Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
  • H10F19/804—Materials of encapsulations
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—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 at least one being terminated by a halogen; Derivatives of such polymers
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—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 at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2427/02—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
  • C08J2427/12—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
  • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
• • 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
• • 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

Definitions

• the present invention relates to a composition comprising a fluoropolymer and zinc oxide of nanometric size.
• the invention also relates to films made from said composition. Due to their transparency in the visible range and opacity to UV radiation, these films are especially intended for use as a front face in a photovoltaic cell.
• a photovoltaic cell is made of a semiconductor material sandwiched between two metal electrodes, the whole being protected by a front face ("frontsheet”) and a backside (“backsheet”).
• the front of a photovoltaic cell must primarily protect the elements of the cell from mechanical aggression. It must also prevent effects due to aging induced in particular by UV radiation and oxygen.
• the front face of a photovoltaic cell In order to use solar light as efficiently as possible, the front face of a photovoltaic cell must of course have a high transmittance in a certain spectral range, which for example ranges from 400 to 1100 nm for a cell based on Crystalline silicon.
• a glass front face has several drawbacks: a transmittance capped at 92% in the range from 400 to 1100 nm, a high weight, a low impact resistance, requiring special care during transport, installation and maintenance. use of photovoltaic cells.
• Front faces made of plastic materials overcome many of these disadvantages. Indeed, there are plastic materials having a transmittance greater than that of glass, lighter and having a satisfactory impact resistance.
• PVDF polyvinylidene fluoride difluoride VDF
• Monolayer films based on fluorinated polymers (copolymer of ethylene and tetrafluoroethylene or ETFE, PVDF, copolymer of ethylene and propylene or FEP, etc.), marketed by companies such as DuPont, Asahi Glass, Saint-Gobain, Rowland Technologies, are already used as front face for photovoltaic cells.
• organic UV absorbers and / or mineral fillers are incorporated therein.
• a fluorinated polymer such as a polymer or copolymer of vinylidene fluoride
• HF fluoride hydride
• One way to implement these charges with eg PVDF is to introduce these inorganic fillers using an acrylic masterbatch.
• the inorganic fillers are dispersed in a polymer or copolymer of methyl methacrylate (PMMA), then this masterbatch is mixed with the PVDF in the molten state.
• PMMA methyl methacrylate
• the presence of a PMMA generates drawbacks such as a limitation of the dimensional stability of the film obtained in temperature, a lower thermal resistance, a characteristic odor of the acrylic during the assembly of the cells and a lower UV stability in comparison with a Pure PVDF.
• a film comprising a tripartite fluorinated polymer / acrylic polymer / mineral filler composition is for example described in the document WO 2009/101343.
• Organic UV absorbers are inert materials that absorb and scatter UV radiation.
• their use is limited because of their disadvantages, namely a limited spectral coverage, their degradation during aging and their migration accompanied by a phenomenon exudation.
• a solution consisting in limiting the UV absorber content has for example been proposed by the Applicant in the document EP 1 382 640, which describes films that are transparent to visible light and opaque to UV radiation, said films consisting of two layers. including one comprising PVDF, PMMA, an acrylic elastomer and a UV absorber.
• the results set out in Examples 1 to 5 show that no exudation is observed when a film of 15 microns thick is kept for 7 days in an oven.
• the limitation of the UV absorber content can not be suitable for the production of films intended for longer periods of use, as is the case for photovoltaic cells.
• composition free of acrylic and organic UV absorber which allows the manufacture of a film having good properties of transparency in the visible range, opacity to UV radiation and a good mechanical resistance and aging.
• the invention relates to a polymeric composition consisting of a fluorinated polymer and zinc oxide (ZnO), said filler being present in said composition in a mass proportion of 0.1 to 10. %, preferably 0.5 to 6%.
• the fluoropolymer is a homopolymer of vinylidene difluoride or a copolymer of vinylidene difluoride and at least one other fluorinated monomer.
• the ZnO particles incorporated in the composition have a size ranging from 25 to 40 nm, preferably from 30 to 35 nm.
• This particular nanometric size allows a good dispersion of the particles in the polymer mass without initiating the degradation of the latter when it is in the molten state during the compounding and transformation steps.
• the surface of the ZnO particles is rendered chemically inert by a treatment of surface ; this increases the compatibility with the fluoropolymer and leads to the production of a homogeneous and stable suspension over time.
• the composition according to the invention is free of acrylic polymers, which eliminates the risk of producing unpleasant odors during processing.
• the invention relates to a monolayer film obtained from the abovementioned composition, said film being opaque to UV radiation and transparent in the visible range and exhibiting long-term stability. These properties particularly recommend it for use as a front face or "frontsheet” in a photo voltaic cell.
• the film according to the invention may, however, be suitable for use as a backside or "backsheet” in a photovoltaic cell.
• the invention also relates to a process for the manufacture of the above-mentioned composition, comprising a step of melt blowing said filler into the fluoropolymer.
• the invention also relates to processes for manufacturing the film according to the invention, comprising, in a variant, an extrusion-blowing step at a flow rate of 300 kg / hour, or, according to another variant, a flat extrusion step, the two operations being carried out at a temperature of between 220 ° C. and 240 ° C.
• FIG. 1 is a diagram representing the variation of the absorbance at 340 nm of the film according to the invention as a function of the mass ratio of ZnO in the composition;
• FIG. 2 is a diagram representing the variation of the transmittance at
• a first subject of the invention is therefore a polymeric composition consisting of a fluorinated polymer and zinc oxide, said filler being present in said composition in a mass proportion of 0.1 to 10%, preferably 0.5 at 6%, characterized in that:
• the fluoropolymer is a homopolymer of vinylidene difluoride or a copolymer of vinylidene difluoride and at least one other fluorinated monomer
• the ZnO particles have a size ranging from 25 to 40 nm, preferably from 30 to 35 nm
• composition is free of acrylic polymers.
• the fluoropolymer entering the composition according to the invention is prepared by polymerization of one or more monomer (s) of formula (I):
• X 2 and X 3 denote H, F, Cl, a fluorinated alkyl group of formula C n F m H p - or a fluorinated alkoxy group C n F m H p O-, n being an integer between 1 and 10, m an integer between 1 and (2n + 1), p being 2n + 1m.
• HFP hexafluoropropylene
• TFE tetra
• the fluoropolymer is a homopolymer or copolymer of VDF.
• the fluorinated comonomer copolymerizable with VDF is chosen for example from vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene
• TFE hexafluoropropylene
• HFP hexafluoropropylene
• 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.
• 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.
• PVDF 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 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 capillary rheometer. in fact, this type of polymer is well suited for extrusion.
• the polymer has a viscosity ranging from 500 Pa.s to 2900 Pa.s, the viscosity being measured at 230 0 C at a gradient shear rate of 100 sec -1 using a capillary rheometer.
• the zinc oxide used in the composition according to the invention has a function of opacifier in the UV range (185 to 400 nm), and acts as a solar filter so that a film prepared from the composition according to the invention is a film opaque to UV radiation, mainly by diffusion / reflection of UV rays.
• the particle size of the charge is between 25 to 40 nm, preferably 30 to 35 nm (inclusive).
• the mass content in inorganic filler in the composition is between 0.1 and 10%, advantageously between 0.5 and 6% (inclusive). This content and the small particle size provide good transparency properties in the visible range (400 to 700 nm) for a film made from the composition according to the invention.
• the ZnO particles have a surface treatment which renders said particles inert chemically relative to the fluorinated polymers. This has the effect of preventing the degradation of fluoropolymers, in particular PVDF, during the compounding and transformation steps.
• surface treatment of the ZnO particles is understood in the context of the invention a chemical or physical operation which has the effect of modifying the surface of the ZnO particles in order to make them chemically inert with respect to the fluoropolymer . This has the effect of preventing yellowing of the fluoropolymer.
• the ZnO particles are coated with silicon-based compounds, such as silane or silane-based compounds.
• silicon-based compounds such as silane or silane-based compounds.
• An example of this type is formed by the ZnO powder of the range marketed under the name Zano ® 20 by UMICORE.
• the composition according to the invention consists of PVDF and ZnO particles of size ranging from 30 to 35 nm, the mass content of the filler being from 0.5 to 6%.
• the composition according to the invention can be prepared by a process comprising a step of melting incorporation of said nanometric filler directly into the fluoropolymer in the absence of acrylic polymer.
• This method of preparation ensures a good dispersion of the nanometric ZnO particles in order to give the film which is manufactured from said composition good opacity to UV, while maintaining a good transparency in the visible.
• the absence of acrylic polymers in the composition ensures on the one hand the absence of acrylic odors during processing, and on the other hand guarantees the excellent properties of PMMA-free PVDF in terms of long-term UV resistance, weather resistance (“wheatherability"), chemical resistance, resistance to certain solvents, temperature resistance, for the film to be made from this composition.
• the invention in another aspect, relates to a monolayer film made from the composition described above.
• This film is opaque to UV radiation and transparent in the visible range while maintaining very good dimensional stability properties at the temperatures used for the manufacture of a front face or a rear face and subsequently a photovoltaic panel.
• the film according to the invention has a long-term stability and can be coated with a layer of silica or aluminum oxide to obtain barrier properties to moisture and oxygen.
• o in the cross-machine direction between 50 and 500%
• o in the cross direction between 20 and 60 MPa;
• the film according to the invention does not have an acrylic odor.
• the film according to the invention is manufactured, according to a first embodiment, by blown film extrusion ("blown film”) at a temperature ranging from 240 to
• 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 is manufactured by flat extrusion of polymer ("extrusion cast") at a temperature ranging from 240 to 260 ° C.
• the molten plastic material is introduced into a flat die.
• the material is cooled on a cooling roll and then stretched to obtain the desired thickness.
• the film is rewound.
• the flat film extrusion process provides excellent optical and dimensional properties.
• the small size of the inorganic filler particles present in the composition used for the manufacture of the film, as well as the nature of these fillers make it possible to obtain the film by these extrusion techniques at temperatures of 240-260 ° C. without causing degradation of the fluoropolymer present in said composition.
• This allows to keep intact the special properties of this polymer, namely its very good resistance to weather, UV radiation and oxygen.
• the film is manufactured by following the steps below:
• Nano-metric ZnO in the molten fluoropolymer, at a temperature ranging from 220 to 260 ° C., preferably at 240 ° C.
• the invention relates to the use of this film for the manufacture of the front panel in a photovoltaic panel.
• the subject of the invention is the use of this film for the manufacture of the rear face in a photovoltaic panel.
• 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 laminated structure can be used as a backsheet in a photovoltaic cell.
• the PET may be pigmented with TiO2 or not according to the wish to have in the end an opaque or transparent backsheet.
• Mixtures S1-A, C, D, E are carried out on a twin-calender at 240 ° C. by introducing 1 to 6% of "nanoscale ZnO with surface treatment” (Zano20) into molten Kynar 740.
• the mixture Sl-B is obtained by preparing, under the same conditions, a 20% “ZnO with surface treatment” (Zano20) masterbatch in Kynar 740, which masterbatch is then diluted to a level of 5% in Kynar 740 to obtain a final composition identical to that of the mixture Sl-A. After cooling, all these mixtures appear white and free of bubbles.
• the Kynar 740 used here is a PVDF homopolymer.
• the Sl-F and Sl-G mixtures were prepared according to the same protocol as the Sl-A and Sl-B mixtures, respectively, but using "nanometric ZnO without surface treatment” and lowering the temperature to 200 ° C. These two mixtures as well as the intermediate masterbatch show visible signs of early degradation of Kynar 740: yellow / brown or even brown coloration the masterbatch, and the presence of fine bubbles. These characteristics indicate a beginning of degradation of the Kynar 740 induced by the "nanometer-free ZnO without surface treatment", and this in spite of a mixing temperature lowered to 200 ° C.
• the absorbance and the transmittance of these films are measured on a CARY 300 spectrophotometer of VARIAN equipped with an integration sphere (with an angle of 8 °):
• the film carrier is installed at the entrance of the sphere and the Spectralon is put on the reflectance sample holder.
• the baseline is recorded with the empty film holder.
• the UV spectra of the films are obtained with the following parameters:
• SERIE-2 mixes on extruder then extrusion of a film
• Kynar 1000HD Kynar 1000HD
• Kynarflex 3120-50 This masterbatch is then incorporated into Kynar 1000HD or Kynarflex 3120-50 by dry blending of granules, to give respectively the mixtures S2-A (in Kynar 1000HD) and S2-B to S2-F (in Kynarflex 3120-50 ).
• the incorporation rate of the masterbatch defines the "ZnO nanoscale with surface treatment" (Zano20) in the final mixture as indicated in the table below.
• Kynarflex 3120-50 is a VDF-HFP copolymer.

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• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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