EP2464515A1 - Feuille de protection remplie de fluoropolymères/particules - Google Patents

Feuille de protection remplie de fluoropolymères/particules

Info

Publication number
EP2464515A1
EP2464515A1 EP10808470A EP10808470A EP2464515A1 EP 2464515 A1 EP2464515 A1 EP 2464515A1 EP 10808470 A EP10808470 A EP 10808470A EP 10808470 A EP10808470 A EP 10808470A EP 2464515 A1 EP2464515 A1 EP 2464515A1
Authority
EP
European Patent Office
Prior art keywords
copolymers
tetrafluoroethylene
multilayer film
fluoropolymer
ethylene
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Withdrawn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
EP10808470A
Other languages
German (de)
English (en)
Other versions
EP2464515A4 (fr
Inventor
Philip C. Guy
Karen Conley
Frank J. Csillag
Julia Dicorleto Gibson
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.)
Saint Gobain Performance Plastics Corp
Original Assignee
Saint Gobain Performance Plastics Corp
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
Priority claimed from US12/576,724 external-priority patent/US20100092759A1/en
Application filed by Saint Gobain Performance Plastics Corp filed Critical Saint Gobain Performance Plastics Corp
Publication of EP2464515A1 publication Critical patent/EP2464515A1/fr
Publication of EP2464515A4 publication Critical patent/EP2464515A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/30—Fillers, e.g. particles, powders, beads, flakes, spheres, chips
    • 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
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/12—Polyvinylhalogenides containing fluorine
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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 invention relates generally to films and multilayer films having at least one particulate embedded into a film, and methods for their manufacture that are useful as packaging materials.
  • Multilayer films or laminates are constructions which attempt to incorporate the properties of dissimilar layers in order to provide an improved performance versus the materials separately. Desirable properties for multilayer films include moisture vapor barrier, weather resistance, cut through resistance, electrical resistance, surface reflectance, opacity, two-sided color, or other two- sided electromagnetic spectral effects.
  • achieving property control by the commonly used method of adding a suitable filler has often resulted in the improvement of one property with a drop in another.
  • the addition of a light blocking filler at levels needed to obtain a high level of opacity can result in an undesirable increase in moisture vapor transmission.
  • addition of a high level of light blocking filler can result in an undesirable decrease in dielectric strength.
  • addition of filler to increase reflectivity of a film can result in a multilayer film surface that adheres poorly when bonded within the photovoltaic device.
  • Previous films have generally provided one or two desirable properties of protective films for electronic devices, but have not been able to provide a better level of combined protection.
  • multilayer films that can be tailored to provide one or more improved properties for a photovoltaic sheet.
  • multilayer films tailored to other protective applications such as protective wrap for wire or cable applications, or protective films for other optoelectronic devices such as OLEDS.
  • the present invention surprisingly provides multilayer films, and processes to prepare such multilayer films, that overcome one or more of the disadvantages known in the art. It has been discovered that it is possible to make and use multilayer films having characteristics, for example, suitable for packaging materials for electronic devices. These films help to protect the components from heat, humidity, chemical, radiation, physical damage and general wear and tear. Such packaging materials help to electrically insulate the active components/circuits of the electronic devices. Additionally, such materials provide protective cushioning to electronic devices, such as photovoltaic devices, provide antisoiling properties, chemical resistance, UV resistance, reflectivity, increased flame retardancy, aesthetics and/or opacity.
  • the present invention provides a casting composition that includes a carrier liquid; a polymer resin matrix material; a particulate filler material; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film that includes varying percentages of volume percent filler material.
  • the opacity of the film can be controlled while providing an aesthetically pleasing appearance as well as providing film integrity.
  • the opacity of the film can be controlled while providing an aesthetically pleasing appearance as well as providing film integrity.
  • Lower levels of particulate filler can also provide a lower moisture transmission, or improvements in dielectric strength. Therefore, in certain embodiments, it is preferable to have less than 15 volume percent filler present in the ultimate film.
  • the particle size can also effect the integrity of the film and in some aspects, the operator would choose filler material(s) where none of the single linear dimensions of particle was greater than 10 ⁇ m and can be from a nanometer (nm) to about 100 nm, e.g., 0.1 ⁇ m.
  • the particulate filler can have a single dimension of from 100 nm to 2 ⁇ m In other aspects, some of the particulate filler can have single linear dimensions greater than 10 ⁇ m.
  • the particulate can be one of, or a mixture, of silica particles, aluminum flakes, glass beads, glass microspheres, glass fibers, titanium dioxide particles, barium titanate particles, calcium carbonate, zinc oxide, mica, clay such as kaolin or others, mullite, talc, iron oxide, carbon black, zinc sulfide, barium sulfate, zinc sulfite, a range of pigments such as cobalt aluminate blue, sodium alumino sulphosilicate, flame retardants such as magnesium hydroxide, antimony trioxide, organophosphates or brominated compounds, or other suitable particulates for the application envisioned.
  • the particle size can be from about 100 nanometers (nm) to about 2 microns ( ⁇ m).
  • the particle may be reflective in the infrared or region of the spectrum. Particles of this type can be effective in reducing IR absorption and consequent heat build up in the film, while at the same choice allowing a range of color choices in the visible spectrum.
  • IR reflective pigments include Arctic Black 10C909, Black 411, Yellow 193, Brown 12 and Brown 8 from Shepherd Color Company, Cincinnati, OH and V-780 Black, V- 778 Black, PC-9415 Yellow, V-9248 Blue, V-13810 Red, and V- 12600
  • the present invention provides films from the casting composition.
  • the present invention provides methods to prepare the films and multilayer films disclosed herein.
  • the present invention provides a
  • the multilayer films of the invention can include from 2 layers to about 12 layers of material.
  • the multilayer films can repeat layering of a first layer and a second layer, and so forth.
  • An outer layer or two outer layers can be included in the multilayer film construction.
  • the outer layers for example, can be a fluoropolymer or a non- fluoropolymer.
  • combinations of various layers are included herein, for example, a first layer, a second layer, a third layer differing from the first or second layers and a fourth layer which differs from the first, second or third layers, etc. This layering, again, can be repeated as needed for the application envisioned.
  • the multilayer films generally have a dielectric break down strength (kV) that is greater than 3 kV measured by ASTM method D3755, a solar reflectance that is greater than 70% measured by ASTM method E424, or a water vapor transmission that is less than 20 g/m 2 /day measured by ASTM method F1249 when the multilayer film has a thickness between about 0.8 mils and about 2.0 mils, e.g., about 1.1 mils.
  • kV dielectric break down strength
  • the present invention also provides methods to prepare the multilayered films noted throughout the specification.
  • the present invention includes various embodiments.
  • the invention pertains to a casting composition comprising:
  • a nonfibrillated non-fluoropolymer or fluoropolymer matrix (a polymer resin or polymer matrix) material
  • a particulate filler material wherein some of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including greater than 15 volume percent filler material.
  • the invention pertains to a casting composition
  • a casting composition comprising:
  • a carrier liquid [030] a carrier liquid; [031] a nonfibrillated non-fluoropolymer or fluoropolymer matrix material;
  • a particulate filler material wherein some of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including less than 15 volume percent filler material.
  • the invention pertains to a casting composition
  • a casting composition comprising:
  • a particulate filler material wherein none of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including less than 15 volume percent filler material.
  • the present invention pertains to a casting composition
  • a casting composition comprising:
  • a particulate filler material wherein some of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including greater than 15 volume percent filler material.
  • the present invention pertains to a casting composition
  • a casting composition comprising: [042] a carrier liquid;
  • a particulate filler material wherein some of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including less than 15 volume percent filler material.
  • the present invention pertains to a casting composition
  • a casting composition comprising:
  • a particulate filler material wherein none of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including greater than 15 volume percent filler material.
  • the present invention pertains to a casting composition
  • a casting composition comprising:
  • a particulate filler material wherein none of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including less than 15 volume percent filler material.
  • the present invention pertains to a casting composition
  • a casting composition comprising:
  • a particulate filler material wherein none of the particles of the particulate filler material exhibit a single linear dimension greater than 10 ⁇ m; and wherein the polymer matrix material and particulate filler material are included in the composition in relative amounts effective to provide a dry composite film including greater than 15 volume percent filler material.
  • a third layer can be disposed upon the second layer to form a composite.
  • the second layer is encapsulated by the first and third layers.
  • the third layer can be a non-fluoropolymer or a fluoropolymer that is also from a castable solution.
  • the present invention also provides casting
  • the multilayer films include a first outer layer, as described above, comprising an aqueous or solvent castable polymer, e.g., a fluoropolymer, a second inner layer, as described above, disposed upon the first layer, the second layer comprising an aqueous or solvent castable polymer, e.g., a fluoropolymer or mixtures thereof and a particulate filler material, as described above, and a third outer layer disposed upon the second layer comprising an aqueous or solvent castable polymer as described above e.g., a fluoropolymer or mixtures thereof.
  • a first outer layer as described above, comprising an aqueous or solvent castable polymer, e.g., a fluoropolymer
  • a second inner layer as described above
  • the second layer comprising an aqueous or solvent castable polymer, e.g., a fluoropolymer or mixtures thereof and a particulate filler material, as
  • the first outer layer has a thickness of from about 0.01 mils to about 0.7 mils, more particularly from about 0.02 mils to about 0.4 mils and most particularly from about 0.05 mils to about 0.3 mils.
  • the second inner layer generally has a thickness of from about 0.1 mils to about 0.8 mils, more particularly from about 0.2 mils to about 0.4 mils and most particularly from about 0.3 mils to about 0.4 mils.
  • the third outer layer has, for example, has a thickness of from about 0.01 mils to about 0.7 mils, more particularly from about 0.02 mils to about 0.4 mils and most particularly from about 0.05 mils to about 0.3 mils.
  • Subsequent layers can have a thickness of from about 0.01 mils to about 0.7 mils, more particularly from about 0.02 mils to about 0.4 mils and most particularly from about 0.05 mils to about 0.3 mils.
  • multilayer film is intended to include multiple layers of film(s) in contact with each other. At a minimum, two layers are present, although three layers are particularly desired. Additional layers can be included in the multilayer film such that the multilayer film can include 4, 5, 6 through 12 etc. layers.
  • the liquid carrier medium may be water, organic solvent, or any other liquid in which the polymer may be dispersed, dissolved, suspended, emulsified or otherwise distributed
  • the liquid carrier medium may be a mixture of suitable liquids. Once distributed within the carrier medium, the polymer and medium is then capable of being deposited or cast upon a supporting material to form a film.
  • the polymer(s) can be mixed with a first carrier liquid.
  • the mixture may comprise a dispersion of polymeric particles in the first carrier liquid, an emulsion of liquid droplets of the polymer, or of a monomeric or oligomeric precursor of the polymer in the first carrier liquid or a solution of the polymer in the first carrier liquid.
  • the castable polymer(s) may also be a monomeric or oligomeric precursor of the polymer distributed within a carrier liquid. Most commonly castable compositions are emulsions or dispersions in aqueous media.
  • the choice of the first carrier liquid is based on the particular polymer and the form in which the material is to be introduced to the casting composition of the present invention. If a solution is desired, a solvent for the particular fluoropolymer is chosen as the carrier liquid. Suitable carriers include, for example, DMAC, NMP, cellosolves, or water and the like. If a dispersion is desired, then a suitable carrier is one in which the polymer is not soluble. An aqueous solution would be a suitable carrier liquid for a dispersion of polymer particles.
  • compositions are emulsions or dispersions in aqueous media.
  • Surfactants can be used to prepare a dispersion in an amount effective to modify the surface tension of the carrier liquid to enable the carrier liquid to wet the filler particles.
  • Suitable surfactant compounds include ionic surfactants, amphoteric, cationic and nonionic surfactants.
  • a mixture of a polymer, a carrier liquid and a dispersion of the filler particles in a second carrier liquid are combined to form a casting composition.
  • Fluoropolymers are generally selected as outer layers to provide chemical resistance, electrical insulation, weatherability and/or a barrier to moisture.
  • fluoropolymer is known in the art and is intended to include, for example polytetrafluoroethylene(PTFE), polyvinylidenefluoride (PVDF), polychlorotrifluoroethlylene (PCTFE), polyvinylfluoride (PVF), tetrafluoroethylene/hexafluoropropylene/ethylene copolymer(HTE),
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidenefluoride
  • PCTFE polychlorotrifluoroethlylene
  • PVF polyvinylfluoride
  • HTE tetrafluoroethylene/hexafluoropropylene/ethylene copolymer
  • chlorotrifluoroethylene/hexafluoropropylene ethylene/chlorotrifluoroethylene copolymers (ECTFE), ethylene/trifluoroethylene copolymers, ethylene/tetrafluoroethylene copolymers (ETFE), tetrafluoroethylene/propylene copolymers(TFE/P), tetrafluoroethylene/ hexafluoropropylene copolymers (FEP), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers (PFAs e.g., tetrafluoroethylene-perfluoro(propyl vinyl ether), polyvinylidene difluoride, hexafluoropropylene/ tetrafluoroethylene/ vinylidene copolymers (i.e., THV) and mixtures thereof.
  • ECTFE ethylene/chlorotrifluoroethylene copolymers
  • ETFE ethylene/t
  • the fluoropolymer can be melt-processable, for example, as in the case of polyvinylidene difluoride; copolymers of vinylidene difluoride;
  • copolymers of tetrafluoroethylene, hexafluoropropylene, and vinylidene difluoride copolymers of tetrafluoroethylene and hexafluoropropylene; and other melt-processable fluoroplastics; or the fluoropolymer may not be melt- processable, for example, as in the case of polytetrafluoroethylene, copolymers of TFE and low levels of fluorinated vinyl ethers), and cured fluoroelastomers.
  • THV polymers examples include those marketed by Dyneon, LLC under the trade designations "DYNEON THV 2030G FLUOROTHERMOPLASTIC", "DYNEON THV 220
  • HTE polymers examples include those marketed, for example, under the trade designation "DYNEON
  • Examples of commercially available vinylidene difluoride- containing fluoropolymers include, for example, those fluoropolymers having the trade designations; "KYNAR” (e.g., "KYNAR 740") as marketed by Atofma,
  • FLUOREL e.g., "FLUOREL FC-2178" as marketed by Dyneon, LLC.
  • Examples of commercially available tetrafluoroethylene- perfluoro(alkyl vinyl ether) copolymers include those marketed for example, under the trade designation "Hyflon PFA", or “Hyflon MFA” by Solvay Solexis; and “Teflon PFA” by E.I.diPont de Nemours & Company
  • Examples of commercially available vinyl fluoride fluoropolymers include, those homopolymers of vinyl fluoride marketed under the trade designation "TEDLAR” by E.I. du Pont de Nemours & Company, Wilmington,
  • TFE/P examples include , those marketed under the trade designations "AFLAS” (e.g., "AFLAS TFE
  • TFE ELASTOMER FA 150L or "AFLAS TFE ELASTOMER FA 150P" as marketed by Dyneon, LLC, or "VITON” (e.g., "VITON VTR-7480" or "VITON
  • VTR-7512 as marketed by E.I. du Pont de Nemours & Company, Wilmington,
  • ETFE polymers examples include, for example, those marketed under the trade designations "DYNEON
  • Examples of commercially available ECTFE polymers include those marketed under the trade designation Halar 350 and Halar 500 resin from
  • the polymer matrix material of the present invention can comprise a thermoplastic or thermosetting polymer other than a fluoropolymer.
  • suitable alternative polymeric matrix materials include polyolefins and copolymers thereof, such as polyethylenes, polypropylenes, polyethylene, polymethylpentene, and polybutadiene, epoxy resins, phenolic resins, cyanate esters, polyesters, polyamides, polycarbonates, polyimides, polyacrylics, polymethacrylics, thermoplastic olefins, ethylene vinyl alcohol (EVOH), ethylene vinyl acetate (EVA), ethylene methacrylate (EMA) thermoplastic urethanes, thermoplastic silicones, ionomers, ethyl butyl acrylate (EBA), polyvinyl butyral (PVB), ethylene propylene diene M-class rubbers (EPDM) or mixtures thereof.
  • polyolefins and copolymers thereof such as polyethylenes, polypropylenes, poly
  • the particulate filler material of the present invention can include any organic or inorganic particulate material.
  • the terms "particulate” and “particles” as used herein are intended to include fibers and flakes.
  • Suitable inorganic filler materials include, e.g. glass particles, ceramic particles, metallic particles, carbon particles and mineral particles.
  • Specific examples of suitable particles and flakes include glass beads, glass microspheres, glass fibers, silica particles, carbon black, titanium dioxide particles, iron oxide particles, aluminum particles and barium titanate particles.
  • Silica particles, particularly amorphous fused silica particles and silica particles made by a sol gel process, and glass particles are applicable, e.g. dielectric layers of laminar electrical circuits, requiring a low dielectric constant.
  • the shape of the filler particles, the size of the filler particles and the size distribution of the filler particles can be important parameters with regard to characterizing the particle filled composite article of the present invention.
  • platelet shaped pigments can give rise to light interfering and other optical effects.
  • Such particles can include as mica coated iron or other metal oxide complexes (for example Taizhu TZ2013 violet from Wenzhou Pearlescent Pigments Co, Taizhu, China; and Xirallic T60-10 WNT crystal silver from Merck KGaA, Darmstadt, Germany)
  • all particles of the particulate filler exhibit a diameter of less than about 10 microns ( ⁇ m).
  • each of the filler particles exhibit no single linear dimension greater than about 10 ⁇ m.
  • the particles of the particulate filler include some particles that are exhibit a single linear dimension greater than 10 ⁇ m.
  • the percentage of the particles that exhibit a single linear dimension greater than 10 ⁇ m relative to particles that have a single linear dimension less than 10 ⁇ m can be from 0.01% to about 50%, from about 0.1% to about 20%, or from about 1% to about 10% of the total amount of particles.
  • the linear dimension can be from about 11 ⁇ m to about 50 ⁇ m, from about 15 ⁇ m to about 20.
  • incorporation of particles that exhibit a single linear dimension greater than 10 ⁇ m can help provide unique properties to the ultimate film. These include increased tensile strength, greater opacity (than that without the larger particles), or decrease water vapor transmission.
  • the particle does not need to be spherical.
  • the particle can be oblong, also known as a "platelet" in the art.
  • each of the filler particles is substantially spherical.
  • the filler particles of the film are of a nonuniform size.
  • the use of nonuniformly sized particles can provide an unexpected advantage in that light scattering and provide more uniform particle distribution.
  • the particles are of an average particle size of between about 0.1 ⁇ m and about 20 ⁇ m, with approximately 80% of the particles having a narrow particle size range of between about 0.2 ⁇ m and about 5 ⁇ m.
  • the particulate filler material can be treated with a surface treatment to improve the moisture resistance, particle dispersion, matrix adhesion or IR reflectance, UV resistance of the film and/or improve the mechanical properties of the composite film of the present invention.
  • a surface treatment to improve the moisture resistance, particle dispersion, matrix adhesion or IR reflectance, UV resistance of the film and/or improve the mechanical properties of the composite film of the present invention.
  • TiO 2 forms are passivated otherwise they are photocatalytic.
  • Suitable hydrophobic coatings useful to treat particles of the present invention may comprise any coating material that is thermally stable, exhibits a low surface energy, and improves the moisture resistance of the composite of the present invention.
  • Suitable coating materials include conventional silane coatings, titanate coatings and zirconate coatings.
  • the polymer matrix material of the present invention is mixed with a first carrier liquid.
  • the mixture may comprise a dispersion of polymeric particles in the first carrier liquid, a dispersion, i.e. an emulsion, of liquid droplets of the polymer or of a monomeric or oligomeric precursor of the polymer in the first carrier liquid or a solution of the polymer in the first carrier liquid.
  • the choice of the first carrier liquid is based on the particular polymeric matrix material and the form in which the polymeric matrix material is to be introduced to the casting composition of the present invention. If a solution is desired, a solvent for the particular polymeric matrix material is chosen as the carrier liquid. Suitable carriers include, for example, DMAC, NMP, cellosolves, or water and the like. If a dispersion is desired, then a suitable carrier is one in which the matrix material is not soluble. An aqueous solution would be a suitable carrier liquid for a dispersion of fluoropolymer particles.
  • a dispersion of the particulate filler of the present invention can be in a suitable second carrier liquid in which the filler is not soluble.
  • Surfactants can be used prepare a dispersion in an amount effective to modify the surface tension of the second carrier liquid to enable the second carrier liquid to wet the filler particles.
  • Suitable surfactant compounds include ionic surfactants, amphoteric, cationic and nonionic surfactants.
  • a mixture of a polymeric matrix material and first carrier liquid and a dispersion of the filler particles in a second carrier liquid are combined to form a casting composition.
  • the casting composition has between about 10 and about 90 weight percent solids (based on particles and polymeric matrix), from between about 20 to about 70 weight percent, or from between about 25 to about 50 weight percent.
  • the viscosity of the casting composition of the present invention can be adjusted by the addition of suitable viscosity modifiers.
  • suitable viscosity modifiers include polyacrylic acid compounds, vegetable gums and cellulose based compounds.
  • suitable viscosity modifiers include polyacrylic acid, methyl cellulose, polyethyleneoxide, guar gum, locust bean gum, sodium carboxymethylcellulose, sodium alginate and gum tragacanth.
  • the casting composition has between about 10 and about
  • the particulate filler material may be present within a castable polymer layer in a range of from about 0% by volume to about 60% by volume
  • the particulate filler is present from about 2% to about 50%, for example, from about 8% by volume to about 25% by volume based on the total volume of the multilayer film. In another aspect, the particulate filler is present from about 9% by volume to about 15% by volume based on the total volume of the multilayer film. It should be understood that subranges that fall within 0% to about 60% are included herein, including ranges that are fractional. That is from about 0.5% to about 5.5%, from about 0.6 to about
  • the viscosity of the casting composition of the present invention can be adjusted by the addition of suitable viscosity modifiers.
  • suitable viscosity modifiers include polyacrylic acid compounds, vegetable gums and cellulose based compounds.
  • suitable viscosity modifiers include polyacrylic acid, methyl cellulose, polyethyleneoxide, guar gum, locust bean gum, sodium carboxymethylcellulose, sodium alginate and gum tragacanth.
  • a layer of the composition is cast on a substrate by conventional methods, e.g. dip coating, reverse roll coating, knife-over-roll, knife-over-plate, and metering rod coating.
  • Suitable substrate materials include, e.g. metallic films, polymeric films or ceramic films.
  • suitable substrates include stainless steel foil, polyimide films, polycarbonate films, titanium, aluminum or fluoropolymer films.
  • films are formed by casting onto a carrier belt having low thermal mass.
  • the carrier belt is part of a casting apparatus.
  • the carrier belt is dipped through a
  • fluoropolymer matrix material/particular filler material dispersion in a dip pan at the base of a casting tower such that a coating of dispersion forms on the carrier belt.
  • the coated carrier belt then passes through a metering zone in which metering bars remove excess dispersion from the coated carrier belt.
  • the coated carrier belt passes into a drying zone which is maintained at a temperature sufficient to remove the carrier liquid from the dispersion giving rise to a dried film.
  • the carrier belt with the dried film then passes to a bake/fuse zone in which the temperature is sufficient to consolidate or fuse the fluoropolymer and particulates in the dispersion.
  • the carrier belt passes through a cooling plenum from which it can be directed either to a subsequent dip pan to begin formation of a further layer of a subsequent film or to a stripping apparatus.
  • the process can be repeated as many times as desired, generally providing up to 7 layers, e.g., 5 layers, 3 of which are fluoropolymer matrix/particular filler material layers and 2 are outer layers of one or more fluoropolymer(s) .
  • the coated film can remain on the carrier substrate such that a combined structure of substrate and cast film results.
  • this can include fluoropolymer and a polyimide substrate, an aluminum substrate, a titanium substrate, a steel substrate or a polycarbonate substrate.
  • a separate substrate film may be introduced between the applied casting composition and the carrier belt, such that the castable fluoropolymer film is built up upon this substrate.
  • the substrate, a polyimide film, an aluminum sheet, titanium sheet, steel sheet, or a polycarbonate film may be supported on a carrier belt and the casting composition may be applied to the substrate.
  • the casting composition can thus be applied to both surfaces of the substrate, such that the substrate is coated on top side and the bottom side.
  • Suitable constructs include, for example a first castable
  • fluoropolymer/aluminum/a second castable fluorpolymer which can be the same or different from the first castable fluoropolymer (e.g., PTFE/A1/PTFE), a first castable fluoropolymer/a polyimide/a second castable fluoropolymer which can be the same or different from the first castable fluoropolymer (e.g., FEP/a polyimide/FEP) and a first castable fluoropolymer/a polycarbonate/a second castable fluoropolymer which can be the same or different from the first castable fluoropolymer (e.g., PVDF/a polycarbonate/PVDF).
  • first castable fluoropolymer e.g., PTFE/A1/PTFE
  • a first castable fluoropolymer/a polyimide/a second castable fluoropolymer which can be the same or different from the first castable fluoropolymer
  • the carrier liquid and processing aids such as a surfactant and/or viscosity modifiers, are removed from the cast layer by evaporation and/or by thermal decomposition, to provide a film of the polymeric matrix material and the particulate filler.
  • the particulate filled polymeric matrix composite film of the present invention is prepared by heating the cast film to evaporate the carrier liquid.
  • the film of polymeric matrix material and particulate filler can be further heated to modify the physical properties of the film. This can include a post cure of the film.
  • the multilayer film has three layers.
  • the first outer layer is a castable fluorpolymer
  • the second inner layer is a castable
  • first and third outer layers can include from about 0.01% by volume to about 12% by volume of a particulate filler and in particular from about 0.01% to about 6% by volume.
  • a fourth layer can be disposed on the first layer.
  • the fourth layer is a castable fluoropolymer as described herein.
  • a fifth layer can be disposed on the third layer.
  • the fifth layer is a castable fluoropolymer as described herein.
  • the fourth and fifth layers are selected from tetrafluoroethylene-perfluoro(alkyl vinyl ether) (PFA) copolymers or fluorinated ethylene propylene copolymers (FEP) or mixtures thereof.
  • fourth and/or fifth layers can include mixtures of PTFE with a
  • the fourth and fifth layers can further include a particular filler as described herein.
  • Either or both of the fourth and fifth outer layers can include from about 0.01% by volume to about 12% by volume of a particulate filler and in particular from about 0.01% to about 6% by volume.
  • the outer layers of the multilayer film can be fabricated from a melt bondable fluoropolymer.
  • Suitable melt bondable materials include, for example, tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers or fluorinated ethylene propylene copolymers (FEP) or mixtures thereof.
  • FEP fluorinated ethylene propylene copolymers
  • the multilayer films of the invention have a total thickness of between about 0.6 mils to about 2 mils, more particularly from about 0.8 to about 1.5 mils.
  • the present multilayer films have a dielectric break down strength (kV) greater than 3 kV measured by ASTM method D3755.
  • the dielectric break down strength is from greater than 3 kV to about
  • test specimen of 5 inch x 5 inch is held in air medium between two opposing cylinders 2 inches in diameter, 1 inch long with edges rounded to
  • the specimen is electrically stressed by the application of an increasing direct voltage, at a uniform rate of 500 V/s, until internal breakdown occurs.
  • Dielectric breakdown is generally accompanied by an increase in current in the test circuit that may activate a sensing element such as a circuit breaker or a fuse. The test voltage at breakdown is recorded.
  • the multilayer films have a solar reflectance on at least one side of the film of greater than 70% measured by
  • the solar reflectance on at least one side of the film is from great than 70% to about 99.9%, from about 75% to about 99% and in particular from about 80% to about 99%.
  • Test Methods for Solar Energy Transmittance and Reflectance (Terristrial) of Sheet Materials The specified procedure for ASTM E424 calls for data collection over the range of 350 to 2100 nm. Summation for data from 400-1100 nm is a commonly used variation of this procedure, and is the method used herein.
  • An integrating sphere spectrophotometer is used to measure the spectral characteristics of the test specimen, 2 in. x 2 in., over the spectrum region of interest.
  • Smoked magnesium oxide is used as a standard for the completely reflecting and diffusing surface.
  • the solar transmittance, and reflectance, in percent, is calculated by integrating the spectral reflectance over the standard solar energy distribution. Solar transmittance is measured through the film while reflectance is generally measured relative to one side of the film. Opacity (%) is defined as 100% - Transmittance %.
  • the multilayer films have a water vapor transmission rate that is less than about 20 g/m /day measured by ASTM method F 1249.
  • the water vapor transmission rate is less than about 16 g/m 2 /day, more particularly less than about 13 g/m 2 /day and most particularly less than about 8 g/m 2 /day.
  • test specimen of 4 in. x 4 in. is tightly sealed using grease and an
  • the multilayer films have a light opacity is greater than about 80% measured by ASTM method E424. In particular the light opacity is greater than about 80, more particularly greater than about 85 and most particularly greater than about 95.
  • the multilayer films described herein have a dielectric break down strength (kV) of greater than 3 kV measured by ASTM method D3755, a solar reflectance of greater than 70% measured by ASTM method E424, a water vapor transmission of less than 20 g/m 2 /day measured by ASTM method F 1249 when the multilayer film has a thickness between about 0.7 mils and about 2.0 mils.
  • kV dielectric break down strength
  • the multilayer films have two sided properties. For example they may have a white, highly reflective surface on one side, and a dark color surface on the other side. In another example they may have a white, highly reflective surface on one side, and a dark, non-reflective surface on the other side. In another embodiment, they may have a white, highly reflective surface on one side and a dark, reflective surface on the other side.
  • Color on either side of the film may be indicated by measuring color using a standard method called the CIE L*a*b* color model.
  • a black side and a white side may be distinguished.
  • Fluoropolymers used in particular for outer layers of the multilayer films described herein, are unique materials because they exhibit an outstanding range of properties such as high transparency, good dielectric strength, high purity, chemical inertness, low coefficient of friction, high thermal stability, excellent weathering, and UV resistance. Fluoropolymers are frequently used in applications calling for high performance in which oftentimes the combination of the above properties is required. However, due to their low surface energy, fluoropolymers are difficult to wet by most if not all non fluoropolymer materials either liquids or solids.
  • the present invention provides novel multilayer films and methods to prepare the multilayer films by using suitable materials in conjunction with multiple deposition of layers followed by a further optional surface treatment.
  • the multilayer films of the invention include an outer layer comprising a modified fluoropolymer and an inner layer(s) described herein having the polymeric matrix/particulate film(s).
  • modified fluoropolymer is intended to include fluoropolymers that are either bulk modified for surface modified, or both.
  • Bulk fluoropolymer modification includes inclusion of polar functionality that is included or grafted into or onto the fluoropolymer backbone.
  • This type of modified fluoropolymer material can be used in combination with an unmodified fluoropolymer layer and a non fluoropolymer layer or as the base fluoropolymer layer.
  • maleic anhydride modified ETFE is suitable to adhere Nylon to an untreated ETFE substrate.
  • fluoropolymers are another way to provide a modified fluoropolymer useful in the present invention.
  • polar functionalities are attached to the fluoropolymer surface, rendering it easier to wet and provides opportunities for chemical bonding.
  • There are several methods to functionalize a fluoropolymer surface including chemical etch, physical- mechanical etch, plasma etch, corona treatment, chemical vapor deposition, or any combination thereof.
  • the chemical etch includes sodium ammonia or sodium naphthalene.
  • An exemplary physical -mechanical etch can include sandblasting and air abrasion with silica.
  • plasma etching includes reactive plasmas such as hydrogen, oxygen, acetylene, methane, and mixtures thereof with nitrogen, argon, and helium.
  • Corona treatment can include the reactive hydrocarbon vapors such as ketones, e.g., acetone, alcohols, p-chlorostyrene, acrylonitrile, propylene diamine, anhydrous ammonia, styrene sulfonic acid, carbon tetrachloride, tetraethylene pentamine, cyclohexyl amine, tetra isopropyl titanate, decyl amine, tetrahydrofuran, diethylene triamine, tertiary butyl amine, ethylene diamine, toluene-2,4-diisocyanate, glycidyl methacrylate, triethylene tetramine, hexane, triethyl amine, methyl alcohol, vinyl acetate, methylisoprop
  • surface activation can be accomplished by plasma or corona in the presence of an excited gas species.
  • surface activation can be accomplished by corona treatment in the presence of a solvent gas such as acetone.
  • the method has been found to provide strong interlayer adhesion between a modified fluoropolymer and a non fluoropolymer interface (or a second modified fluoropolymer). In one way, a fluoropolymer and a non fluoropolymer shape are each formed separately.
  • the fluoropolymer shape is surface treated by the treatment process described in US patents 3030290, 3255099, 3274089, 3274090, 3274091, 3275540, 3284331, 3291712, 3296011, 3391314, 3397132, 3485734, 3507763, 3676181, 4549921 and 6,726,979, the teachings of which are incorporated herein in their entirety for all purposes.
  • the resultant modified fluoropolymer and non fluoropolymer shapes are contacted together for example by heat lamination to form a multilayer film.
  • the multilayer film can be submitted to a UV radiation with wavelengths in the UVA; UVB and/or UVC range.
  • the surface of the fluoropolymer substrate is treated with a corona discharge where the electrode area was flooded with acetone, tetrahydrofuran methylethyl ketone, ethyl acetate, isopropyl acetate or propyl acetate vapors.
  • Corona discharge is produced by capacitative exchange of a gaseous medium which is present between two spaced electrodes, at least one of which is insulated from the gaseous medium by a dielectric barrier. Corona discharge is somewhat limited in origin to alternating currents because of its capacitative nature. It is a high voltage, low current phenomenon with voltages being typically measured in kilovolts and currents being typically measured in milliamperes. Corona discharges may be maintained over wide ranges of pressure and frequency. Pressures of from 0.2 to 10 atmospheres generally define the limits of corona discharge operation and atmospheric pressures generally are preferred. Frequencies ranging from 20 Hz to 100 MHz can conveniently be used: in particular ranges are from 500 Hz, especially 3000 Hz to 10 MHz.
  • corona discharge is used throughout this specification to denote both types of corona discharge, i.e. both electrodeless discharge and semi- corona discharge.
  • the fluoropolymer can be treated on both sides of the film/shape to increase the adhesion.
  • the material can then be placed on a non-siliconized release liner for storage. Materials that are C-treated last more than 1 year without significant loss of surface wettability, cementability and adhesion.
  • the surface of the fluoropolymer substrate is treated with a plasma.
  • plasma enhanced chemical vapor deposition (PECVD) is known in the art and refers to a process that deposits thin films from a gas state (vapor) to a solid state on a substrate. There are some chemical reactions involved in the process, which occur after creation of a plasma of the reacting gases.
  • the plasma is generally created by RF (AC) frequency or DC discharge between two electrodes where in between the substrate is placed and the space is filled with the reacting gases.
  • a plasma is any gas in which a significant percentage of the atoms or molecules are ionized, resulting in reactive ions, electrons, radicals and UV radiation.
  • At least one major surface of the fluoropolymer layer includes colloidal silica.
  • the colloidal silica typically is present in a solution at an amount to provide adhesion between the first layer and the second layer.
  • the colloidal silica is present in a solution that does not adversely impact the adhesive properties of the colloidal silica.
  • the solution may be aqueous.
  • a commercially available colloidal silica solution is available as Ludox®.
  • a binding solution may be used in addition to the colloidal silica solution. Any known binding solution that is compatible with the colloidal silica is envisioned.
  • a binding fluoropolymer such as FEP or PFA may be used.
  • the binding solution and colloidal silica are applied at a ratio of at least about 25/75 by weight, such as about 40/60 by weight, such as about 50/50 by weight, or even about 75/25 by weight.
  • the multilayer films of the invention can be used to protect, in particular, electronic components from moisture, weather, heat, radiation, physical damage and/or insulate the component.
  • optoelectronic components include, but are not limited to, packaging for crystalline-silicon based photovoltaic modules, amorphous silicon, CIGS, DSC, OPV or CdTe based thin photovoltaic modules, OLEDS, LEDs, LCDs, printed circuit boards, flexible displays and printed wiring boards.
  • any of the disclosed layers may contain common formulation additives including antioxidants, UV blockers, UV stabilizers, hindered amine stabilizers, curatives, crosslinkers, additional pigments, process aids and the like.
  • the present invention provides a multilayer film comprising:
  • a first layer comprising an aqueous or solvent castable fluoropolymer and a particulate filler material
  • a second layer having top and bottom sides, selected from a polyimide, a polycarbonate, titanium, steel, or aluminum; and
  • a third layer comprising an aqueous or solvent castable
  • the first layer is disposed on the top side and the third layer is disposed on the bottom side of the second layer.
  • fluoropolymers are each independently is selected from polytetrafluoroethylene, polyvinylidenefluoride, polychlorotrifluoroethlylene, polyvinylfluoride, tetrafluoroethylene/hexafluoropropylene/ethylene copolymer,
  • chlorotrifluoroethylene/hexafluoropropylene chlorotrifluoroethylene/ethylene copolymers, ethylene/trifluoroethylene copolymers, ethylene/tetrafluoroethylene copolymers, tetrafluoroethylene/hexafluoropropylene copolymers,
  • the fiuoropolymers are each independently selected from polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers (PFA), ethylene/tetrafluoroethylene copolymers (ETFE), fluorinated ethylene propylene copolymers (FEP), polyvinylidenefluoride (PVDF), polychlorotrifluoroethlylene (PCTFE) or mixtures thereof and the particulate filler of the fluoropolymer layers is titanium dioxide.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers
  • ETFE ethylene/tetrafluoroethylene copolymers
  • FEP fluorinated ethylene propylene copolymers
  • PVDF polyvinylidenefluoride
  • PCTFE polychlorotrifluoroethlylene
  • a multilayer film comprising:
  • a first layer comprising an aqueous or solvent castable fluoropolymer and a particulate filler material
  • a second layer having top and bottom sides selected from a polyimide, a polycarbonate, titanium, steel, or aluminum, wherein the first layer is disposed on one side of the second layer.
  • chlorotrifluoroethylene/hexafluoropropylene chlorotrifluoroethylene/ethylene copolymers, ethylene/trifluoroethylene copolymers, ethylene/tetrafluoroethylene copolymers, tetrafluoroethylene/hexafiuoropropylene copolymers,
  • microspheres glass fibers, titanium dioxide particles, barium titanate particles, calcium carbonate, zinc oxide, mica, clay, talc, iron oxide, carbon black, zinc sulfide, barium sulfate, zinc sulfite, cobalt aluminate blue, sodium alumino sulphosilicate, magnesium hydroxide, antimony trioxide, organophosphates, brominated compounds or mixtures thereof.
  • fluoropolymer is selected from polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers (PFA),
  • ETFE ethylene/tetrafluoroethylene copolymers
  • FEP fluorinated ethylene propylene copolymers
  • PVDF polyvinylidenefluoride
  • PCTFE PCTFE or mixtures thereof and the particulate filler of the fluoropolymer layer is titanium dioxide.
  • An optoelectronic device comprising:
  • a process to prepare a multilayer film comprising the steps:
  • casting composition onto a a polyimide, a polycarbonate, titanium, steel, or aluminum support, wherein the casting composition comprises:
  • chlorotrifluoroethylene/hexafiuoropropylene chlorotrifluoroethylene/ethylene copolymers, ethylene/trifluoroethylene copolymers, ethylene/tetrafluoroethylene copolymers, tetrafluoroethylene/hexafluoropropylene copolymers,
  • microspheres glass fibers, titanium dioxide particles, barium titanate particles, calcium carbonate, zinc oxide, mica, clay, talc, iron oxide, carbon black, zinc sulfide, barium sulfate, zinc sulfite, cobalt aluminate blue, sodium alumino sulphosilicate, magnesium hydroxide, antimony trioxide, organophosphates, brominated compounds or mixtures thereof.
  • ETFE ethylene/tetrafluoroethylene copolymers
  • FEP fluorinated ethylene propylene copolymers
  • PVDF polyvinylidenefluoride
  • PCTFE polychlorotrifluoroethlylene
  • first casting composition onto a top side of a a polyimide, a polycarbonate, titanium, steel, or aluminum support, wherein the first casting composition comprises:
  • a second casting composition onto a bottom side of the a polyimide, a polycarbonate, titanium, steel, or aluminum support, wherein the second casting composition comprises:
  • chlorotrifluoroethylene/hexafluoropropylene chlorotrifluoroethylene/ethylene copolymers, ethylene/trifluoroethylene copolymers, ethylene/tetrafluoroethylene copolymers, tetrafluoroethylene/hexafluoropropylene copolymers,
  • particulate fillers are each independently selected from silica particles, glass beads, glass microspheres, glass fibers, titanium dioxide particles, barium titanate particles, calcium carbonate, zinc oxide, mica, clay, talc, iron oxide, carbon black, zinc sulfide, barium sulfate, zinc sulfite, cobalt aluminate blue, sodium alumino sulphosilicate, magnesium hydroxide, antimony trioxide, organophosphates, brominated compounds or mixtures thereof.
  • fluoropolymers are each independently selected from polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers (PFA), ethylene/tetrafluoroethylene copolymers (ETFE), fluorinated ethylene propylene copolymers (FEP), polyvinylidenefluoride (PVDF), polychlorotrifluoroethlylene (PCTFE) or mixtures thereof and the particulate filler of the fiuoropolymer layer is titanium dioxide.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers
  • ETFE ethylene/tetrafluoroethylene copolymers
  • FEP fluorinated ethylene propylene copolymers
  • PVDF polyvinylidenefluoride
  • PCTFE polychlorotrifluoroethlylene
  • the multilayer films noted in above-identified paragraphs 1 through 34 provide certain advantages not generally found with other multilayer films.
  • inclusion of a polyimide layer acts as a good dielectric insulator as it has a nominal value of about 7000 vpm of dielectric breakdown strength.
  • the polyimide material also provides excellent thermal stability, good mechanical properties, radiation resistance and excellent chemical resistance.
  • the bond integrity between the two dissimilar materials provides an advantage over a laminated construct. For example, a coated multilayer film will not exhibit air gaps or bubbles between the layers which could cause delamination or create an electrical weak spot that might develop a partial discharge.
  • the combination of different fluoropolymers (on one or both sides of the substrate, e.g., polyimide, polycarbonate, aluminum, titanium or steel) can be tailored utilizing a multiple dip coating process in order to impart desired characteristics to the ultimate multilayer film.
  • particulates can be added to provide an opaque film that provides increased reflectivity and overall efficiency of a photovoltaic module.
  • the particulate material can be applied during the coating process as part of the fluoropolymer casting composition or afterward with a high temperature, highly pigmented coating such as those noted on Bar code label.
  • aqueous dispersion is prepared with organic or inorganic fillers, such as a white pigment (TiO 2 , ZnO or others described herein).
  • organic or inorganic fillers such as a white pigment (TiO 2 , ZnO or others described herein).
  • aqueous dispersion is prepared that includes a film forming polymeric material chosen from any of those described throughout the specification, and in particular, a fluoropolymer. This dispersion may contain the aqueous dispersion described in step (a).
  • step (c) A carrier belt can then be dipped through the dispersion described in step (b) such that a coating of the dispersion is formed on the carrier belt.
  • Step (c) to Step (f) can be repeated if necessary for casting multiple-layer films. At least one of the dispersion coatings will contain the dispersion described in steps (a) or (b).
  • the film is stripped off the carrier (such as a polyimide).
  • the carrier such as a polyimide
  • the multilayer film can be C-treated on one side or both sides or otherwise, so that the surface can be treated to be bondable.
  • TiO 2 slurry (DuPont R-900 TiO 2 , 60% solids,) and 1,400 deionized water for 30 minutes.
  • TiO 2 slurry (DuPont R-900 TiO 2 , 60% solids,) and 800 deionized water for 30 minutes. Add 24 g of modified surfactant (Ciba, 60% solids) to the mixture and mix for additional 10 minutes. Filter the solution through a 10 micron screen.
  • modified surfactant Ciba, 60% solids
  • TiO 2 slurry (DuPont R-900 TiO 2 , 60% solids,) and 550 deionized water for 30 minutes.
  • TiO 2 slurry (DuPont R-900 TiO 2 , 60% solids,) and 3,500 g deionized water for 30 minutes.
  • TiO 2 slurry (DuPont R-900 TiO 2 , 60% solids,) and 1,625 g deionized water for 30 minutes.
  • TiO 2 slurry (DuPont R-900 TiO 2 , 60% solids,) and 3,110 g deionized water for 30 minutes.
  • Tedlar PV2111 is a commercial film sold by DuP ont and is used in
  • PV backsheet lamination Film thickness is 1.0 mil.
  • Example 4 through 8 were tested as follows: Dielectric break down strength was measured according to ASTM D3755, Standard Test Method for Dielectric Breakdown Voltage and Dielectric Strength of Solid Electrical Insulating Materials Under Direct- Voltage Stress; Solar Reflectance was measured according to ASTM E424, Standard Test Methods for Solar Energy Transmittance and Reflectance (Terrestrial) of Sheet Materials; Water vapor transmission rate was measured according to ASTM Fl 249, Water Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated Infrared Sensor; and Opacity was measured according to ASTM method E424.

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Abstract

L’invention concerne un film rempli de particules, destiné à être utilisé comme feuille arrière pour une construction photovoltaïque.
EP10808470.8A 2009-08-10 2010-04-14 Feuille de protection remplie de fluoropolymères/particules Withdrawn EP2464515A4 (fr)

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US23269409P 2009-08-10 2009-08-10
US12/576,724 US20100092759A1 (en) 2008-10-13 2009-10-09 Fluoropolymer/particulate filled protective sheet
PCT/US2009/060354 WO2010045149A2 (fr) 2008-10-13 2009-10-12 Feuille de protection remplie de fluoropolymère/particules
PCT/US2010/031048 WO2011019415A1 (fr) 2009-08-10 2010-04-14 Feuille de protection remplie de fluoropolymères/particules

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CN102481767A (zh) 2012-05-30
JP2013505851A (ja) 2013-02-21
RU2508202C2 (ru) 2014-02-27
EP2464515A4 (fr) 2013-12-04
RU2012107591A (ru) 2013-09-20

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