EP2701906A1 - Use of a multilayer pvc/fluorinated polymer structure for protecting the rear of solar panels - Google Patents

Use of a multilayer pvc/fluorinated polymer structure for protecting the rear of solar panels

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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Withdrawn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
German (de)
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/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor 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
    • H01L31/04—Semiconductor 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
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/00—Layered 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition 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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Abstract

The invention relates to a novel use of a multilayer structure, combining fluorinated polymers and PVC, as protection for use at the rear of a photovoltaic solar panel, said structure having improved durability in outdoor environments, while retaining the other properties associated with a back-sheet, namely good electric insulation, thermal stability in terms of volume and dimensions and good adhesion to the encapsulating material. The invention relates to the use of a multilayer structure as protection at the rear of a solar panel, said structure comprising at least one layer of fluorinated polymer and one layer of PVC.

Description

UTILISATION D'UNE STRUCTURE MULTICOUCHE PVC/POLYMERE FLUORE POUR LA PROTECTION ARRIERE DES PANNEAUX SOLAIRES  USE OF A MULTILAYER PVC / POLYMERIC FLUORINE STRUCTURE FOR THE REAR PROTECTION OF SOLAR PANELS
La présente invention concerne d'une manière générale le domaine des films multicouches, et en particulier les structures multicouches à base de polymères fluorés et de PVC. L'invention se rapporte également aux différents procédés de fabrication de telles structures, notamment par coextrusion ou par enduction, et à leur utilisation pour la protection arrière des panneaux solaires. 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.
Les panneaux ou modules solaires suscitent un intérêt croissant, en raison du caractère renouvelable et non polluant de l'énergie ainsi obtenue. Un module solaire comprend un ensemble de cellules photovoltaïques constituées de composants optoélectroniques (habituellement, à base de silicium cristallin), qui génèrent une tension électrique lors de l'exposition à la lumière. Les cellules photovoltaïques sont placées entre un matériau de couverture transparent, qui est une plaque en verre ou en plastique, et un matériau protecteur à l'arrière, souvent un film plastique.  Solar panels or modules are attracting increasing interest because of the renewable and non-polluting nature of the energy thus obtained. 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.
Le film de protection venant se positionner à l'arrière du panneau solaire photovoltaïque, appelé back-sheet, est exposé à un environnement comprenant des facteurs aussi divers que l'eau, l'oxygène et/ou les radiations UV. La première fonction d'un back-sheet est donc de fournir au panneau solaire une bonne isolation électrique, une transmission réduite de la vapeur d'eau, la protection aux rayonnements UV et des propriétés barrière à l'oxygène. Comme les photocellules sont généralement encapsulées dans un encapsulant à base de copolymère d'éthylène - acétate de vinyle (EVA) ou un encapsulant thermoplastique, une autre fonction du back-sheet consiste à assurer une bonne adhésion à l'EVA ou au matériau encapsulant thermoplastique, lorsque ces différents matériaux sont laminés ensemble. De plus, le film protecteur doit avoir une stabilité thermique en volume ou dimensionnelle pour éviter une expansion thermique et en particulier un retrait pendant l'assemblage des cellules.  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. Since the photocells are generally encapsulated in an ethylene-vinyl acetate (EVA) copolymer encapsulant or a thermoplastic encapsulant, 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. In addition, 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.
On connaît des back-sheets en métal, sous forme des feuilles d'acier ou d'aluminium. Plus récemment, les back-sheets ont été fabriqués en matériaux polymériques, comme le PET ou le TEDLAR® (matériau à base de polyfiuorure de vinyle). Les back-sheets sont composés généralement d'une couche de polyester protégée par deux couches externes en polymère fluoré. Le multicouche le plus répandu est assemblé à l'aide de colles polyuréthanes déposées par voie solvant : polymère fluoré / colle / PET biorienté / colle / polymère fluoré. Le PET biorienté est une feuille d'une épaisseur de 75 à 350 microns alors que le film fluoré barrière aux UV (protection du PET) a une épaisseur de 10 à 40 microns. Il existe maintenant sur le marché de nouveaux films pour back-sheet utilisant soit une seule couche de fluoré (par exemple : EVA / PET / polymère fluoré), soit aucune (back-sheet 100% PET ; back-sheet en polyamide 12 (commercialisé par Isovolta), back-sheet à base de polyamide et de polyoléfine (Apolhya®)). 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. There are now new back-sheet films on the market using either a single fluoride layer (eg EVA / PET / fluoropolymer) or none (100% PET back-sheet, polyamide 12 back-sheet). by Isovolta), back-sheet based on polyamide and polyolefin (Apolhya ® )).
Les films PET ont pour avantage d'être stables dimensionnellement et possèdent d'excellentes caractéristiques d'isolation électrique. Ces films sont cependant sensibles à la dégradation suite à l'exposition aux facteurs environnementaux tels que les rayonnements UV et l'humidité. Il s'est avéré que l'utilisation de PET ne permet pas d'obtenir de back-sheets avec de bonnes propriétés de durabilité en milieu extérieur.  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.
Il a donc été recherché à substituer la couche de PET par un autre polymère qui confère plus de résistance à l'humidité et aux rayonnements, autrement dit qui présente une durabilité améliorée en milieu extérieur (en anglais « weatherability ») lorsqu'il est utilisé en combinaison avec une couche de polymère fluoré. Un tel polymère est représenté par le PVC, qui est un matériau thermoplastique bon marché, facilement extrudable, qui présente, par rapport au PET, une meilleure tenue à l'hydrolyse et une meilleure stabilité aux rayonnements UV.  It has therefore been sought to substitute the 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. Such 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.
La présente invention se propose de fournir une nouvelle utilisation d'une structure multicouche combinant les polymères fluoré et le PVC, comme protection à l'arrière d'un panneau solaire photovoltaïque, qui présente une durabilité améliorée en milieu extérieur, tout en gardant les autres propriétés d'un back-sheet à savoir une bonne isolation électrique, stabilité thermique en volume ou dimensionnelle et bonne adhésion au matériau encapsulant.  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.
A cet effet, l'invention a pour objet l'utilisation pour la protection à l'arrière d'un panneau solaire d'une structure multicouche comprenant au moins une couche de polymère fluoré et une couche de PVC.  To this end, 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.
Selon une première variante de réalisation, ladite structure multicouche est constituée de deux couches à savoir une couche externe comprenant un polymère fluoré et une couche interne de PVC.  According to a first variant embodiment, said multilayer structure consists of two layers, namely an outer layer comprising a fluoropolymer and an inner layer of PVC.
Par « couche externe » on comprend la couche qui vient en contact avec le milieu extérieur ; par « couche interne » on comprend la couche qui vient en contact avec le matériau encapsulant de la cellule photovoltaïque. Selon une deuxième variante de réalisation, ladite structure multicouche est constituée de trois couches à savoir une couche externe de polymère fluoré, une couche intermédiaire de PVC et une couche interne de polymère fluoré. By "outer layer" is meant the layer which comes into contact with the external environment; the term "inner layer" includes the layer that comes into contact with the encapsulating material of the photovoltaic cell. According to a second variant embodiment, said multilayer structure consists of three layers, namely an outer layer of fluoropolymer, an intermediate layer of PVC and an inner layer of fluoropolymer.
Par ailleurs, dans chacune de ces variantes, un liant de type acrylique, fluoré ou polyuréthanne peut être employé entre la couche de polymère fluoré et la couche de PVC.  Furthermore, in each of these variants, a binder of acrylic, fluorinated or polyurethane type can be used between the fluoropolymer layer and the PVC layer.
Dans chacune de ces variantes, ladite couche de polymère fluoré peut être constituée d'un seul ou de plusieurs films de polymères fluorés. De même, la couche de PVC peut être constituée d'un seul ou plusieurs films de PVC.  In each of these variants, said fluoropolymer layer may consist of one or more fluoropolymer films. Similarly, the PVC layer may consist of one or more PVC films.
Ces structures sont réalisables par coextrusion, par enduction ou par lamination avec des colles.  These structures are achievable by coextrusion, coating or lamination with glues.
L'invention sera maintenant décrite en détail.  The invention will now be described in detail.
La présente invention concerne l'utilisation pour la protection à l'arrière d'un panneau solaire d'une structure multicouche comprenant au moins une couche de polymère fluoré et une couche de PVC, dans laquelle chaque couche de polymère fluoré contient un homopolymère de VDF ou un copolymère de VDF et d'un comonomère fluoré copolymérisable avec le VDF.  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.
Le polymère fluoré est un homopolymère ou un copolymère de VDF et d'un comonomère fluoré copolymérisable avec le VDF. Chaque couche de polymère fluoré consiste ainsi en un polymère à base de 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.
Avantageusement, le comonomère fluoré copolymérisable avec le VDF est choisi par exemple parmi le fluorure de vinyle; le trifluoroéthylène (VF3); le chlorotrifluoroethylène (CTFE); le 1 ,2-difluoroéthylène; le tetrafiuoroéthylène (TFE); l'hexafiuoropropylène (HFP); les perfiuoro(alkyl vinyl) éthers tels que le perfluoro(méthyl vinyl)éther (PMVE), le perfluoro(éthyl vinyl) éther (PEVE) et le perfiuoro(propyl vinyl) éther (PPVE); le perfiuoro(l ,3-dioxole); le perfluoro(2,2-diméthyl-l ,3-dioxole) (PDD), et leur mélanges.  Advantageously, 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.
De préférence le comonomère fluoré est choisi parmi le chlorotrifluoroéthylène (CTFE), l'hexafiuoropropylène (HFP), le trifluoroéthylène (VF3) et le tétrafiuoroéthylène (TFE), et leurs mélanges. Le comonomère est avantageusement l'HFP car il copolymérise bien avec le VDF et permet d'apporter de bonnes propriétés thermomécaniques. De préférence, le copolymère ne comprend que du VDF et de l'HFP.  Preferably, the fluorinated comonomer is chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) and tetrafluoroethylene (TFE), and mixtures thereof. The comonomer is advantageously HFP because it copolymerizes well with VDF and provides good thermomechanical properties. Preferably, the copolymer comprises only VDF and HFP.
De préférence, le polymère fluoré est un homopolymère de VDF (PVDF) ou un copolymère de VDF comme VDF-HFP contenant au moins 50% en masse de VDF, avantageusement au moins 75% en masse de VDF et de préférence au moins 90% en masse de VDF. On peut citer par exemple plus particulièrement les homopolymères ou copolymères de VDF contenant plus de 75% de VDF et le complément de HFP suivants : KY AR® 710, KY AR® 720, KY AR® 740, KYNAR FLEX® 2850, KYNAR FLEX® 3120, commercialisés par la société ARKEMA. Preferably, 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. We can cite for example more particularly homopolymers or VDF copolymers containing more than 75% of VDF and complement following HFP: KY AR ® 710, KY AR ® 720, KY AR ® 740, KYNAR FLEX ® 2850, KYNAR FLEX ® 3120, marketed by the company ARKEMA.
Avantageusement, le homopolymère ou un copolymère de VDF ont une viscosité allant de 100 Pa.s à 3000 Pa.s, la viscosité étant mesurée à 230°C, à un gradient de cisaillement de 100 s"1 à l'aide d'un rhéomètre capillaire. En effet, ce type de polymère est bien adapté à l'extrusion. De préférence, le polymère a une viscosité allant de 500 Pa.s à 2900 Pa.s, la viscosité étant mesurée à 230°C, à un gradient de cisaillement de 100 s"1 à l'aide d'un rhéomètre capillaire. Advantageously, 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 In fact, 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.
Dans un mode de réalisation, le polymère fluoré comprend au moins un additif sous forme d'un polymère additionnel qui peut être un homopolymère ou copolymère de méthacrylate de méthyle (MMA), éventuellement additionné de particules inorganiques.  In one embodiment, 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.
La couche de polymère fluoré peut comprendre une ou plusieurs charges formées de particules inorganiques et/ou organiques, en plus de la présence du polymère additionnel MMA.  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.
S'agissant du polymère de MMA, on utilise avantageusement les homopolymères du méthacrylate de méthyle (MMA) et les copolymères contenant au moins 50% en masse de MMA et au moins un autre monomère copolymérisable avec le MMA.  As regards the 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.
A titre d'exemple de comonomère copolymérisable avec le MMA, on peut citer les (méth)acrylates d'alkyle, l'acrylonitrile, le butadiène, le styrène, l'isoprène. Des exemples de (méth)acrylates d'alkyle sont décrits dans KIRK-OTHMER, Encyclopedia of chemical technology, 4ème édition (1991) dans le Vol. 1 pages 292-293 et dans le Vol. 16 pages 475-478. 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.
Avantageusement, le polymère (homopolymère ou copolymère) de MMA comprend en masse de 0 à 20% et de préférence 5 à 15% d'un (méth)acrylate d'alkyle en Ci-Cs, qui est de préférence l'acrylate de méthyle et/ou l'acrylate d'éthyle. Le polymère (homopolymère ou copolymère) de MMA peut être fonctionnalisé, c'est-à-dire qu'il contient des fonctions acide, chlorure d'acide, alcool, anhydride. Ces fonctions peuvent être introduites par greffage ou par copolymérisation. Avantageusement, la fonctionnalité est en particulier la fonction acide apportée par le comonomère acide acrylique. On peut aussi utiliser un monomère à deux fonctions acide acrylique voisines qui peuvent se déshydrater pour former un anhydride. La proportion de fonctionnalité peut être de 0 à 15% en masse du polymère de MMA, de préférence de 0 à 10% en masse.  Advantageously, 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. Advantageously, 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.
Le polymère de MMA peut contenir avantageusement au moins un additif modifiant choc. Il existe des qualités commerciales de polymère de MMA dit résistant aux chocs, qui contiennent un additif modifiant choc acrylique sous forme de particules multicouches. L'additif modifiant choc est alors présent dans le polymère de MMA tel qu'il est commercialisé (c'est-à- dire introduit dans la résine de MMA au cours du procédé de fabrication) mais il peut aussi être ajouté lors de la fabrication du film. La proportion d'additif modifiant choc varie de 0 à 30 parts pour 70 à 100 parts de polymère de MMA, le total faisant 100 parts. The MMA polymer may advantageously contain at least one impact modifying additive. There are commercial grades of so-called 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.
Les additifs modifiant choc du type particules multicouches, appelées aussi couramment core-shell (noyau-écorce), comprennent au moins une couche élastomérique (ou molle), c'est-à- dire une couche formée d'un polymère ayant une température de transition vitreuse (Tg) inférieure à -5°C et au moins une couche rigide (ou dure), c'est-à-dire formée d'un polymère ayant une Tg supérieure à 25°C. La taille des particules est en général inférieure au μπι et avantageusement comprise entre 50 et 300 nm. On trouvera des exemples d'additif modifiant choc sous forme de particules multicouches de type core-shell dans les documents suivants : EP 1061 100 Al , US 2004/0030046 Al, FR-A-2446296 ou US 2005/0124761 Al . On préfère des particules de type core-shell ayant au moins 80% en masse de phase élastomérique molle.  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. The size of the particles is generally less than μπι 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.
Le MVI (melt volume index ou indice de fluidité en volume à l'état fondu) du polymère de MMA peut être compris entre 2 et 25 cm3/10 min, mesuré à 230°C sous une charge de 3,8 kg. 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.
La teneur en polymère de MMA dans la couche de polymère fluoré est comprise entre 1 et 55% massique, avantageusement entre 2 et 40% massique, préférentiellement entre 3 et 25% massique.  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.
S 'agissant des particules inorganiques, on peut utiliser un oxyde métallique comme par exemple le dioxyde de titane (Ti02), des oxydes de zinc ou des sulfures de zinc, la silice, le quartz, l'alumine, un carbonate comme par exemple le carbonate de calcium, le talc, le mica, la dolomite (CaC03 »MgC03), la montmorillonite (aluminosilicate), BaSÛ4, ZrSi04, Fe3C>4, et leurs mélanges. With regard to the inorganic particles, it is possible to use 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.
Ces particules ont pour fonction d'opacifier la composition dans le domaine de l'UV/visible. Une charge de Ti02 est tout particulièrement préférée de ce point de vue-là. La charge minérale par exemple de type Ti02 joue le rôle de filtre solaire pour avoir un film opaque, principalement par diffusion/réflexion des rayons UV, mais également du lumière visible. 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.
Il est possible d'associer un absorbeur UV organique aux particules inorganiques pour renforcer la protection contre les rayonnements UV, par exemple des benzophénones ou des benzotriazoles. Le Tinuvin® 234 est particulièrement préféré. Des particules pigmentées en noir peuvent également être ajoutées. Il s'agit du noir de carbone ou bien des nanotubes de carbone, utilisés à des taux inférieurs à leur seuil de percolation. It is possible to associate 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.
Ces particules ont une taille exprimée en diamètre moyen généralement comprise entre 0,05 et 20 microns, avantageusement entre 0,1 μηι et ΙΟμηι, préférentiellement entre 0,2 μηι et 5μηι. La teneur particules inorganiques dans la couche de polymère fluoré est comprise entre 0,1 et 30% massique, avantageusement entre 5 et 28% massique, préférentiellement entre 10 et 27% massique et de manière encore plus préférée entre 15 et 25% massique.  These particles have a size expressed in average diameter generally between 0.05 and 20 microns, advantageously between 0.1 μηι and ΙΟμηι, preferably between 0.2 μηι and 5μηι. 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.
Selon l'invention, la composition de la couche de polymère fluoré peut être préparée par toute méthode qui permet d'obtenir un mélange homogène des polymères et éventuels additifs et/ou charges, entrant dans la composition de la couche de polymère fluoré.  According to the invention, 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.
Parmi ces méthodes, on peut notamment citer l'extrusion à l'état fondu, le compactage, ou encore le malaxeur à rouleau.  Among these methods, mention may in particular be made of extrusion in the molten state, compacting, or roll kneader.
Plus particulièrement, la composition selon l'invention est préparée par mélange à l'état fondu de tous les polymères et éventuels additifs et fibres puis est transformée, par exemple sous forme de granulés, par compoundage sur un outil connu de l'homme de l'art comme une extrudeuse bi-vis, un co-malaxeur ou un mélangeur. Cette composition peut être soit co-extrudée avec un autre matériau, soit extradée sous forme d'un film.  More particularly, the 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.
L'épaisseur de la couche de polymère fluoré varie du 10 à 150 microns, de préférence de 15 à 40 microns, bornes comprises.  The thickness of the fluoropolymer layer ranges from 10 to 150 microns, preferably from 15 to 40 microns, inclusive.
La couche de PVC est constituée de PVC rigide, semi-rigide ou plastifié. Le PVC peut être tout polymère ou copolymère de chlorure de vinyle : homopolymère de chlorure de vinyle, éventuellement surchloré (PVCC), et copolymères, facultativement réticulés, résultant de la copolymérisation du chlorure de vinyle avec un ou plusieurs comonomères éthyléniques insaturés. Ces derniers sont choisis parmi : le chlorure ou le fluorure de vinylidène, les carboxylates de vinyle, tels que l'acétate de vinyle, le propionate de vinyle ou le butyrate de vinyle, les acides acryliques et méthacryliques, les nitriles, amides et alkylesters dérives des acides acryliques et méthacryliques, notamment l'acrylonitrile, l'acrylamide, le méthacrylamide, le méthacrylate de méthyle, l'acrylate de méthyle, l'acrylate de butyle, l'acrylate d'éthyle, l'acrylate de 2-éthylhexyle, les dérivés vinyl aromatiques, tels que le styrène ou les oléfines comme l'éthylène, le propène ou 1 -butène. Des charges, en particulier minérales, peuvent également être ajoutées au PVC pour améliorer la tenue thermomécanique de la composition. De façon non limitative, on donnera comme exemples la silice, l'alumine ou les carbonates de calcium ou les nanotubes de carbone ou encore les fibres de verre. 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. 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.
Les PVC préférés sont les homo- et copolymères de chlorure de vinyle. Avantageusement, ceux-ci possèdent un coefficient de transmission thermique U d'environ 65 W/m2K. Preferred PVCs are homo- and copolymers of vinyl chloride. Advantageously, these have a thermal transmission coefficient U of approximately 65 W / m 2 K.
La couche PVC, PVCC ou PVC/PVCC, peut comprendre en poids :  The PVC layer, CPVC or PVC / CPVC, may comprise by weight:
- 50 à 82% en poids d'une ou plusieurs résines PVC et/ou PVCC. Le coefficient U de la résine PVC peut être compris entre 50 et 100 W/m2K. Une telle résine est obtenue par un procédé de polymérisation en suspension, en masse, en émulsion ou en microsuspension. Le coefficient U de la résine PVCC, obtenue par un procédé de chloration d'une résine PVC masse, peut être compris entre 60 et 70 W/m2K; - 50 to 82% by weight of one or more PVC resins and / or CPVC. 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;
- 0,1 à 30% d'additifs, choisis parmi des stabilisants, des additifs de mise en œuvre, des lubrifiants ou des agents ignifugeants. En particulier, parmi les additifs communément utilisés dans des compositions à base de résine vinylique, on peut citer des sels métalliques d'acide carboxylique organique, des acides phosphorique organique, des zéolites, des hydrotalcites, des composés époxydés, des béta-dicétones, des alcools polyhydriques, des antioxydants phosphores, soufrés ou phénolique, des absorbeurs ultraviolet par exemple des benzophénones, benzotriazoles, et dérivés d'oxanilide, des cyanoacrylates, des stabilisants lumière à aminé encombrées de type HALS (« hindered aminé light stabilizer »), des sels d'acide perchlorique, et d'autres composés inorganiques à base de métaux, des lubrifiants par exemple des cires organiques, des alcools gras, des acides gras, des esters, des sels métalliques, des charges par exemple de la craie ou du talc, et des pigments tels le dioxyde de titane ;  - 0.1 to 30% of additives, chosen from stabilizers, processing additives, lubricants or flame retardants. In particular, among the additives commonly used in compositions based on vinyl resin, mention may be made of metal salts of organic carboxylic acid, organic phosphoric acids, zeolites, hydrotalcites, epoxidized compounds, beta-diketones, polyhydric alcohols, phosphorus, sulfur or phenolic antioxidants, ultraviolet absorbers, for example benzophenones, benzotriazoles, and oxanilide derivatives, cyanoacrylates, hindered amine light stabilizers of the HALS ("hindered amine light stabilizer") type, salts perchloric acid, and other inorganic compounds based on metals, lubricants for example organic waxes, fatty alcohols, fatty acids, esters, metal salts, fillers for example chalk or talc, and pigments such as titanium dioxide;
- 0 à 1 1% de charge opacifiante comme par exemple du dioxyde de titane, de l'oxyde zinc, du sulfure de zinc;  - 0 to 1 1% opacifying filler such as titanium dioxide, zinc oxide, zinc sulfide;
- 0 à 20% d'un ou plusieurs plastifiants ;  0 to 20% of one or more plasticizers;
- 0 à 20% de composé thermoplastique à base acrylonitrile ou acrylate ;  0 to 20% of thermoplastic compound based on acrylonitrile or acrylate;
- 0 à 20% de fibres de verre.  0 to 20% of glass fibers.
Le(s) plastifiant(s) mis en œuvre dans la couche PVC, PVCC ou PVC/PVCC, est (sont) choisi(s) dans le groupe comprenant des azélates, trimellitates, sébaçates, adipates, phtalates, citrates, benzoates, tallates, glutarates, fumarates, maléates, oléates, palmitates, acétates, huile de soja époxydée et leurs mélanges. Afin de renforcer la tenue thermomécanique du PVC, un ou plusieurs substrats tissés ou non tissés peuvent être utilisés en association avec celui ci. Ces substrats peuvent être constitués de fibre de verre, de carbone, de fibres polymères (telles que polyester, polyamide...), de fibres naturelles (lin, chanvre, etc). Dans ce cas, la couche de PVC est formée de l'ensemble PVC- substrat. 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. In order to enhance the thermomechanical behavior of PVC, 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.). In this case, the PVC layer is formed of the PVC-substrate assembly.
Le composé thermoplastique mis en œuvre dans la couche PVC, PVCC ou PVC/PVCC, est de préférence un composé thermoplastique à base acrylonitrile ou acrylate. Il peut être obtenu à partir de composés choisis parmi des copolymères de styrène-acrylonitrile, acrylonitrile- styrène-acrylate, éthylène-méthyl acrylate.  The 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.
La couche PVC, PVCC ou PVC/PVCC permet de garantir une bonne conservation de la tenue thermomécanique jusqu'à la température de lamination du panneau solaire (120-150°C, 5- 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-
30 minutes) ainsi qu'une bonne tenue au vieillissement UV. 30 minutes) and a good resistance to UV aging.
Le mode de transformation utilisé pour obtenir cette couche de PVC, PVCC ou The mode of transformation used to obtain this layer of PVC, CPVC or
PVC/PVCC est préférentiellement l'extrusion dans une gamme de température entre 100°C et 180°C, voire 220°C. L'épaisseur de la couche PVC, PVCC ou PVC/PVCC ainsi obtenue varie du 150 à 450 microns, de préférence de 200 à 30 microns, bornes comprises.Un exemple de composition PVC est donné dans le tableau 1 suivant : 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:
Tableau 1 Table 1
L'utilisation du PVC dans un back-sheet consistant en une structure multicouche apporte de nombreux avantages : un prix compétitif comparable aux structures comprenant du PET ; The use of PVC in a back-sheet consisting of a multilayer structure brings many advantages: a competitive price comparable to structures comprising PET;
une meilleure tenue à l'hydrolyse que le PET ;  better resistance to hydrolysis than PET;
une stabilité aux UV améliorée par rapport au PET ;  improved UV stability over PET;
d'excellentes propriétés feux (VO selon la norme UL94). Ceci est un avantage dans le cas de panneaux solaires intégrés aux bâtiments (BIPV) ;  excellent fire properties (VO according to UL94). This is an advantage in the case of building-integrated solar panels (BIPV);
des propriétés électriques suffisantes pour le cahier des charges PV ;  sufficient electrical properties for the PV specification;
fabrication du back-sheet en une seule étape.  manufacture of the back-sheet in one step.
L'utilisation de structures multicouche associant les polymères fluorés au PVC permet d'obtenir de back-sheets pour module photovoltaïque dont les principales caractéristiques sont :  The use of multilayer structures combining fluoropolymers with PVC makes it possible to obtain back-sheets for photovoltaic modules whose main characteristics are:
de bonnes propriétés barrières à l'eau (< lg/m2/24h pour 200 microns) ; good water barrier properties (<lg / m 2 / 24h for 200 microns);
d'excellentes propriétés électriques (tension maximale d'utilisation élevée déterminée par un test de décharge partielle, rigidité diélectrique élevée)  excellent electrical properties (high maximum operating voltage determined by partial discharge test, high dielectric strength)
un faible retrait (inférieur à 3% à 150°C) ;  low shrinkage (less than 3% at 150 ° C);
de bonnes propriétés thermomécaniques jusqu'à la température de lamination du panneau solaire (120°C-150°C) ;  good thermomechanical properties up to the lamination temperature of the solar panel (120 ° C-150 ° C);
de bonnes propriétés au feu ;  good fire properties;
une tenue au fiuage correcte pour une température comprise entre 85 et 150°C ;  a correct behavior at the fi ber for a temperature between 85 and 150 ° C;
adhésion avec les films encapsulants (EVA, polyolefïnes...)  adhesion with encapsulating films (EVA, polyolefins ...)
facilité d'ajouter des pigments colorés / barrières aux UV.  ease of adding color pigments / UV barriers.
Afin de simuler les extrêmes sollicitations rencontrées par un back-sheet lors de la phase de lamination, le protocole ci-après est appliqué.  In order to simulate the extreme stresses encountered by a back-sheet during the lamination phase, the following protocol is applied.
Les essais suivants ont été réalisés sur des échantillons de composition de 300 μηι d'épaisseur. Les échantillons ont été préparés à partir d'un mélange des différentes matières premières travaillées, dans des proportions telles que définies dans le tableau ci-dessous sur un mélangeur bi-cylindre à 205°C pendant 5 minutes. Puis la matière a été compressée sous presse à 185°C sous une pression de 200 bars pendant 240 secondes.  The following tests were performed on samples of composition 300 μηι 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.
L'essai consiste en une mesure du retrait. Avant les mesures, l'échantillon doit être laissé à reposer à température ambiante pendant 2 h minimum. Sur une plaque de 140x140 mm, on trace un repère dans la direction longitudinale ainsi que dans la direction transversale à 20mm des bords. On marque le milieu du carré ainsi obtenu. On marque et on mesure les distances longitudinales et transversales (respectivement L0 et T0) obtenues au centre du carré. On place l'échantillon sur une planche en bois de dimensions appropriées puis on introduit le tout dans une étuve à la température spécifiée pendant un temps donné. Une fois le temps écoulé, on retire l'échantillon de étuve et on le laisse à reposer 30 minutes minimum dans les mêmes conditions utilisées pour le conditionnement de l'échantillon avant le test. Puis on remesure les distances longitudinales et transversales (respectivement L et T). 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).
Le retrait peut alors être calculé selon les formules suivantes (voir norme NF EN ISO The withdrawal can then be calculated according to the following formulas (see standard NF EN ISO
11 501) : 11,501):
• Retrait longitudinal DL = (L0-L)* 100/L0  • Longitudinal withdrawal DL = (L0-L) * 100 / L0
• Retrait transversal DT = (Τ0-Τ)* 100/T0.  • Transverse withdrawal DT = (Τ0-Τ) * 100 / T0.
La couche de PVC, PVCC ou PVC/PVCC conforme à l'invention permet d'obtenir des valeurs de retrait entre 0,85 et 2,7%, comme indiqué dans le tableau 2 ci-dessous :  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:
Tableau 2  Table 2
Les exemples de structures multicouches présentés ci-après, illustrant l'invention, sont non exhaustifs. Ils peuvent tous être utilisés comme back-sheet pour protéger la face arrière de panneaux solaires (SiC, couche mince...). The examples of multilayer structures presented below, illustrating the invention, are not exhaustive. They can all be used as a back-sheet to protect the back side of solar panels (SiC, thin layer ...).
Dans ces exemples ont été utilisés comme polymères fluorés les produits suivants :  In these examples, the following products were used as fluoropolymers:
Kynar 740 : homopolymère de fluorure de vinylidène ayant une température de fusion Kynar 740: homopolymer of vinylidene fluoride having a melting temperature
(Tf ) de 169°C et un module élastique de 1700 MPa; (Mp) 169 ° C and an elastic modulus of 1700 MPa;
Kynar Flex 3120-50, ayant une température de fusion de 165°C et un module élastique de 690 MPa.  Kynar Flex 3120-50, having a melting temperature of 165 ° C and an elastic modulus of 690 MPa.
Les Tf ont été mesurées par DSC ou calorimétrie différentielle à balayage. Les modules élastiques ont été mesurés selon la norme ISO 527. Le PMMA utilisé dans les compositions ci dessous est le PMMA ALTUGLAS BS 550 (copolymère de méthacrylate de méthyle et d'acrylate d'éthyle - MFR 17-20g/10min (230°C; 3,8kg)). 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)).
L'Elastollan C85 est un polyuréthane base polyester.  Elastollan C85 is a polyester-based polyurethane.
1. Exemples de structures obtenues par coextrusion 1. Examples of structures obtained by coextrusion
Les films multicouches ont été réalisés par calandrage (CAST) sur une ligne d'extrusion de marque AMUT. Cette ligne se compose de 3 extrudeuses :  The multilayer films were made by calendering (CAST) on an AMUT extrusion line. This line consists of 3 extruders:
une extrudeuse bivis conique de diamètre 60 mm de marque Krausmaffei spécial pour l'extrusion du PVC  a Krausmaffei brand 60 mm diameter twin-screw extruder special for PVC extrusion
une extrudeuse monovis de diamètre 45 mm de marque Samafor pour l'extrusion du Samafor single-screw extruder 45 mm diameter for the extrusion of the
PVDF ou du liant PVDF or binder
une extrudeuse monovis de diamètre 30mm de marque Dr Collin pour l'extrusion de la couche externe de PVDF.  a 30-mm diameter single screw extruder from Dr Collin for the extrusion of the PVDF outer layer.
La ligne est aussi équipée d'une filière Verbugren « multimanifold » de 500mm. Le système The line is also equipped with a Verbugren "multimanifold" 500mm die. The system
« multimanifold » permet la production d'un film ou d'une feuille 3 couches (Couche 1 / Couche 21 Couche 3) avec une distribution d'épaisseurs variables (exemple : 30/30/350 microns). Les paramètres procédés ont été fixés comme indiqué ci-dessous: "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:
- T° extrusion couche 1 et 2 : 240°C  - Extrusion layer 1 and 2: 240 ° C
- T° extrusion couche 3 : 180°C  - Extrusion layer 3: 180 ° C
- T° de la filière : 200°C  - T ° of the die: 200 ° C
la vitesse de ligne est de 3 m/min.  the line speed is 3 m / min.
Les exemples suivants de structures selon l'invention ont été obtenus par coextrusion : The following examples of structures according to the invention were obtained by coextrusion:
1.1 - PVCC ou PVC/ PMMA V0825 50% - Kynarflex 3120-50 50% / Kynar 740 (350 / 10 / 30 microns)  1.1 - CPVC or PVC / PMMA V0825 50% - Kynarflex 3120-50 50% / Kynar 740 (350/10/30 microns)
La couche interne est réalisée par mélange à sec en pied de machine au moment de la production. The inner layer is made by dry mixing at the bottom of the machine at the time of production.
1.2 - PVCC ou PVC / PMMA V0825 50% - Kynarflex 3120-50 50% / Kynar 740 60% - PMMA 24% - 16%Ti02 1.2 - CPVC or PVC / PMMA V0825 50% - Kynarflex 3120-50 50% / Kynar 740 60% - PMMA 24% - 16% TiO2
La couche interne est réalisée par mélange à sec en pied de machine au moment de la production. La couche externe PVDF contenant du Ti02 est réalisé par compoundage dans un co-malaxeur à une température ne dépassant pas 240°C. Dans un premier temps, il est procédé à la préparation d'un masterbatch PMMA/ Ti02 sur extrudeuse bi-vis ; celui-ci est ensuite mélangé au PVDF dans le co-malaxeur ou dans l'extrudeuse bi-vis. 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.
1.3 - PVCC ou PVC / Kynar 740 40% - PMMA 44% - 16%Ti02 / Kynar 740  1.3 - CPVC or PVC / Kynar 740 40% - PMMA 44% - 16% TiO 2 / Kynar 740
La couche interne contenant du Ti02 est réalisé par compoundage comme décrit pour l'exemple 1.2. The inner layer containing TiO 2 is produced by compounding as described for Example 1.2.
1.4 - PVCC ou PVC / PMMA 35% - Kynar 740 35% - Modifiant S2001 (Mitsubishi Rayon) 30% / Kynar 740 60% - PMMA 24% - 16%Ti02  1.4 - CPVC or PVC / PMMA 35% - Kynar 740 35% - Modifying S2001 (Mitsubishi Rayon) 30% / Kynar 740 60% - PMMA 24% - 16% Ti02
La couche interne contenant du modifiant S2001 est réalisée par compoundage dans une extrudeuse bivis. La couche externe contenant du Ti02 est réalisée par compoundage comme décrit plus haut pour 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.
1.5 - PVCC ou PVC / PMMA 50%- PVDF 50% / PVDF 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02  1.5 - CPVC or PVC / PMMA 50% - PVDF 50% / PVDF 73.3% - PMMA 4.7% - ZnO 15% - 7% TiO2
La couche externe contenant du Ti02 et du ZnO est réalisée par compoundage. L'introduction Ti02 dans le PVDF nécessite au préalable la préparation d'un masterbatch PMMA/ Ti02 sur extrudeuse bi-vis ; celui-ci est ensuite mélangé au PVDF dans le co-malaxeur ou dans l'extrudeuse bi-vis. 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.
1.6 - PVCC ou PVC / PVDF 60% - PMMA 24% - Ti02 16%  1.6 - CPVC or PVC / PVDF 60% - PMMA 24% - TiO2 16%
La couche externe contenant du Ti02 est réalisée par compoundage comme décrit pour 1.2. The outer layer containing TiO 2 is compounded as described for 1.2.
1.7 - PVCC ou PVC / PVDF 60% - PMMA 16% - 24%ZnO 1.7 - CPVC or PVC / PVDF 60% - PMMA 16% - 24% ZnO
La couche externe contenant du ZnO est réalisée par compoundage dans une extrudeuse bivis.The outer layer containing ZnO is made by compounding in a twin-screw extruder.
1.8 - PVCC ou PVC / Elastollan C85 /Kynar 740 60% - PMMA 24% - 16%Ti02 1.8 - CPVC or PVC / Elastollan C85 / Kynar 740 60% - PMMA 24% - 16% TiO2
La couche externe contenant du Ti02 est réalisée par compoundage comme décrit pour 1.2. The outer layer containing TiO 2 is compounded as described for 1.2.
1.9 - PVCC ou PVC / Elastollan C85 / Kynar 740 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02 L'introduction Ti02 dans le PVDF nécessite au préalable la préparation d'un masterbatch PMMA/ Ti02 sur extrudeuse bi-vis ; celui-ci est ensuite mélangé au PVDF dans le co-malaxeur ou dans l'extrudeuse bi-vis. 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.
1.10 - Kynar 740 60% - PMMA 24% - 16%Ti02 / PVCC ou PVC / Elastollan C85 /Kynar 740 60% - PMMA 24% - 16%Ti02 1.10 - Kynar 740 60% - PMMA 24% - 16% Ti0 2 / CPVC or PVC / Elastollan C85 / Kynar 740 60% - PMMA 24% - 16% TiO 2
La couche externe contenant du Ti02 est réalisée par compoundage comme décrit pour 1.2. 1.1 1 - PVDF 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02 / 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 /
PVCC ou PVC / PMMA 50%- PVDF 50% / PVDF 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02 La couche externe contenant du Ti02 et du ZnO est réalisée par compoundage. L'introduction Ti02 dans le PVDF nécessite au préalable la préparation d'un masterbatch PMMA/ Ti02 sur extrudeuse bi-vis ; celui-ci est ensuite mélangé au PVDF dans le co -malaxeur ou dans l'extrudeuse bi-vis. CPVC or PVC / PMMA 50% - PVDF 50% / PVDF 73.3% - PMMA 4.7% - ZnO 15% - 7% TiO 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-mixer or in the twin-screw extruder.
2. Exemples de structures obtenues par extrusion couchage 2. Examples of structures obtained by extrusion coating
Les structures réalisées par extrusion couchage sont réalisées sur une ligne d'extrusion de la marque Dr Collin. Cette ligne se compose de trois extrudeuses équipées d'un profil de vis standard polyolèfine, d'un bloc de coextrusion variable, et d'une filière porte manteaux de 250mm (« coat hanger die »). Le bloc de coextrusion autorise la production d'un film de 1 à 5 couches avec une distribution d'épaisseurs variables ( exemple : 30/250 microns). Un système de dévidoirs permet de dérouler divers support dont un film PVDF. Les paramètres procédés ont été fixés comme indiqué ci-dessous:  The structures produced by extrusion coating are carried out on an 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 couche 1 : 200°C  T extrusion layer 1: 200 ° C.
- T° extrusion couche 2 : 180°C  - Extrusion layer 2: 180 ° C
T° boite de coextrusion et filière : 200°C.  T ° coextrusion box and die: 200 ° C.
La vitesse de ligne est de 2 m /min. The line speed is 2 m / min.
Exemples de structures réalisées par extrusion couchage ou extrusion lamination:  Examples of structures made by extrusion coating or extrusion lamination:
2.1 - PVCC ou PVC/ Elastollan C85 (TPU base polyester) (30/250 microns) : film coextrudé puis couché sur un film Kynar multicouches de 30 microns (PVDF/ Kynar 740 40% - 2.1 - CPVC or PVC / Elastollan C85 (TPU polyester base) (30/250 microns): coextruded film then coated on a 30 micron multilayer Kynar film (PVDF / Kynar 740 40% -
PMMA 44% - 16%Ti02/PVDF 5/20/5 microns). PMMA 44% - 16% TiO 2 / PVDF 5/20/5 microns).
2.2 - PVCC ou PVC/ Elastollan C85 (TPU base polyester) (30/250 microns) : film coextrudé puis couché sur un film monocouche 18 μιη ( Kynar 740 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02). 2.2 - CPVC or PVC / Elastollan C85 (TPU based on polyester) (30/250 microns): coextruded film then coated on a monolayer film 18 μιη (Kynar 740 73.3% - PMMA 4.7% - ZnO 15% - 7% Ti0 2 ).
2.3 - PVCC ou PVC/ Elastollan C85 (TPU base polyester) (30/250 microns) : film coextrudé puis laminé entre deux films multicouches de 30 microns (PVDF/ Kynar 740 40% - PMMA 44% - 16%Ti02/PVDF 5/20/5 microns). 2.3 - CPVC or PVC / Elastollan C85 (TPU polyester base) (30/250 microns): Coextruded film then laminated between two 30 micron multilayer films (PVDF / Kynar 740 40% - PMMA 44% - 16% Ti0 2 / PVDF 5 / 20/5 microns).
2.4 - PVCC ou PVC/ Elastollan C85 (TPU base polyester) (30/250 microns) : film coextrudé puis laminé entre deux films monocouches 18 μηι ( Kynar 740 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02). Les films Kynar sont réalisés au préalable par soufflage de gaine sur une ligne gaine 5 couches de marque Dr Collin équipée d'une filière de type « pancake ». 2.4 - CPVC or PVC / Elastollan C85 (TPU polyester base) (30/250 microns): Coextruded film then laminated between two monolayer films 18 μηι (Kynar 740 73.3% - PMMA 4.7% - ZnO 15% - 7% Ti0 2 ). The Kynar films are made beforehand by blowing the sheath on a Dr Collin brand 5-layer sheath line equipped with a "pancake" type die.
3. Exemples de structures obtenues par lamination (colle) 3. Examples of structures obtained by lamination (glue)
Les structures multicouches peuvent aussi être assemblées par des adhésifs solvantés en deux étapes selon le protocole suivant : The multilayer structures can also be assembled by solvent adhesives in two steps according to the following protocol:
i) extrusion des films i) extrusion of films
film PVCC 250 microns réalisé par extrusion de film à plat, selon une technique connue de l'homme de l'art ;  250 micron PVCP film made by extrusion of flat film, according to a technique known to those skilled in the art;
- Kynar film 1 : film multicouche de 30 microns (PVDF/ Kynar 740 60% - PMMA 24% - - Kynar film 1: 30 micron multilayer film (PVDF / Kynar 740 60% - PMMA 24% -
16%Ti02/PVDF 5/20/5 microns) 16% TiO2 / PVDF 5/20/5 microns)
- Kynar film 2 : film monocouche 18 μιη ( Kynar 740 73,3% - PMMA 4,7% - ZnO 15% - 7%Ti02).  - Kynar film 2: monolayer film 18 μιη (Kynar 740 73.3% - PMMA 4.7% - ZnO 15% - 7% TiO 2).
Les films 1 et 2 sont réalisés au préalable par soufflage de gaine sur une ligne gaine 5 couches de marque Dr Collin équipée d'une filière de type « pancake ».  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.
if) Application des adhésifs if) Application of adhesives
La structure visée (feuille PVC (350 microns) / colle / film PVDF (film 1 ou 2) est réalisée de la façon suivante :  The target structure (PVC sheet (350 microns) / glue / PVDF film (film 1 or 2) is produced as follows:
• un applicateur spiralé (« barcoater ») est utilisé pour appliquer sur la feuille PVC une couche de 30 microns de colle (non séchée). La formulation de la colle utilisée est la suivante (fournisseur Bostick) : HBTS ESP 877 (100 parts) + durcisseur Biscodur 1621 (9 parts). On laisse ensuite la feuille de PVC enduite de colle une minute à température ambiante puis 5 min à 50°C.  • 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.
• le film Kynar est ensuite laminé à la main sur la feuille PVC enduite d'une couche de colle ;  • The Kynar film is then rolled by hand on the PVC sheet coated with a layer of glue;
• la structure est ensuite pressée à 80°C, 5mn, 3 bars.  The structure is then pressed at 80 ° C., 5 minutes, 3 bars.
Avant d'être testée ou utilisée, la structure est ensuite laissée pendant 3 jours dans une étuve à 60°C dans l'objectif de réticuler totalement la colle.  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.
Les structures suivantes ont été obtenues par lamination :  The following structures were obtained by lamination:
3.1 - PVCC ou PVC/adhésif solvanté PU ester bicomposant / Kynar film 1 3.2 - PVCC ou PVC /Adhésif solvanté PU ester bicomposant / Kynar film 2 3.1 - CPVC or PVC / solvent-based adhesive PU two-component ester / Kynar film 1 3.2 - CPVC or PVC / solvent-based adhesive PU two-component ester / Kynar film 2
3.3 - Kynar film 1 / adhésif solvanté PU ester bicomposant/ PVCC ou PVC/adhésif solvanté PU ester bicomposant / Kynar film 1  3.3 - Kynar film 1 / solvent-based adhesive PU two-component ester / CPVC or PVC / solvent-based adhesive PU two-component ester / Kynar film 1
3.4 - Kynar film 2/ adhésif solvanté PU ester bicomposant /PVCC ou PVC /Adhésif solvanté PU ester bicomposant / Kynar film 2  3.4 - Kynar film 2 / solvent-based adhesive PU two-component ester / CPVC or PVC / solvent-based adhesive PU two-component ester / Kynar film 2
4. Exemple de fabrication d'une feuille PVC multicouche 4. Example of manufacturing a multilayer PVC sheet
Une structure multicouche PVC / tissé fibre de verre / PVC (150 μπι / 50 μπι / 150 μπι) est réalisée par thermolamination à chaud de 2 feuilles PVC sur le tissé de verre à l'aide d'une ligne de calandrage. La feuille PVC est préchauffée sur des rouleaux thermostatés, puis est thermolaminée dans une calandre. Les températures, force de fermeture de la calandre ainsi que la vitesse de ligne sont ajustées en fonction de la formulation PVC et du tissu de verre utilisé. ABREVIATIONS :  A PVC / fiberglass / PVC multilayer structure (150 μπι / 50 μπι / 150 μπι) 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. ABBREVIATIONS:
PV - photovoltaïque PV - photovoltaic
PVC - terme générique englobant le polychlorure de vinyle et ses dérivés notamment chlorés, tel que le PVCC  PVC - a generic term encompassing polyvinyl chloride and its especially chlorinated derivatives, such as CPVC
PVCC - polychlorure de vinyle surchloré CPVC - Chlorinated Polyvinyl Chloride
back-sheet - face arrière d'un panneau photovoltaïque back-sheet - back side of a photovoltaic panel
PVDF - polyfiuorure de vinylidène  PVDF - polyvinylidene fluoride
PET - polyéthylène téréphtalate  PET - polyethylene terephthalate
MMA - méthacrylate de méthyle  MMA - methyl methacrylate
Tf- température de fusion Tf- melting temperature
MVI - « melt volume index » ou indice de fluidité en volume à l'état fondu  MVI - "melt volume index" or melt volume melt index
MFR - « melt fiow rate » ou indice de fluidité exprimé en g/min  MFR - "melt fiow rate" or melt index expressed in g / min

Claims

REVENDICATIONS 1. Utilisation pour la protection à l'arrière d'un panneau solaire d'une structure multicouche comprenant au moins une couche de polymère fluoré et une couche de PVC, dans laquelle ledit polymère fluoré est un homopolymère de VDF ou un copolymère de VDF et d'un comonomère fluoré copolymérisable avec le VDF.  1. Use for the protection behind a solar panel of a multilayer structure comprising at least one fluoropolymer layer and a PVC layer, wherein said fluoropolymer is a VDF homopolymer or a VDF copolymer and a fluorinated comonomer copolymerizable with VDF.
2. Utilisation selon la revendication 1 dans laquelle le comonomère fluoré copolymérisable avec le VDF est choisi parmi le fluorure de vinyle, le trifluoroéthylène, le chlorotrifluoroéthylène, le 1 ,2-difluoroéthylène, le tétrafluoroéthylène, l'hexafluoropropylène, les perfluoro(alkyl vinyl) éthers tels que le perfluoro(méthyl vinyl)éther, le perfluoro(éthyl vinyl) éther et le perfluoro(propyl vinyl) éther, le perfluoro(l,3-dioxole), le perfluoro(2,2-diméthyl-l,3-dioxole), et leur mélanges. 2. Use according to claim 1 wherein the fluorinated comonomer copolymerizable with VDF is selected from vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, 1,2-difluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether, perfluoro (ethyl vinyl) ether and perfluoro (propyl vinyl) ether, perfluoro (1,3-dioxole), perfluoro (2,2-dimethyl-1,3- dioxole), and mixtures thereof.
3. Utilisation selon la revendication 1 dans laquelle ledit copolymère est un copolymère3. Use according to claim 1 wherein said copolymer is a copolymer
VDF-HFP contenant au moins 50% en masse de VDF, avantageusement au moins 75% en masse de VDF et de préférence au moins 90% en masse de VDF. 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 of VDF.
4. Utilisation selon l'une quelconque des revendications 1 à 3 dans laquelle le polymère fluoré comprend en outre au moins un homopolymère ou copolymère de méthacrylate de méthyle.  4. Use according to any one of claims 1 to 3 wherein the fluoropolymer further comprises at least one homopolymer or copolymer of methyl methacrylate.
5. Utilisation selon la revendication 4 dans laquelle ledit polymère fluoré comprend en outre des particules inorganiques choisies parmi le dioxyde de titane, les oxydes de zinc ou les sulfures de zinc, la silice, le quartz, l'alumine, le carbonate de calcium, le talc, le mica, la dolomite, la montmorillonite, BaSC , ZrSiC>4, Fe3C>4, et leurs mélanges. 5. Use according to claim 4 wherein said fluorinated polymer further comprises inorganic particles selected from titanium dioxide, zinc oxides or zinc sulfides, silica, quartz, alumina, calcium carbonate, talc, mica, dolomite, montmorillonite, BaSC, ZrSiC> 4, Fe 3 C> 4, and mixtures thereof.
6. Utilisation selon l'une quelconque des revendications 1 à 5 dans laquelle le PVC est un polymère choisi parmi les homopolymères de chlorure de vinyle, éventuellement surchlorés (PVCC), et copolymères, facultativement réticulés, résultant de la copolymérisation du chlorure de vinyle avec un ou plusieurs comonomères éthyléniques insaturés. 6. Use according to any one of claims 1 to 5 wherein the PVC is a polymer selected from homopolymers of vinyl chloride, optionally superchlorinated (CPVC), and copolymers, optionally crosslinked, resulting from the copolymerization of vinyl chloride with one or more unsaturated ethylenic comonomers.
7. Utilisation selon la revendication 6 dans laquelle lesdits comonomères éthyléniques insaturés sont choisis parmi : le chlorure ou le fluorure de vinylidène, l'acétate de vinyle, le propionate de vinyle, le butyrate de vinyle, les acides acryliques et méthacryliques, les nitriles, l'acrylonitrile, l'acrylamide, le méthacrylamide, le méthacrylate de méthyle, l'acrylate de méthyle, l'acrylate de butyle, l'acrylate d'éthyle, l'acrylate de 2-éthylhexyle, le styrène, l'éthylène, le propène et le 1 -butène. 7. Use according to claim 6 wherein said unsaturated ethylenic comonomers are selected from: vinylidene chloride or fluoride, vinyl acetate, vinyl propionate, vinyl butyrate, acrylic and methacrylic acids, nitriles, acrylonitrile, acrylamide, methacrylamide, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, styrene, ethylene, propene and 1-butene.
8. Utilisation selon l'une quelconque des revendications 1 à 7 dans laquelle ladite structure multicouche est constituée de deux couches à savoir une couche externe comprenant un polymère fluoré et une couche interne de PVC.  8. Use according to any one of claims 1 to 7 wherein said multilayer structure consists of two layers, namely an outer layer comprising a fluoropolymer and an inner layer of PVC.
9. Utilisation selon l'une quelconque des revendications 1 à 7 dans laquelle ladite structure multicouche est constituée de trois couches à savoir une couche externe de polymère fluoré, une couche intermédiaire de PVC et une couche interne de polymère fluoré.  9. Use according to any one of claims 1 to 7 wherein said multilayer structure consists of three layers namely an outer layer of fluoropolymer, an intermediate layer of PVC and an inner layer of fluoropolymer.
10. Utilisation selon l'une quelconque des revendications 1 à 9 dans laquelle un liant de type acrylique, fluoré ou polyuréthanne est placé entre la couche de polymère fluoré et la couche de PVC.  10. Use according to any one of claims 1 to 9 wherein a binder of acrylic, fluorinated or polyurethane type is placed between the fluoropolymer layer and the PVC layer.
1 1. Utilisation selon l'une quelconque des revendications 1 à 10 dans laquelle ladite couche de polymère fluoré est constituée d'un seul ou de plusieurs films de polymères fluorés. The use of any one of claims 1 to 10 wherein said fluoropolymer layer is comprised of one or more fluoropolymer films.
12. Utilisation selon l'une quelconque des revendications 1 à 1 1 dans laquelle ladite couche de PVC est constituée d'un seul ou plusieurs films de PVC. 12. Use according to any one of claims 1 to 1 1 wherein said PVC layer consists of one or more PVC films.
13. Utilisation selon l'une quelconque des revendications 1 à 12 dans laquelle ladite structure multicouche est fabriquée par coextrusion.  13. Use according to any one of claims 1 to 12 wherein said multilayer structure is manufactured by coextrusion.
14. Utilisation selon l'une quelconque des revendications 1 à 12 dans laquelle ladite structure multicouche est fabriquée par extrusion couchage.  14. Use according to any one of claims 1 to 12 wherein said multilayer structure is manufactured by extrusion coating.
15. Utilisation selon l'une quelconque des revendications 1 à 12 dans laquelle ladite structure multicouche est fabriquée par lamination.  15. Use according to any one of claims 1 to 12 wherein said multilayer structure is manufactured by lamination.
EP12725066.0A 2011-04-27 2012-04-27 Use of a multilayer pvc/fluorinated polymer structure for protecting the rear of solar panels Withdrawn EP2701906A1 (en)

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PCT/FR2012/050944 WO2012146880A1 (en) 2011-04-27 2012-04-27 Use of a multilayer pvc/fluorinated polymer structure for protecting the rear of solar panels

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