[go: up one dir, main page]

WO2020257411A1 - Films de polyéthylène haute densité à orientation biaxiale dotés d'une revêtement d'étanchéité amélioré - Google Patents

Films de polyéthylène haute densité à orientation biaxiale dotés d'une revêtement d'étanchéité amélioré Download PDF

Info

Publication number
WO2020257411A1
WO2020257411A1 PCT/US2020/038372 US2020038372W WO2020257411A1 WO 2020257411 A1 WO2020257411 A1 WO 2020257411A1 US 2020038372 W US2020038372 W US 2020038372W WO 2020257411 A1 WO2020257411 A1 WO 2020257411A1
Authority
WO
WIPO (PCT)
Prior art keywords
multilayer film
film
ethylene
layer
propylene
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.)
Ceased
Application number
PCT/US2020/038372
Other languages
English (en)
Other versions
WO2020257411A8 (fr
Inventor
Eric T. Gohr
Robert M. Sheppard
Benoît AMBROISE
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.)
Jindal Films Americas LLC
Original Assignee
Jindal Films Americas LLC
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 Jindal Films Americas LLC filed Critical Jindal Films Americas LLC
Priority to EP20825737.8A priority Critical patent/EP3986712A4/fr
Publication of WO2020257411A1 publication Critical patent/WO2020257411A1/fr
Priority to US17/307,230 priority patent/US12485658B2/en
Publication of WO2020257411A8 publication Critical patent/WO2020257411A8/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • 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
    • B32B27/18—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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B32B27/205—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents the fillers creating voids or cavities, e.g. by stretching
    • 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
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)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
    • 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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)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
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B32B2250/03—3 layers
    • 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
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0264—Polyamide particles
    • 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
    • B32B2264/0278—Polyester particles
    • B32B2264/0285—PET or PBT
    • 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
    • B32B2264/101—Glass
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2264/105—Metal
    • 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
    • B32B2264/107—Ceramic
    • 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
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • 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
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/732—Dimensional 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • 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 application relates to multilayer films that may have oriented layer(s), such as the core, tie, and/or skin layers, and include polyethylene in the core layer.
  • This disclosure provides for new multilayer films and methods that combine improved sealing properties, e.g. , high seal strengths, in films by lowering the minimum seal temperature while avoiding an increase in coefficient of friction and/or providing an increase in solvent adhesive bonds. These are significant functional improvements in films, which may be used in laminating, packaging and/or labelling applications.
  • compositions and methods for multilayer films which, in one embodiment may include a core layer comprising at least 50 wt.% of high-density polyethylene. Further, the multilayer film may include a first skin layer comprising an ethylene-propylene polymer, and a second skin layer comprising at least one or more a-olefin copolymers and antiblock.
  • One or more of the at least one or more a-olefin copolymers in the second skin layer which may be a sealant skin layer, may include at least one ethylene- propylene-butylene polymer in combination with a plastomer and/or elastomer that contain propylene, ethylene, or a combination thereof.
  • the one or more a-olefin copolymers may be metallocene-catalyzed, elastomers, propylene- ethylene polymers, ethylene-based plastomers, propylene-based elastomers, or olefm-block- copoly er eia stomers .
  • PE films comprising, consisting essentially of, or consisting of a high-density polyethylene (“HDPE”) and at least one functional terpolymer skin.
  • MO monoaxially
  • BO biaxially
  • PE films comprising, consisting essentially of, or consisting of a high-density polyethylene (“HDPE”) and at least one functional terpolymer skin.
  • the standard sealant resins when used in BOHDPE films show an unexpected increase in minimum seal temperature (“MST”); that is, the control resin formulation has a documented MST of 167°F, but its MST increases to 228°F when used on BOHDPE.
  • “polymer” may be used to refer to homopolymers, copolymers, interpolymers, terpolymers, etc.
  • a“copolymer” may refer to a polymer comprising two monomers or to a polymer comprising three or more monomers.
  • intermediate is defined as the position of one layer of a multilayered film, wherein said layer lies between two other identified layers.
  • the intermediate layer may be in direct contact with either or both of the two identified layers.
  • additional layers may also be present between the intermediate layer and either or both of the two identified layers.
  • “elastomer” is defined as a propylene-based or ethylene-based copolymer that can be extended or stretched with force to at least 100% of its original length, and upon removal of the force, rapidly (e.g., within 5 seconds) returns to its original dimensions.
  • plastomer is defined as a propylene-based or ethylene-based copolymer having a density in the range of 0.850 g/cm 3 to 0.920 g/cm 3 and a DSC melting point of at least 40 °C.
  • substantially free is defined to mean that the referenced film layer is largely, but not wholly, absent a particular component. In some embodiments, small amounts of the component may be present within the referenced layer as a result of standard manufacturing methods, including recycling of film scraps and edge trim during processing.
  • “about” means the number itself and/or within 5% of the stated number. For instance, with about 5%, this means 5 and/or any number or range within the range of 4.75 to 5.25, e.g., 4.75 to 4.96, 4.81 to 5.1, etc.
  • the core layer of a multilayered film is most commonly the thickest layer and provides the foundation of the multilayered structure.
  • the core layer comprises, consists essentially of, or consists of biaxially oriented polyethylene (“BOPE”), such as a high-density polyethylene film (“HDPE”) and/or other PE’s having a density greater than 0.94 g/cm 3 .
  • the core layer comprises at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, or more of HDPE.
  • the core layer may also include other polymers, including, for instance, biaxially oriented polypropylene (“BOPP”), biaxially oriented polyester (“BOPET”), biaxially oriented polylactic acid (“BOPLA”), and combinations thereof.
  • the core layer may also contain lesser amounts of additional polymer(s) selected from the group consisting of ethylene polymer, ethylene-propylene copolymers, ethylene-propylene-butene terpolymers, elastomers, plastomers, different types of metallocene-LLDPEs (m-LLDPEs), and combinations thereof.
  • the core layer may further include a hydrocarbon resin.
  • Hydrocarbon resins may serve to enhance or modify the flexural modulus, improve processability, or improve the barrier properties of the film.
  • the resin may be a low molecular weight hydrocarbon that is compatible with the core polymer.
  • the resin may be hydrogenated.
  • the resin may have a number average molecular weight less than 5000, preferably less than 2000, most preferably in the range of from 500 to 1000.
  • the resin can be natural or synthetic and may have a softening point in the range of from 60 °C to 180 °C.
  • Suitable hydrocarbon resins include, but are not limited to petroleum resins, terpene resins, styrene resins, and cyclopentadiene resins.
  • the hydrocarbon resin is selected from the group consisting of aliphatic hydrocarbon resins, hydrogenated aliphatic hydrocarbon resins, aliphatic/aromatic hydrocarbon resins, hydrogenated aliphatic aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenated cycloaliphatic resins, cycloaliphatic/aromatic hydrocarbon resins, hydrogenated cycloaliphatic/aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, polyterpene resins, terpene- phenol resins, rosins and rosin esters, hydrogenated rosins and rosin esters, and combinations thereof.
  • the amount of such hydrocarbon resins, either alone or in combination, in the core layer is preferably less than 20 wt %, more preferably in the range of from 1 wt % to 5 wt %, based on the total weight of the core layer.
  • the core layer may further comprise one or more additives such as opacifying agents, pigments, colorants, cavitating agents, slip agents, antioxidants, anti-fog agents, anti static agents, fillers, moisture barrier additives, gas barrier additives, and combinations thereof, as discussed in further detail below.
  • additives such as opacifying agents, pigments, colorants, cavitating agents, slip agents, antioxidants, anti-fog agents, anti static agents, fillers, moisture barrier additives, gas barrier additives, and combinations thereof, as discussed in further detail below.
  • a suitable anti-static agent is ARMOSTATTM 475 (commercially available from Akzo Nobel of Chicago, Ill.).
  • Cavitating agents may be present in the core layer in an amount less than 30 wt %, preferably less than 20 wt %, most preferably in the range of from 2 wt % to 15 wt %, based on the total weight of the core layer.
  • the total amount of additives in the core layer comprises up to about 20 wt. % of the core layer, but some embodiments may comprise additives in the core layer in an amount up to about 30 wt % of the core layer.
  • the core layer preferably has a thickness in the range of from about 5 pm to 100 pm, more preferably from about 5 pm to 50 pm, most preferably from 5 pm to 25 pm.
  • Tie layer(s) of a multilayered film is typically used to connect two other layers of the multilayered film structure, e.g., a core layer and a sealant layer, and is positioned intermediate these other layers.
  • the films may have zero, one or two tie layers.
  • the tie layer(s) may have the same or a different composition as compared to the core layer.
  • the tie layer is in direct contact with the surface of the core layer.
  • another layer or layers may be intermediate the core layer and the tie layer.
  • the tie layer may comprise one or more polymers.
  • the polymers may include C2 polymers, maleic-anhydride-modified polyethylene polymers, C3 polymers, C2C3 random copolymers, C2C3C4 random terpolymers, heterophasic random copolymers, C4 homopolymers, C4 copolymers, metallocene polymers, propylene-based or ethylene-based elastomers and/or plastomers, ethyl-methyl acrylate (EMA) polymers, ethylene-vinyl acetate (EVA) polymers, polar copolymers, and combinations thereof.
  • EMA ethyl-methyl acrylate
  • EVA ethylene-vinyl acetate
  • one polymer may be a grade of VISTAMAXXTM polymer (commercially available from ExxonMobil Chemical Company of Baytown, Tex.), such as VM6100 and VM3000 grades.
  • suitable polymers may include VERSIFYTM polymer (commercially available from The Dow Chemical Company of Midland, Mich.), Basell CATALLOYTM resins such as ADFLEXTM T100F, SOFTELLTM Q020F, CLYRELLTM SM1340 (commercially available from Basell Polyolefins of The Netherlands), PB (propylene-butene- 1) random copolymers, such as Basell PB 8340 (commercially available from Basell Polyolefins of The Netherlands), Borealis BORSOFTTM SD233CF, (commercially available from Borealis of Denmark), EXCEEDTM 1012CA and 1018CA metallocene polyethylenes, EXACTTM 5361, 4049, 5371, 8201, 4150, 3132 polyethylene plastomers, EM
  • the tie layer may further comprise one or more additives such as opacifying agents, pigments, colorants, cavitating agents, slip agents, antioxidants, anti-fog agents, anti-static agents, anti-block agents, fillers, moisture barrier additives, gas barrier additives, and combinations thereof, as discussed in further detail below.
  • additives such as opacifying agents, pigments, colorants, cavitating agents, slip agents, antioxidants, anti-fog agents, anti-static agents, anti-block agents, fillers, moisture barrier additives, gas barrier additives, and combinations thereof, as discussed in further detail below.
  • the thickness of the tie layer is typically in the range of from about 0.50 to 25 pm, preferably from about 0.50 pm to 12 pm, more preferably from about 0.50 pm to 6 pm, and most preferably from about 2.5 pm to 5 pm. However, in some thinner films, the tie layer thickness may be from about 0.5 pm to 4 pm, or from about 0.5 pm to 2 pm, or from about 0.5 pm to 1.5 pm.
  • the skin layer comprises at least one polymer selected from the group comprising, consisting essentially of, and/or consisting of polypropylene copolymers or terpolymers, which may be grafted or copolymerized, and a metallocene based material of either polypropylene or ethylene propylene copolymer.
  • the skin layer may also comprise processing aid additives, such as anti-block agents, anti-static agents, slip agents and combinations thereof, as discussed in further detail below.
  • processing aid additives such as anti-block agents, anti-static agents, slip agents and combinations thereof, as discussed in further detail below.
  • the thickness of the skin layer depends upon the intended function of the skin layer, but is typically in the range of from about 0.20 pm through 3.5 pm, or from 0.30 pm through 2 pm, or in many embodiments, from 0.50 pm through 1.0 pm. In thin film embodiments, the skin layer thickness may range from about 0.20 pm through 1.5 pm, or 0.50 pm through 1.0 pm.
  • Additives present in the film’s layer(s) may include, but are not limited to opacifying agents, pigments, colorants, cavitating agents, slip agents, antioxidants, anti-fog agents, anti-static agents, anti-block agents, fillers, moisture barrier additives, gas barrier additives, gas scavengers, and combinations thereof. Such additives may be used in effective amounts, which vary depending upon the property required, and may be added to one or more of the film’s layer(s) in solid or solution form, e.g. , part of a masterbatch solution or otherwise.
  • Suitable opacifying agents, pigments or colorants are iron oxide, carbon black, aluminum, titanium dioxide (TiCk), calcium carbonate (CaCCk), and combinations thereof.
  • Cavitating or void-initiating additives may include any suitable organic or inorganic material that is incompatible with the polymer material(s) of the layer(s) to which it is added, at the temperature of biaxial orientation, in order to create an opaque film.
  • suitable void-initiating particles are PBT, nylon, solid or hollow pre-formed glass spheres, metal beads or spheres, ceramic spheres, calcium carbonate, talc, chalk, or combinations thereof.
  • the average diameter of the void-initiating particles typically may be from about 0.1 to 10 pm.
  • Slip agents may include higher aliphatic acid amides, higher aliphatic acid esters, waxes, silicone oils, and metal soaps. Such slip agents may be used in amounts ranging from 0.1 wt % to 2 wt % based on the total weight of the layer to which it is added.
  • An example of a slip additive that may be useful is erucamide.
  • Non-migratory slip agents used in one or more skin layers of the multilayered films, may include polymethyl methacrylate (PMMA).
  • PMMA polymethyl methacrylate
  • the non-migratory slip agent may have a mean particle size in the range of from about 0.5 pm to 8 pm, or 1 pm to 5 pm, or 2 pm to 4 pm, depending upon layer thickness and desired slip properties.
  • the size of the particles in the non-migratory slip agent, such as PMMA may be greater than 20% of the thickness of the skin layer containing the slip agent, or greater than 40% of the thickness of the skin layer, or greater than 50% of the thickness of the skin layer.
  • the size of the particles of such non-migratory slip agent may also be at least 10% greater than the thickness of the skin layer, or at least 20% greater than the thickness of the skin layer, or at least 40% greater than the thickness of the skin layer.
  • PMMA resins such as EPOSTARTM (commercially available from Nippon Shokubai Co., Ltd. of Japan).
  • EPOSTARTM commercially available from Nippon Shokubai Co., Ltd. of Japan
  • Other commercial sources of suitable materials are also known to exist.
  • Non-migratory means that these particulates do not generally change location throughout the layers of the film in the manner of the migratory slip agents.
  • a conventional polydialkyl siloxane, such as silicone oil or gum additive having a viscosity of 10,000 to 2,000,000 centistokes is also contemplated.
  • Suitable anti-oxidants may include phenolic anti-oxidants, such as IRGANOX® 1010 (commercially available from Ciba-Geigy Company of Switzerland). Such an anti oxidant is generally used in amounts ranging from 0.1 wt % to 2 wt %, based on the total weight of the layer(s) to which it is added.
  • Anti-static agents may include alkali metal sulfonates, poly ether- modified polydiorganosiloxanes, poly alky lphenylsiloxanes, and tertiary amines. Such anti-static agents may be used in amounts ranging from about 0.05 wt % to 3 wt %, based upon the total weight of the layer(s).
  • Suitable anti-blocking agents may include silica-based products such as SYLOBLOC ® 44 (commercially available from Grace Davison Products of Colombia, Md.), PMMA particles such as EPOSTARTM (commercially available from Nippon Shokubai Co., Ltd. of Japan), or polysiloxanes such as TOSPEARLTM (commercially available from GE Bayer Silicones of Wilton, Conn.).
  • silica-based products such as SYLOBLOC ® 44 (commercially available from Grace Davison Products of Colombia, Md.), PMMA particles such as EPOSTARTM (commercially available from Nippon Shokubai Co., Ltd. of Japan), or polysiloxanes such as TOSPEARLTM (commercially available from GE Bayer Silicones of Wilton, Conn.).
  • Such an anti-blocking agent comprises an effective amount up to about 3000 ppm of the weight of the layer(s) to which it is added.
  • Useful fillers may include finely divided inorganic solid materials such as silica, fumed silica, diatomaceous earth, calcium carbonate, calcium silicate, aluminum silicate, kaolin, talc, bentonite, clay and pulp.
  • nonionic or anionic wax emulsions can be included in the coating(s), i.e. , skin layer(s), to improve blocking resistance and /or lower the coefficient of friction.
  • emulsion of Michem Lube 215, Michem Lube 160 may be included in the skin layer(s).
  • Any conventional wax, such as, but not limited to CamaubaTM wax (commercially available from Michelman Corporation of Cincinnati, Ohio) that is useful in thermoplastic films is contemplated.
  • the outer surface (i.e., side facing away from the core) of a skin layer and/or laminating substrate may undergo metallization after optionally being treated.
  • Metallization may be carried out through conventional methods, such as vacuum metallization by deposition of a metal layer such as aluminum, copper, silver, chromium, or mixtures thereof.
  • a coating may be applied to the outer metallized layer“outside” or“inside” the vacuum chamber to result in the following structure: metallized layer/skin layer/optional tie layer/core/optional tie layer/skin layer/metallized layer.
  • a primer may be applied on the metal surface(s) followed by top coating(s).
  • the thickness of the deposited layer(s) is typically in the range from 100 to 5,000 Angstrom or preferably from 300 to 3000 Angstrom.
  • One or both of the outer surfaces of the multilayered films may be surface-treated to increase the surface energy to render the film receptive to metallization, coatings, printing inks, adhesives, and/or lamination.
  • the surface treatment can be carried out according to one of the methods known in the art including corona discharge, flame, plasma, chemical treatment, or treatment by means of a polarized flame.
  • An intermediate primer coating may be applied to multilayered films.
  • the film may be first treated by one of the foregoing methods to provide increased active adhesive sites thereon and to the thus-treated film surface there may be subsequently applied a continuous coating of a primer material.
  • primer materials are well known in the art and include, for example, epoxy, poly(ethylene imine) (PEI), and polyurethane materials.
  • PEI poly(ethylene imine)
  • the primer provides an overall adhesively active surface for thorough and secure bonding with the subsequently applied coating composition and can be applied to the film by conventional solution coating means, for example, by roller application.
  • the films herein are also characterized in certain embodiments as being biaxially oriented.
  • the films can be made by any suitable technique known in the art, such as a tentered or blown process, LISIMTM, and others. Further, the working conditions, temperature settings, lines speeds, etc. will vary depending on the type and the size of the equipment used. Nonetheless, described generally here is one method of making the films described throughout this specification.
  • the films are formed and biaxially oriented using the tentered method. In the tentered process, line speeds of greater than 100 m/min to 400 m/min or more, and outputs of greater than 2000 kg/h to 4000 kg/h or more are achievable.
  • sheets/films of the various materials are melt-blended and coextruded, such as through a 3, 4, 5, 7-layer die head, into the desired film structure.
  • Extruders ranging in diameters from 100 mm to 300 or 400 mm, and length to diameter ratios ranging from 10/1 to 50/1 can be used to melt blend the molten layer materials, the melt streams then metered to the die having a die gap(s) within the range of from 0.5 or 1 to an upper limit of 3 or 4 or 5 or 6 mm.
  • the extruded film is then cooled using air, water, or both.
  • a single, large diameter roll partially submerged in a water bath, or two large chill rolls set at 20 or 30 to 40 or 50 or 60 or 70 °C are suitable cooling means.
  • an air knife and edge pinning are used to provide intimate contact between the melt and chill roll.
  • the unoriented film Downstream of the first cooling step in this embodiment of the tentered process, the unoriented film is reheated to a temperature of from 80 to 100 or 120 or 150 °C, in one embodiment by any suitable means such as heated S-wrap rolls, and then passed between closely spaced differential speed rolls to achieve machine direction orientation. It is understood by those skilled in the art that this temperature range can vary depending upon the equipment, and in particular, upon the identity and composition of the components making up the film. Ideally, the temperature will be below that which will melt the film, but high enough to facilitate the machine direction orientation process. Such temperatures referred to herein refer to the film temperature itself.
  • the film temperature can be measured by using, for example, infrared spectroscopy, the source aimed at the film as it is being processed; those skilled in the art will understand that for transparent films, measuring the actual film temperature will not be as precise.
  • the heating means for the film line may be set at any appropriate level of heating, depending upon the instrument, to achieve the stated film temperatures.
  • the lengthened and thinned film is passed to the tenter section of the line for TD orientation.
  • the edges of the sheet are grasped by mechanical clips on continuous chains and pulled into a long, precisely controlled hot air oven for a pre-heating step.
  • the film temperatures range from 100 or 110 to 150 or 170 or 180 °C in the pre-heating step. Again, the temperature will be below that which will melt the film, but high enough to facilitate the step of transverse direction orientation.
  • the edges of the sheet are grasped by mechanical clips on continuous chains and pulled into a long, precisely controlled hot air oven for transverse stretching.
  • the process temperature is lowered by at least 2°C but typically no more than 20°C relative to the pre-heat temperature to maintain the film temperature so that it will not melt the film.
  • the film is annealed at a temperature below the melting point, and the film is then cooled from 5 to 10 or 15 or 20 or 30 or 40°C below the stretching temperature, and the clips are released prior to edge trim, optional coronal, printing and/or other treatment can then take place, followed by winding.
  • TD orientation is achieved by the steps of pre-heating the film having been machine oriented, followed by stretching and annealing it at a temperature below the melt point of the film, and then followed by a cooling step at yet a lower temperature.
  • the films described herein are formed by imparting a transverse orientation by a process of first pre-heating the film, followed by a decrease in the temperature of the process within the range of from 2 or 3 to 5 to 10 or 15 or 20 °C relative to the pre-heating temperature while performing transverse orientation of the film, followed by a lowering of the temperature within the range of from 5 °C to 10 or 15 or 20 or 30 or 40°C relative to the melt point temperature, holding or slightly decreasing (more than 5%) the amount of stretch, to allow the film to anneal.
  • the stretch temperature may be 114°C
  • the cooling step may be 98°C, or any temperature within the ranges disclosed.
  • the steps are carried out for a sufficient time to affect the desired film properties as those skilled in the art will understand.
  • the film(s) described herein are biaxially oriented with at least a 5 or 6 or 7 or 11 -fold TD orientation and at least a 2 or 3 or 7-fold MD orientation.
  • the at least three-layer possess an ultimate tensile strength within the range of from 100 or 110 to 80 or 90 or 250 MPa in the TD in certain embodiments; and possess an ultimate tensile strength within the range of from 30 or 40 to 150 or 130 MPa in the MD in other embodiments.
  • the disclosed multilayered films may be stand-alone films, laminates, or webs. Or, the multilayered films may be sealed, coated, metallized, and/or laminated to other film structures.
  • the laminating substrate itself, may for instance, be a BOPE or a non-oriented, cast or blown PE film with or without the assistance of adhesive(s), increases in temperature and/or pressure, water or solvents, etc.; furthermore, the laminating substrate may or may not be metallized and/or coated.
  • the disclosed multilayered films may be prepared by any suitable methods comprising the steps of co-extruding a multilayered film according to the description and claims of this specification, orienting and preparing the film for intended use such as by coating, printing, slitting, or other converting methods.
  • the multilayered films may be desirable to laminate the multilayered films to other polymeric film or paper products for purposes such as package decor including printing and metallizing. These activities are typically performed by the ultimate end-users or film converters who process films for supply to the ultimate end-users.
  • the prepared multilayered film may be used as a flexible packaging film to package an article or good, such as a food item or other product.
  • the film may be formed into a pouch type of package, such as may be useful for packaging a beverage, liquid, granular, or dry-powder product.
  • Table 1 shows the structure and components in an example PE films in line with this disclosure, and Table 2 shows an example thereof; further examples include modifying the following based on the foregoing disclosure.
  • sealant skin blends and corresponding heat-seal data for each sample are shown in Table 3.
  • heat-seal testing was done using a LAKO unit with vertical crimp jaws, jaw pressure of 60 psi, dwell time of 0.75 seconds, and cooling time of 20 seconds. Testing was done from 180 through 270°F at 10°F increments.
  • the data below shows the minimum seal temperature (“MST”) to form a 200 g/in seal and the seal strength at 240, 250, and 260°F.
  • a multilayer film comprising:
  • a core layer comprising at least 50 wt.% of high-density polyethylene
  • a first skin layer comprising an ethylene-propylene polymer
  • a second skin layer comprising an ethylene-propylene-terpolymer, one or more a-olefin copolymers and antiblock,
  • the multilayer film is oriented in at least one direction.
  • the multilayer film of claim 1 wherein the core layer further comprises hydrocarbon resin, optionally in a masterbatch.
  • the core layer further comprises 20 wt.% or less of linear, low-density polyethylene, hydrocarbon resin or combination thereof.
  • the core layer comprises at least 80 wt% of the high-density polyethylene.
  • the multilayer film of claim 1 wherein at least one of the one or more a-olefin copolymers are propylene-ethylene polymers.
  • concentration of the one or more a-olefin copolymers is from about 15 wt.% through about 25 wt.%.
  • one or more of the at least one or more a-olefin copolymers comprise at least an ethylene-propylene-butylene polymer in combination with a plastomer and/or elastomer comprising propylene, ethylene, or combination thereof.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des compositions et des procédés destinés à des films multicouches, qui, dans un mode de réalisation, peuvent comprendre une couche centrale comprenant au moins 50 % en poids de polyéthylène haute densité. En outre, le film multicouche peut comprendre une première couche de revêtement comprenant un polymère éthylène-propylène, et une seconde couche de revêtement comprenant au moins un ou plusieurs copolymères a-oléfine et un agent antiadhérant. Un ou plusieurs desdits copolymères a-oléfine dans la seconde couche de revêtement, qui peuvent être une couche de revêtement d'étanchéité, peuvent comprendre au moins un polymère éthylène-propylène-butylène en combinaison avec un plastomère et/ou un élastomère qui contiennent du propylène, de l'éthylène, ou une combinaison de ces derniers.
PCT/US2020/038372 2019-06-20 2020-06-18 Films de polyéthylène haute densité à orientation biaxiale dotés d'une revêtement d'étanchéité amélioré Ceased WO2020257411A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20825737.8A EP3986712A4 (fr) 2019-06-20 2020-06-18 Films de polyéthylène haute densité à orientation biaxiale dotés d'une revêtement d'étanchéité amélioré
US17/307,230 US12485658B2 (en) 2019-06-20 2021-05-04 Biaxially oriented high-density polyethylene films with improved sealant skin

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US201962863938P 2019-06-20 2019-06-20
US62/863,938 2019-06-20
US201962865570P 2019-06-24 2019-06-24
US201962865558P 2019-06-24 2019-06-24
US62/865,558 2019-06-24
US62/865,570 2019-06-24
US201962908628P 2019-10-01 2019-10-01
US62/908,628 2019-10-01

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/307,230 Continuation US12485658B2 (en) 2019-06-20 2021-05-04 Biaxially oriented high-density polyethylene films with improved sealant skin

Publications (2)

Publication Number Publication Date
WO2020257411A1 true WO2020257411A1 (fr) 2020-12-24
WO2020257411A8 WO2020257411A8 (fr) 2021-09-23

Family

ID=74040418

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/038372 Ceased WO2020257411A1 (fr) 2019-06-20 2020-06-18 Films de polyéthylène haute densité à orientation biaxiale dotés d'une revêtement d'étanchéité amélioré

Country Status (1)

Country Link
WO (1) WO2020257411A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4151677A1 (fr) 2021-09-21 2023-03-22 Borealis AG Film à orientation biaxiale
EP4163323A1 (fr) 2021-10-07 2023-04-12 Borealis AG Film à orientation biaxiale
CN118288653A (zh) * 2024-04-16 2024-07-05 广东鼎孚新材料科技有限公司 一种高阻隔聚乙烯醇双向拉伸薄膜及其制备方法
EP4431552A1 (fr) 2023-03-14 2024-09-18 Borealis AG Film de polyéthylène orienté biaxialement présentant une rigidité améliorée
EP4247640A4 (fr) * 2021-08-14 2024-10-09 Jindal Films Americas LLC Film de goutte-à-goutte pour sac amélioré et emballage utilisant du polyéthylène haute densité orienté
EP4636015A1 (fr) 2024-04-16 2025-10-22 Borealis GmbH Films de polyéthylène à orientation biaxiale (beo) comprenant un agent de nucléation polymère

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753769A (en) 1966-06-29 1973-08-21 Mobil Oil Corp Coating composition and plastic articles coated therewith
US4058645A (en) 1973-08-24 1977-11-15 Mobil Oil Corporation Heat sealable thermoplastic films
US4439493A (en) 1983-02-04 1984-03-27 Mobil Oil Corporation Multilayer heat sealable oriented packaging film and method of forming same
US20030152791A1 (en) 2002-02-08 2003-08-14 Pang-Chia Lu Extruded multilayer film structure including an ethylene acid terpolymer layer for improved heat seal and metal adhesion
US20040053066A1 (en) 2002-09-06 2004-03-18 Cretekos George F. Metallized, metallocene-catalyzed, polypropylene films
US20160136935A1 (en) 2013-07-12 2016-05-19 Upm Raflatac Oy Multilayer film for label and a method for providing such
US20170223879A1 (en) 2016-01-28 2017-08-03 Upm Raflatac Oy Label arrangement and an item comprising said label arrangement

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3753769A (en) 1966-06-29 1973-08-21 Mobil Oil Corp Coating composition and plastic articles coated therewith
US4058645A (en) 1973-08-24 1977-11-15 Mobil Oil Corporation Heat sealable thermoplastic films
US4439493A (en) 1983-02-04 1984-03-27 Mobil Oil Corporation Multilayer heat sealable oriented packaging film and method of forming same
US20030152791A1 (en) 2002-02-08 2003-08-14 Pang-Chia Lu Extruded multilayer film structure including an ethylene acid terpolymer layer for improved heat seal and metal adhesion
US20040053066A1 (en) 2002-09-06 2004-03-18 Cretekos George F. Metallized, metallocene-catalyzed, polypropylene films
US6773818B2 (en) * 2002-09-06 2004-08-10 Exxonmobil Oil Corporation Metallized, metallocene-catalyzed, polypropylene films
US20160136935A1 (en) 2013-07-12 2016-05-19 Upm Raflatac Oy Multilayer film for label and a method for providing such
US20170223879A1 (en) 2016-01-28 2017-08-03 Upm Raflatac Oy Label arrangement and an item comprising said label arrangement

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3986712A4

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4247640A4 (fr) * 2021-08-14 2024-10-09 Jindal Films Americas LLC Film de goutte-à-goutte pour sac amélioré et emballage utilisant du polyéthylène haute densité orienté
EP4151677A1 (fr) 2021-09-21 2023-03-22 Borealis AG Film à orientation biaxiale
EP4151678A1 (fr) 2021-09-21 2023-03-22 Borealis AG Film à orientation biaxiale
WO2023046754A1 (fr) 2021-09-21 2023-03-30 Borealis Ag Film à orientation biaxiale
EP4163323A1 (fr) 2021-10-07 2023-04-12 Borealis AG Film à orientation biaxiale
WO2023057620A1 (fr) 2021-10-07 2023-04-13 Borealis Ag Film à orientation biaxiale
EP4431552A1 (fr) 2023-03-14 2024-09-18 Borealis AG Film de polyéthylène orienté biaxialement présentant une rigidité améliorée
WO2024188667A1 (fr) 2023-03-14 2024-09-19 Borealis Ag Film de polyéthylène à orientation biaxiale présentant une rigidité améliorée
CN118288653A (zh) * 2024-04-16 2024-07-05 广东鼎孚新材料科技有限公司 一种高阻隔聚乙烯醇双向拉伸薄膜及其制备方法
EP4636015A1 (fr) 2024-04-16 2025-10-22 Borealis GmbH Films de polyéthylène à orientation biaxiale (beo) comprenant un agent de nucléation polymère
WO2025219391A1 (fr) 2024-04-16 2025-10-23 Borealis Gmbh Films de polyéthylène à orientation biaxiale (bope) comprenant un agent de nucléation polymère

Also Published As

Publication number Publication date
WO2020257411A8 (fr) 2021-09-23

Similar Documents

Publication Publication Date Title
US12485658B2 (en) Biaxially oriented high-density polyethylene films with improved sealant skin
EP3368308B1 (fr) Films, orientés et revêtus, de polyéthylène linéaire basse densité
US11247440B2 (en) Metallized, oriented, linear, low-density, polyethylene films
US20200369014A1 (en) Polyethylene film compositions, laminates, and methods for making the same
US20180272671A1 (en) Bi-Oriented, Cavitated, Linear, Low-Density Films with Good Sealing Properties
WO2020257411A1 (fr) Films de polyéthylène haute densité à orientation biaxiale dotés d'une revêtement d'étanchéité amélioré
US11794397B2 (en) Heat-stable, biaxially oriented, polypropylene films
US20240294001A1 (en) Metallized, Oriented, and Thin LLDPE Films
EP4247640A1 (fr) Film de goutte-à-goutte pour sac amélioré et emballage utilisant du polyéthylène haute densité orienté
US12179462B2 (en) Pressure-sensitive-adhesive release film for oriented HDPE

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20825737

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2020825737

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2020825737

Country of ref document: EP

Effective date: 20220120