FLEXIBLE FILM BASED ON FLUORINATED POLYMER

• US 20090275251A1
• Filed: 01/25/2007
• Published: 11/05/2009
• Est. Priority Date: 01/25/2006
• Status: Abandoned Application

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Duc, Sandrine, Bonnet, Anthony, Laffargue, Johann, Mathieu, Cyrille
• Application Number:
  US12/162,144
• Publication Number:
  US 20090275251A1
• Time in Patent Office: Days
• US Class Current: 442/133
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/08 flexible, e.g. films
• CPC Class Codes: B29C 48/10 flexible, e.g. blown foils
• CPC Class Codes: B29C 48/21 the layers being joined at their surfaces
• CPC Class Codes: B29C 48/22 with means connecting the layers, e.g. tie layers or undercuts
• CPC Class Codes: B29K 2027/16 PVDF, i.e. polyvinylidene fluoride
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 2262/0238 Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 2262/0269 Aromatic polyamide fibres
• CPC Class Codes: B32B 2262/101 Glass fibres
• CPC Class Codes: B32B 2264/10 Inorganic particles
• CPC Class Codes: B32B 2307/542 Shear strength
• CPC Class Codes: B32B 2307/71 Resistive to light or to UV
• CPC Class Codes: B32B 2307/712 Weather resistant
• CPC Class Codes: B32B 2457/12 Photovoltaic modules
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/12 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/304 comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 27/308 comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 : comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/322 : comprising halogenated polyolefins, e.g. PTFE
• CPC Class Codes: B32B 27/36 : comprising polyesters
• CPC Class Codes: B32B 7/06 : permitting easy separation
• CPC Class Codes: B32B 7/12 : using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08L 2205/03 : containing three or more polymers in a blend
• CPC Class Codes: C08L 2666/02 : Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 : Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/16 : Homopolymers or copolymers or vinylidene fluoride
• CPC Class Codes: C08L 33/12 : Homopolymers or copolymers of methyl methacrylate
• CPC Class Codes: C08L 71/02 : Polyalkylene oxides
• CPC Class Codes: H01L 31/049 : Protective back sheets
• CPC Class Codes: Y02E 10/50 : Photovoltaic [PV] energy
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/3154 : Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 : Addition polymer is perhalogenated
• CPC Class Codes: Y10T 442/2607 : Radiation absorptive

Abstract

The invention concerns a multilayer structure comprising: a PVDF-based film F1 affixed to a PET or PEN sheet; or a PVDF-based film F1 bonded to a PET or PEN sheet which is itself affixed to a PVDF-based film F2. The F1 and/or F2 films comprising (starting from the PET or PEN sheet): optionally a layer of composition B comprising 5 to 40 parts of at least one PVDF, 60 to 95 parts of at least one PMMA and 0 to 5 parts of at least one UV absorber, the total making 100 parts; a layer of composition A, comprising 50 to 100 parts of at least one PVDF, 0 to 50 parts of at least one PMMA, 0 to 30 parts of at least one mineral filler and 0 to 3 parts of at least one dispersant, the total making 100 parts; optionally a layer of composition C comprising 80 to 100 parts of at least one PVDF, 0 to 20 parts of at least one PMMA, 0 to 30 parts of at least one mineral filler and 0 to 3 parts of at least one dispersant, the total making 100 parts; such that an adhesive layer is interposed between the PET or PEN sheet and the F1 and/or F2 films; said adhesive layer being optional if the layer of composition B is present and not including any polyolefin functionalized by an unsaturated carboxylic acid or anhydride, or a homo- or copolymer including as monomer(s) acrylic acid, acrylates and alkyl acrylates optionally modified by an unsaturated acid or anhydride; such that the compositions A and/or B do not contain any acrylic elastomer particle nor any core-coat particle.

Claims

1. A multilayer structure comprising:

a polyvinylidene fluoride (PVDF)—

based film F1 bonded to a polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) sheet;

or

a PVDF-based film F1 bonded to a PET or PEN sheet which is itself bonded to a PVDF-based film F2,

the film F1 and/or F2 comprising (in the order starting from the PET or PEN sheet);

optionally, a layer of composition B comprising 5 to 40 parts of at least one PVDF, 60 to 95 parts of at least one PMMA and 0 to 5 parts of at least one UV absorber, the total making 100 parts;

a layer of composition A, comprising 50 to 100 parts of at least one PVDF, 0 to 50 parts of at least one polymethyl methacrylate (PMMA), 0 to 30 parts of at least one mineral filler and 0 to 3 parts of at least one dispersing agent, the total making 100 parts; and

optionally, a layer of composition C comprising 80 to 100 parts of at least one PVDF, 0 to 20 parts of at least one PMMA, 0 to 30 parts of at least one mineral filler and 0 to 3 parts of at least one dispersing agent, the total making 100 parts,

wherein an adhesive layer is placed between the PET or PEN sheet and the film F1 and/or F2;

wherein said adhesive layer is optional if the layer of composition B is present and containing no polyolefin functionalized by an unsaturated carboxylic acid or anhydride, or else a homopolymer or copolymer comprising, as monomer(s), acrylic acid, alkyl acrylates and acrylates, which is optionally modified by an unsaturated acid or anhydride; and

wherein compositions A and/or B contain no acrylic elastomer nor any core-shell particle.

2. The structure as claimed in claim 1, wherein the PVDF is a flexible PVDF comprising, by weight, 5 to 20%, of a fluorinated comonomer per 80 to 95%, of VDF.

3. The structure as claimed in claim 1, wherein the PVDF of composition A and/or composition B comprises, by weight, 5 to 20% of a fluorinated comonomer per 80 to 95% of VDF.

4. The structure as claimed in claim 1, wherein the PVDF of composition C is a PVDF homopolymer.

5. The structure as claimed in claim 1, wherein the PVDF is a copolymer with a fluorinated comonomer, and wherein the fluorinated comonomer is selected from the group consisting of vinyl fluoride;

trifluoroethylene (VF3);

chlorotrifluoroethylene (CTFE);

1,2-difluoroethylene;

tetrafluoroethylene (TFE);

hexafluoropropylene (HFP);

perfluoro(alkyl vinyl)ethers, perfluoro(methyl vinyl)ether (PMVE), perfluoro(ethyl vinyl)ether (PEVE), perfluoro(propyl vinyl)ether (PPVE);

perfluoro(1,3-dioxole); and

perfluoro(2,2-dimethyl-1,3-dioxole) (PDD).

6. The structure as claimed in claim 1, wherein the PMMA comprises, by weight, 0 to 20% of a C₁-C₈ alkyl(meth)acrylate.

7. The structure as claimed in claim 1, wherein the optional adhesive layer consists of a urethane, epoxy, acrylic or polyester adhesive.

8. The structure as claimed in claim 1, wherein the UV absorber is of the benzotriazole, benzophenone, benzylidene malonate or quinazoline type.

9. The structure as claimed in claim 1, wherein the dispersing agent is a polyethylene glycol.

10. The structure as claimed in claim 9, wherein the polyalkylene glycol has a number-average molecular weight of between 1000 and 10 000 g/mol.

11. The structure as claimed in claim 1, wherein the mineral filler is selected from the group consisting of a metal oxide titanium dioxide (TiO₂), silica, quartz, alumina, a carbonate, calcium carbonate, talc, mica, dolomite (CaCO₃.MgCO₃), montmorillonite (aluminosilicate), BaSO₄, ZrSiO₄, Fe₃O₄, antimony oxide (Sb₂O₃, Sb₂O₅), Al(OH)₃, Mg(OH)₂, huntite (3MgCO₃.CaCO₃), hydromagnesite (3MgCO₃.Mg(OH)₂.3H₂O), carbon black and carbon nanotubes.

20. A process for manufacturing a PVDF-based film as claimed in claim 1, comprising coextruding:

a) the various layers of the PVDF-based film (of compositions A, B, C);

b) a layer L1 of a polyolefin adjacent the layer of composition A or the layer of composition C; and

c) optionally, another layer L2 of a polyolefin adjacent the combination of the layers extruded at a) and b), on the side opposite the layer extruded at b),

and, cooling the coextrudate, and recovering the PVDF-based film by separating it from the polyolefin layer(s).

21. The structure as claimed in claim 2, wherein the PVDF comprising, by weight, 7 to 13%, of a fluorinated comonomer 87 to 93%, of VDF.

22. The structure as claimed in claim 6, wherein said C₁-C₈ alkyl(meth)acrylate comprises methyl acrylate and/or ethyl acrylate.

13. A substrate/PVDF-based film structure, comprising:

a) a substrate selected from the group consisting of;

a photovoltaic module;

a technical textile;

or

a metal, and

b) a PVDF-based film comprising (in the order starting from the substrate);

optionally, a layer of composition B comprising 5 to 40 parts of at least one PVDF, 60 to 95 parts of at least one PMMA and 0 to 5 parts of at least one UV absorber, the total making 100 parts;

a layer of composition A, comprising 50 to 100 parts of at least one PVDF, 0 to 50 parts of at least one PMMA, 0 to 30 parts of at least one mineral filler and 0 to 3 parts of at least one dispersing agent, the total making 100 parts; and

optionally, a layer of composition C comprising 80 to 100 parts of at least one PVDF, 0 to 20 parts of at least one PMMA, 0 to 30 parts of at least one mineral filler and 0 to 3 parts of at least one dispersing agent, the total making 100 parts, wherein an adhesive layer is placed between the substrate and the PVDF-based film, this adhesive layer being optional if the layer of composition B is present.

12. The structure as claimed in claim 13, wherein in a photovoltaic module, the PVDF-based film being placed on the module via the PVDF-based film F1.

14. The structure as claimed in claim 13, wherein composition A comprises 50 to 70 parts of at least one PVDF, 10 to 40 parts of at least one PMMA and 10 to 25 parts of at least one mineral filler, the total making 100 parts.

16. The structure as claimed in claim 13, wherein the technical textile is woven or non-woven.

17. The structure as claimed in claim 13, wherein the technical textile is made of PVC, of polyester or of polyamide, a glass fabric, a glass mat, an aramid or a KEVLAR fabric.

15. (canceled)

18. (canceled)

19. (canceled)