US20050235611A1 - Multilayer heat shrinkable film comprising styrene polymer or a blend of styrene polymers - Google Patents

Multilayer heat shrinkable film comprising styrene polymer or a blend of styrene polymers Download PDF

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Publication number
US20050235611A1
US20050235611A1 US11/063,029 US6302905A US2005235611A1 US 20050235611 A1 US20050235611 A1 US 20050235611A1 US 6302905 A US6302905 A US 6302905A US 2005235611 A1 US2005235611 A1 US 2005235611A1
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US
United States
Prior art keywords
heat shrinkable
copolymer
shrinkable film
film
multilayer heat
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.)
Abandoned
Application number
US11/063,029
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English (en)
Inventor
George Roussos
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.)
Flexopack SA
Original Assignee
Individual
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=34707354&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20050235611(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Individual filed Critical Individual
Assigned to FLEXOPACK S.A. PLASTICS INDUSTRY reassignment FLEXOPACK S.A. PLASTICS INDUSTRY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROUSSOS, GEORGE
Publication of US20050235611A1 publication Critical patent/US20050235611A1/en
Priority to US13/948,305 priority Critical patent/US9950501B2/en
Priority to US14/498,423 priority patent/US20150017358A1/en
Abandoned legal-status Critical Current

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Classifications

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    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
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    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y10T428/31917—Next to polyene polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • This invention relates to multilayer heat shrinkable films.
  • films in accordance with the present invention may find use in other packaging applications such as packaging for curable putties and sealants and for various types of respiring and non respiring cheese.
  • Primal meat cuts are generally smaller than a side of beef, but larger than the ultimate cut sold to the retail consumer. Primal cuts are prepared at the slaughter house and shipped to retail meat stores or restaurants where they are butchered into smaller cuts of meat commonly referred to as sub-primal meat cuts. Sub-primal cuts, however, may also be prepared at the slaughterhouse.
  • Primal and sub-primal cuts are packaged to minimize air (i.e. oxygen) exposure and prevent meat spoilage and discoloration during shipping and handling.
  • One common way to package primal and sub-primal cuts and protect them from the adverse effects of air is to shrink package the cuts in a film having good oxygen barrier properties.
  • a multilayer film having a barrier layer containing polyvinylidene chloride (PVDC) is a well-known packaging material.
  • PVDC polyvinylidene chloride
  • the other layers of the multilayer film function to protect the PVDC layer and provide the requisite low temperature and abrasion resistance properties, which the PVDC layer lacks.
  • Shrinkage properties may be produced in a film by biaxially stretching the film in the machine and transverse direction.
  • the resulting film will heat shrink within a specified range of percentages such as from about 20 to about 50 percent at about 90° C.
  • the shrinkage should be more than 30 percent in at least one of machine and transverse directions at 90° C.
  • a multilayer heat shrinkable film may also be formed into packaging bags. Bags are generally made by transversely sealing a tubular stock of multilayer film and cutting or splitting the tube, or by superimposing flat sheets of multilayer film and sealing on three sides, or by end folding flat sheets and sealing the two sides.
  • a common type of seal used in manufacturing bags is a hot bar seal.
  • the adjacent thermoplastic layers, referred to as the inner layers, are sealed together by application of heat and pressure across the area to be sealed, using contact with opposing bars of which at least one is heated to cause the adjacent layers to fusion bond. Bags manufactured from a tube stock generally require one hot bar seal transverse to the tube. This seal is also referred to as a bottom seal.
  • the tube stock is transversely cut to form the mouth of the bag.
  • the strength of seals may be measured by determining the time for a seal to fail when under certain conditions. For example, the seal is immersed in hot water at 95° C. and the hot water seal strength (“HWSS”) may be measured by a test such as that described as the “restrained shrinkage-seal strength test” in Funderburk et al U.S. Pat. No. 3,900,635.
  • the package is evacuated and the bag mouth must be sealed.
  • the standard method for sealing a bag was to fasten a clip around the mouth of the bag.
  • impulse heat sealing techniques are employed to seal the bag mouth.
  • a bag mouth is impulse sealed by application of heat and pressure using opposing bars. At least one of the bars has a covered wire or ribbon through which electric current is passed for a very brief time period (hence the name “impulse”) to cause the adjacent film layers to fusion bond. Following the impulse of heat the bars are cooled while continuing to hold the bag inner surfaces together to achieve adequate seal strength.
  • Irradiation of a multilayer film causes the various irradiated layers in the film to cross-link.
  • cross-linking by irradiation not only provides a higher temperature impulse heat sealing range, but also enhances the puncture resistance of the film.
  • polymeric multilayer films can be irradiated to produce a cross-linked product having greater puncture resistance characteristics and other enhancements.
  • Prior art films typically used may have low haze and high gloss in unshrunk configuration, but much worse optical properties after shrinking. Alternatively, they may keep their optical properties after shrinkage, but do not shrink enough for an acceptable product presentation.
  • This invention in one aspect resides broadly in a multilayer heat shrinkable film including a layer of styrene polymer or a blend of styrene polymers and an oxygen barrier polymer layer.
  • the film shrinks at least 30% in at least one of machine and transverse directions by measuring unrestrained shrink of the stretched film at 90° C. for five seconds, or equivalent shrinkage thereof.
  • polymer refers to the product of a polymerization reaction and is inclusive of homopolymers, copolymers, terpolymers etc.
  • homopolymer is used with reference to a polymer resulting from the polymerization of a single monomer.
  • copolymer refers to polymers formed by the polymerization reaction of at least two different monomers.
  • polypropylene refers to any polymer comprising propylene polymerization units regardless of whether the polymer is a homopolymer or a copolymer and further includes blends of such homopolymers and copolymers.
  • ethylene propylene copolymer refers to polypropylene copolymerized with ethylene monomer.
  • ethylene alpha-olefin copolymer refers to such heterogeneous materials as linear low density polyethylene (LLDPE), linear medium density polyethylene (LMDPE) and very low and ultra low density polyethylene (VLDPE and ULDPE), as well as homogeneous polymers such as TAFMERTM supplied by Mitsui Petrochemical corporation and metallocene catalysed polymers such as Exact materials supplied by Exxon.
  • LLDPE linear low density polyethylene
  • LLDPE linear medium density polyethylene
  • VLDPE and ULDPE very low and ultra low density polyethylene
  • homogeneous polymers such as TAFMERTM supplied by Mitsui Petrochemical corporation and metallocene catalysed polymers such as Exact materials supplied by Exxon.
  • Other ethylene alpha olefin copolymers such as the long chain branched homogeneous alpha olefin copolymers available from Dow Chemical Company, known as Affinity resins, are also included in the present invention.
  • EVOH refers to ethylene vinyl alcohol copolymer
  • PVDC vinylidene chloride homopolyers and copolymers
  • polyamide refers to high molecular weight polymers having amide linkages along the molecular chain and refers more specifically to synthetic polyamides such as nylons.
  • barrier is used with reference to the ability of films to serve as barrier to oxygen or other gases.
  • oriented refers to a polymer containing material which has been stretched at an elevated temperature, followed by being “set” in the stretched configuration by cooling the material while substantially retaining the stretched dimensions.
  • heat shrinkable refers to the tendency of a film, especially an oriented film, to shrink upon the application of heat.
  • ethylene vinyl acetate refers to a copolymer formed from ethylene and vinyl acetate monomers, wherein the ethylene derived units in the copolymer are present in major amounts, preferably between about 60 to about 98 percent, while the vinyl acetate derived units in the copolymer are present in minor amounts, preferably between about 2 and 40 percent.
  • ethylene methyl acrylate refers to a copolymer formed from ethylene and methyl acrylate monomers, wherein the ethylene derived units in the copolymer are present in major amounts, preferably between about 60 to about 98 percent, while the methyl acrylate derived units in the copolymer are present in minor amounts, preferably between about 2 and 40 percent.
  • cycloolefin copolymer refers to a copolymer composed of ethylene units and/or of units comprising an alpha olefin with a cyclic, bicyclic or multicyclic olefin.
  • the COC is a copolymer of ethylene and norbornene.
  • the styrene content in the polymers used in the present invention is preferably more than 50 wt. % of styrene in the styrene copolymer. Preferably, more than 60 wt. %, further preferably more than 70%, more than 80% or even more than 90% by weight of styrene in the styrene copolymer is used. In another preferred embodiment a styrene homopolymer is used.
  • ionomer is a copolymer of ethylene with an ethylenically unsaturated acidic monomer, for instance acrylic or methacrylic acid.
  • the ionomer is preferably in its ionised form, the neutralizing cation being any suitable metal.
  • a well known ionomer material is Surlyn from Dupont.
  • the invention provides a multilayer heat shrinkable film comprising at least
  • the layer of the styrene polymer or blend of styrene polymers is the outer layer of the structure, being exposed to the environment.
  • a bonding layer which may include ethylene ester copolymers or ethylene alpha olefin copolymers.
  • the multilayer heat shrinkable film of the invention may comprise a heat sealable inner layer.
  • the inner layer may be made of a heat sealable thermoplastic polymer or polymer blend.
  • the heat sealable inner layer may be of any material conventionally used for its heat sealing capability.
  • Heat sealable thermoplastic polymers are recognized by those skilled in the art as being capable of heat sealing to themselves at a variety of time, pressure and temperature conditions. For example, at a given pressure either a relatively high temperature may be applied briefly or a lower temperature may be applied for a longer period of time to obtain similarly suitable seals. It is to be appreciated that persons skilled in the art will be able to select sealing parameters such as temperature, pressure and time of application that depend upon such factors as the type of heat sealing equipment used.
  • the term “inner layer” generally relates to that side of the multilayer heat shrinkable film, which is not exposed to the environment in a given product form (e.g. bag), but the good to be packaged.
  • This inner sealing layer may for instance be an alpha olefin copolymer or a blend of alpha olefin copolymers, e.g. a VLDPE, EVA, plastomer or a blend thereof.
  • a styrene polymer or a blend of styrene polymers may also be used as the inner heat sealing layer.
  • a cycloolefin copolymer or a blend of cycloolefin copolymer and alpha olefin copolymer may be the inner sealing layer.
  • Suitable polymers and copolymers may include alpha olefins such as members of the polyethylene family such as linear low-density polyethylene (LLDPE); very low-density polyethylene sometimes referred to as ultra low-density polyethylene (VLDPE and ULDPE respectively), plastomers or blends thereof.
  • alpha olefins such as members of the polyethylene family such as linear low-density polyethylene (LLDPE); very low-density polyethylene sometimes referred to as ultra low-density polyethylene (VLDPE and ULDPE respectively), plastomers or blends thereof.
  • Still other suitable thermoplastic polymers as the heat sealable inner layer include polypropylene, ethylene-propylene copolymer or an ionomer. It is to be understood however that the thermoplastic polymers mentioned herein are not intended to be an exhaustive list, but merely exemplary.
  • the outer layer (directly exposed to the environment) comprises a styrene copolymer in a blend with a slip agent.
  • Preferred styrene polymers are polystyrene homopolymer, SBC (styrene butadiene copolymers), SBS copolymers, SIS copolymers, SEBS copolymers, Ethylene Styrene interpolymers and blends thereof. Suitable materials are K RESIN from Chevron Philips Chemical, FINACLEAR from Atofina and Styrolux from BASF. A preferred styrene homopolymer is STYRON from Dow. In one preferred embodiment, the styrene content of the material is more than 50% by weight. This increases the stiffness of the material, thus making it more easy to convert.
  • barrier layer may be that together with the other layers, the oxygen transmission rate through the entire multilayer film may be below about 20 cc/l m 2 /24 hrs/atm, measured at 23 C, 75% RH. This is to avoid spoilage of certain food products, for example meat enclosed in the multilayer film package due to oxygen passage from the environment through the film wall.
  • barrier layer materials may include certain of the polyamides (Nylon), hydrolyzed ethylene vinyl acetate copolymer (EVOH) and preferably a vinylidene copolymer.
  • Vinylidene chloride-vinyl chloride (PVDC) is a commonly used copolymer but vinylidene chloride-methyl acrylate copolymer (MA-VDC) may also be used.
  • the thickness of the heat sealable inner thermoplastic first layer may be between about 0.4 mils and about 2.0 mils. Thinner layers may not perform the described functions while thicker layers may not appreciably improve processability of the film and may reduce total film performance.
  • the barrier layer thickness may be between about 0.1 mils to about 0.5 mils. Thinner barrier layers may not perform the intended functions and thicker layers do not appreciably improve performance.
  • one or more film additives may be incorporated, such as slip agents, antiblock agents, colorants, odor inhibitors, oxygen inhibitors etc.
  • slip agents such as slip agents, antiblock agents, colorants, odor inhibitors, oxygen inhibitors etc.
  • antiblock agents such as slip agents, antiblock agents, colorants, odor inhibitors, oxygen inhibitors etc.
  • composition of the film may eliminate the need for irradiation of the multilayer film, it is to be understood that the multilayer heat shrinkable film in accordance with the invention may be irradiated to further enhance puncture and temperature resistance.
  • the multilayer heat shrinkable film of the invention comprises the following components:
  • the heat shrinkable multilayer film in accordance with the present invention may be in the form of a tubular article or flat sheets.
  • the multilayer film may be formed into bags useful for the packaging of meats.
  • the multilayer film may be especially useful for those bags manufactured by hot bar or impulse sealing, and after meat is inserted therein, impulse heat sealing may be used to seal the mouth.
  • One end of the bag may be heat sealed by adhesion between contiguous inner layer surfaces in a direction transverse to the oppositely located sidewalls of the bag.
  • the mouth end of the bag may be impulse heat sealable by fusion bonding between contiguous inner layer surfaces after filling the bag with food.
  • a bag from the multilayer film may be manufactured such that the inner layer forms the inside portion of the bag while the outer layer forms the outside portion of the bag. Accordingly, the inner layer of the tubular multilayer film may be the heat sealable layer, which is easily sealed by hot bar sealing. Moreover, because of the latter, the mouth of the bag may be more easily sealed by impulse heat sealing.
  • the invention is directed to a method for manufacturing a bag from a multilayer shrinkable film as defined above, comprising the steps of:
  • bags of the same size 400 mm long ⁇ 230 mm wide
  • films comprising a heat sealable thermoplastic inner layer, an adjacent layer adhered on one side to the sealable inner layer, an oxygen barrier layer, an adjacent layer and an outer layer.
  • the core layer in most tests was a vinylidene chloride copolymer type oxygen barrier.
  • the film was the biaxially oriented heat shrinkable type, prepared by the double or trapped bubble method as broadly described in the aforementioned Palkhe U.S. Pat. No. 3,456,044. In particular, all layers were simultaneously coextruded.
  • Shrinkage values were obtained by measuring unrestrained shrink of the stretched film at 90° C. for five seconds.
  • Four test specimens were cut from a given sample of the oriented film to be tested. The specimens were cut to 10 cm in the machine direction by 10 cm. in the transverse direction. Each specimen was completely immersed for 5 seconds in a 90° C. water bath. The distance between the ends of the shrunken specimen was measured. The difference in the measured distance for the shrunken specimen and the original 10 cm was multiplied by ten to obtain the percent of shrinkage for the specimen.
  • the shrinkage for the four specimens was averaged for the MD shrinkage values of the given film sample, and the shrinkage for the four specimens was averaged for the TD shrinkage value.
  • the tensile modulus compared below has been measured according to ASTM D 882 with an Instron testing device.
  • the optical properties were tested according to ASTM D1003(haze) and BS 2782(gloss).
  • the bag making testing was done with a use of a commercial bag making machine.
  • a heat shrinkable multilayer film was produced having:
  • a heat shrinkable multilayer film was produced having:

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  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
US11/063,029 2004-02-20 2005-02-22 Multilayer heat shrinkable film comprising styrene polymer or a blend of styrene polymers Abandoned US20050235611A1 (en)

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US14/498,423 US20150017358A1 (en) 2004-02-20 2014-09-26 Multilayer heat shrinkable film comprising styrene polymer or a blend of styrene polymers

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EP1566266B2 (de) 2022-09-14
EP1566265A1 (de) 2005-08-24
US9950501B2 (en) 2018-04-24
AU2005200786B2 (en) 2010-07-01
DE202005021828U1 (de) 2010-07-08
US20150017358A1 (en) 2015-01-15
AU2005200786A1 (en) 2005-09-08
JP2005246969A (ja) 2005-09-15
EP1566266A1 (de) 2005-08-24
EP1566266B1 (de) 2017-04-26
US20140023843A1 (en) 2014-01-23

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