AU2008253723A1 (en) |
CA (1) | CA2673018A1 (en) |
MX (1) | MX2009008763A (en) |
TW (1) | TW200933902A (en) |
WO (1) | WO2008143719A2 (en) |
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JP2010278256A (en) * | 2009-05-28 | 2010-12-09 | Ma Packaging:Kk | Back sheet for solar cell module |
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KR101721577B1 (en) * | 2011-01-06 | 2017-03-31 | 에스케이씨 주식회사 | Backsheet for solor cells having Polyvinylidene fluoride film |
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2008
- 2008-02-01 KR KR1020097013982A patent/KR101388381B1/en not_active IP Right Cessation
- 2008-02-01 EP EP08794278A patent/EP2121311A4/en not_active Withdrawn
- 2008-02-01 JP JP2009550092A patent/JP2010519742A/en active Pending
- 2008-02-01 MX MX2009008763A patent/MX2009008763A/en unknown
- 2008-02-01 CN CN200880002193.7A patent/CN101605657B/en not_active Expired - Fee Related
- 2008-02-01 WO PCT/US2008/001351 patent/WO2008143719A2/en active Application Filing
- 2008-02-01 AU AU2008253723A patent/AU2008253723A1/en not_active Abandoned
- 2008-02-01 KR KR1020137001154A patent/KR20130027038A/en not_active Application Discontinuation
- 2008-02-01 CA CA002673018A patent/CA2673018A1/en not_active Abandoned
- 2008-10-07 TW TW097138537A patent/TW200933902A/en unknown
Also Published As
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MX2009008763A (en) | 2009-10-08 |
WO2008143719A3 (en) | 2009-02-26 |
KR20130027038A (en) | 2013-03-14 |
JP2010519742A (en) | 2010-06-03 |
WO2008143719A2 (en) | 2008-11-27 |
CN101605657A (en) | 2009-12-16 |
TW200933902A (en) | 2009-08-01 |
EP2121311A2 (en) | 2009-11-25 |
AU2008253723A1 (en) | 2008-11-27 |
EP2121311A4 (en) | 2012-10-31 |
KR101388381B1 (en) | 2014-04-28 |
CN101605657B (en) | 2015-01-14 |
KR20090121273A (en) | 2009-11-25 |
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