WO2001042008A1 - Films de resine phenoxy soudables par hautes frequences - Google Patents

Films de resine phenoxy soudables par hautes frequences Download PDF

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Publication number
WO2001042008A1
WO2001042008A1 PCT/US2000/032253 US0032253W WO0142008A1 WO 2001042008 A1 WO2001042008 A1 WO 2001042008A1 US 0032253 W US0032253 W US 0032253W WO 0142008 A1 WO0142008 A1 WO 0142008A1
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Prior art keywords
hydroxy
polymer
moiety
film structure
polymers
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PCT/US2000/032253
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English (en)
Inventor
Robert Harold Kelch
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The Dow Chemical Company
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Priority to AU17979/01A priority Critical patent/AU1797901A/en
Publication of WO2001042008A1 publication Critical patent/WO2001042008A1/fr

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    • 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
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2363/00—Epoxy resins
    • 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
    • B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone

Definitions

  • This invention generally concerns films and film structures containing at least one layer made from a thermoplastic epoxy (phenoxy) resin.
  • phenoxy resin is a hydroxy-phenoxyether polymer.
  • This invention more particularly concerns multi-layer film structures, such as coextruded film structures, containing at least one layer made from such a phenoxy resin.
  • This invention still more particularly concerns such multilayer film structures wherein at least one layer comprises a polymer other than a phenoxy resin.
  • Such other polymers include olefin polymers in general and polyolefins, olefin copolymers, glycol modified polyesters such as glycol modified polyethylene terephthalate (PETG), and functionalized or grafted polyolefins and olefin copolymers in particular.
  • the resulting film structures can, and desirably are, activated (bonded or sealed) with high frequency (HF) or radio frequency (RF) electromagnetic energy.
  • HF high frequency
  • RF radio frequency
  • f- PVC contains a large percentage (typically from 10 to 40 percent (%)) of phthalate plasticizer.
  • Plasticizer migration from products e.g. medical products, food products or toys
  • Similar concerns result from leaching of the plasticizer from such products to the environment when such products are buried in landfills.
  • F- PVC film and sheet materials find use in many packaging, containment, decorative and protective applications that rely on the physical strength, flexibility, gas impermeability, low cost and HF sealability characteristics of the polymer.
  • olefin polymers such as polypropylene (PP), polyethylene (PE), metallocene PE (m-PE), styrenic/olefinic block copolymers and ethylene copolymers like ethylene/vinyl acetate (EVA).
  • PP polypropylene
  • PE polyethylene
  • m-PE metallocene PE
  • styrenic/olefinic block copolymers ethylene copolymers like ethylene/vinyl acetate (EVA).
  • EVA ethylene/vinyl acetate
  • Literature references describe various halogen-free polymers that exhibit 5 dielectric properties that permit HF or RF welding or sealing.
  • Such polymers include, for example, thermoplastic polyurethane (TPU), polyamide (nylon) and PETG.
  • TPU thermoplastic polyurethane
  • Nylon polyamide
  • PETG PETG
  • these polymers cost more than PVC, making direct substitution for f- PVC economically unattractive.
  • some alternative RF active polymers have a significantly higher tensile modulus or stiffness than f- PVC, making the substitution in l o flexible film packaging or bag applications unfeasible.
  • Another approach to replace f- PVC with halogen-free polymers employs copolymers of olefins with acrylate esters or vinyl acetate (VA). By copolymerizing higher levels (generally greater the 15 percent by weight, based upon copolymer weight) of VA or methyl acrylate with ethylene, some measure of RF
  • EP 193,902 discloses RF sensitized compositions that include inorganic additives such as zinc oxide, bentonite clay, and
  • alkaline earth metal aluminosilicates at levels of 1 to 20 weight percent, based on composition weight.
  • WO 92/09415 describes incorporating RF receptors such as phosphonate compounds, phosphate compounds, quaternary ammonium salts, polystyrene sulfonate sodium salt, alkaline earth metal sulfate, and aluminum trihydrate into thermoset compounds and films.
  • U.S. Patent (USP) 5,627,223 discloses adding 1
  • CO carbon monoxide
  • a series of USPs (4,600,614; 4,601,865; 4,601,948; 4,660,354; 4,671,992; 4,678,713; 4,728,566; 4,766,035; 4,787,194; 4,847,155; and 4,895,457) teaches the use of CO-containing ethylene copolymers, e.g., ethylene-CO (ECO), ethylene-acrylic acid-CO (EAACO) and ethylene-vinyl acetate-CO (EVACO) 0 for applications involving RF weldability and susceptibility to microwave heating.
  • ECO ethylene-CO
  • EAACO ethylene-acrylic acid-CO
  • EVACO ethylene-vinyl acetate-CO
  • WO 96/05056 teaches a thermoplastic polymer blend of a non-polar polyolefin (PO) such as PE or EVA and a polar ethylene copolymer having CO functionality.
  • PO non-polar polyolefin
  • the blend contains from 1-90 weight percent polar copolymer, based on blend weight.
  • the blend forms a peelable seal layer for an easy opening package rather 5 than a permanent seal. In general, seal strength decreases with increasing polar copolymer content.
  • a first aspect of the present invention is a high frequency sealable multilayer polymer film structure consisting essentially of at least one layer of a hydroxy- phenoxyether polymer and at least one layer of an organic polymer other than a o hydroxy-phenoxyether polymer, the hydroxy-phenoxyether polymer having a dielectric loss factor (DLF) of at least 0.1.
  • DPF dielectric loss factor
  • a second aspect of the present invention is an article of manufacture fabricated from the film structure of the first aspect.
  • the article of manufacture desirably includes at least one segment wherein the film structure is sealed to itself, a 5 substrate or both at a seal interface. Sealing preferably results from exposure of the film to HF or RF energy.
  • the seal interface preferably has a bond strength of at least one pound per inch (lb/in) (0.18 Newton per millimeter (N/mm)).
  • the substantially plasticizer-free, HF or RF sealable films of the present invention readily replace f- PVC films in a variety of applications.
  • Such applications 0 include, for example, medical or urological collection bags, medical ostomy bags, medical infusion or intravenous (IV) bags, inflatable devices such as air mattresses, flotation devices or toys, food packaging, retail product blister packaging, children's articles and toys, general adhesive films, reinforced laminates for tents and tarpaulins, roofing membranes and geotextiles, and stationery applications such as binder covers.
  • the phenoxy-based film structures of the present invention contain no halogen or plasticizer, both of which are present in f- PVC film.
  • compositions that yield the films of the present invention can also be extruded into a tubing with an RF active outer layer.
  • Such tubing can readily be used in conjunction with RF weldable films to provide a complete RF welded polyolefin film structure such as a medical collection bag.
  • Skilled artisans can easily expand this illustrative listing to include virtually any device or application that requires an HF or RF sealable, flexible, mono-layer or multilayer film structure.
  • the relatively low (compared to f- PVC) cost of polyolefin materials used to make the films of the present invention and the performance features of such films opens many opportunities for replacement of flexible, plasticized, halogenated films such as f- PVC.
  • the film structures of the present invention also find use in comparatively non-flexible or rigid coextruded structures having utility in RF weldable packaging such as blister packages or "clam shell" packaging.
  • Blister packages have typically been made from clear rigid PVC sheet of 5 to 30 mils (0.13 to 0.78 mm) thick which is thermally molded or formed into a desired shape to hold a desired content.
  • Blister packs are used for retail packaging to hold hand tools and hardware, cassette tapes and CDs, cosmetics and health and beauty aids, sports equipment, etc. After the item is inserted into a blister package or clamshell, the package is typically RF sealed together.
  • rigid PETG copolymer sheet has been used.
  • DDF dielectric dissipation factor
  • An especially preferred test fixture utilizes a Hewlett-Packard Impedance / Material Analyzer, model 429 IB coupled with a Hewlett-Packard Dielectric Test Fixture, model 16453 A.
  • Dielectric properties can be measured on compression molded plaques (diameter of 2.5 inches (64 mm) and a thickness of 0.050 inch (1.3 mm) formed from a material such as a polymer or a blended polymer compound.
  • HF sealability refers to bonding of a sealable polymer to a portion of itself or to another material using electromagnetic energy or waves over a broad frequency range of 0.1-30,000 megahertz (MHz). This includes RF heating and microwave (MW) heating rather than conventional heat sealing.
  • the HF range generically covers three frequency ranges more commonly referred to as an ultrasonic frequency range (18 kilohertz (KHz)- 1000 KHz), the RF range (1 MHz-300 MHz), and the MW frequency range (300 MHz- 10,000 MHz).
  • KHz kilohertz
  • the RF and MW ranges are of particular interest.
  • activating activating", “sealing”, “bonding”, and “welding” (and variations of each word) are used interchangeably herein.
  • skilled artisans regard a material with a DLF of less than ( ⁇ ) 0.05 as RF or HF inactive. They classify materials with a DLF of 0.05 - 0.1 as weakly RF or HF active. They consider materials with a DLF above 0.1 to have good RF or HF activity, and materials with a DLF above 0.2 to be very RF or HF active. While a DLF of 0.1 may produce satisfactory results, skilled artisans typically prefer a DLF in excess of (>) 0.1, more often > 0.2, in order to obtain sufficient sealing by application of HF waves in general and RF waves in particular.
  • hydroxy-phenoxyether polymers employed in the practice of the present invention for preparing the polymer layer(s) are:
  • each Ar individually represents a divalent aromatic moiety, substituted divalent aromatic moiety or heteroaromatic moiety, or a combination of different divalent aromatic moieties, substituted aromatic moieties or heteroaromatic moieties;
  • R is individually hydrogen or a monovalent hydrocarbyl moiety;
  • each Ar 1 is a divalent aromatic moiety or combination of divalent aromatic moieties bearing amide or hydroxymethyl groups;
  • each Ar 2 is the same or different than Ar and is individually a divalent aromatic moiety, substituted aromatic moiety or heteroaromatic moiety or a combination of different divalent aromatic moieties, substituted aromatic moieties or heteroaromatic moieties;
  • R 1 is individually a predominantly hydrocarbylene moiety, such as a divalent aromatic moiety, substituted divalent aromatic moiety, divalent heteroaromatic moiety, divalent alkylene moiety, divalent substituted alkylene moiety or divalent heteroalkylene moiety or a combination of such moieties;
  • R" is individually a
  • Y is nil, a covalent bond, or a linking group, wherein suitable linking groups include, for example, an oxygen atom, a sulfur atom, a carbonyl atom, a sulfonyl group, or a methylene group or similar linkage; n is an integer from 10 to 1000; x is 0.01 to 1.0; and y is 0 to 0.5.
  • suitable linking groups include, for example, an oxygen atom, a sulfur atom, a carbonyl atom, a sulfonyl group, or a methylene group or similar linkage; n is an integer from 10 to 1000; x is 0.01 to 1.0; and y is 0 to 0.5.
  • the term "predominantly hydrocarbylene” means a divalent radical that is predominantly hydrocarbon, but which optionally contains a minor amount of heteroatomic moiety such as oxygen, sulfur, imino, sulfonyl, sulfoxyl, and the like.
  • the hydroxy-functional polyethers represented by Formula I can be prepared, for example, by allowing a diglycidyl ether or combination of diglycidyl ethers to react with a dihydric phenol or a combination of dihydric phenols using the process described in U.S. Patent 5,164,472, incorporated herein by reference in its entirety.
  • the process includes conditions sufficient to cause hydroxyl moieties to react with epoxy moieties to form a polymer backbone having ether linkages and pendant hydroxyl moieties. Such conditions may be found in U. S. Patent 4,647,648, the teachings of which are incorporated herein by reference.
  • Illustrative diglycidyl ethers of dihydric phenols include those of bisphenol ketone, bisphenol sulfone, resorcinol, hydroquinone and mixtures thereof. Specific dihydric phenols are found at column 2, line 60 through column 3, line 5, with those of bisphenol A, bisphenol and mixtures thereof being preferred.
  • the hydroxy-functional polyethers are obtained by allowing a dihydric phenol or combination of dihydric phenols to react with an epihalohydrin by the process described by Reinking, Barnabeo and Hale in the Journal of Applied Polymer Science, Volume 7, Page 2135 (1963).
  • the amide- and hydroxymethyl-functionalized polyethers represented by Formula II can be prepared, for example, by reacting the diglycidyl ethers, such as the diglycidyl ether of bisphenol A, with a dihydric phenol having pendant amido, N- substituted amido and/or hydroxyalkyl moieties, such as 2,2-bis(4- hydroxyphenyl)acetamide and 3,5-dihydroxybenzamide.
  • diglycidyl ethers such as the diglycidyl ether of bisphenol A
  • a dihydric phenol having pendant amido, N- substituted amido and/or hydroxyalkyl moieties such as 2,2-bis(4- hydroxyphenyl)acetamide and 3,5-dihydroxybenzamide.
  • the hydroxy-functional poly(ether sulfonamides) represented by Formula III are prepared, for example, by polymerizing an N,N'-dialkyl or N,N'- diaryldisulfonamide with a diglycidyl ether as described in U.S. Patent 5,149,768, incorporated herein by reference in its entirety.
  • the poly(hydroxy amide ethers) represented by Formula IV are prepared by contacting a bis(hydroxyphenylamido)alkane or arene, or a combination of 2 or more of these compounds, such as N,N'-bis(3-hydroxyphenyl) adipamide or N,N'-bis(3- hydroxyphenyl)glutaramide, with an epihalohydrin as described in U.S. Patent 5,134,218, incorporated herein by reference in its entirety.
  • the poly(hydroxy ester ethers) represented by Formula V are prepared by reacting diglycidyl ethers of aliphatic or aromatic diacids, such as diglycidyl terephthalate, or diglycidyl ethers of dihydric phenols with, aliphatic or aromatic diacids such as adipic acid or isophthalic acid.
  • diglycidyl ethers of aliphatic or aromatic diacids such as diglycidyl terephthalate
  • diglycidyl ethers of dihydric phenols such as adipic acid or isophthalic acid.
  • poly(hydroxy amide ethers) represented by Formula VI are preferably prepared by contacting an N,N'-bis(hydroxyphenylamido)alkane or arene with a diglycidyl ether as described in U.S. Patents 5,089,588 and 5,143,998, incorporated herein by reference in their entireties.
  • the poly(hydroxy amino ethers) represented by Formula VII are prepared by contacting one or more of the diglycidyl ethers of a dihydric phenol with an amine having two amine hydrogens under conditions sufficient to cause the amine moieties to react with epoxy moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties.
  • These poly(hydroxy amino ethers) are described in U.S. 5,275,853, incorporated herein by reference in its entirety.
  • Preferred diglycidyl ethers are diglycidyl ether of Bisphenol A (DGEBPA) and resorcinol diglycidyl ether (RDGE).
  • An especially preferred amine moiety is monoethanol amine or MEA.
  • the hydroxy-phenoxyether polymers represented by Formula VIII are prepared, for example, by contacting at least one dinucleophilic monomer with at least one diglycidyl ether of a cardo bisphenol, such as 9,9-bis(4-hydroxyphenyl)fluorene, phenolphthalein, or phenolphthalimidine or a substituted cardo bisphenol, such as a substituted bis(hydroxyphenyl)fluorene, a substituted phenolphthalein or a substituted phenolphthalimidine under conditions sufficient to cause the nucleophilic moieties of the dinucleophilic monomer to react with epoxy moieties to form a polymer backbone containing pendant hydroxy moieties and ether, imino, amino, sulfonamido or ester linkages.
  • a cardo bisphenol such as 9,9-bis(4-hydroxyphenyl)fluorene, phenolphthalein, or phenolphthalimidine
  • a substituted cardo bisphenol such as a substituted bis(hydroxyphen
  • hydroxy-phenoxyether polymers are described in U.S. ,5,814,373, incorporated herein by reference in its entirety.
  • the hydroxy-phenoxyether polymers commercially available from Inchem Corporation, formerly known as Phenoxy Associates, Inc., under the Paphen® phenoxy tradename are suitable for use in the present invention.
  • These hydroxy- phenoxyether polymers are the condensation reaction products of a dihydric polynuclear phenol, such as bisphenol A, and an epihalohydrin and have the repeating units represented by Formula I wherein Ar is an isopropylidene diphenylene moiety. The process for preparing them are described in U.S. Patent 3,305,528, incorporated herein by reference in its entirety.
  • the hydroxy-phenoxyether polymers employed in the practice of the present invention are the poly (hydroxy amino ethers) (PHAE) represented by Formula VII. These PHAE polymers are available from The Dow Chemical Company either as experimental products or under the trademark BLOXTM.
  • the hydroxy-phenoxyether polymers exhibit a molecular weight of at least 20,000 but less than 100,000, and preferably at least 30,000 and less than 80,000. Hydroxy-phenoxyether polymers having low molecular weight or exceedingly high molecular weight are difficult to process and exhibit insufficient physical properties to form into flexible films or adequately wet-out and adhere to a metal substrate.
  • the polymers can be modified by known copolymerization or graft copolymerization techniques or by crosslinking with ethylenically unsaturated dicarboxylic acid anhydride or anhydride precursor such as succinic or maleic anhydride; diisocyanates, or formaldehydes, such as phenol-, urea- or melamine formaldehyde.
  • Such reactions can be performed by a reactive extrusion process wherein the reactants are fed into and reacted in an extruder using the conditions described in U.S. Patent No. 4,612,156. which is incorporated herein by reference.
  • Monolayer and multilayer films can be prepared from the hydroxy- phenoxyether polymers by using conventional extrusion techniques such as feedblock extrusion, multimanifold or die coextrusion or combinations of the two. or by slot-die casting or annular blown film extrusion; extrusion coating onto another substrate layer; or by solvent spraying or solution casting.
  • Solution casting is a well known process and is described, for example, in the Plastics Engineering Handbook of the Society of the Plastics Industry, Inc, 4th Edition, Page 448.
  • multiple plies of hydroxy- phenoxyether polymers and/or other organic polymers can be adhered together via a conventional process such as hot-roll thermal lamination in order to produce a multi-ply structure.
  • This lamination of multiple separate layers or plies is especially beneficial when significant melt viscosity differences between the various layers prevent uniform coextrusion of the layers.
  • the films can be subsequently oriented monoaxially, in the machine or transverse direction, or biaxially, in both machine and transverse directions, to further improve their physical properties, such as increased tensile strength and secant modulus and reduced elongation.
  • multilayer films can be formed from the hydroxy- phenoxy ether polymers of the present invention by coextruding one or more layers of the hydroxy-phenoxyether polymers and one or more layers of an organic polymer that is not a hydroxy-phenoxyether polymer.
  • Such multilayered structures can be beneficially used to achieve composite properties not attainable by monolayer film or multicomponent blends.
  • TPU thermoplastic elastomer
  • PET polyester
  • PETG polyolefins or other thermoplastic resins
  • TPU thermoplastic elastomer
  • PET polyester
  • polyolefins or other thermoplastic resins can be blended with the hydroxy- phenoxyether polymer at levels of less than 50 weight percent and, preferably less than 30 weight percent, based on the weight of the hydroxy-phenoxyether polymer layer.
  • These other polymers can be blended into the hydroxy-phenoxyether polymer in order to reduce composition cost, to modify physical properties, barrier or permeability properties, or adhesion characteristics.
  • the HF -weldable multi-layer polymer film structures of the present invention have at least one hydroxy-phenoxyether polymer layer and at least one layer formed from an organic polymer that is not a hydroxy-phenoxyether polymer.
  • Organic polymers that are not hydroxy-phenoxyether polymers include polyolefins (homopolymers, copolymers and interpolymers) such as PE, PP, ethylene- styrene interpolymers (ESI), and various ethylene copolymers such as EVA, ethylene- methyl acrylate (EMA), and EVACO; styrenic block copolymers such as styrene/butadiene/styrene (SBS) and styrene/isoprene/styrene (SIS) block copolymers; carboxylic acid modified olefin copolymers, such as ethylene-acrylic acid (EAA), ethylene-methacrylic acid (EMAA); ionomers of EAA or
  • Polyamides that can be employed in the practice of the present invention include the various grades of nylon, such as nylon-6, nylon-66 and nylon 12. Also included are lower molecular weight and lower viscosity polyamide copolymers that are used as hot-melt adhesives, well known in the art and commercially available from numerous suppliers.
  • Preferred polyolefins include PP, linear high density polyethylene
  • HDPE heterogeneously branched linear low density polyethylene
  • LLDPE linear low density polyethylene
  • ULDPE ultra low linear density polyethylene
  • homogeneously - branched, linear ethylene/ ⁇ -olefin copolymers such as TAFMERTM (a trademark of Mitsui Petrochemicals Company Limited) and EXACTTM (a trademark of Exxon Chemical Company)
  • homogeneously -branched, substantially linear ethylene/alpha ( ⁇ )- olefin polymers such as AFFINITYTM (a trademark of The Dow Chemical Company) and ENGAGETM (a trademark of DuPont Dow Elastomers L.L.C.) polyolefin elastomers, which can be prepared as disclosed in U.S. Patents 5,272,236 and
  • the more preferred polyolefins are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) of 0.85 to 0.965 g/cm 3 , a weight average molecular weight to number average molecular weight ratio (M w /Mschreib) from 1.5 to 3.0, a measured melt index (measured in accordance with ASTM D-1238 (190°C/2.16 kilogram (kg) also referred to as I 2 ) of from 0.01 to 100 grams per 10 minutes (g/10 min), and an I ⁇ 0 /I 2 (melt flow ratio or MFR) of from 6 to 20 ( where I ⁇ 0 is measured in accordance with ASTM D-1238 (190°C /10 kg).
  • the ⁇ -olefin monomer desirably contains 3 to 20 carbon atoms (C -20 ), especially 3-8 carbon atoms (C 3-8 ).
  • Styrenics based on monovinyl aromatic monomers that can be employed in the practice of the present invention include polystyrene, polymethylstyrene, styrene- acrylonitrile, styrene-maleic anhydride copolymers, styrene/methylstyrene or styrene/chlorostyrene copolymers.
  • organic polymers that can be employed in the practice of the present invention for preparing the multilayer film include polyhexamethylene adipamide, polycaprolactone, polyhexamethylene sebacamide, polyethylene 2,6- naphthalate and polyethylene 1 ,5-naphthalate, polytetramethylene 1 ,2-dioxybenzoate and copolymers of ethylene terephthalate and ethylene isophthalate.
  • interpolymer to refer to polymers having polymerized therein at least two monomers. While adopting that convention, the above illustrations use copolymers to refer to the presence of two polymerized monomers and terpolymers to refer to the presence of three polymerized monomers. In that context, four polymerized monomers could be called a tetrapolymer, but is more often referred to as an interpolymer.
  • Preferred hydroxy-phenoxyether polymers include poly(hydroxy ether) (PHE), poly(hydroxy aminoether) (PHAE) and poly(hydroxy estere her) (PHEE) phenoxy resins. These resins are typically reaction products of diglycidal ethers of bisphenol A and one or more additional comonomers.
  • the HF or RF active phenoxy 5 resins of the present invention exhibit a DLF of at least 0.05 and preferably at least 0.1.
  • a especially preferred phenoxy resin is PHAE made with monoethanol amine (ME A).
  • the hydroxy-phenoxyether polymer resins yield polymer films with desirable barrier properties relative to atmospheric gases such as oxygen and carbon dioxide.
  • PHAE resins typically provide films with an oxygen barrier or l o oxygen transmission rate of from 0.1 to 1.0 cc of oxygen/mil of film thickness/100 square inches of film/day /atmosphere and a carbon dioxide barrier of 0.4 to 4.0 cc of oxygen/mil of film thickness/100 square inches of film/day /atmosphere.
  • Such barrier properties make the films viable candidates for applications such as medical packaging, food packaging or any other application where a satisfactory barrier to oxygen, carbon
  • 15 dioxide or both is a selection criterion.
  • the film structures of the present invention may be of any gauge that serves a given need, but typically fall within a range of 0.5 to 100 mils (12 to 2540 micrometers ( ⁇ m)), preferably 1 to 50 mils (25 to 1270 ⁇ m) and more preferably 2 to 20 mils (50 to 508 ⁇ m). Any conventional film forming process may be used to
  • Illustrative processes include, without limitation, an annular extruded blown film process, a slot die cast extrusion film or sheet process, sheet calendaring, and extrusion coating of one or more layers upon a film or substrate.
  • the film structures of the present invention can be prepared by coextrusion processes as well as lamination processes. Additionally, HF active blend compositions of the current
  • a RF -weldable monolayer or coextruded, multi-layer, tubular structure may be bonded to a film or other substrate to fabricate a composite part such as a medical collection bag.
  • the polymer blend compositions described herein can be dissolved in solvent or dispersed as an aqueous dispersion or emulsion and coated from a liquid
  • the phenoxy layer must be at least 10% of the film gauge, preferably at least 20% of the gauge, and most preferably at least 30% of the film gauge in order to impart RF sealability.
  • the polymer compositions that form the films of the present invention may also include one or more conventional additives that impart a functional attribute to the films, but do not significantly detract from film sealability via exposure to HF or RF irradiation.
  • additives include, without limitation, fillers, biocides, pigments, antioxidant or process stabilizers, ultraviolet (UV) stabilizers, tackifiers, fire retardants, impact modifiers, plasticizers, carbon black, conductive metal particles, abrasives and lubricating polymers may be incorporated into the hydroxy-phenoxyether polymer films, the organic polymer films or both.
  • UV ultraviolet
  • tackifiers fire retardants
  • impact modifiers plasticizers
  • carbon black conductive metal particles
  • abrasives and lubricating polymers may be incorporated into the hydroxy-phenoxyether polymer films, the organic polymer films or both.
  • the method of incorporating the additives is not critical.
  • the additives can conveniently be added to or combined or mixed with the hydroxy-phenoxyether polymer, the organic polymer or both prior to preparing the film structures or layers thereof. If the polymer is prepared in solid form, the additives can be added to the melt prior to preparing the films.
  • Organic polymers that are not hydroxy-phenoxyether polymers can be adhered to one or both sides, optionally with an intermediate adhesive layer, of the hydroxy-phenoxyether polymer film layer to produce a multilayer film.
  • the multilayer film can be in the form of the following structures: (1) a two-layer film comprising a first layer of the hydroxy-phenoxyether polymer and a second layer comprising an organic polymer which is not a hydroxy- phenoxyether polymer.
  • (2) a three-layer film comprising a first outer layer of an organic polymer, a core layer of the hydroxy-phenoxyether polymer and a second outer layer of an organic polymer which is the same as or different from the organic polymer of the first outer layer;
  • a three-layer film comprising a first outer layer of the hydroxy- phenoxyether polymer, a core layer of an organic polymer which is not a hydroxy- phenoxyether polymer and a second outer layer of an organic polymer which is the same as or different from the organic polymer of the core layer; or (4) a three-layer film comprising a first outer layer of the hydroxy- phenoxyether polymer, a core layer of an organic polymer which is not a hydroxy- phenoxyether polymer and a second outer layer of a hydroxy-phenoxyether polymer which is the same as or different from the hydroxy-phenoxyether polymer of the first outer layer.
  • the foregoing four film strucUires merely illustrate some of a wide variety of potential structures that a skilled artisan can readily envision.
  • one or more additional layers can be added to the above examples to provide films having four or more layers.
  • the additional layers can be organic polymer or organic polymer blend layers, hydroxy-phenoxyether polymer or hydroxy-phenoxyether polymer blend layers (with or without organic polymers), adhesive layers, and combinations thereof.
  • the resulting film structures whether they be one of the four specified structtires or any variation thereof as proposed in this paragraph, may be laminated to virtually any substrate.
  • Illustrative substrates include, without limitation, non- woven webs, cellulosics, wood products, metals, ceramics, and glass.
  • any of the films described herein can be sealed or welded to itself or to another substrate using a conventional HF sealer, such as a RF sealer.
  • a conventional HF sealer such as a RF sealer.
  • RF welders such as those available from Callanan Company. Weldan, Colpitt, Kiefel Technologies, Thermatron, Radyne and others, typically operate at a frequency of 27.12 MHz. Two less frequently used radio frequencies are 13.56 MHz and 40.68 MHz.
  • Typical MW sealing or welding apparatus function at frequencies of 2450 MHz (2.45 gigahertz or GHz), 5.8 GHz and 24.12 GHz.
  • HF, RF or MW activation offers a performance advantage over conventional thermal or heat sealing when rapid sealing becomes a dominant factor, such as is the case in high speed manufacturing.
  • HF (including RF and MW) bonding technologies allow energy to be concentrated at the HF active layer, thus eliminating a need to transfer heat through an entire structure.
  • This advantage becomes more evident with increasing film gauge, particularly for relatively thick (gauge > 5 mils or 125 ⁇ m) films where conventional thermal sealing techniques require relatively (compared to RF sealing) long contact times to permit thermal transfer through the film to the bonding interface.
  • RF sealing can occur in as little as 0.4 seconds whereas conventional thermal contact or impulse sealing of a film having the same thickness typically requires at least several seconds to attain a comparable seal.
  • HF bonding or sealing also has an advantage over conventional thermal sealing when a composite structure contains a thermally sensitive material, such as a color sensitive dyed fabric or nonwoven material or an oriented film that can soften and undesirably shrink upon heating.
  • RF dies can also be fabricated in very complex shapes, a difficult task when dealing with thermal sealing equipment.
  • the films of the present invention facilitate fabrication of a variety of structures via HF sealing.
  • a film can be folded over and at least partially HF sealed to itself to form a bag, a pouch or a blister pouch.
  • Two plies of the same film readily form a like bag or pouch without a fold.
  • HF sealing also promotes bonding of such a film to a substrate such as a different film, a nonwoven fabric, an injection molded or extruded part, or paper.
  • sufficient HF sealing or bonding equates to an adhesive strength of at least 1 pound per inch (lb/in) (0.18 Newton per millimeter or N/mm).
  • Medical collection bags or drainage pouches require that an RF weld between two plies of film have a strength that exceeds tear strength of the film itself. In other words, an effort to peel the films apart results in tearing at least one of the films.
  • Thicker film structures, such as those used for inflatable applications, generally require even greater weld or bond strengths.
  • films of the present composition can also be thermally laminated, sealed or welded using conventional thermal processes such as hot roll lamination, flame lamination, and heat sealing.
  • thermal process with HF welding.
  • One illustration of such a combination involves a first step of thermally laminating a film of the present invention to a substrate such as a fabric thereby forming a film/fabric composite and a second, sequential step of HF welding two composites together at a film/film interface, thereby providing film interior surfaces and fabric exterior surfaces.
  • Ex 1 5 Determine dielectric properties of a number of polymers using the apparatus and procedure described above and a frequency of 27.12 megahertz (MHz) a a temperature of 23°C.
  • LLDPE linear low density polyethylene
  • PETG Eastar®6763 PETG, Eastman Chemical
  • LDPE 501 low l o density polyethylene
  • PP polypropylene
  • ESA ethylene/styrene interpolymer
  • EAA-1 and concentrate 25 combined weight of EAA-1 and concentrate), a 30% (1.2 mil, 30 ⁇ m) PHAE-1 core layer and an innermost 60% (2.4 mil, 60 ⁇ m) EAA skin layer (EAA-2 plus 3 weight percent of an antiblock concentrate, based on combined weight of EAA-1 and concentrate).
  • the antiblock concentrate (CN-734, Southwest Plastics) is 15 weight percent silicon dioxide and 85 weight percent LDPE, both percentages based on
  • EAA-2 is a 9.7 weight percent acrylic acid (AA) content, 1.5 g/10 minutes melt index EAA copolymer ( Primacor® 1410, The Dow Chemical Company) Dielectrically seal two plies of the above film together with the plies oriented seal side to seal side using a Callanan 1.5 kilowatt (kW) RF welding machine that operates at 70% power setting and 0.5 second seal time and is fitted with a unheated 0.125 in. (0.3 cm) wide by 10 in. (25 cm) long brass bar seal die. Cut the sealed plies into 1 in. (2.5 cm) wide strips perpendicular to the seal.
  • kW Callanan 1.5 kilowatt
  • Ex 2 Coextrude a 3-layer film structure having a thickness of 4.0 mil (100 ⁇ m) using a conventional 3-extruder cast film line at a temperature of 380°F (193°C).
  • the three layers are, in order a 10% (0.4 mil, 10 ⁇ m) PHAE phenoxy seal layer (100% PHAE-1), a 30% (1.2 mil, 30 ⁇ m) EAA (100% EAA-2) tie layer and a 60% (2.4 mil, 60 ⁇ m) outermost polyethylene skin layer (100% polyolefin plastomer made using a metallocene (constrained geometry) catalyst, 0.896 g/cm 3 density, 1.6 g/10 min I 2 ,
  • Comp Ex B Coextrude a 2-layer film structure having a thickness of 8 mil (200 ⁇ m) using a conventional multi-layer cast film line and two extruders.
  • One layer is PHE and the other is PETG.
  • the two layers each have a thickness of 4 mils (100 ⁇ m).
  • Each extruder uses zone temperatures ramped from 360°F (182°C) to 380°F (193°C) to feed molten polymer to a slot die operating at a set temperature of 380°F (193°C). Recover the coextruded structure as in Example 3 but use a casting roll operating at 140°F (60°C).
  • Example 2 Effect dielectric sealing as in Example 2 with the film structures oriented to place the two PHE layers in contact with each other but use a Callanan 2.0 KW RF sealer (operating at 70% power) fitted with an unheated 0.5 inch (1.3 cm) wide by 8 inch (20 cm) long brass bar seal die and a seal time of 6 second.
  • the plies are sealed, but can be peeled apart. As such, they do not form a desired permanent seal. It is believed that use of a heated brass bar (e.g. 40-50°C) would improve adhesion to an acceptable level and provide a permanent seal.
  • Comp Ex C Extrude a monolayer PETG film having a thickness 8 mil (200 ⁇ m) as in
  • Comp Ex B but using a single extruder. Effect sealing as in Comp Ex B to provide sealed plies that can be pulled apart. As with Comp Ex B, it is believed that a heated brass bar would effectively seal the plies together.
  • Ex 4 Duplicate Comp Ex B, but substitute PHAE-1 for the PHE. The plies exhibit excellent adhesion even when the seal time is reduced to 4 seconds. Attempts to peel the plies apart results in destruction of the film.
  • Each extruder uses zone temperatures ramped from 360°F (182°C) to 380°F (193°C) to feed molten polymer to a slot die operating at a set temperature of 380°F (193°C).
  • the three layers are, in order an outermost 15% (0.9 mil, 23 ⁇ m) EAA seal layer (100% EAA-1), a 70% (4.2 mil, 107 ⁇ m) PHAE-1 core layer and an innermost 15% (0.9 mil, 23 ⁇ m) EAA skin layer (100% EAA-1). Effect dielectric sealing as in Example 2, but increase the sealing time to 3 seconds, to provide a strong permanent seal. By way of contrast, single plies of a comparable gauge of the same EAA films do not provide any dielectric sealing, even at sealing times as long as 6 seconds.
  • Duplicate Ex 5 but substitute an ionomer (Surlyn® 1605, a sodium ionomer having 2.8 g/10 min I 2 , 0.95 g/cc density, E. I. du Pont de Nemours and Company) for the PHAE.
  • the plies exhibit a strong seal between ionomer layers, but the structure suffers from interlayer failure between the PHAE and ionomer layer of each ply. Optimization of ionomer and phenoxy resin choices and operating parameters should overcome such interlayer failure.
  • single plies of a comparable gauge of the same ionomer films do not provide any dielectric sealing, even at sealing times as long as 6 seconds.
  • Ex 7 Coextrude a 2-layer film structure having a thickness of 10 mil (254 ⁇ m) using a conventional multi-layer cast film line and two extruders.
  • the two layers each have a thickness of 50% of the total film thickness, or 5 mil (127 ⁇ m) each.
  • the PHAE-3 extruder uses zone temperatures ramped from 360°F (182°C) to 380°F (193°C) and the PETG extruder uses zone temperatures ramped from 410°F (210°C) to 430°F (221°C) to feed molten polymer to a slot die operating at a set temperature of 430°F (221 °C). Quench the coextruded structure using a casting roll operating at 140°F (60°C) and wind it up into a roll.
  • the PHAE-4 layer is 30% (8 mil, 203 ⁇ m) of the 27 mil film thickness and the PETG layer is 70% (19 mil. 483 ⁇ m) of the 27 mil film thickness.
  • the PHAE-4 extruder uses zone temperatures ramped from 320°F (160°C) to 330°F (165°C) and the PETG extruder uses zone temperatures ramped from 392°F (200°C) to 430°F (221°C) to feed molten polymer to a slot die operating at a set temperature of 375°F (190°C). Feed the coextruded structure between the top two rolls of a 3-roll vertical stack, wherein the top roll operates at 85°F (29°C), the middle roll at 120°F (49°C), and the bottom roll at 115°F (46°C), and wind the sheet up into a roll.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention porte sur une structure laminée scellable par hautes fréquences comportant une ou plusieurs couches d'un polymère d'hydroxy-phénoxyéther et une ou plusieurs couches d'un polymère organique différent de l'hydroxy-phénoxyéther. Selon le choix du polymère organique, la structure peut être considérée comme souple ou rigide. De telles structures peuvent donner une variété d'articles utiles lorsqu'on les soumet à un rayonnement à haute fréquence.
PCT/US2000/032253 1999-12-10 2000-11-22 Films de resine phenoxy soudables par hautes frequences WO2001042008A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17979/01A AU1797901A (en) 1999-12-10 2000-11-22 High frequency weldable phenoxy resin films

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17004499P 1999-12-10 1999-12-10
US60/170,044 1999-12-10

Publications (1)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675373A (en) * 1985-04-18 1987-06-23 Mitsui Petrochemical Industries, Ltd. Polyhydroxy polyether, process for its production, and its use
US5731094A (en) * 1996-10-22 1998-03-24 The Dow Chemical Company Hydroxy-phenoxyether polyester coextruded laminates
US5840146A (en) * 1991-12-11 1998-11-24 Baxter International Inc. Method and compositions that render materials RF responsive
US5849843A (en) * 1993-11-16 1998-12-15 Baxter International Inc. Polymeric compositions for medical packaging and devices
WO1999032281A1 (fr) * 1997-12-19 1999-07-01 The Dow Chemical Company Stratifies polyethers a fonction hydroxy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675373A (en) * 1985-04-18 1987-06-23 Mitsui Petrochemical Industries, Ltd. Polyhydroxy polyether, process for its production, and its use
US5840146A (en) * 1991-12-11 1998-11-24 Baxter International Inc. Method and compositions that render materials RF responsive
US5849843A (en) * 1993-11-16 1998-12-15 Baxter International Inc. Polymeric compositions for medical packaging and devices
US5731094A (en) * 1996-10-22 1998-03-24 The Dow Chemical Company Hydroxy-phenoxyether polyester coextruded laminates
WO1999032281A1 (fr) * 1997-12-19 1999-07-01 The Dow Chemical Company Stratifies polyethers a fonction hydroxy

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