Classifications

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  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • 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
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
  • F24S40/00—Safety or protection arrangements of solar heat collectors; Preventing malfunction of solar heat collectors
  • F24S40/40—Preventing corrosion; Protecting against dirt or contamination
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
  • F24S80/00—Details, accessories or component parts of solar heat collectors not provided for in groups F24S10/00-F24S70/00
  • F24S80/50—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings
  • F24S80/52—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings characterised by the material
  • F24S80/525—Elements for transmitting incoming solar rays and preventing outgoing heat radiation; Transparent coverings characterised by the material made of plastics
• • 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
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  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy

Definitions

• compositions based on fluoropolymers and their uses for the manufacture of transparent monolayer or multilayer films intended to protect various polymer substrates, in particular the rear face of solar panels.
• Protective layers based on fluoropolymers often contain mineral fillers that can totally or partially absorb UV radiation from the solar spectrum, in order to minimize the degradation of said polymers and substrates to be protected.
• This highly efficient technology has the disadvantage of leading to non-transparent films (with less than 90% transmission).
• transparency constraints are imposed: the material must not absorb in the visible.
• a transparent protective layer that cuts UV rays, whether in solar panels or for other applications such as sheet / plate protection for outdoor use.
• UV absorbers It is known to use organic UV absorbers to prevent the degradation mechanisms of polymers by photooxidation, chain cleavage, crosslinking or uncontrolled recombination reaction during exposure to UV radiation. These components help dissipate the light absorbed during UV exposure by an intramolecular proton transfer mechanism.
• the UV absorbers have at least one peak of absorbance in the UV waves.
• PVDF-protective dual-layer films / coextrudable composition with PVDF said composition consisting of 20 to 40 parts of polyvinylidene fluoride (PVDF), 40 to 60 parts of PMMA, 5 to 18 parts of an acrylic elastomer and 1 to 4 parts of a UV absorber, the total being 100 parts.
• PVDF polyvinylidene fluoride
• acrylic elastomer polyacryl elastomer
• UV absorber 1 to 4 parts
• fluorinated polymers in general and in particular PVDF (polyvinylidene fluoride) to manufacture fluorinated films intended to protect the back faces (also called “back sheets”) of photovoltaic panels, because of their very good resistance to weather, ultraviolet radiation, visible light and chemicals.
• PVDF polyvinylidene fluoride
• These fluorinated films have a very good thermal resistance allowing them to withstand harsh climatic conditions (rain, cold, hot), as well as good flexibility and good resistance to breakage so as to withstand mechanical stresses when they are laid on the photovoltaic panel.
• the invention relates to a polymer composition consisting of at least one vinylidene fluoride-based polymer (called PVDF), at least one acrylic polymer (called PMMA) and at least one UV absorber, in which the mass proportion said fluoropolymer varies from 60 to 90%, the proportion the mass of said UV absorber varies from 0.5 to 5% and the molecular weight of the latter is greater than 500 g / mol.
• PVDF vinylidene fluoride-based polymer
• PMMA acrylic polymer
• UV absorber in which the mass proportion said fluoropolymer varies from 60 to 90%, the proportion the mass of said UV absorber varies from 0.5 to 5% and the molecular weight of the latter is greater than 500 g / mol.
• the vinylidene fluoride-based polymer (called "PVDF”) is chosen from homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and at least one other fluorinated monomer.
• the proportion by mass PVDF varies from 60 to 90% of the weight of the composition, preferably from 60 to 80%.
• the UV absorber is selected from benzophenones, benzotriazoles, triazines, cyanoacrylates and oxalanilides having a molecular weight greater than 500 g / mol, this list not being exclusive.
• the UV absorber is chosen from: 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis- ⁇ [2'-cyano-3'] , 3'-diphenylacryloyl) oxy] methyl] propane, 2,2'-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl)), 2 [4,6-Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol; Poly-4- (2-acryloxyethoxy) -2-hydroxybenzophenone.
• These 4 products correspond respectively to Uvinul ® 3030, Tinuvin ® 360, CYASORB ® 1164 and CYASORB ® 2126.
• the invention also relates to monolayer or multilayer films intended to protect various polymeric substrates, manufactured from the composition described above.
• the invention also relates to a method of manufacturing a multilayer structure comprising at least one layer consisting of the composition described above.
• the invention also relates to the use of the composition described above to protect the rear face of a photovoltaic panel.
• the present invention overcomes the disadvantages of the state of the art mentioned above. More particularly, it provides a novel polymer composition having, in addition to the visible transparency and absorbance of UV radiation, enhanced durability properties such as long-term UV resistance and wet heat resistance. This composition makes it possible to manufacture transparent films having improved high temperature mechanical properties while avoiding the phenomenon of exudation of the UV absorber. These films are suitable for the protection of various polymeric substrates.
• the composition according to the invention is particularly suitable for protecting the rear face of a photovoltaic panel.
• the PVDF contains, by weight, at least 50% VDF, more preferably at least 75% and more preferably at least 85%.
• HFP hexafluoropropylene
• TFE tetrafluoroethylene
• VDF vinylidene fluoride
• CFE chlorotrifluoroethylene
• perfluoroalkyl vinyl ethers such as CF 3 -O-
• diolefms such as perfluorodiallyl ether and perfluoro-1,3-butadiene.
• the fluorinated polymers that can be used in the composition according to the invention are chosen from:
• VDF homo- or copolymers of VDF, in particular PVDF and copolymers
• VDF-HFP homo- or copolymers of CTFE, in particular PCTFE (polychlorotrifluoroethylene) and ⁇ -CTFE (ethylene-chlorotrifluoroethylene copolymer).
• PCTFE polychlorotrifluoroethylene
• ⁇ -CTFE ethylene-chlorotrifluoroethylene copolymer
• the fluoropolymer is a homopolymer of VDF or a copolymer of VDF and at least one other fluorinated monomer.
• 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-HFP 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-HFP 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.
• the fluoropolymer has 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 capillary rheometer.
• 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 acrylic polymer is a homopolymer of methyl methacrylate (MMA) or a copolymer containing at least 50% by weight of MMA and minus another monomer copolymerizable with MMA.
• Comonomers copolymerizable with MMA are alkyl (meth) acrylates, acrylonitrile, butadiene, styrene, isoprene.
• the acrylic 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 the acrylate of methyl and / or ethyl acrylate.
• the acrylic polymer can be functionalized, that is to say it contains, for example, acid, acid chloride, alcohol or anhydride functions.
• 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.
• UV absorber it may be, for example, the additives mentioned in US Pat. No. 5,256,472. Benzotriazole, benzophenone or benzylidene malonate or quinazoline type compounds are advantageously used.
• a stabilizer is advantageously used.
• UV type HALS (“Hindered Amine Light Stabilizer”) can be used in combination with the UV absorber.
• the UV absorber is chosen from: 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis - ⁇ [2'-cyano-3'] 3'-diphenylacryloyl) oxy] methyl] propane, 2,2'-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl)), 2 -
• the composition according to the invention consists of a fluorinated polymer based on VDF (60 to 90% by weight), an acrylic polymer and a UV absorber with a molecular mass greater than 500 g / mol and whose mass varies from 0.5 to 5%.
• the composition according to the invention is 68.6% PVDF homopolymer (such as the product sold by Arkema under the name KYNAR ® 740), 29.4% PMMA BS580 and 2% Uvinul ® 3030.
• composition according to the invention makes it possible to manufacture monolayer films that can serve as protection for various polymeric substrates.
• the constituents of the composition are mixed by any method which makes it possible to obtain a homogeneous mixture of fluorinated and acrylic polymers and of the UV absorber, used in the composition according to the invention.
• composition according to the invention is prepared by melt blending all these constituents and then is transformed, for example in the form of granules, by compounding on a tool known to those skilled in the art as an extruder twin-screw, co-kneader or blender.
• This composition may be co-extruded with another material or extruded into a film.
• the film according to the invention can be manufactured by blown film extrusion ("blown film”) at a temperature ranging from 220 to 260 ° C.
• blown film blown film extrusion
• This technique consists in coextruding, generally from bottom to top, a thermoplastic polymer through an annular die.
• the extrudate is simultaneously pulled longitudinally by a pulling device, usually in rolls, and inflated by a constant volume of air trapped between the die, the pull system and the wall of the sheath.
• the inflated sheath is cooled generally by an air blowing ring at the outlet of the die.
• the film can also be manufactured by flat extrusion or "cast film”; this process consists in stretching a sheet or a polymer film in the air between a flat die and a thermostatic roll. It makes it possible to manufacture sheets of thickness between 0.2 mm and 2 mm and films with a thickness of less than 0.2 mm.
• the thickness of the film varies from 5 to 500 microns, preferably from 10 to 50 microns, inclusive.
• the transparency of the monolayer film according to the invention is greater than 90% in the range of 400 to 800 nm.
• the film has a UV absorbance of at least 1 from 280 nm to 380 nm.
• the subject of the invention is a transparent multilayer film comprising at least one layer consisting of the composition described above.
• the transparency of this multilayer film is greater than 90% in the range 400 to 800 nm.
• the film has a UV absorbance of at least 1 from 280 nm to 380 nm. Its thickness is from 5 to 500 microns.
• the film consists of two layers, an inner layer being as described above and an outer layer which contains 100 to 0% PVDF and 0 to 40% PMMA.
• the mass ratio between the inner layer and the outer layer varies from 90/10 to 50/50.
• the film consists of three layers, namely an inner layer that contains 100 to 0% PVDF and 0 to 40% PMMA, a core layer comprising a UV absorber as described above, and an outer layer containing 100 to 0% PVDF and 0 to 40% PMMA.
• a multilayer film according to the invention is preferably manufactured by the coextrusion technique, for example by blowing, but it is also possible to use flat extrusion or a technique of implementation by solvent or using the technique. of plaxage.
• the subject of the invention is the use of a film (monolayer or multilayer film) for the protection of various polymeric substrates, such as polyester substrates (for example poly (ethylene terephthalates), poly ( ethylene naphthalates) or polybutylene terephthalate), polycarbonate, polyolefin (eg polypropylene, thermoplastic polyolefins, high density polyethylenes, cyclic polyolefins), polystyrene (eg syndiotactic polystyrenes), styrene-acrylate copolymers, acrylonitrile copolymers styrene (for example ABS, ASA or SAN), polysulfone (for example polyethersulfones, polysulfones, etc.), poly (urethanes) (aliphatic ether or aliphatic ester or aromatic ether or aromatic ester or polyurethane ester thermoplastics), acrylic polymers (PMMA), polyvinyl
• the film according to the invention can also serve to protect a flexible substrate such as a technical textile (PVC, glass fabric, glass mat, aramid, Kevlar ® or poly (p-phenyleneterephthalamide)).
• a PVC tarpaulin is an example of a flexible PVC substrate.
• the film can be applied via an adhesive layer using the rolling technique.
• Adhesives which are used as exemplary are polyester formulations or polyurethanes containing methyl ethyl ketone (MEK) or toluene.
• the invention relates to the use of a film (monolayer or multilayer) for the manufacture of the rear face in a panel photovoltaic.
• the film according to the invention undergoes at first on both sides a surface treatment of Corona type. Then, it is hot rolled on each side of a PET sheet previously induced with adhesive. One of the faces of the laminate thus obtained is then pressed onto a film of the EVA type, the other face of the latter being glued against a cleaned glass plate.
• This structure can be used as a backsheet in a photovoltaic cell.
• the invention also relates to a photovoltaic panel whose rear face is protected by said film.
• PVDF 1 is a homopolymer of vinilydene fluoride having an MFR of 17.5-22.5 g / 10 min (230 ° C, 3.8 kg), a melting temperature (T f) of 169 ° C and a Young's modulus ranging from 1800 to 2000 MPa at 23 ° C. Tf was measured by DSC or differential scanning calorimetry. The elastic modules were measured according to ISO 527.
• the PMMA used is a grade of ALTUGLAS BS 550 (methyl methacrylate copolymer with 11-12% ethyl acrylate - MFR 17-20g / 10min (230 ° C, 3.8kg) -MW: 70000 -80000 g / mol).
• UV absorbers they are listed in table 1. Trade name Tinuvin -234 Cyasorb ® 1164 Uvinul ® -3030 Tinuvin 1577 Cyasorb ® 3638F
• Extrusion Film The films are then produced by blow-molding on a 5-layer laboratory line with a pancake die (50mm diameter, 1.2mm air gap). The films have a symmetrical structure PE / PVDF / PVDF / PVDF / PE.
• the implementation conditions used for the production of the films are as follows:
• Extrusion temperature PE (230 ° C), PVDF and compound 1 (240 ° C), die
• the PE film is then laminated to obtain a 100% fluorinated film.
• the films are placed in a climatic chamber at 85 ° C./85% RH (relative humidity) for 100 h.
• the films are then analyzed by UV-Visible spectrometry to quantify the UV absorbance and the exudation.
• the films were analyzed by UV-Vis spectrometry on the Cary 300 spectrometer in transmission with the vessel holder accessories and integrating sphere.
• the sphere of integration makes it possible to measure the total transmission.
• the transmission analysis with the vessel holder does not take into account the diffusing effect of the material.
• the exudation is quantified by making the ratio between the transmittance measured at 700 nm in "sphere” configuration on the transmittance measured at 700 nm in the "cell holder” configuration on single-layer films extruded in jacket blowing (30 microns). This ratio is determined before the test and after 2000 hours of testing.
• Films are made by blowing sheath from the compounds mentioned in Example 1. These films are monolayers of 30 microns or multilayers PVDF / Compound / PVDF (5/25/5 microns)
• the films are then made by blow-molding on a 5-layer laboratory line with a pancake die (diameter 50 mm, gap 1.2 mm).
• the films have a symmetrical structure PE / PVDF / PVDF / PVDF / PE.
• the implementation conditions used for the production of the films are as follows:
• Extrusion temperature PE (230 ° C), PVDF and compound 1 (240 ° C), die (240 ° C)
• the PE film is then rolled to obtain a 100% fluorinated film.

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• 2013
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