EP1879734A1 - Structure d'un film de protection multi-couches - Google Patents

Structure d'un film de protection multi-couches

Info

Publication number
EP1879734A1
EP1879734A1 EP05737535A EP05737535A EP1879734A1 EP 1879734 A1 EP1879734 A1 EP 1879734A1 EP 05737535 A EP05737535 A EP 05737535A EP 05737535 A EP05737535 A EP 05737535A EP 1879734 A1 EP1879734 A1 EP 1879734A1
Authority
EP
European Patent Office
Prior art keywords
layer
resin
laminate film
containing layer
polyetheramine
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Withdrawn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
EP05737535A
Other languages
German (de)
English (en)
Other versions
EP1879734A4 (fr
Inventor
Tien-Kuei Su
Keunsuk P. Chang
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.)
Toray Plastics America Inc
Original Assignee
Toray Plastics America Inc
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
Application filed by Toray Plastics America Inc filed Critical Toray Plastics America Inc
Publication of EP1879734A1 publication Critical patent/EP1879734A1/fr
Publication of EP1879734A4 publication Critical patent/EP1879734A4/fr
Withdrawn legal-status Critical Current

Links

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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0207—Particles made of materials belonging to B32B25/00
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/025—Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/70—Other properties
    • B32B2307/746—Slipping, anti-blocking, low friction
    • 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
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • This invention relates to a biaxially oriented film comprising a polyolefin or polyester layer, a layer of epoxy-amine polymer contiguously formed on one side of the polyolefin or polyester layer, and an optional contiguous polyolefin or copolyester layer formed on the polyolefin or polyester layer side opposite the epoxy-amine polymer.
  • This invention exhibits exceptional gas barrier characteristics over a polyolefin or polyester film alone, rivals the gas barrier of EVOH-containing polyolefin films without the need for adhesion promoters or tie-layers, and the epoxy-amine layer exhibits a high surface energy suitable for printing, metallizing, adhesive laminations and coatings without the need for additional discharge-treatment to provide this functionality.
  • This invention is also contemplated as a basefilm for metallizing wherein the epoxy-amine polymer layer serves as a metal adhesion layer.
  • Ethylene vinyl alcohol copolymers show excellent oxygen and flavor barrier properties at low humidity, typically in the range of 0 to 60%. However, its barrier property deteriorates dramatically under high humidity conditions when the humidity is in the range of 75 to 90%. In fact, due to the polar nature of EVOH, such films made with EVOH generally exhibit poor moisture barrier. Therefore, EVOH is typically laminated with polyolefins on both sides to provide barrier properties for practical packaging applications in order to protect the EVOH from humidity effects. Moreover, EVOH is relatively brittle and difficult to stretch, tending to form cracks during stretching in biaxial orientation processes, for example, due to its crystalline nature.
  • EVOH grades that are suitable for stretching are typically limited to 48 mole % ethylene content.
  • Lower ethylene content EVOH grades which often exhibit better gas barrier properties - are unusable in orientation processes due to the brittle nature of these materials and will crack or fracture under the stretching forces involved.
  • Another disadvantage of EVOH materials is that they require the use of costly adhesion promoters and/or tie-layer resins in order for them to bond adequately to polyolefin or polyester substrates. Without such tie resins, EVOH materials or related materials like polyviny alcohol (PVOH), tend to peel off easily from the polyolefin or polyester substrate resulting in loss of barrier properties and poor appearance.
  • PVOH polyviny alcohol
  • U.S. Patent 4,650,721 describes a process to improve the otherwise poor bonding of EVOH or PVOH in oriented films through the use of tie resins, namely maleic anhydride acid grafted polyolefins.
  • U.S. Patent 5,153,074 teach a metallized oriented multilayer film design of EVOH and blends of a maleic anhydride modified propylene homopolymer or copolymer as the substrate to which the EVOH is contiguously adhered.
  • the EVOH layer is used as a metallizing surface for the vapor deposition of aluminum. Again, the use of an adhesion promoting material is essential in this invention. It is known that EVOH is relatively hard to stretch compared to polypropylene. Consequently, only limited grades of EVOH like the one with 48 mole % of ethylene can be co-processed with OPP without forming any surface defects. Using lower ethylene mole % EVOH (e.g. 44% or 38%) in biaxial orientation causes surface defects like stress fractures or process issues like film breaks due to the higher crystallinity of the EVOH.
  • U.S. Patent 5,175,054 teaches the solution coating of a mixture of solution-grade EVOH or PVOH containing about 80% of vinyl alcohol and aqueous dispersion-grade of the ionomer of the alkali salt of ethylene-methacrylic acid copolymer. This coating is applied to an oriented polymer substrate and subsequently metallized.
  • the ionomer acts as an adhesion promoter to assure adequate adhesion of the EVOH or PVOH to the polyolefin (polypropylene) substrate which is otherwise poor without the presence of the ionomer.
  • This invention seeks to avoid some of the disadvantages of EVOH containing laminate films.
  • One embodiment is a laminate film comprising a polyetheramine resin-containing layer on a first polyolefin resin-containing layer.
  • the polyetheramine resin- containing layer is directly on the first polyolefin resin-containing layer and there is no tie layer between the polyetheramine resin-containing layer and the first polyolefin resin- containing layer.
  • the laminate could further comprise a second polyolefin resin- containing layer on the first polyolefin resin-containing layer.
  • the polyetheramine resin is a copolymer of bis-phenol A diglycidyl ether (BADGE) and resorcinol diglycidyl ether (RDGE) with ethanolamine while the first polyolefin resin- containing layer comprises a propylene homopolymer.
  • the second polyolefin resin-containing layer comprises a heat sealable polyolefin selected from the group consisting of polypropylene copolymers, terpolymers, polyethylene and combinations thereof.
  • the heat sealable layer comprises an antiblock component selected from the group consisting of amorphous silicas, aluminosilicates, sodium calcium aluminum silicate, a crosslinked silicone polymer, and polymethylmethacrylate.
  • the first polyolefin resin-containing layer is a discharge-treated polyolefin resin-containing layer while the second polyolefin resin-containing layer comprises a winding layer comprising a crystalline polypropylene and an inorganic antiblocking agent.
  • the second polyolefin resin-containing layer comprises a winding layer comprising a matte layer of a block copolymer blend of polypropylene and one or more other polymers, the matte layer having a roughened surface while the winding layer is a discharge treated winding layer having a surface for lamination or coating with adhesives or inks.
  • the winding layer comprises an antiblock component selected from the group consisting of amorphous silicas, aluminosilicates, sodium calcium aluminum silicate, a crosslinked silicone polymer, and polymethylmethacrylate.
  • the polyetheramine resin-containing layer is a discharge-treated polyetheramine resin- containing layer.
  • the discharge-treated polyetheramine resin-containing layer has a discharge-treated surface formed in an atmosphere of CO 2 and N 2 .
  • the laminate film could further comprise a vacuum deposited metal layer on the polyetheramine resin-containing layer.
  • the metal layer has a thickness of about 5 to 100 nm, has an optical density of about 1.5 to 5.0, and comprises aluminum.
  • the laminate film is an extruded laminate film.
  • Another embodiment is a laminate film comprising a polyetheramine resin- containing layer on a polyethylene terephthalate resin.
  • the polyetheramine resin-containing layer is directly on the first polyethylene terephthalate resin-containing layer with no tie layer between the polyetheramine resin-containing layer and the first polyethylene terephthalate resin-containing layer.
  • the laminate film could further comprise a second polyethylene terephthalate resin-containing layer or an amorphous copolyester layer on the first polyethylene terephthalate resin-containing layer.
  • the second polyethylene terephthalate resin containing layer or the amorphous copolyester layer comprises an antiblock component selected from the group consisting of amorphous silicas, aluminosilicates, sodium calcium aluminum silicate, a crosslinked silicone polymer and polymethylmethacrylate.
  • the polyetheramine resin-containing layer is a discharge-treated polyetheramine resin-containing layer.
  • the discharge-treated polyetheramine resin-containing layer has a discharge- treated surface formed in an atmosphere of N 2 and CO 2 .
  • the laminate film could further comprise a vacuum-deposited metal layer on the polyetheramine resin-containing layer.
  • the metal layer has a thickness of about 5 - l OOnm, an optical density of 1.5- 5.0, and comprises aluminum.
  • Another embodiment is a method for flexible packaging comprising obtaining a laminate film comprising a polyetheramine resin-containing layer on a first polyolefin resin-containing layer and surrounding a product by the laminate film.
  • Another embodiment is a method for flexible packaging comprising obtaining a laminate film comprising a polyetheramine resin-containing layer on a polyethylene terephthalate resin- containing layer and surrounding a product by the laminate film.
  • the product is a food product.
  • this invention provides biaxially oriented polyolefin or polyester multi-layer films with a skin of polyetheramine to enhance barrier and printing properties for flexible packaging purposes.
  • Another embodiment provides a metallized biaxially oriented polyolefin or polyester multi-layer barrier films.
  • An additional embodiment provides laminate structures of polyolefin layers and polyetheramine layers for barrier applications in flexible packaging.
  • Another embodiment is a laminate film comprising a polyetheramine resin- containing layer on a mixed resin layer comprising a polyethylene terephthalate resin and a polyolefin resin, wherein preferably the polyolefin resin is a polypropylene but could also be a heat sealable polyolefin such as polypropylene copolymers, terpolymers, polyethylene and combinations thereof.
  • the mixed resin layer could further comprise a compatibilizer that provides compatibility between the polyethylene terephthalate resin and the polyolefin resin.
  • the compatibilizer could be a polymer having polyolefin molecules and polyethylene terephthalate molecules within the polymer, preferably at the two ends of the polymer chain.
  • the mixed resin layer could further comprise an antiblock component such as amorphous silicas, aluminosilicates, sodium calcium aluminum silicate, a crosslinked silicone polymer and polymethylmethacrylate.
  • This invention provides a method to improve the barrier of biaxially oriented films and metallized films resulting in a high barrier packaging film with excellent gas barrier properties.
  • An embodiment of the invention helps solve the problem associated with the prior art of surface defects, processability issues, and limitations of using lower ethylene content EVOH in biaxial orientation. Additionally, this invention allows the use of more economical laminate film structures by avoiding the use of intermediate tie resin layers or blends of tie resins in conjunction with lower cost substrates.
  • the laminate film of an embodiment of the invention includes at least a 2-layer laminate film wherein the core layer or substrate layer is an oriented film, either monoaxially or biaxially, the preferred being biaxially oriented.
  • This core or substrate layer may be comprised of polyolefins such as propylene homopolymer, ethylene homopolymer, copolymers of propylene and ethylene, copolymers of butylene and propylene, terpolymers of ethylene, propylene and butylene, or blends thereof; or polyethylene terephthalate.
  • a skin layer of polyetheramine is applied contiguously upon at least one of the surfaces of the substrate layer.
  • the method of applying the polyetheramine layer to the substrate layer can be of various means well known in the art, such as solution coating an aqueous solution of the polyetheramine resin onto the substrate layer by means of a coating roll (e.g. gravure roll) or other coating means, and drying of the coating.
  • a coating roll e.g. gravure roll
  • Another method is to employ extrusion coating of the polyetheramine onto the substrate whereby a molten stream of the polyetheramine is coated onto the substrate by means of a die.
  • Another method is to coextrude the polyetheramine along with the substrate or core layer through a compositing die whereupon the molten multilayer film structure is quenched upon a chilled casting roll system or casting roll and water bath system.
  • polyetheramine layer is sandwiched between two outer film substrates (which may be multilayer structures themselves).
  • the outer film substrates may be the same in composition or not; the polyetheramine in this case can be thought of as a laminating adhesive adhering the two outer substrates together.
  • these examples can also be metallized via vapor-deposition, preferably a vapor-deposited aluminum layer, with at least an optical density of about 1.5, preferably with an optical density of about 2.0 to 4.0, and even more preferably between 2.3 and 3.2.
  • an additional layer of a heat sealable surface or a winding surface containing antiblock and/or slip additives for good machinability and low coefficient of friction (COF) can be disposed on the polyolefin or polyester substrate layer, opposite the side with the polyetheramine layer.
  • this third layer is used as a winding surface, its surface may also be modified with a discharge treatment to make it suitable for laminating or converter applied adhesives and inks.
  • tie-layer or adhesion promoting materials such as anhydride- grafted polyolefins are required to bond the polar layer to such a polyolefin or amorphous copolyesters or primers to a polyethylene terephthalate film substrate.
  • Adequate adhesion of the polyetheramine is found without the need of such intermediate adhesion promoting layers or tie resins.
  • product cost can be reduced as expensive tie-layers and capital for specialty multi-layer compositing dies can be avoided.
  • polyetheramine because of the amorphous nature of polyetheramine, biaxial orientation of a layer of polyetheramine upon the polyolefin or polyester substrate is easily achieved, with no attendant cracking or peeling of the polyetheramine under stretching forces and temperatures.
  • a layer's surface energy is sufficiently high enough that no discharge- treatment method is required post-film-forming. This inherently high surface energy makes it readily suitable as a printing, metallizing, coating, or laminating surface.
  • polyetheramine is sensitive to humidity in that high humidity conditions can negatively impact its gas barrier properties.
  • polyetheramine should be protected against humidity effects if used as part of a multilayer film or laminate, whereby the polyetheramine layer should be buried between other layers or by a metal coating such as vapor-deposited metal.
  • Phenoxy-type thermoplastics including polyhydroxy ether, polyhydroxy ester ethers, and polyhydroxy amino ethers, are described in the literature such as Polymer Preprints, 34(1), 904-905 (1993).
  • Polyhydroxy amino ether (PHAE) also called polyetheramine, is an epoxy-based thermoplastic. Its repeating unit is composed of aromatic ether and ring or linear amine in the backbone chain, and hydroxyl groups in the pendants from the opening of the epoxy groups.
  • the basic PHAE is made of bis-phenol A diglycidyl ether (BADGE) and ethanol amine.
  • Property modification can be achieved by copolymerization of BADGE and resorcinal diglycidyl ether (RDGE) with ethanol amine which improves gas barrier properties.
  • RDGE resorcinal diglycidyl ether
  • the amount of the RDGE component in the PHAE copolymer could determine the effectiveness of the gas barrier properties.
  • U.S. Patent 5,275,853 describes the composition and process of making polyetheramine.
  • the polyetheramine for the laminate film of this invention could be made by the process of U.S. Patent 5,275,853.
  • the laminate film comprises: an isotactic polypropylene resin layer with one side discharge-treated for high surface energy suitable for printing or coating, a heat sealable ethylene-propylene-butylene terpolymer layer coextruded onto one side of the core layer opposite the discharge-treated surface; and a polyetheramine layer coated onto the discharge-treated surface of the polypropylene resin layer.
  • the polypropylene resin layer is a crystalline polypropylene of a specific isotactic content and can be uniaxially or biaxially oriented. Crystalline polypropylenes are generally described as having an isotactic content of about 90% or greater. Suitable examples of crystalline polypropylenes for this invention are Fina 3270 and ExxonMobil PP4772. These resins also have melt flow rates of about 0.5 to 5 g/10min, a melting
  • the core resin layer is typically 5 ⁇ m to 50 ⁇ m in thickness after biaxial orientation, preferably between 10 ⁇ m and 25 ⁇ m, and more preferably
  • antiblocking agent may be optionally added up to 1000 ppm to this resin layer. Preferably 300-500 ppm of antiblock may be added.
  • Suitable antiblock agents comprise those such as inorganic silicas, sodium calcium aluminosilicates, crosslinked silicone polymers such as polymethylsilsesquioxane, and polymethylmethacrylate spheres. Typical useful particle sizes of these antiblocks range from 1 - 12 urn, preferably in the range of 2-6 um.
  • the polypropylene resin layer can be surface treated with either a corona- discharge method, flame treatment, atmospheric plasma, or corona discharge in a controlled atmosphere of nitrogen, carbon dioxide, or a mixture thereof.
  • a corona- discharge method flame treatment, atmospheric plasma, or corona discharge in a controlled atmosphere of nitrogen, carbon dioxide, or a mixture thereof.
  • the latter treatment method in a mixture of CO 2 and N 2 is preferred.
  • This method of discharge treatment results in a treated surface that comprises nitrogen-bearing functional groups, preferably 0.3% or more nitrogen in atomic %, and more preferably 0.5% or more nitrogen in atomic %.
  • This treated core layer can then be metallized, printed, coated, or extrusion or adhesive laminated.
  • a heat sealable layer or non-heat sealable layer may be coextruded with the core layer opposite the polar resin layer having a thickness after biaxial orientation between
  • the heat sealable layer may contain an anti-blocking agent and/or slip additives for
  • the heat sealable layer will be a copolymer of propylene, either ethylene-propylene or butylene-propylene, and preferably comprise a ternary ethylene- propylene-butene copolymer. If an embodiment of the invention comprises a non-heat sealable, winding layer, this layer will comprise a crystalline polypropylene with antiblocking and/or slip additives or a matte layer of a block copolymer blend of polypropylene and one or more other polymers whose surface is roughened during the film formation step so as to produce a matte finish on the winding layer.
  • the surface of the winding layer is discharge-treated to provide a functional surface for lamination or coating with adhesives and/or inks.
  • the coextrusion process includes a three-layered compositing die.
  • the polymer core layer is sandwiched between the polar resin layer and the heat sealable or winding layer.
  • the three layer laminate sheet is cast onto a cooling drum whose surface
  • the non-oriented laminate sheet is stretched in the longitudinal direction at about
  • the uniaxially oriented laminate sheet is introduced into a tenter and
  • the biaxially oriented film has a total thickness between
  • the polyetheramine layer is aqueous solution-coated onto the discharge-treated side of the polypropylene resin layer.
  • the polyetheramine polymer is preferably 10-70% RDGE comonomer content, more preferably 30-50% RDGE comonomer content.
  • the % solids of the aqueous solution is from 10 - 50%, preferably 15-40%, and more preferably 25 - 35% with a viscosity of less than 50 cps.
  • the dry coating weight of the polyetheramine layer is 0.5 — 5 mg/in , preferably 1.0 - 3.0 mg/in 2 , and more preferably 1.5 - 2.5 mg/in 2 .
  • Suitable types of polyetheramine is that obtainable from Dow Chemicals under the tradename "BLOX®” or from ICI Packaging Coatings under the tradename "OXYBLOC®.”
  • BLOX® 5000 series grade is suitable for solution coating which has an RDGE comonomer content of 50% in the polyetheramine polymer .
  • ICFs polyetheramine coating grade OXYBLOC® 670C 1370 is also suitable and can be made available with RDGE comonomer content of 30%, 40%, and 50% or other amounts. The resulting clear film was tested for gas barrier properties and adhesion of the coating to the polypropylene substrate.
  • the aqueous coating can be applied either "in-line” or "out-of-line.”
  • the coating station is located after the machine direction stretching process of a monoaxial or biaxial orientation process and dried in a drying oven or using the tenter oven preheating zones as a dryer.
  • the coated monoaxially stretched film is then stretched in the transverse direction.
  • the finished monoaxial or biaxial film is wound up in a roll form, and is mounted on a separate coating machine.
  • the monoaxial or biaxial film substrate should have the desired surface for coating with the polyetheramine solution discharge-treated in order that the solution adequately wets the surface. This separate coating line will then apply the solution, dry it, and rewind the finished product.
  • the polyetheramine resin can also be extrusion-coated onto the polymer substrate rather than solution-coated.
  • Dow Chemical BLOX® grades for extrusion-coating that are suitable include but are not limited to BLOX® 4000 series and 0000 series. Similar to the solution-coating method, the extrusion-coating can be done either in-line - whereby the extrusion coating station is located after the first direction stretching process onto the monoaxially oriented film ⁇ or out-of-line whereby the extrusion-coating process is done on a separate machine onto the monoaxially or biaxially stretched substrate. It may also be desirable for the substrate to have the surface designated for coating to be discharge- treated in order that adequate adhesion of the BLOX® coating is obtained.
  • the polyetheramine layer may also be applied via coextrusion with the substrate layer.
  • a compositing die is used to combine the melt streams of the polyetheramine extrudate with the substrate extrudate which is either a polyolefin of polyester.
  • the substrate extrudate which is either a polyolefin of polyester.
  • no discharge-treatment of the substrate is necessary as enough intermolecular mixing at the interface of the polyetheramine extrudate and substrate extrudate assures adequate bonding of the two layers.
  • This coextrudate can then be cast onto a chill roll, quenched, then monoaxially or biaxially stretched into the final film product.
  • the coextruded polyetheramine skin resin layer in this case has a thickness
  • a preferred embodiment is to metallize the surface of the polyetheramine layer.
  • the unmetallized laminate sheet is first wound in a roll.
  • the roll is placed in a metallizing chamber and the metal vapor-deposited on the polyetheramine resin layer surface.
  • the metal film may include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, gold, or palladium, the preferred being aluminum.
  • the metal layer shall have a thickness between 5 and 100 nm, preferably between 20 and 80 nm, more preferably between 30 and 60 nm; and an optical density between 1.5 and 5.0, preferably between 2.0 and 4.0, more preferably between 2.3 and 3.2.
  • the metallized film is then tested for oxygen and moisture permeability, optical density, metal adhesion, and film durability.
  • a 2-layer coextrusion article comprising a core layer of a polypropylene resin with one surface discharge-treated and, upon the opposite surface, a layer of a terpolymer sealant is disposed, was coated with a solution of polyetheramine resin comprising 50% RDGE.
  • the total thickness of this film substrate after biaxial orientation is 7OG or 0.7 mil.
  • the thickness of the respective core and sealant skin layers after biaxial orientation is 64-66G and 4-6G.
  • the core is comprised of polypropylene and 300 ppm of antiblock additive such as silica of about 6um in average particle size.
  • the sealant layer comprises an ethylene-propylene-butylene terpolymer such as Sumitomo SPX78H8 and 4000ppm of an inorganic antiblock additive such as Toshiba Tospearl 120, a crosslinked silicone polymer of nominal 2.0um particle size and is melt
  • the propylene homopolymer core layer surface and wound into roll form was then place on a coating machine and the discharge- treated surface was coated via a gravure roll with an OXYBLOC® 6701370 aqueous solution, which has about 50% comonomer of RDGE.
  • the OXYBLOC® solution comprises the epoxy-amine polymer dispersed in water. The amount of solid in water was about 30% and the solution viscosity less than 50 cps.
  • the OXYBLOC®-coated substrate was passed through a drying oven to achieve a dry coating weight of about 2
  • the dried coating had a T g ranging from 50 to 95 0 C.
  • the coated and dried resultant clear film was tested for properties and was then metallized by vapor deposition of aluminum under vacuum to an optical density of 2.3 and tested for properties.
  • Example 3 A process similar to Example 1 was repeated except that the OXYBLOC® polyetheramine resin had a RDGE comonomer content of 40%. . The clear and metallized films were tested for properties.
  • Example 3 A process similar to Example 1 was repeated except that the OXYBLOC® polyetheramine resin had a RDGE comonomer content of 40%. . The clear and metallized films were tested for properties.
  • Example 2 A process similar to Example 1 was repeated except that the OXYBLOC® polyetheramine's comonomer content was about 30% RDGE. The resultant clear film was then tested for properties and was then metallized by vapor deposition of aluminum under vacuum to an optical density of 2.3 and tested for properties.
  • a 3-layer coextrusion article comprises a core layer of a blend of polypropylene and adhesion promoter, one skin layer of polar resin on the cast roll side, and the opposite skin layer of a terpolymer sealant on the air knife side.
  • the total thickness of the film after biaxial orientation is 7OG or 0.7 mil.
  • the thickness of the respective polar and sealant skin layers after biaxial orientation is 3-5G and 4-6G.
  • the core is a 70/30 blend
  • the polar skin is a 70/30 blend of
  • sealant skin is melt extruded at 400-480 0 F and is a terpolymer sealant such as Sumitomo SPX78H8. No polyetheramine coating or layer was applied in the film structure. The resultant clear film was tested for properties and was then metallized by vapor deposition of aluminum under vacuum to an optical density of 2.3 and tested for properties.
  • the resultant clear films of Examples 1 to 3 provide excellent oxygen barrier with O2TR of 12 - 27 cc/m 2 /day versus over 2000 cc/m 2 /day for a typical OPP film without the polyetheramine layer and 150 cc/m 2 /day for an EVOH coextruded OPP film.
  • the metallized films of Examples 1 to 3 also exhibit excellent oxygen barrier of 2 cc/m 2 /day or less versus 25 cc/m 2 /day for Comparative Example 1. .
  • barrier properties of Example 1 to 3 compare favorably with Comparative Example 3 after metallizing; with clear film, gas barrier properties of the polyetheramine are far superior to that of EVOH.
  • Examples 1 to 3 show better metal adhesion results than the respective Comparative Example 1. Furthermore, the polar skin adhesion of Examples 1 to 3's polyetheramine is extremely good in comparison to Comparative Example 2's EVOH which requires an adhesion promoter such as anhydride-grafted polyolefin. Lastly, Table 1 shows that the untreated wetting tension of the polyetheramine layers are as high or higher than that of the Comparative Examples' treated surfaces.
  • Oxygen transmission rate of the film was measured by using a Mocon Oxtran 2/20 unit substantially in accordance with ASTM D3985.
  • the preferred value was an average value equal to or less than 15.5 cc/m 2 /day with a maximum of 46.5 cc/m 2 /day.
  • Moisture transmission rate of the film was measured by using a Mocon Permatran 3/31 unit measured substantially in accordance with ASTM F 1249. In general, the preferred value was an average value equal to or less than 0.155 g/m 2 /day with a maximum of 0.49 g/m 2 /day.
  • Optical density was measured using a Tobias Associates model TBX transmission densitometer. Optical density is defined as the amount of light reflected from the test specimen under specific conditions. Optical density is reported in terms of a logarithmic conversion. For example, a density of 0.00 indicates that 100% of the light falling on the sample is being reflected. A density of 1.00 indicates that 10% of the light is being reflected; 2.00 is equivalent to 1%, etc.
  • Polar skin adhesion was measured by adhering a strip of 1 -inch wide 610 tape to the polar skin surface of a single sheet of film and removing the tape from the surface. The amount of polar skin removed was rated qualitatively as follows:

Landscapes

  • Laminated Bodies (AREA)

Abstract

Le film stratifié selon l'invention comprend une couche à base de résine de polyétheramine sur une première couche à base de résine de polyoléfine ou sur une première couche à base de résine de polyéthylène téréphtalate, la résine de polyétheramine renfermant un contenu comonomère contenant au moins 30 % d'éther résorcine-diglycidique. Le film stratifié peut également contenir des couches supplémentaires comme une seconde couche à base de résine de polyoléfine, une seconde couche à base de résine de polyéthylène téréphtalate, une couche de métal ou une combinaison de celles-ci.
EP05737535A 2005-04-18 2005-04-18 Structure d'un film de protection multi-couches Withdrawn EP1879734A4 (fr)

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US20210301126A1 (en) * 2018-08-09 2021-09-30 Polyplex Corporation Limited Biaxially oriented formable polyester film

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Publication number Priority date Publication date Assignee Title
WO1999020673A1 (fr) * 1997-10-22 1999-04-29 The Dow Chemical Company Polyetheramines thermostables

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US6589621B1 (en) * 1998-07-01 2003-07-08 Dow Global Technologies Inc. Thermally stable polyetheramines

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Publication number Priority date Publication date Assignee Title
WO1999020673A1 (fr) * 1997-10-22 1999-04-29 The Dow Chemical Company Polyetheramines thermostables

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See also references of WO2006112836A1 *

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