WO2005081859A2 - Films multicouche resistant a l'ecoulement pulse - Google Patents

Films multicouche resistant a l'ecoulement pulse Download PDF

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Publication number
WO2005081859A2
WO2005081859A2 PCT/US2005/005172 US2005005172W WO2005081859A2 WO 2005081859 A2 WO2005081859 A2 WO 2005081859A2 US 2005005172 W US2005005172 W US 2005005172W WO 2005081859 A2 WO2005081859 A2 WO 2005081859A2
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WO
WIPO (PCT)
Prior art keywords
layer
polymer
film
multilayer film
fluoropolymer
Prior art date
Application number
PCT/US2005/005172
Other languages
English (en)
Other versions
WO2005081859A3 (fr
Inventor
Kevin G. Hetzler
Viktor Skatchkov
Xixian Zhou
JR. Gordon Vincent SHARPS
Original Assignee
Saint-Gobain Performance Plastics Corporation
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 US10/783,946 external-priority patent/US20050186431A1/en
Priority claimed from US10/901,456 external-priority patent/US7297391B2/en
Priority claimed from US10/901,910 external-priority patent/US7267865B2/en
Application filed by Saint-Gobain Performance Plastics Corporation filed Critical Saint-Gobain Performance Plastics Corporation
Priority to JP2006554224A priority Critical patent/JP4643595B2/ja
Priority to EP05723265A priority patent/EP1722972A4/fr
Publication of WO2005081859A2 publication Critical patent/WO2005081859A2/fr
Publication of WO2005081859A3 publication Critical patent/WO2005081859A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/17—Articles comprising two or more components, e.g. co-extruded layers the components having different colours
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/22—Articles comprising two or more components, e.g. co-extruded layers the components being layers with means connecting the layers, e.g. tie layers or undercuts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine

Definitions

  • TECHNICAL FIELD This invention, in general, relates to draw resonant resistant multilayer films, methods for manufacturing same, and articles including same.
  • fluorinated polymers exhibit a resistance to damage caused by exposure to chemicals, such a methyl ethyl ketone (MEK), a resistance to stains, and a resistance to damage caused by exposure to environmental conditions.
  • MEK methyl ethyl ketone
  • Such polymers have been used in applications, such as airplane and train cargo hold liners, vinyl siding surface treatments, and photovoltaic protective coverings.
  • processing of such films for use in these applications is difficult. Line speed in production is often limited by the appearance of draw resonance at relatively low line speeds, such as below 50 feet per minute.
  • a multilayer film includes a first layer and a second layer.
  • the first layer has a fluorinated polymer.
  • the second layer comprises at least about 70% by weight of a melt strain-hardening component and forms no more than about 30% by volume of the multilayer film.
  • a multilayer film has a first layer and a second layer.
  • the first layer includes greater than about 70% by weight of a non-polyolefin melt strain-hardening polymer.
  • the non-polyolefin melt-strain hardening polymer has an increasing tensile force in a draw ratio domain between draw ratios of about 5:1 and about 30:1.
  • the first layer forms no more than about 30% by volume of the multilayer film.
  • the second layer includes a second polymer.
  • the second polymer has a generally flat tensile force in the draw ratio domain.
  • a method of manufacturing a multilayer film includes extruding a first layer having greater than about 70% by weight of a non-polyolefin melt strain-hardening polymer.
  • the non-polyolefin melt-strain hardening polymer has an increasing tensile force in a draw ratio domain between draw ratios of about 5:1 and about 30:1.
  • the first layer forms no more than about 30% by volume of the multilayer film.
  • the method further includes extruding a second layer including a second polymer.
  • the second polymer has a generally flat tensile force in the draw ratio domain.
  • the disclosure is directed to a multilayer film comprising a first polymer layer and a second polymer layer.
  • the first polymer layer comprises a blend of a first fluoropolymer having a first average molecular weight and a second fluoropolymer having a second average molecular weight.
  • the first average molecular weight is greater than the second average molecular weight.
  • the disclosure is directed to a multilayer polymeric film comprising a first polymer layer and a second polymer layer.
  • the first polymer layer comprises a fluoropolymer having a bimodal molecular weight distribution.
  • the disclosure is directed to a multilayer film comprising a polymeric layer including a first fluoropolymer having a first average molecular weight and a second fluoropolymer having a second average molecular weight.
  • the first average molecular weight is greater than the second average molecular weight.
  • the multilayer film is adapted to be drawn at a linespeed of at least about 50 ft/min with a thickness variance no more than about 5%.
  • the disclosure is directed to a method of manufacturing a multilayer film.
  • the method includes extruding a first polymer layer and extruding a second polymer layer.
  • the first polymer layer comprises a blend of a first fluoropolymer having a first average molecular weight and a second fluoropolymer having a second average molecular weight.
  • the first average molecular weight is greater than the second average molecular weight.
  • a multilayer polymeric film comprises a first polymer layer and a second polymer layer.
  • the first polymer layer comprises a fluoropolymer having a bimodal molecular weight distribution of molecules and the first polymer layer has a melt phase tensile strength at least about 50% greater than the melt phase tensile strength of the second layer.
  • FIGS. 1, 2 and 3 depict exemplary embodiments of multilayer films.
  • FIGS.4 and 5 depict extensional velocity data for exemplary film components.
  • the use of the same reference symbols in different drawings indicates similar or identical items.
  • MOPES FOR CARRYING OUT THE INVENTION the disclosure is directed to a multilayer film.
  • the multilayer film typically has a layer including a material that is resistant to damage caused by chemical and/or environmental exposure.
  • the multilayer film also has a second layer comprising a melt strain- hardening material.
  • the multilayer film may further include additional layers including materials having desirable mechanical properties.
  • the disclosure is directed to a multilayer film typically including a layer having properties useful for the processing of the multilayer film and a layer having properties that provide mechanical properties in the resulting multilayer film.
  • the multilayer film may further include a layer that provides desirable surface properties. These surface properties may include chemical resistance or adhesiveness.
  • the multilayer film may be used in fluoropolymer processing.
  • FIG. 1 depicts an exemplary multilayer film.
  • the exemplary film 100 has at least two layers, 102 and 104.
  • Layer 102 comprises a damage resistant polymer that is resistant to damage by chemical and environmental exposure.
  • Layer 104 includes a polymer or polymer blend that provides processing characteristics and desired processing behaviors.
  • layer 104 may comprise a melt strain- hardening component that exhibits higher tensile force than the polymer of first layer in the melt phase.
  • layer 104 comprises a blend of fluoropolymers having different molecular weight.
  • layer 104 forms no more than about 30% by volume of the multilayer film 100.
  • layer 104 may form no more than about 10% by volume of the multilayer film, such as about 5% by volume of the multilayer film.
  • Layer 102 comprises a polymer component resistant to chemical and/or environmental exposure.
  • the material may have nonstick properties and be resistant to staining.
  • the polymer component may be a fluorinated polymer.
  • the polymer component may be a fluorinated polymer, such as a fluorine substituted olefin polymer comprising at least one monomer selected from the group consisting of vinylidene fluoride, vinylfluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, ethylene- chlorotrifluoroethylene, and mixtures of such fluoropolymers.
  • the fluoropolymer polymers include polyvinylidene fluoride (PVDF) and PVDF copolymers, such as vinylidene fluoride/hexafluoropropylene copolymer.
  • PVDF polyvinylidene fluoride
  • Many fluoropolymers are commercially available from suppliers in various grades. For example suppliers can supply multiple resins having nominally the same composition but different properties, such as different molecular weights to provide specific viscosity characteristics.
  • Exemplary PVDF polymers include PVDF 1010 and PVDF 21510 by Solvay and Kynar 760, Kynar 740 and Kynar 720 by Atofina.
  • the fluoropolymer component of the layer 102 can include a melt blend of multiple fluoropolymers in place of one such polymer. Alloys of PVDF homopolymer and PVDF copolymer may provide the film with improved elastic modulus and gloss reduction.
  • the polymer may consist essentially of fluorinated polymer and substantially no melt strain-hardening components.
  • Layer 104 may comprise a polymer component exhibiting melt strain hardening and/or higher multiphase tensile force at processing conditions. Melt strain hardening is exhibited when the melt- phase tensile force smoothed slope relative to a draw ratio domain is significantly positive for a polymeric component.
  • the melt strain hardening component is a non- polyolefin polymer that exhibits melt strain hardening at draw ratios greater than 10:1.
  • the melt strain hardening component is a non-polyolefin polymer component exhibiting a melt-phase tensile force smoothed slope in the melt phase of greater than about 0.03 cN between the draw ratios of 0 and greater than 30:1.
  • the melt-phase tensile force to draw ratio slope may be greater than about 0.04 cN, such as at least about 0.05cN or at least about 0.08 cN, in the draw ratio domain between about 10:1 to about 20:1 or about 10:1 to about 15:1.
  • the melt strain hardening component may exhibit increasing smoothed melt-phase tensile force in the draw ratio domain between about 5:1 and about 30:1, such as between about 10:1 and about 1 :1 or between about 20:1 and about 30:1.
  • the melt strain hardening polymer exhibits melt strain hardening in which the polymer exhibits a positive ratio of change in melt-phase tensile force to change in draw ratio in the draw ratio domain between a first draw ratio and a second draw ratio, wherein the damage resistant polymer may exhibit a melt plateau in the same domain.
  • the melt strain hardening polymer exhibits a melt-phase tensile force to draw ratio slope of greater than about 0.03 cN in the desired draw ratio domain.
  • the melt strain-hardening polymer may exhibit a slope of not less than about 0.03 cN over a specific draw ratio domain, such as not less than about 0.04 cN, not less than about 0.05 cN, or not less than about 0.08 cN, over a specific draw ratio domain.
  • a mechanical property or surface property polymer may exhibit a small slope or generally flat slope of less than about 0.03 cN, such as less than about 0.005 cN or substantially zero cN over the specific draw ratio domain.
  • the melt strain hardening polymer exhibits a positive ratio change in melt-phase tensile force to change in draw ratio in the draw ratio domain of about 10:1 and about 15: 1 during processing at about 230°C.
  • the damage resistant polymer exhibits a generally flat slope in the same draw ratio domain under the same processing conditions.
  • the melt strain hardening component may exhibit a greater melt-phase tensile force to draw ratio slope than the mechanical or surface components over a draw ratio domain, such as at least about 30%, at least about 50%, at least about 80%, at least about 100%, or at least about 300%. greater slope.
  • the melt strain hardening polymer may, for example, be a non-polyolefin polymer, such as an acrylic polymer, and not a polyethylene or polypropylene.
  • the melt strain hardening polymer may be a high average molecular weight fluoropolymer.
  • the non-polyolefin polymer may be a branched polymer.
  • the non-polyolefin polymer may be a linear polymer.
  • the acrylic polymer may be an alkyl group having from 1-4 carbon atoms, a glycidyl group or a hydroxyalkyl group having from 1-4 carbon atoms.
  • Acrylic polymers include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyglycidyl methacrylate, polyhydroxyethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyglycidyl acrylate, polyhydroxyethyl acrylate and mixtures thereof.
  • the acrylic polymer may, for example, be an impact grade or impact modified acrylic.
  • Impact-modified acrylic polymers generally comprise a copolymer of monomers of acrylic monomers with an effective amount of suitable comonomer or graft moiety to produce the desired elastic modulus and impact resistance.
  • An acrylic elastomer sometimes referred to as acrylate rubber, polyacrylate rubber, polyacrylic elastomer or "ACM” and which is a composition based on a mixture of a polyacrylate and poly ethacrylate, a polyacrylate and ethylene methacrylate copolymer (“EMAC”), [such as Chevron Chemicals EMAC 2260] or a polyacrylate and ethylene butylacrylate (“EBAC”) can be used.
  • EBAC ethylene methacrylate copolymer
  • thermoplastic impact-modified acrylic polymer can be a blend of a clear glassy acrylic polymer, such as a plastic copolymer of ethylene and a carboxylic acid compound selected from acrylic acid, methacrylic acid and mixtures thereof, with elastomeric components, for example.
  • a clear glassy acrylic polymer such as a plastic copolymer of ethylene and a carboxylic acid compound selected from acrylic acid, methacrylic acid and mixtures thereof, with elastomeric components, for example.
  • the impact-modified acrylic polymer generally includes fine particles of the elastomer dispersed uniformly in the plastic copolymer.
  • the impact grade acrylic may comprise transparent toughened thermoplastic blends prepared by blending 10 to 99 weight percent of a block copolymer; 0.1 to 1 weight percent of particulate rubber having a particle size from 0.1 to 10 microns; and the balance a clear glassy polymer.
  • Another suitable technique for making impact-modified acrylic polymer employs the use of a so-called "core/shell" product, such as Atofina DR-101 resin. These generally are polymer particles that have a central core of one polymer surrounded by a shell of another polymer.
  • the core can be either the plastic or elastomer component and the shell will be the opposite, i.e., elastomer or plastic component.
  • the core/shell particles are fed to a melt mixing apparatus, such as a melt extruder in which the core and shell domains are blended in the melt phase to form a homogeneous blend on a much smaller scale and a film is formed from the extrudate of this homogeneous blend.
  • the melt strain hardening material may be a linear impact modified acrylic.
  • the melt strain hardening acrylic may be a branched impact modified acrylic.
  • linear acrylic polymers that are not impact modified, such as those typically used in adhesive layers, are not suitable.
  • an acrylic exemplifying melt strain hardening behavior in the desired draw ratio domain is suitable.
  • the layer 104 comprises a blend of melt strain-hardening polymer and other components.
  • the layer 104 may comprise greater than about 70% of the melt strain-hardening component, such as, impact grade acrylic.
  • the layer may comprise greater than about 75% impact grade acrylic or greater than about 80% impact grade acrylic.
  • Layer 104 may also include other components, such as the damage resistant polymer.
  • the layer 104 may include a polymer blend having impact grade acrylic and no more than about 25% PVDF, PVDF copolymer or blends thereof by weight.
  • the blend may include no more than about 20% PVDF by weight, such as no more than about 10% PVDF by weight.
  • layer 104 consists essentially of the melt-strain hardening component.
  • the melt strain hardening components or higher melt-phase tensile force component may include a higher average molecular weight polymer.
  • layer 104 may include a blend of fluoropolymers that includes a low to medium average molecular weight fluoropolymer and a high average molecular weight fluoropolymer that exhibits melt strain hardening and higher melt-phase tensile force at a given draw ratio.
  • the lower average molecular weight polymer may include PVDF having a weight average molecular weight not greater than about 200 kg/mol, such as not greater than about 190 kg/mol or not greater than about 180 kg/mole.
  • the higher average molecular weight polymer may include PVDF having a molecular weight at least about 200 kg/mole, such as at least about 250 kg/mole, at least about 285 kg/mole, or at least about 365 kg/mole.
  • the average molecular weight may be determined using number average molecular weight and z-average molecular weight methods.
  • the higher average molecular weight polymer may have a molecular weight distribution that peaks at a molecular weight at least about 25% higher than the peak of the molecular weight distribution of the lower average molecular weight polymer.
  • the higher average molecular weight polymer distribution peak may be at least about 50%, at least about 60%, at least about 80% or at least about 90% higher than the peak of the lower average molecular weight polymer distribution.
  • the fluoropolymers are derived from the same monomer, the resulting blend produces a bimodal molecular weight distribution of polymer molecules.
  • Exemplary fluoropolymers include fluorine substituted olefin polymers and polymers comprising at least one monomer selected from the group consisting of vinylidene fluoride, vinylfluoride, tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylele, ethylene-chlorotrifluoroethylene, and mixtures of such fluoropolymers.
  • the fluoropolymer polymers include polyvinylidene fluoride (PVDF) and PVDF copolymers, such as vinylidene fluoride/hexafluoropropylene copolymer. Many fluoropolymers are commercially available from suppliers in various grades.
  • exemplary PVDF polymers include PVDF 1010 and PVDF 21510 by Solvay Solexis.
  • Other examples include Kynar 720, Kynar 740, and Kynar 760 by Atofina. Kynar 760 has a higher average molecular weight than Kynar 720 and Kynar 740.
  • the polymer component of the layer 104 may include a melt blend of multiple fluoropolymers in place of one such polymer. Alloys of PVDF homopolymer and PVDF copolymer may provide the film with improved elastic modulus and gloss reduction.
  • the polymer may consist essentially of fluorinated polymer.
  • layer 104 includes a blend of the higher average molecular weight polymer and the low or moderate average molecular weight polymer.
  • the blend includes at least about 60% by weight of the high average molecular weight polymer.
  • the blend may include at least about 70%, at least about 75%, at least about 80%), at least about 85%, at least about 90%, or as high as 100% by weight of the high average molecular weight polymer.
  • the polymer blend may include not more than about 40% by weight of the low or moderate average molecular weight polymers.
  • the polymer blend may include not more than about 30%, not more than about 25%, not more than about 20%, not more than about 15% or not more than about 10% of the low or moderate average molecular weight polymer.
  • the high average molecular weight polymer is Kynar 760
  • the moderate average molecular weight polymer is Kynar 740
  • the low average molecular weight polymer is Kynar 720.
  • layers 102 and 104 may include inorganic fillers, organic fillers, antioxidants, UV additives, flame retardants, antidegradation additives, and adjuvants, among others.
  • layer 102 may include minor but significant fractions of antidegradation additives and adjuvants.
  • the inorganic filler may, for example, include titanium dioxide, zinc oxide, iron oxide, calcium carbonate, carbon black, color pigments and clays.
  • FIG. 2 depicts another exemplary embodiment of a multilayer film.
  • the multilayer film 200 includes layers 202, 204, and 206.
  • Layer 202 may, for example, include a damage resistant polymer.
  • layer 202 may be an adhesive layer.
  • Layer 204 may provide the desired processing properties and behaviors in the melt phase and may include polymers or polymer blends that exhibit the desired processing behaviors.
  • layer 204 may include melt strain hardening polymers or higher melt-phase tensile force polymers that exhibit desired processing behaviors within specified draw ratio domains or at specific draw ratios.
  • layer 204 may include acrylic or acrylic blends.
  • layer 204 may include a high average molecular weight polymer or a bimodal molecular weight distribution of molecules formed from a common monomer.
  • Layer 206 may include a polymer component exhibiting a desirable mechanical property.
  • layer 206 includes a fluoropolymer/acrylic blend.
  • layer 204 and layer 206 may be interchanged.
  • layer 202 comprises no more than about 30% by volume of the multilayer film.
  • layer 202 may comprise no more than about 20% by volume, no more than about 10% by volume or no more than about 5% by volume of the multilayer film.
  • Layer 204 may comprises no more than about 30% by volume of the multilayer film.
  • layer 204 may comprise no more than about 20%), no more than about 10% of the multilayer film or no more than about 5% of the multilayer film.
  • Layer 206 may comprise greater than about 40% by volume of the multilayer film.
  • layer 206 may comprise greater than about 60% by volume, greater than about 80% by volume, or at least about 90% by volume of the multilayer film.
  • Layer 202 may comprise blends of damage resistant polymers, other polymers, and inorganic fillers.
  • layer 202 may include a damage resistant polymer, such as a fluorinated polymer, such as PVDF.
  • layer 202 may comprise an adhesive component, other polymers, and inorganic fillers.
  • Layer 204 may comprise a melt strain-hardening component and may be a blend including other polymers, such as the damage resistant component.
  • layer 204 may include a blend of fluorinated polymers including a high average molecular weight, high tensile force fluorinated polymer.
  • Layer 206 may comprise a component with desirable mechanical properties, which are manifested in the resulting multilayer film. Such mechanical properties include elongation, flexibility and drape. These properties may, for example, be similar to the properties of fluoropolymer film.
  • layer 206 comprises the damage resistant component in a blend of other components.
  • Layer 206 may comprise a fluorinated polymer. In a particular embodiment, layer 206 comprises greater than about 20% by weight of a fluorinated polymer, such as those fluorinated polymers listed above, such as PVDF.
  • Layer 206 may also include inorganic fillers, organic fillers, antioxidants, UV additives, flame retardants, antidegradation additives, adjuvants, the melt strain- hardening component, such as impact grade acrylic, and other acrylics, among others.
  • layer 206 may include minor but significant fractions of antidegradation additives and adjuvants.
  • the inorganic filler may, for example, be titanium dioxide, zinc oxide, iron oxide, calcium carbonate, carbon black, color pigments and clays.
  • layer 206 comprises greater than about 30% by weight PVDF, no more than about 35% impact grade acrylic, an inorganic filler, and antidegradation additive.
  • Layers should have adequate compatibility with the adjacent layers and the substrate compositions to adhere well to both.
  • layers 206 and 204 may be reversed in order.
  • layer 202 may be absent or substituted with a layer identical to layer 206.
  • FIG. 3 depicts an exemplary embodiment of a multilayer film.
  • the multilayer film includes five layers, 302, 304, 306, 308, and 310.
  • Layers 302 and 310 may, for example, comprise damage resistant polymer components, such as fluorinated polymers, such as PVDF, or an adhesive polymer, such as an acrylic.
  • Layers 304 and 308 may, for example, comprise a melt strain-hardening component, such as impact grade acrylic polymers or may, for example, comprise high molecular weight fluoropolymers.
  • Layer 306 may, for example, comprise a polymer with desirable mechanical properties and may, for example, be a blend of the fluorinated polymer and acrylic.
  • layers 304 and 308 may comprise a polymer with desirable mechanical properties and layer 306 may comprise a melt strain-hardening component.
  • the film structure may be A/C/B/C/A where each letter represents a different material extruded from a unique extruder.
  • Layer A may, for example, be a 100% Solvay PVDF 1010 and each layer A may form about 10% by volume of the multilayer film.
  • Layer B may be a PVDF/ acrylic blend comprising greater than about 60% by weight PVDF homopolymer and/ or copolymer and not more than about 40% acrylic by weight. Layer B may form greater than about 40%) by volume of the multilayer film.
  • Layers C may be formed of Atofina impact grade acrylic DR101 and each of the C layers may make up less than about 10% by volume of the multilayer film, such as about 5% by volume.
  • the C layers may be formed of a blend of a higher average molecular weight, high melt-phase tensile force component and a lower average molecular weight component, such as a blend of PVDF polymers.
  • the film structure may be A/C/B/C/D where each letter represents a different material extruded from a unique extruder.
  • Layer A may, for example, be a 100%) Solvay PVDF 1010 and may form about 10%> by volume of the multilayer film.
  • Layer B may be a PVDF/acrylic blend comprising greater than about 60% by weight PVDF and not more than about 40%) acrylic by weight. Layer B may form greater than about 40% by volume of the multilayer film.
  • Layers C may be formed of Atofina impact grade acrylic DR101, each of the C layers making up less than about 10%, such as about 5% by volume of the multilayer film.
  • the C layers may be formed of a blend of a high average molecular weight, high melt- phase tensile force component and a lower average molecular weight component, such as a blend of PVDF polymers.
  • Each of the C layers may comprise about 5% by volume of the total film volume.
  • the film structure may be A/B/C wherein layer A is 100% Solvay PVDF 1010, comprising about 5-10% by volume of the film.
  • Layer B is a PVDF and acrylic blend comprising about 30-80 wt% PVDF, such as about 60 wt% PVDF, and about 40 wt% acrylic. Layer B comprises about 80-90%) by volume of the film.
  • Another exemplary structure may be an A/B or an A B/A structure.
  • layer A may include a melt strain hardening polymer and fluorinated polymer, such as a PVDF/acrylic blend having 70%) impact modified or melt strain hardening acrylic
  • layer B may include a polymer blend of PVDF and acrylic polymers including at least about 70% PVDF.
  • layer A includes a non-melt strain hardening fluoropolymer
  • layer B includes a blend of PVDF and acrylic including at least about 70% melt strain hardening polymer or bimodal molecular weight fluoropolymer.
  • a further exemplary embodiment includes at least 3 layers extruded via 3 extruders.
  • a first layer includes a fluoropolymer.
  • a second layer includes a melt strain hardening component and a third layer is an adhesive layer comprising greater than about 55 wt% adhesive acrylic, such as greater than about 70 wt% acrylic.
  • Such multilayer films may be manufactured by co-extruding the foregoing embodiments.
  • the co-extruded film may be drawn at linespeeds of at least about 50 ft/min, such as at least about 60 ft/min or at least about 100 ft/min.
  • the resulting multilayer film has a thickness variance of not more than about 5%, such as not more than about 4%, not more than about 3%, not more than about 2%, or not more than about 1%, and is substantially free of draw resonance.
  • the thickness may statistically vary from the average thickness by not more than about 5% of the average thickness.
  • FIG. 4 characterizes the behavior of several materials, including damage resistant polymers

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film multicouche qui comprend des première et seconde couches. La première couche comporte un polymère fluoré. La seconde couche renferme une composante de durcissement par fusion et ne représente pas plus d'environ 30 % du film multicouche, en volume.
PCT/US2005/005172 2004-02-20 2005-02-18 Films multicouche resistant a l'ecoulement pulse WO2005081859A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2006554224A JP4643595B2 (ja) 2004-02-20 2005-02-18 引取共振抵抗多層フィルム
EP05723265A EP1722972A4 (fr) 2004-02-20 2005-02-18 Films multicouche resistant a l'ecoulement pulse

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US10/783,946 US20050186431A1 (en) 2004-02-20 2004-02-20 Draw resonant resistant multilayer films
US10/783,946 2004-02-20
US10/901,456 2004-07-28
US10/901,456 US7297391B2 (en) 2004-02-20 2004-07-28 Draw resonance resistant multilayer films
US10/901,910 2004-07-29
US10/901,910 US7267865B2 (en) 2004-02-20 2004-07-29 Draw resonant resistant multilayer films

Publications (2)

Publication Number Publication Date
WO2005081859A2 true WO2005081859A2 (fr) 2005-09-09
WO2005081859A3 WO2005081859A3 (fr) 2005-12-22

Family

ID=34916371

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/005172 WO2005081859A2 (fr) 2004-02-20 2005-02-18 Films multicouche resistant a l'ecoulement pulse

Country Status (4)

Country Link
EP (1) EP1722972A4 (fr)
JP (1) JP4643595B2 (fr)
KR (1) KR100900159B1 (fr)
WO (1) WO2005081859A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2412523A1 (fr) 2006-01-25 2012-02-01 Arkema France Film flexible à base de polymere fluoré
US8603628B2 (en) 2007-04-30 2013-12-10 Saint-Gobain Performance Plastics Corporation Turbine blade protective barrier
EP2237950B2 (fr) † 2008-02-06 2016-01-13 Arkema France Film tricouche pour cellule photovoltaïque

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US3253060A (en) * 1964-08-03 1966-05-24 Pennsalt Chemicals Corp Molding compositions comprising polyvinylidene fluoride and polymethyl methacrylate
US4076929A (en) * 1975-10-30 1978-02-28 Pennwalt Corporation Vinylidene fluoride polymer having improved melt flow properties
IT1119928B (it) * 1978-09-25 1986-03-19 Ugine Kuhlmann Materiale composito di polifluoruro di vinilidene e di polimero termoplastico incompatibile e procedimento per la sua fabbricazione
FR2436676A1 (fr) * 1978-09-25 1980-04-18 Ugine Kuhlmann Materiau composite polyfluorure de vinylidene et thermoplastique non compatible et son procede d'obtention par coextrusion
FR2477463A1 (fr) * 1980-03-07 1981-09-11 Ugine Kuhlmann Procede de fabrication d'un composite polyfluorure de vinylidene et polymere non compatible par coextrusion-moulage
JPH0671785B2 (ja) * 1984-06-23 1994-09-14 電気化学工業株式会社 フッ化ビニリデン樹脂系複合フイルムの製造方法
JP3328330B2 (ja) * 1992-09-02 2002-09-24 呉羽化学工業株式会社 フッ化ビニリデン樹脂フィルム、その用途およびその製造方法
FR2731943B1 (fr) * 1995-03-24 1997-07-18 Atochem Elf Sa Materiau complexe a proprietes ameliorees constitue de polyfluorure de vinylidene et d'un thermoplastique non compatible
US6444311B1 (en) * 1999-10-19 2002-09-03 Saint-Gobain Performance Plastics Corporation Impact resistant protective multilayer film
US6716945B2 (en) * 2000-05-19 2004-04-06 North Carolina State University Multimodal fluoropolymers and methods of making the same
US6489420B1 (en) * 2000-06-27 2002-12-03 Dyneon Llc Fluoropolymers with improved characteristics
DE60129354T2 (de) * 2000-12-01 2008-03-13 3M Innovative Properties Co., Saint Paul Zusammensetzung zur herstellung eines fluorelastomers
US6916871B2 (en) 2001-10-31 2005-07-12 3M Innovative Properties Company Composition and method for making a fluoroelastomer

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2412523A1 (fr) 2006-01-25 2012-02-01 Arkema France Film flexible à base de polymere fluoré
US8603628B2 (en) 2007-04-30 2013-12-10 Saint-Gobain Performance Plastics Corporation Turbine blade protective barrier
EP2237950B2 (fr) † 2008-02-06 2016-01-13 Arkema France Film tricouche pour cellule photovoltaïque

Also Published As

Publication number Publication date
WO2005081859A3 (fr) 2005-12-22
EP1722972A4 (fr) 2010-12-22
JP2007524532A (ja) 2007-08-30
KR100900159B1 (ko) 2009-06-02
EP1722972A2 (fr) 2006-11-22
KR20070007109A (ko) 2007-01-12
JP4643595B2 (ja) 2011-03-02

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