EP2701906A1 - Verwendung einer mehrschichtigen pvc/fluorierten polymerstruktur zum schutz der rückseite von solarmodulen - Google Patents

Verwendung einer mehrschichtigen pvc/fluorierten polymerstruktur zum schutz der rückseite von solarmodulen

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Publication number
EP2701906A1
EP2701906A1 EP12725066.0A EP12725066A EP2701906A1 EP 2701906 A1 EP2701906 A1 EP 2701906A1 EP 12725066 A EP12725066 A EP 12725066A EP 2701906 A1 EP2701906 A1 EP 2701906A1
Authority
EP
European Patent Office
Prior art keywords
pvc
layer
use according
fluoropolymer
vdf
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.)
Withdrawn
Application number
EP12725066.0A
Other languages
English (en)
French (fr)
Inventor
Anthony Bonnet
Samuel Devisme
Barbara Ramfel
Stéphane Bizet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2701906A1 publication Critical patent/EP2701906A1/de
Withdrawn legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042PV modules or arrays of single PV cells
    • H01L31/048Encapsulation of modules
    • H01L31/049Protective back sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/101Glass fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00Resin or rubber layer containing a blend of at least two different polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/308Heat stability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/712Weather resistant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/732Dimensional properties
    • B32B2307/734Dimensional stability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/12Photovoltaic modules
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544Addition polymer is perhalogenated

Definitions

  • the present invention relates generally to the field of multilayer films, and in particular to multilayer structures based on fluoropolymers and PVC.
  • the invention also relates to the various methods of manufacturing such structures, in particular by coextrusion or by coating, and to their use for the rear protection of solar panels.
  • a solar module comprises a set of photovoltaic cells consisting of optoelectronic components (usually based on crystalline silicon), which generate an electrical voltage upon exposure to light.
  • the photovoltaic cells are placed between a transparent cover material, which is a glass or plastic plate, and a protective material at the back, often a plastic film.
  • the protective film which is positioned at the rear of the photovoltaic solar panel, called the back-sheet, is exposed to an environment comprising factors as diverse as water, oxygen and / or UV radiation.
  • the first function of a back-sheet is therefore to provide the solar panel with good electrical insulation, reduced transmission of water vapor, protection against UV radiation and oxygen barrier properties.
  • EVA ethylene-vinyl acetate
  • another function of the back-sheet is to provide good adhesion to the EVA or thermoplastic encapsulant material. when these different materials are rolled together.
  • the protective film must have a thermal stability in volume or size to avoid thermal expansion and in particular a shrinkage during assembly of the cells.
  • Metal back-sheets are known in the form of steel or aluminum sheets. More recently, back-sheets have been made of polymeric materials, such as PET or TEDLAR ® (polyvinyl chloride-based material). The back-sheets are generally composed of a polyester layer protected by two fluoropolymer outer layers. The most common multilayer is assembled using solvent-deposited polyurethane glues: fluoropolymer / glue / bioriented PET / glue / fluoropolymer.
  • the bioriented PET is a sheet with a thickness of 75 to 350 microns while the fluorinated film UV barrier (PET protection) has a thickness of 10 to 40 microns.
  • PET films have the advantage of being dimensionally stable and have excellent electrical insulation characteristics. However, these films are susceptible to degradation following exposure to environmental factors such as UV radiation and moisture. It has been found that the use of PET does not make it possible to obtain back-sheets with good durability properties in an external environment.
  • PET layer with another polymer which confers more resistance to moisture and radiation, that is, which has improved weatherability when it is used. in combination with a fluoropolymer layer.
  • a polymer is represented by PVC, which is an inexpensive, easily extrudable thermoplastic material which has better hydrolysis resistance and better UV radiation stability than PET.
  • the present invention proposes to provide a new use of a multilayer structure combining fluorinated polymers and PVC, as protection on the back of a photovoltaic solar panel, which has improved durability in external environment, while keeping the others properties of a back-sheet ie good electrical insulation, thermal stability in volume or dimensional and good adhesion to the encapsulating material.
  • the invention relates to the use for the rear protection of a solar panel of a multilayer structure comprising at least one fluoropolymer layer and a PVC layer.
  • said multilayer structure consists of two layers, namely an outer layer comprising a fluoropolymer and an inner layer of PVC.
  • said multilayer structure consists of three layers, namely an outer layer of fluoropolymer, an intermediate layer of PVC and an inner layer of fluoropolymer.
  • a binder of acrylic, fluorinated or polyurethane type can be used between the fluoropolymer layer and the PVC layer.
  • said fluoropolymer layer may consist of one or more fluoropolymer films.
  • the PVC layer may consist of one or more PVC films.
  • the present invention relates to the use for the rear protection of a solar panel of a multilayer structure comprising at least one fluoropolymer layer and a PVC layer, wherein each fluoropolymer layer contains a homopolymer of VDF or a copolymer of VDF and a fluorinated comonomer copolymerizable with VDF.
  • the fluoropolymer is a homopolymer or copolymer of VDF and a fluorinated comonomer copolymerizable with VDF.
  • Each fluoropolymer layer thus consists of a VDF-based polymer.
  • the fluorinated comonomer copolymerizable with VDF is chosen for example from vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE) and perfluoro (propyl vinyl) ether (PPVE); perfluoro (1,3-dioxole); perfluoro (2,2-dimethyl-1,3-dioxole) (PDD), and mixtures thereof.
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • perfluoro (alkyl vinyl) ethers
  • the fluorinated comonomer is chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) and tetrafluoroethylene (TFE), and mixtures thereof.
  • CTFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • VF3 trifluoroethylene
  • TFE tetrafluoroethylene
  • the comonomer is advantageously HFP because it copolymerizes well with VDF and provides good thermomechanical properties.
  • the copolymer comprises only VDF and HFP.
  • the fluoropolymer is a homopolymer of VDF (PVDF) or a VDF copolymer such as VDF-HFP containing at least 50% by weight of VDF, advantageously at least 75% by weight of VDF and preferably at least 90% by weight. mass of VDF.
  • VDF VDF
  • VDF copolymer such as VDF-HFP containing at least 50% by weight of VDF, advantageously at least 75% by weight of VDF and preferably at least 90% by weight. mass of VDF.
  • HFP HFP
  • the homopolymer or a copolymer of VDF have a viscosity ranging from 100 Pa.s to 3000 Pa.s, the viscosity being measured at 230 ° C., at a shear rate of 100 s -1 using a
  • this type of polymer is well suited to extrusion, preferably the polymer has a viscosity ranging from 500 Pa.s to 2900 Pa.s, the viscosity being measured at 230.degree. shear rate of 100 sec -1 using a capillary rheometer.
  • the fluoropolymer comprises at least one additive in the form of an additional polymer which may be a homopolymer or copolymer of methyl methacrylate (MMA), optionally supplemented with inorganic particles.
  • an additional polymer which may be a homopolymer or copolymer of methyl methacrylate (MMA), optionally supplemented with inorganic particles.
  • MMA methyl methacrylate
  • the fluoropolymer layer may comprise one or more inorganic and / or organic particle shaped charges, in addition to the presence of the additional MMA polymer.
  • MMA polymer homopolymers of methyl methacrylate (MMA) and copolymers containing at least 50% by weight of MMA and at least one other monomer copolymerizable with MMA are advantageously used.
  • alkyl (meth) acrylates As an example of comonomer copolymerizable with MMA, there may be mentioned alkyl (meth) acrylates, acrylonitrile, butadiene, styrene, isoprene. Examples of alkyl (meth) acrylates are described in Kirk-Othmer, Encyclopedia of Chemical Technology, 4 th edition (1991) in Vol. 1 pages 292-293 and in Vol. 16 pages 475-478.
  • the polymer (homopolymer or copolymer) of MMA comprises, by weight, from 0 to 20% and preferably 5 to 15% of a (C 1 -C 8) alkyl (meth) acrylate, which is preferably methyl acrylate. and / or ethyl acrylate.
  • the polymer (homopolymer or copolymer) of MMA can be functionalized, that is to say it contains functions acid, acid chloride, alcohol, anhydride. These functions can be introduced by grafting or by copolymerization.
  • the functionality is in particular the acid function provided by the acrylic acid comonomer. It is also possible to use a neighboring two-functional acrylic acid monomer which can dehydrate to form an anhydride.
  • the proportion of functionality may be from 0 to 15% by weight of the MMA polymer, preferably from 0 to 10% by weight.
  • the MMA polymer may advantageously contain at least one impact modifying additive.
  • impact-resistant MMA polymer which contain an acrylic impact modifying additive in the form of multilayer particles.
  • the impact modifying additive is then present in the MMA polymer as it is marketed (that is to say introduced into the MMA resin during the manufacturing process) but it can also be added during manufacture. of the film.
  • the proportion of impact modifying additive ranges from 0 to 30 parts per 70 to 100 parts of MMA polymer, the total being 100 parts.
  • Multilayer particle impact modifier additives also commonly referred to as core-shell, comprise at least one elastomeric (or soft) layer, ie a layer formed of a polymer having a temperature of vitreous transition (Tg) less than -5 ° C and at least one rigid (or hard) layer, that is to say formed of a polymer having a Tg greater than 25 ° C.
  • Tg temperature of vitreous transition
  • the size of the particles is generally less than ⁇ and advantageously between 50 and 300 nm.
  • Examples of impact modifier additive in the form of core-shell type multi-layer particles can be found in the following documents: EP 1061 100 A1, US 2004/0030046 A1, FR-A-2446296 or US 2005/0124761 A1. Core-shell type particles having at least 80% by weight of soft elastomeric phase are preferred.
  • the MVI (melt volume index or melt volume index in the molten state) of the MMA polymer may be between 2 and 25 cm 3/10 min, measured at 230 ° C under a load of 3.8 kg.
  • the content of MMA polymer in the fluoropolymer layer is between 1 and 55% by weight, advantageously between 2 and 40% by weight, preferably between 3 and 25% by weight.
  • a metal oxide such as, for example, titanium dioxide (TiO 2 ), zinc oxides or zinc sulphides, silica, quartz, alumina, a carbonate, for example calcium carbonate, talc, mica, dolomite (CaC0 3 'MgC0 3), montmorillonite (aluminosilicate), Basu 4, ZrSi0 4, Fe 3 C> 4, and mixtures thereof.
  • TiO 2 titanium dioxide
  • zinc oxides or zinc sulphides silica, quartz, alumina
  • a carbonate for example calcium carbonate, talc, mica, dolomite (CaC0 3 'MgC0 3), montmorillonite (aluminosilicate), Basu 4, ZrSi0 4, Fe 3 C> 4, and mixtures thereof.
  • These particles have the function of opacifying the composition in the UV / visible range.
  • a charge of Ti0 2 is particularly preferred from this point of view.
  • the mineral filler for example of the TiO 2 type, acts as a sunscreen to obtain an opaque film, mainly by diffusion / reflection of the UV rays, but also by visible light.
  • an organic UV absorber with inorganic particles to enhance protection against UV radiation, for example benzophenones or benzotriazoles.
  • Tinuvin ® 234 is particularly preferred.
  • Black pigmented particles may also be added. It is carbon black or carbon nanotubes, used at rates below their percolation threshold.
  • These particles have a size expressed in average diameter generally between 0.05 and 20 microns, advantageously between 0.1 ⁇ and ⁇ , preferably between 0.2 ⁇ and 5 ⁇ .
  • the content of inorganic particles in the fluoropolymer layer is between 0.1 and 30% by weight, advantageously between 5 and 28% by weight, preferably between 10 and 27% by weight and even more preferably between 15 and 25% by weight.
  • the composition of the fluoropolymer layer may be prepared by any method which makes it possible to obtain a homogeneous mixture of the polymers and any additives and / or fillers which form part of the fluoropolymer layer.
  • composition according to the invention is prepared by melt blending all the polymers and any additives and fibers and then is transformed, for example in the form of granules, by compounding on a tool known to those skilled in the art. art as a twin-screw extruder, a co-kneader or a mixer. This composition may be coextruded with another material or extruded into a film.
  • the thickness of the fluoropolymer layer ranges from 10 to 150 microns, preferably from 15 to 40 microns, inclusive.
  • the PVC layer consists of rigid, semi-rigid or plasticized PVC.
  • the PVC may be any vinyl chloride polymer or copolymer: optionally superchlorinated vinyl chloride homopolymer (CPVC), and optionally crosslinked copolymers resulting from the copolymerization of vinyl chloride with one or more unsaturated ethylenic comonomers.
  • CPVC superchlorinated vinyl chloride homopolymer
  • the latter are chosen from: vinylidene chloride or fluoride, vinyl carboxylates, such as vinyl acetate, vinyl propionate or vinyl butyrate, acrylic and methacrylic acids, nitriles, amides and alkyl esters derived from acrylic and methacrylic acids, especially acrylonitrile, acrylamide, methacrylamide, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, vinyl aromatic derivatives, such as styrene or olefins such as ethylene, propene or 1-butene.
  • Fillers in particular mineral fillers, may also be added to the PVC to improve the thermomechanical behavior of the composition.
  • Non-limiting examples are silica, alumina or calcium carbonates or carbon nanotubes or glass fibers.
  • Preferred PVCs are homo- and copolymers of vinyl chloride.
  • these have a thermal transmission coefficient U of approximately 65 W / m 2 K.
  • the PVC layer, CPVC or PVC / CPVC may comprise by weight:
  • the coefficient U of the PVC resin may be between 50 and 100 W / m 2 K.
  • Such a resin is obtained by a slurry, bulk, emulsion or microsuspension polymerization process.
  • the coefficient U of the resin CPVC obtained by a chlorination process of a PVC resin mass, can be between 60 and 70 W / m 2 K;
  • additives chosen from stabilizers, processing additives, lubricants or flame retardants.
  • opacifying filler such as titanium dioxide, zinc oxide, zinc sulfide
  • thermoplastic compound based on acrylonitrile or acrylate
  • the plasticizer (s) used in the PVC, CPVC or PVC / CPVC layer is (are) chosen from the group comprising azelates, trimellitates, sebacates, adipates, phthalates, citrates, benzoates and tallates. , glutarates, fumarates, maleates, oleates, palmitates, acetates, epoxidized soybean oil and mixtures thereof.
  • one or more woven or non-woven substrates may be used in combination therewith. These substrates may consist of fiberglass, carbon, polymer fibers (such as polyester, polyamide, etc.), natural fibers (flax, hemp, etc.).
  • the PVC layer is formed of the PVC-substrate assembly.
  • thermoplastic compound used in the PVC, CPVC or PVC / CPVC layer is preferably a thermoplastic compound based on acrylonitrile or acrylate. It can be obtained from compounds chosen from styrene-acrylonitrile, acrylonitrile-styrene-acrylate and ethylene-methyl acrylate copolymers.
  • the PVC, CPVC or PVC / CPVC layer makes it possible to ensure good thermomechanical behavior retention up to the solar panel lamination temperature (120-150 ° C, 5-
  • PVC / CPVC is preferably extrusion in a temperature range between 100 ° C and 180 ° C or 220 ° C.
  • the thickness of the PVC, CPVC or PVC / CPVC layer thus obtained varies from 150 to 450 microns, preferably from 200 to 30 microns, inclusive.
  • An example of a PVC composition is given in Table 1 below:
  • thermomechanical properties up to the lamination temperature of the solar panel (120 ° C-150 ° C);
  • composition 300 ⁇ thick The samples were prepared from a mixture of the various raw materials worked, in proportions as defined in the table below on a twin-cylinder mixer at 205 ° C for 5 minutes. Then the material was press-packed at 185 ° C under a pressure of 200 bar for 240 seconds.
  • the test consists of a measurement of the withdrawal. Before measurements, the sample should be allowed to stand at room temperature for a minimum of 2 hours. On a plate of 140x140 mm, a mark is drawn in the longitudinal direction as well as in the direction transversal to 20mm of the edges. We mark the middle of the square thus obtained. We mark and measure the longitudinal and transverse distances (respectively L0 and T0) obtained at the center of the square.
  • the sample is placed on a wooden board of appropriate size and then an oven at the specified temperature for a given time. Once the time has elapsed, the sample is removed from the oven and allowed to rest for a minimum of 30 minutes under the same conditions used for conditioning the sample before the test. Then we remeasure the longitudinal and transverse distances (respectively L and T).
  • the PVC, CPVC or PVC / CPVCC layer according to the invention makes it possible to obtain shrinkage values between 0.85 and 2.7%, as indicated in Table 2 below:
  • Kynar 740 homopolymer of vinylidene fluoride having a melting temperature
  • Kynar Flex 3120-50 having a melting temperature of 165 ° C and an elastic modulus of 690 MPa.
  • Tf were measured by DSC or differential scanning calorimetry.
  • the elastic modules were measured according to ISO 527.
  • the PMMA used in the compositions below is PMMA ALTUGLAS BS 550 (copolymer of methyl methacrylate and ethyl acrylate - MFR 17-20 g / 10 min (230 ° C., 3.8 kg)).
  • Elastollan C85 is a polyester-based polyurethane.
  • the multilayer films were made by calendering (CAST) on an AMUT extrusion line.
  • This line consists of 3 extruders:
  • the line is also equipped with a Verbugren "multimanifold" 500mm die.
  • the system is also equipped with a Verbugren "multimanifold" 500mm die.
  • Multimanifold allows the production of a film or a 3-layer sheet (layer 1 / layer 21 layer 3) with a variable thickness distribution (example: 30/30/350 microns).
  • the process parameters have been set as shown below:
  • the line speed is 3 m / min.
  • the inner layer is made by dry mixing at the bottom of the machine at the time of production.
  • the inner layer is made by dry mixing at the bottom of the machine at the time of production.
  • the PVDF outer layer containing TiO 2 is produced by compounding in a co-kneader at a temperature not exceeding 240 ° C. At first, the preparation is carried out a PMMA / Ti02 masterbatch on twin-screw extruder; it is then mixed with the PVDF in the co-kneader or in the twin-screw extruder.
  • the inner layer containing TiO 2 is produced by compounding as described for Example 1.2.
  • the inner layer containing S2001 modifier is made by compounding in a twin-screw extruder.
  • the outer layer containing TiO 2 is compounded as described above for 1.2.
  • the outer layer containing Ti0 2 and ZnO is produced by compounding.
  • the introduction Ti0 2 in the PVDF requires the preparation of a masterbatch PMMA / Ti0 2 on twin-screw extruder beforehand; it is then mixed with the PVDF in the co-kneader or in the twin-screw extruder.
  • the outer layer containing TiO 2 is compounded as described for 1.2.
  • the outer layer containing ZnO is made by compounding in a twin-screw extruder.
  • the outer layer containing TiO 2 is compounded as described for 1.2.
  • PVDF 1.9 - CPVC or PVC / Elastollan C85 / Kynar 740 73.3% - PMMA 4.7% - ZnO 15% - 7% TiO2 Introduction Ti0 2 in PVDF requires the preparation of a PMMA / TiO 2 masterbatch beforehand on twin-screw extruder; it is then mixed with the PVDF in the co-kneader or in the twin-screw extruder.
  • the outer layer containing TiO 2 is made by compounding as described for 1.2. 1.1 1 - PVDF 73.3% - PMMA 4.7% - ZnO 15% - 7% Ti0 2 /
  • Ti0 2 in the PVDF requires the preparation of a masterbatch PMMA / Ti0 2 on twin-screw extruder beforehand; it is then mixed with the PVDF in the co-mixer or in the twin-screw extruder.
  • extrusion line of the Dr Collin brand.
  • This line consists of three extruders fitted with a standard polyolefin screw profile, a variable coextrusion block, and a coat hanger die.
  • the coextrusion block allows the production of a film of 1 to 5 layers with a variable thickness distribution (example: 30/250 microns).
  • a system of reels allows to unroll various supports including a PVDF film.
  • the process parameters have been set as shown below:
  • T extrusion layer 1 200 ° C.
  • T ° coextrusion box and die 200 ° C.
  • the line speed is 2 m / min.
  • the multilayer structures can also be assembled by solvent adhesives in two steps according to the following protocol:
  • Kynar film 1 30 micron multilayer film (PVDF / Kynar 740 60% - PMMA 24% -
  • Kynar film 2 monolayer film 18 ⁇ (Kynar 740 73.3% - PMMA 4.7% - ZnO 15% - 7% TiO 2).
  • the films 1 and 2 are made beforehand by blowing the sheath on a Dr Collin 5-layer sheath line equipped with a "pancake" type die.
  • the target structure (PVC sheet (350 microns) / glue / PVDF film (film 1 or 2) is produced as follows:
  • a spiral applicator (“barcoater”) is used to apply a layer of 30 microns of glue (not dried) to the PVC sheet.
  • the formulation of the glue used is as follows (Bostick supplier): HBTS ESP 877 (100 parts) + hardener Biscodur 1621 (9 parts). The PVC sheet coated with glue is then left for one minute at room temperature and then for 5 minutes at 50.degree.
  • the structure is then pressed at 80 ° C., 5 minutes, 3 bars.
  • the structure Before being tested or used, the structure is then left for 3 days in an oven at 60 ° C in order to completely crosslink the glue.
  • a PVC / fiberglass / PVC multilayer structure (150 ⁇ / 50 ⁇ / 150 ⁇ ) is produced by hot thermolamination of 2 PVC sheets on the glass weave using a calender line.
  • the PVC sheet is preheated on thermostatically controlled rolls, then is thermolaminated in a calender.
  • the temperatures, calender closing force and line speed are adjusted according to the PVC formulation and the glass fabric used.
  • PVC - a generic term encompassing polyvinyl chloride and its especially chlorinated derivatives, such as CPVC
  • PVDF polyvinylidene fluoride
  • melt volume index or melt volume melt index
  • melt fiow rate or melt index expressed in g / min

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Laminated Bodies (AREA)
  • Photovoltaic Devices (AREA)
EP12725066.0A 2011-04-27 2012-04-27 Verwendung einer mehrschichtigen pvc/fluorierten polymerstruktur zum schutz der rückseite von solarmodulen Withdrawn EP2701906A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1153585A FR2974535A1 (fr) 2011-04-27 2011-04-27 Utilisations d'une structure multicouche pvc/polymere fluore pour la protection arriere des panneaux solaires
PCT/FR2012/050944 WO2012146880A1 (fr) 2011-04-27 2012-04-27 Utilisation d'une structure multicouche pvc/polymere fluore pour la protection arriere des panneaux solaires

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EP2701906A1 true EP2701906A1 (de) 2014-03-05

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US (1) US20140044976A1 (de)
EP (1) EP2701906A1 (de)
CN (1) CN103619585A (de)
FR (1) FR2974535A1 (de)
WO (1) WO2012146880A1 (de)

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US9492988B2 (en) * 2013-03-14 2016-11-15 Schneller Llc Soft touch laminates constructed with improved fire retardant properties for transportation
JP6611642B2 (ja) * 2016-03-04 2019-11-27 ダイヤプラスフィルム株式会社 ポリ塩化ビニル系樹脂組成物および反射フィルム
WO2019097033A1 (en) * 2017-11-16 2019-05-23 Argotec, LLC Polyvinylidene fluoride-acrylate and thermoplastic polyurethane multilayer protective film
CN112863336B (zh) * 2021-01-11 2022-07-12 武汉华星光电半导体显示技术有限公司 显示模组及显示装置

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FR2974535A1 (fr) 2012-11-02
WO2012146880A1 (fr) 2012-11-01
CN103619585A (zh) 2014-03-05
US20140044976A1 (en) 2014-02-13

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