US20130236612A1 - Thermoformable Copolyester Laminate - Google Patents
Thermoformable Copolyester Laminate Download PDFInfo
- Publication number
- US20130236612A1 US20130236612A1 US13/822,886 US201113822886A US2013236612A1 US 20130236612 A1 US20130236612 A1 US 20130236612A1 US 201113822886 A US201113822886 A US 201113822886A US 2013236612 A1 US2013236612 A1 US 2013236612A1
- Authority
- US
- United States
- Prior art keywords
- laminate
- film layer
- layer
- heat
- film
- 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
Links
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 80
- 239000010410 layer Substances 0.000 claims abstract description 164
- -1 Polyethylene terephthalate Polymers 0.000 claims abstract description 28
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 22
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 22
- 239000012939 laminating adhesive Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 11
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 11
- 239000004952 Polyamide Substances 0.000 claims abstract description 10
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 5
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229920000554 ionomer Polymers 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 239000004743 Polypropylene Substances 0.000 claims abstract description 4
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 4
- 229920001155 polypropylene Polymers 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 10
- 235000013372 meat Nutrition 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 244000144977 poultry Species 0.000 claims description 8
- 235000013594 poultry meat Nutrition 0.000 claims description 8
- 230000013011 mating Effects 0.000 claims description 5
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- 238000009835 boiling Methods 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 26
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
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- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 229920001778 nylon Polymers 0.000 description 15
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 238000003856 thermoforming Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
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- 230000009477 glass transition Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 235000013622 meat product Nutrition 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004278 EU approved seasoning Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229910006127 SO3X Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920006097 Ultramide® Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920006344 thermoplastic copolyester Polymers 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 238000003855 Adhesive Lamination Methods 0.000 description 1
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- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 206010034203 Pectus Carinatum Diseases 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000005035 Surlyn® Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 238000003851 corona treatment Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
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- 230000001066 destructive effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 235000019692 hotdogs Nutrition 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
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- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
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Classifications
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/34—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging foodstuffs or other articles intended to be cooked or heated within the package
-
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- 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
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- 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
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B1/00—Packaging fluent solid material, e.g. powders, granular or loose fibrous material, loose masses of small articles, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
- B65B1/02—Machines characterised by the incorporation of means for making the containers or receptacles
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- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B25/00—Packaging other articles presenting special problems
- B65B25/22—Packaging articles of food, e.g. fish fillets, intended to be cooked in the package
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- B32B2307/30—Properties of the layers or laminate having particular thermal properties
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
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- 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
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- 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
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- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31736—Next to polyester
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- 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]
- Y10T428/31725—Of polyamide
- Y10T428/31739—Nylon type
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- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
-
- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
Definitions
- Articles such as food items and more specifically meat, poultry and seafood products are often packaged in thermoplastic films or laminates to protect the product from exterior abuse and environmental contamination, and to provide a convenient and durable package for distribution of the product and display in a display case or other point of sale.
- Packages made from films that are formed, filled with product and sealed exist in many shapes and forms for many applications, and are commonly used for such packaging.
- a package that can be used to cook the contained foodstuff without removing the packaging material (a “cook-in” package). It is also desirable that such packages be suitable for heating or cooking in conventional, convection or microwave ovens (“dual-ovenable”) or for heating in boiling water. It is particularly convenient to be able to purchase a fresh, partially, or fully cooked or value-added foodstuff in a package at the retail level and merely insert the package directly into a conventional or microwave oven and cook and reheat the foodstuff.
- thermoforming involves heating a thermoplastic film or laminate and forming it into a shape suitable for containing the product, which is subsequently inserted.
- the film or laminate is sometimes referred to as a “forming web”, and the package is closed with a “capping web” film that is adhered to the thermoformed package.
- Coextruded films comprising polyolefins such as polyethylene are sometimes useful in producing thermoformed packages.
- Laminate films have also been employed.
- U.S. Pat. No. 4,940,634 discloses biaxially oriented thermoplastic composite films comprising polyolefins, suitable for use as forming webs in thermoforming operations. It is common practice to join the capping web to the thermoformed package by heat-sealing the two together. Each films accordingly has a heat-sealable layer on its surface, or consists entirely of a heat-sealable polymer. The two films are pressed together with heating to effect the bond.
- films comprising polyolefins generally do not possess high temperature heat resistance, which limits their application to microwave cooking or reheating.
- PET films have high heat resistance, making them suitable for cook-in uses, but PET itself is not heat-sealable except at exceptionally high temperatures. If a heat-seal layer is provided on both PET surfaces, an acceptable seal can be obtained, but this adds time and expense to the film manufacturing process.
- the bond strength is unacceptably weak for most applications.
- thermoformable polyester film that does not bear a separate heat-seal layer, but that is nonetheless capable of being effectively heat-sealed to a polyester capping web that does.
- the invention provides a laminate including the following substantially coextensive layers in the following order:
- thermoformable copolyester film layer having a first surface and a second surface, the second surface constituting an outermost, exposed surface of the laminate
- thermoformable copolyester film layer (b) a laminating adhesive layer on the first surface of the thermoformable copolyester film layer;
- thermoformable structural film layer having a first surface and a second surface, the first surface contacting the laminating adhesive layer.
- Polyethylene terephthalate constitutes at least 80% by weight of the self-supporting thermoformable copolyester film layer
- thermoformable structural film layer includes a polymer selected from the group consisting of polyamides, polypropylene, polyethylene, polyethylene terephthalate, ionomers, ethylene acrylic acid copolymers, ethylene vinyl acetate copolymers, polystyrene, ethylene vinyl alcohol copolymers and polyvinylidene chloride;
- thermoformable copolyester film layer the structural film layer and the laminate each shrink less than 5% in length and width upon exposure to boiling water for five seconds;
- the laminate is thermoformable and its chloroform-soluble extractives meet the requirements of paragraph h(1) of 21 CFR ⁇ 177.1630 as defined herein.
- the invention provides a package including a laminate as described above, wherein the laminate is in the shape of a thermoformed receptacle having a pocket with a flange and an opening, the second surface of the copolyester film layer forming an inner surface of the pocket and a mating surface of the flange, and a heat-sealable film.
- the opening of the receptacle is closed by the heat-sealable film, which includes a self-supporting polymeric film having on a surface thereof a substantially coextensive heat-seal layer.
- the heat-seal layer of the heat-sealable film is in contact with and bonded to the mating surface of the flange of the thermoformed receptacle, and chloroform-soluble extractives of the heat-sealable film meet the requirements of paragraph h(1) of 21 CFR ⁇ 177.1630 as defined herein.
- the invention provides a method of packaging a foodstuff, including placing the foodstuff in the pocket of the laminate as described above and subsequently sealing the opening by heat-sealing a film to the flange.
- Laminates according to the invention include a non-sealable thermoformable copolyester film layer on a surface of the laminate, bonded by a laminating adhesive to a thermoformable structural film layer.
- non-sealable means that attempts to bond two like pieces of the material together by heat-sealing using the test method specified in the Examples fail to produce a bond strength of at least 200 g/25 mm.
- copolyester face of such a laminate is not itself heat-sealable, it is receptive to heat-sealing, meaning that another film having a heat-sealable surface layer can form a strong bond to the copolyester face of the inventive film under heat-sealing conditions.
- Laminates according to the invention meet the requirements of paragraph h(1) of 21 CFR ⁇ 177.1630 dated Apr. 1, 2003, incorporated herein as Appendix A, and are dual-ovenable. Laminates and multilayer films described herein will be understood to have all of the layers mutually coextensive, unless the context makes it clear otherwise. Each of the layers of the laminate will now be described in detail, followed by a description of the structure and use of suitable capping webs that may be used to seal thermoformed packages made from the laminates.
- Thermoforming comprises heating a film to a temperature (T 1 ) above the glass transition temperature (T g ) of the material but below the crystalline melting temperature (T m ) of the material (if it has a crystalline component), and then applying a deforming force to the material while it is in its softened, rubbery, solid state.
- T 1 a temperature above the glass transition temperature (T g ) of the material but below the crystalline melting temperature (T m ) of the material (if it has a crystalline component)
- T m crystalline melting temperature
- strain elongation at break
- UTS tensile strength at maximum elongation
- thermoformability requires that the deformed film retains the deformed shape, once cooled. Accordingly, an important characteristic of a thermoformable film is relaxation of induced stress at the processing temperature after stretching the film to the desired strain. This characteristic is usually expressed as a percentage of stress retained after a defined time period (in seconds), or as the time required to relax stress by a defined percentage, and in a thermoformable film the values of these parameters should be as low as possible, as is well known in the art (see for instance “Viscoelastic Properties of Polymers”; John D. Ferry, page 8 et seq., 3rd Ed, Wiley, NY; ISBN 0-471- 04894-1 ; and “Mechanical Properties of Solid Polymers”, I. M. Ward, 2 nd Ed., John Wiley)).
- a film or laminate will be considered thermoformable if the elongation (strain) at break when measured at 130° C. is greater than 220% in both machine (MD) and transverse (TD) directions.
- thermoformable copolyester film layer is partially amorphous, with the result that shrinkage of the layer (prior to any thermoforming) is typically very low upon heating. Typically the shrinkage is less than 5%, more typically less than 3%, in both the machine (MD) and transverse (TD) directions (i.e., in both length and width).
- MD machine
- TD transverse
- the ability of the layer to be thermoformed without substantial shrinkage is important, because excessive shrinkage may lead to forming difficulties such as loss of ability to maintain grip on the film during the forming step.
- the thermoformable copolyester has a crystallinity percentage below about 50%, more preferably below about 45%, more preferably in the range from 5 to about 42%, more preferably in the range from 3 to about 40%.
- thermoformable copolyester film layer is a self-supporting film or sheet, by which is meant a film or sheet capable of independent existence in the absence of a supporting base.
- a film-forming thermoplastic copolyester resin constitutes the major component of the thermoformable copolyester film layer, and makes up at least 50%, preferably at least 65%, preferably at least 80%, preferably at least 90%, and preferably at least 95% by weight of the total weight of the layer.
- one or more fillers may make up the balance of the layer.
- the layer consists of the film-forming thermoplastic copolyester resin.
- the synthetic linear copolyesters useful for the thermoformable copolyester film layer may be obtained by condensing the dicarboxylic acids or their lower alkyl diesters, e.g. terephthalic acid (TA), isophthalic acid, phthalic acid, 2,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, 4,4′-diphenyldicarboxylic acid, hexahydro-terephthalic acid or 1,2-bis-p-carboxyphenoxyethane (optionally with a monocarboxylic acid, such as pivalic acid) with one or more glycols, particularly an aliphatic or cycloaliphatic glycol, e.g.
- TA terephthalic acid
- isophthalic acid phthalic acid
- phthalic acid 2,5-, 2,6- or 2,7-naphthalenedicarboxylic
- ethylene glycol 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and diethylene glycol.
- suitable glycols are of low molecular weight (i.e. below about 250), and in some embodiments it is desirable to avoid the use of glycols having an average molecular weight of over 250, such as poly(alkylene oxide) glycols.
- Aliphatic glycols are preferred, particularly ethylene glycol.
- diethylene glycol constitutes at least 1.5 mol % of the total diol, or at least 2 mol %, with the balance being ethylene glycol. In some embodiments, at most 5 mol % is diethylene glycol, or at most 3.5%.
- the copolyester contains at least one aromatic dicarboxylic acid, preferably selected from the aromatic dicarboxylic acids noted above, and preferably said at least one aromatic dicarboxylic acid is TA. In one embodiment, the copolyester contains only one aromatic dicarboxylic acid, which is preferably TA. In some embodiments, it is desirable to avoid the use of dicarboxylic acid monomers that are sulphonated, i.e. dicarboxylic acids containing a sulphonic acid group or salt thereof (i.e. dicarboxylic acids which contain an —SO 3 X moiety where X is H or an alkali metal, such as sodium sulfo-isophthalate).
- the copolyester further contains at least one (typically only one) saturated aliphatic dicarboxylic acid of the general formula C n H 2n (COOH) 2 wherein n is 2 to 8, such as azelaic acid.
- the dicarboxylic acid fraction of the copolyester of the thermoformable copolyester film layer consists of at least one (and preferably only one) aromatic dicarboxylic acid, as defined above, and at least one (and preferably only one) aliphatic dicarboxylic acid, as defined above.
- the copolyester comprises at least 90 mol % relative to the total diacid fraction of the copolyester of an aromatic dicarboxylic acid, with the remainder being an aliphatic dicarboxylic acid. More typically, the amount is at least 92 mol %. Typically, at most 97 mol % of the total diacid is aromatic, more typically at most 95 mol %.
- the thermoformable copolyester film layer may contain recycle material up to a level of 50% by weight of the layer, and preferably at least 10%, preferably at least 25%, and more preferably at least 40% by weight of the layer.
- recycle material we mean waste material consisting of the composite film of the present invention, and such waste material may be derived from edge-trimming (typically the edge portions of the film which are held by the stenter clips during film manufacture), from excess film left over after the film has been slit along its longitudinal dimension, from start-up film (i.e. the film produced at the start of a manufacturing run), or from film that has been failed for other reasons, as is well-known in the art. It is surprising that recycle material may be used in the thermoformable copolyester film layer in such high proportions given that it contains the wax from the heat-sealable layer without causing problems in the film making process.
- the thermoformable copolyester film layer may comprise one or more discrete coextruded sublayers of the above film-forming materials.
- the polymeric materials of the respective sublayers may be the same or different.
- the thermoformable copolyester film layer may comprise one, two, three, four or five or more sublayers, and typical multi-layer structures may be of the AB, ABA, ABC, ABAB, ABABA or ABCBA type.
- the thermoformable copolyester film layer is monolithic and comprises only one layer, i.e., multiple coextruded copolyester layers are not present.
- the thermoformable copolyester layer typically has a thickness in a range from 0.5 mil to 4 mil, depending on the desired end structure. It can be unoriented, but typically it is biaxially oriented.
- Laminates according to the invention are capable of forming a heat-seal bond (on the thermoformable copolyester side) to a capping web with a bond strength typically of at least 250 g/25 mm, and more typically at least 400 g/25 mm, when measured as described in the Examples, using MYLAR® OL13 film (DuPont Teijin Films, Richmond, Va.) as the capping web.
- the heat-seal bond strength will typically be at most 2500 g/25 mm, and more typically at most 1000 g/25 mm.
- Packages according to the invention may use capping webs other than MYLAR® OL13 film, but the ranges of heat-seal bond strengths between the laminate and the capping web will still fall within the ranges described above.
- the thermoformable copolyester film layer of laminates according to the invention is itself non-sealable, meaning that when bonded to itself the heat-seal strength is less than 200 g/25 mm when measured as described in the Examples.
- thermoformable copolyester layer is laminated to the structural film layer by use of a laminating adhesive, which may for example be a polyester urethane.
- the adhesive may typically be applied as a solution.
- Solvent-based adhesives can be applied to one side (or two sides) of the base sheet by any means known to those of skill in the art.
- the film may be coated by roller (e.g. doctor roll) coating, spray coating, gravure coating, or slot coating, preferably roller or gravure coating using a solution coating process.
- a two-part polyester urethane adhesive can be applied to the thermoformable PET via a gravure cylinder to serve as the laminating adhesive.
- the laminating adhesive is applied across the web from solution. Removal of any solvent may require the application of heat.
- the two film layers are then laminated using standard laminating conditions.
- the laminating adhesive may also be “solventless.”
- Solventless laminating adhesives are well known in the art and illustratively include waterborne acrylic emulsions, polyurethane dispersions and one and two part polyurethane systems with 100% solids. Waterborne systems require dryers after adhesive application at elevated temperatures to eliminate the water before combining with another substrate. On the other hand, polyurethane systems with 100% solids rely on a chemical reaction for curing and little or no heat is required. In some applications it is preferred that the laminating adhesive be elastomeric, with exemplary embodiments being polyurethanes.
- the laminating adhesive can be applied either to the thermoformable copolyester film layer or the structural film layer, or both.
- One or both of these films may also be surface treated, such as by corona. In some cases both surfaces may be corona treated prior to application of an adhesive in order to promote better bonding between the film surfaces in contact with the applied adhesive.
- the laminating adhesive can be applied by well known coating techniques such as metering a low viscosity adhesive onto a multiple application roll system configuration that applies the adhesive to a first web or substrate. The first web is then mated to a second web or substrate by use of a heated nip roll.
- Thermosetting compositions may also be used for the laminating adhesive.
- One such adhesive consists of equal parts by volume of MOR-FREETM 225 polyester polyol and MOR-FREETM C-33 isocyanate, both available from Rohm and Haas of Spring House, Pa.
- Other examples include solvent adhesives such as ADCOTETM 812 and ADCOTETM 811B or a mixture of ADCOTETM 250HV and Coreactant 86, all available from Rohm and Haas of Spring House, Pa.
- the laminating layer typically has a thickness in a range from 0.5 mil to 10 mil including the thickness of the adhesive layer.
- thermoformable copolyester film layer is adhesively laminated to a thermoformable structural film layer to enhance performance of the overall structure, depending on the packaging need and intended condition of use.
- polymeric films useful for the structural film layer are polyamide (for example, nylon), polypropylene, polyethylene, ionomer, ethylene acrylic acid copolymer, ethylene vinyl acetate copolymer, polyethylene terephthalate, polystyrene, ethylene vinyl alcohol and polyvinylidene chloride.
- One exemplary ionomer is sold by E.I. du Pont de Nemours and Company, Wilmington, Del. (DuPont) under the trade name SURLYN®.
- the layer may be an abuse layer comprising oriented polyamide (nylon).
- This layer is preferably unaffected by the sealing temperatures used to make the package.
- the thickness of this layer can control the stiffness of the package, and may be in a range from about 10 to about 250 ⁇ m (0.4 to 10 mils), typically in a range from 50 to 200 ⁇ m (2 to 8 mils).
- This layer may be provided with graphic elements such as printing and embossing to provide information for the consumer and/or a pleasing appearance to the package. Preferably this layer is reverse printable.
- the particular film used will in part depend upon the end use of the package. For example, packages containing bones or other hard projections will require thicker film laminate structures.
- the thickness of the laminate structure will also depend on the depth of the draw desired during thermoforming.
- a preferred material for the strength layers is a polyamide such as biaxially oriented nylon from about 0.5 mil to about 5 mils in thickness.
- Nylon used as an outer layer can be from about 1 to 5 mils thick.
- Nylon used as an inner layer in combination with another layer can be from about 0.5 to 10 mils thick.
- Polyamides suitable for use in making the structural film layer include aliphatic polyamides, amorphous polyamides, or a mixture thereof.
- “Aliphatic polyamides” as the term is used herein can refer to aliphatic polyamides, aliphatic copolyamides, and blends or mixtures of these.
- Preferred aliphatic polyamides for use in the invention are nylon 6,6; nylon 6; nylon 6.66; nylon 6,10; and blends and mixtures thereof.
- Nylon 6,6 is commercially available, for example, under the trade name DARTEK® from Exopack Performance Films Inc., Whitby, Canada.
- Nylon 6 is commercially available, for example, under the trade name Nylon 4.12 from DuPont.
- Nylon 6.66 is commercially available under the trade names “ULTRAMID® C4” and “ULTRAMID® C35” from BASF, or under the trade name “UBE 5033FXD27” from Ube Industries Ltd. Heat stabilizer-modified version of the above nylons, and blends and mixtures of the nylons, may also be used.
- the laminates of this invention comply with the requirements of paragraph h(1) of 21 CFR ⁇ 177.1630 dated Apr. 1, 2003.
- This paragraph requires that the food contact surface, when exposed to distilled water at 250° F. (121° C.) for 2 hours, yields chloroform-soluble extractives not to exceed 0.02 mg/in 2 (0.0031 mg/cm 2 ) of food contact surface exposed to the solvent; and that the food contact surface, when exposed to n-heptane at 150° F. (66° C.) for 2 hours, yields chloroform-soluble extractives not to exceed 0.02 mg/in 2 (0.0031 mg/cm 2 ) of food contact surface exposed to the solvent.
- Suitable capping webs comprise a heat-sealable polymer layer, either alone or on the surface of a substrate layer, and in use the heat-sealable layer is eventually heat-sealed to the laminate on its thermoformable copolyester surface.
- the substrate layer of the capping web (if present) is typically polymeric and may be monolithic, although other layers may be added on the side of the substrate layer opposite the heat-sealable polymer layer.
- a polymeric material is the major component of the heat-sealable layer, constituting at least 50%, preferably at least 65%, preferably at least 80%, preferably at least 90%, and preferably at least 95% by weight of the total weight of the heat-sealable layer.
- one or more tackifiers, antifog agents, etc. may make up the balance of the layer.
- the heat-sealable layer consists of the polymeric material.
- the polymeric material of the heat-sealable layer softens to a sufficient extent that its viscosity becomes low enough to allow adequate wetting for it to adhere to the surface to which it is being bonded.
- the heat-seal bond is effected by heating to soften the polymeric material of the heat-sealable layer without melting any of the other layers in either film, and applying pressure.
- the polymeric material of the heat-sealable layer should begin to soften at a temperature such that the heat-seal bond can be formed at a temperature which is less than the melting temperature of the polymeric material of the substrate.
- the polymeric material of the heat-sealable layer should begin to soften at a temperature such that the heat-seal bond can be formed at a temperature which is between about 5 and 50° C. below, preferably between about 5 and 30° C. below, and preferably at least about 10° C. below the melting temperature of the polymer material of the substrate.
- the heat-sealable layer comprises, and typically consists essentially of, a copolyester resin derived from at least one (and preferably only one) aromatic dicarboxylic acid and at least one (and preferably only one) aliphatic dicarboxylic acid (or their lower alkyl (i.e. up to 14 carbon atoms) diesters) with one or more glycol(s). Formation of the copolyester is conveniently effected in known manner by condensation, or ester-interchange, at temperatures generally up to 275° C.
- Preferred aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, and 2,5-, 2,6- or 2,7-naphthalenedicarboxylic acid, and preferably the aromatic dicarboxylic acid is terephthalic acid.
- Preferred aliphatic dicarboxylic acids are saturated aliphatic dicarboxylic acids of the general formula C n H 2n (COOH) 2 wherein n is 2 to 8, such as succinic acid, sebacic acid, adipic acid, azelaic acid, suberic acid or pimelic acid, preferably sebacic acid, adipic acid and azelaic acid, and more preferably azelaic acid.
- the polyester contains no more than 90% of aromatic dicarboxylic acid (preferably TA) and at least 10% of aliphatic dicarboxylic acid, the percentages being the mole percentage of the total diacid content of the polyester, provided that the copolyester of the heat-sealable layer is of different composition than the substrate layer, as discussed hereinabove with regard to relative softening temperatures.
- aromatic dicarboxylic acid preferably TA
- aliphatic dicarboxylic acid the percentages being the mole percentage of the total diacid content of the polyester, provided that the copolyester of the heat-sealable layer is of different composition than the substrate layer, as discussed hereinabove with regard to relative softening temperatures.
- the concentration of the aromatic dicarboxylic acid present in the heat-sealable copolyester is no more than about 80 mole %, and preferably in the range from 45 to 80 mole %, more preferably 50 to 70 mole %, and particularly 55 to 65 mole % based on the dicarboxylic acid components of the copolyester.
- the concentration of the aliphatic dicarboxylic acid present in the heat-sealable copolyester is at least about 20 mole %, and preferably in the range from 20 to 55, more preferably 30 to 50, and particularly 35 to 45 mole % based on the dicarboxylic acid components of the copolyester.
- dicarboxylic acid monomers that are sulphonated i.e. dicarboxylic acids containing a sulphonic acid group or salt thereof
- dicarboxylic acids which contain an —SO 3 X moiety where X is H or an alkali metal, such as sodium sulfo-isophthalate i.e. dicarboxylic acids which contain an —SO 3 X moiety where X is H or an alkali metal, such as sodium sulfo-isophthalate.
- Preferred glycols are aliphatic glycols, and more preferably alkylene glycols.
- suitable glycol(s) include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol and 1,6-hexanediol.
- Ethylene glycol or 1,4-butanediol is preferred.
- the glycols are suitably low molecular weight diols (i.e. having a molecular weight below about 250).
- glycols having an average molecular weight of over 250 such as poly(alkylene oxide) glycols.
- the copolyester of the heat-sealable layer is thus suitably a linear copolyester.
- the heat-sealable layer typically uses but a single polyester species, rather than a blend of different polyesters.
- the T g of the copolyester is no more than about 20° C., preferably no more than about 10° C., preferably no more than about 0° C., and preferably no more than about ⁇ 20° C.
- the melting point T m of the copolyester is preferably no more than about 160° C., preferably no more than about 150° C., more preferably no more than about 140° C., and preferably no more than about 130° C.
- copolyesters are (i) copolyesters of azelaic acid and terephthalic acid with an aliphatic glycol, preferably ethylene glycol; (ii) copolyesters of adipic acid and terephthalic acid with an aliphatic glycol, preferably ethylene glycol; and (iii) copolyesters of sebacic acid and terephthalic acid with an aliphatic glycol, preferably butylene glycol.
- Preferred polymers include a copolyester of sebacic acid/terephthalic acid/butylene glycol (preferably having the components in the relative molar ratios of 45-55/55-45/100, more preferably 50/50/100) having a glass transition point (T g ) of ⁇ 40° C. and a melting point (T m ) of 117° C.), and a copolyester of azelaic acid/terephthalic acid/ethylene glycol (preferably having the components in the relative molar ratios of 40-50/60-50/100, more preferably 45/55/100) having a T g of ⁇ 15° C. and a T m of 150° C.
- the heat-sealable layer typically has a thickness in a range from 0.5 mil to 2.0 mil (13 to 51 ⁇ m), depending on the desired end structure.
- the substrate layer may consist of any of a wide variety of materials, including but not limited to biaxially oriented polyethylene terephthalate films, PET scrim, and Nylon films.
- One exemplary coextruded film suitable for use as a capping web comprises a clear, crystalline PET layer and an amorphous copolyester heat seal layer.
- a film of this type is available from DuPont Teijin Films under the trade name MYLAR® 851.
- the substrate layer typically has a thickness in a range from 0.5 mil to 2.0 mil (13 to 51 ⁇ m).
- the substrate layer may be unoriented, but preferably it is biaxially oriented.
- the capping web is surface printed or reverse printed (i.e. printed on a face that will be internal in the final film) to provide graphics, product information and the like.
- Printing is advantageously applied to the capping web, which is not subjected to thermoforming, so that the graphics are not distorted.
- Specific examples of capping webs including printed features include, from outermost layer to innermost layer: PVDC Coating/nylon/ink/adhesive/PET/heat-seal layer; Nylon/PVDC Coating/ink/adhesive/PET/heat-seal layer; or Nylon/ink/adhesive/PVDC Coating/PET/heat-seal layer.
- the ink layer represents printed graphics that are applied to the second film prior to adhesive lamination, which may be effected with any of the laminating adhesives described earlier herein.
- base films comprising oriented PET with an amorphous copolyester heat-seal layer can be adhesively laminated to a second film comprising a nylon layer and a PVDC barrier coating.
- the PVDC coating may also face the PET film.
- Films useful preparing the laminates or the capping webs may be made by virtually any method of film forming known to those skilled in this art. They may for example be cast, extruded, co-extruded, laminated and the like, including orientation (either uniaxially or biaxially) by various methodologies (e.g., blown film, mechanical stretching or the like). Various additives known to one skilled in the art can be present in the respective film layers including the presence of tie layers and the like. Additives include antioxidants and thermal stabilizers, ultraviolet (UV) light stabilizers, pigments and dyes, fillers, delustrants, anti-slip agents, plasticizers, anti-block agents, other processing aids, and the like.
- UV light stabilizers ultraviolet
- pigments and dyes fillers, delustrants, anti-slip agents, plasticizers, anti-block agents, other processing aids, and the like.
- Film manufacture can be carried out according to any known methods. It is possible, for example, to manufacture a primary film by extruding the compositions using so-called “blown film” or “flat die” methods.
- a blown film is made by extruding a polymeric composition through an annular die and expanding the resulting tubular film with an air current to provide a blown film.
- Cast flat films are made by extruding a composition through a flat die.
- the film leaving the die can be cooled by at least one roll containing internally circulating fluid (a chill roll) or by a water bath to provide a cast film.
- a monolayer or multilayer film may be hot-blown from an extrusion die at a relatively high blow-up ratio.
- Suitable thermoplastic polyesters are preferably crystalline and of relatively high molecular weight to maintain film integrity during the blow-up procedure.
- the polyester can be stretched sufficiently during the hot blowing process to provide balanced orientation in both the longitudinal (machine) and transverse directions.
- thermoplastic crystalline materials may be stretch oriented to obtain a biaxially oriented film.
- a tubing is extruded and then cooled and reheated, and then stretched by, for example, a blown bubble process. This process is well known in the art.
- stretch-oriented materials the tubing is being stretched and oriented at a relatively low temperature in comparison with the hot blown process disclosed above.
- the film laminate can be used in a myriad of applications such as to form packages using existing form, fill and seal (FFS) machines available from a number of manufacturers (e.g., Repak, Tiromat ULMA, and Multi-Vac).
- FFS form, fill and seal
- the laminate is thermoformed into the shape of a receptacle having a pocket with a flange and an opening, with the copolyester film layer forming an inner surface of the pocket and a mating surface of the flange.
- the heat-sealable layer of the capping web is sealed under vacuum to the flange to hermetically seal the package.
- the packages may typically contain foodstuffs such as meat, poultry, seafood, non-meat products.
- foodstuffs that may be packaged in packages of this invention include processed meats such as sausages, hot dogs and the like.
- the foodstuffs also include value-added, seasoned, marinated and/or precooked meat products or prepared meals.
- the foodstuffs may also be whole-muscle and/or bone-in meat and poultry portions such as, for example but not limitation, pork loin, turkey or chicken breasts and the like. Poultry also includes ready-to-cook whole birds.
- Packages may also be used to enclose fresh meat, poultry and seafood in modified atmospheric packaging applications or vacuum packaging applications.
- the packages are dual-ovenable, and can be designed to self-vent during cooking as the heat-seal layer softens.
- a preferred package of this invention consists essentially of (a) a thermoformable laminate disclosed herein and (b) a capping web, in which the capping web is heat sealed to the laminate after it has been thermoformed.
- the thermoformable laminate can be used to form pockets and then the pockets are filled with contents (for example, poultry) in an in-line packaging machine.
- the pockets can then be closed by heat sealing the margins of the laminate to a capping web in horizontal form, fill and seal applications such that the laminate and the capping web are hermetically sealed to each other.
- Vent areas can be made anywhere on the package simply by providing a slit in the package face at the time of heating.
- Packages made as described above are dual-ovenable, and may also be self-venting at typical cooking temperatures, depending on the choice of laminate and capping web.
- Self venting is a desirable safety feature to minimize the occurrence of steam blast on opening the package.
- the sealant thickness and seal temperature can be designed to provide a vent (via rupture) once the foodstuff reaches 170° F. (76.7° C.). This may be useful when heating a foodstuff in a microwave, where the self-venting feature serves as a temperature indicator to show that the food is heated to the proper temperature and is ready for consumption.
- One exemplary heat-seal polymer suitable for making seals that vent on heating is an amorphous copolyester.
- a coextruded film suitable for preparation of forming webs or capping webs that can be used in self-venting packages comprises a clear PET layer and an amorphous heat seal layer. Films of this type (having various thicknesses of clear PET and heat seal layer) are available from DuPont Teijin Films under the trade name MYLAR® OL.
- the package may vent when the temperature of the package reaches 150® F. (65.6® C.) to 450® F. (232.2® C.). In some embodiments, the package vents only at a temperature above 210® F. (98.9® C.), or only at a temperature above 250® F. (121.1® C.).
- Packages according to the invention may incorporate other features such as perforations, tear zones and the like that facilitate opening the package.
- Polyamide and PET (heat sealable) combinations provide excellent directional tear properties in that a pre-notched package can be torn open in a straight line in either the machine direction or transverse direction. These tear properties provide greater flexibility in package configuration and design.
- the opening area to access the foodstuff after heating is not limited to a particular part (e.g. the top) of the package. This can allow for locating a notch at the side of the package in the desired area for opening.
- test methods may be used to determine certain properties of the laminates of this invention, and packages made from them.
- Heat-seal strength of the composite film to the capping web is measured as follows.
- the capping web is sealed to the surface of the thermoformable copolyester layer of the thermoformable laminate using a Sentinel sealer at a temperature of 160° C. for 1.0 second under a pressure of 80 psi (0.55 N/mm 2 ).
- Strips (25 mm wide) of the sealed capping web and thermoformable laminate are cut out at 90° to the seal, and the load required to pull the seal apart measured using an Instron operating at a crosshead speed of 0.25 m/minute.
- the procedure is generally repeated 5 times, and a mean value of 5 results calculated.
- Heat-seal strength of the composite film to itself to itself is measured by positioning together and heating the heat-sealable layers of two samples of the film at 160° C. for 0.5 second under a pressure of 80 psi (0.55 N/mm 2 ). The sealed film is cooled to room temperature, and the sealed composite cut into 25 mm wide strips. The heat-seal strength is determined by measuring the force required under linear tension per unit width of seal to peel the layers of the film apart at a constant speed of 0.25 m/minute.
- Shrinkage is measured by placing the sample in an oven at a temperature of 190° C. for 5 minutes and determining the average % shrinkage in both the machine and transverse directions, based on five film samples.
- Glass transition temperature is measured by Differential Scanning Calorimetry (DSC).
- DSC Differential Scanning Calorimetry
- a 10 mg polymer specimen taken from the film is dried for 12 hours under vacuum at 80° C.
- the dried specimen is heated at 290° C. for 2 minutes and then quenched onto a cold block.
- the quenched specimen is heated from 0° C. to 290° C. at a rate of 20° C./minute using a Perkin-Elmer DSC7B Differential Scanning Calorimeter.
- the calorimeter is calibrated at a heating rate of 20° C./minute, so cooling temperatures are corrected by adding 3.9° C. to the computer-generated results.
- the crystallinity percentage is measured using a Perkin Elmer DSC7B Differential Scanning Calorimeter. A 5 mg sample taken from the film is heated from 0 to 300° C. at 80° C./minute, and the percent crystallinity is calculated by methods well known in the art.
- a typical process for forming a laminate according to the invention is as follows.
- the thermoformable copolyester film and the structural film are corona-treated on the surfaces to be joined.
- a 1:1 mixture by volume of MOR-FREETM 225 (polyester)/MOR-FREETM C-33 (isocyanate) is applied by a gravure roll at room temperature at a rate of 2.0-2.5g/m 2 .
- the laminated film goes through a heated nip roll at 52-56° C. at a speed of about 500 ft/min, and the film is then rolled up and stands at room temperature for 48 h for the initial curing to take place.
- the film rolls are then transferred to heated room which is at 40-45° C. and kept for 5 days at which time the curing is complete.
- the lamination bond strengths typically range from 1000 g/25 mm to destructive.
- Examples 1-4 describe exemplary laminates according to the invention.
- thermoforming the laminate according to the invention is as follows.
- the thermoformable laminate is heated and formed using a Multivac packaging machine such as a Multivac 530 which is equipped with a pear-shaped mold where the deepest point is about 4 inches.
- the forming temperature is set in a range from 130° C. to 215° C., and the forming time and vacuum are typically set at 2.0 seconds and 10 mbar, respectively.
- a 2-mil biaxially oriented polyester film was laminated with 4-mil DARTEK® H917 heat-stabilized nylon 6,6 film (Exopack Performance Films Inc., Whitby, Canada) using a solventless adhesive consisting of MOR-FREETM 225 and MOR-FREETM C-33 mixed at a 1:1 ratio at room temperature. Both films were corona treated prior to lamination.
- the diacid content of the polyester was 93/7 wt/wt terephthalic acid/azelaic acid, and the diol content was 95.7/4.3 wt/wt ethylene glycol/diethylene glycol.
- the amount of adhesive applied was 2.5 g/m 2 .
- the adhesive was applied to the corona treated H917 surface and the films were laminated together at 500 ft/minute.
- the temperature of the nip roll was 54° C.
- the composite film was kept at ambient temperature for 2 days and then moved to the heated room which was at 43° C. for 5 days to complete the curing process.
- a corona-treated 2-mil polyester film having the same polyester composition as in Example 1 but with a 1.5 ⁇ m PVdC coating on the side opposite the corona treatment is laminated to a corona-treated 4-mil DARTEK® H917 heat-stabilized nylon 6,6 film.
- the laminating adhesive is a solventless adhesive consisting of MOR-FREETM 225 and MOR-FREETM C33 mixed at a 1:1 ratio at room temperature.
- the adhesive loading is 2.5 g/m 2 .
- the adhesive is applied to the corona treated H917 surface and the PET film surface.
- the temperature of the nip roll is 54° C.
- the composite laminate is kept at ambient temperature for 2 days and then placed in a heated room at 43° C. for 5 days to complete the curing process.
- a 2-mil polyester film having the same composition as the polyester in Example 1 was laminated to 2-mil DARTEK® H917 heat-stabilized nylon 6,6 film. A process similar to that of Example 1 was followed.
- a corona-treated 2-mil PVdC coated polyester film as described in Example 2 is laminated to 2-mil DARTEK® H917 heat-stabilized nylon 6,6 film, using a process similar to that of Example 2.
- Examples 5-7 describe exemplary capping webs suitable for use with the thermoformable copolyester laminates of this invention.
- a 1-mil biaxially oriented PET film with an amorphous copolyester sealant layer (MYLAR® OL13, DuPont Teijin Films, Richmond, Va.) was laminated to 1-mil DARTEK® H917 heat-stabilized nylon 6,6 film.
- MYLAR® OL13 amorphous copolyester sealant layer
- DARTEK® H917 heat-stabilized nylon 6,6 film A similar process to Example 1 was followed. The non sealant side of the polyester film was corona treated and in contact with the adhesive when the laminate was formed.
- a 1-mil polyester film with an amorphous copolyester sealant layer on one side and a PVdC barrier layer on the other (Mylar® OB13, DuPont Teijin Films, Richmond, Va.) was laminated to 1-mil DARTEK® H917 heat-stabilized nylon 6,6 film, with the barrier layer adhered to the nylon.
- a process similar to that of Example 2 was followed.
- a 1.2-mil polyester film having an amorphous copolyester heat-seal layer on one side (MYLAR® OL22, DuPont Teijin Films, Richmond, Va.) was laminated to 1-mil DARTEK® H917 heat-stabilized nylon 6,6 film.
- MYLAR® OL22 DuPont Teijin Films, Richmond, Va.
- a process similar to that of Example 1 was followed.
- the non sealant side of the MYLAR® OL22 was corona treated and in contact with the adhesive when the laminate was formed.
- thermoformable copolyester laminate made as in Example 1 was used as a formable web, and a laminate made as in Example 5 was used as the capping web, as follows.
- a Multivac R530 packaging machine was equipped with a pear-shaped mold where the deepest point was about 4 inches, and the form temperature was set to 160° C.
- the thermoformable laminate was heated and formed at the same location, using a forming time of about 2.0 seconds and a vacuum of about 10 mbar.
- the cavity was then filled with product, a marinated sirloin roast having a weight of about 1 lb 12 oz, leaving about 1 ⁇ 2-1 inch head space, and the package was sealed with the capping web at 180° C. with a dwell or sealing time of about 1.0 second.
- a total heating seal plate was used, but in typical practice a perimeter sealing plate may be used.
- a turkey roast having a weight of about 9 lbs was marinated with seasonings and vacuum packaged as follows.
- a Multivac R530 packaging machine was equipped with a pear shaped mold where the deepest point was about 4 inches, and the form temperature was set to 160° C.
- the laminate film of Example 1 was heated and formed at the same location, using a forming time of about 2.0 seconds and a vacuum of about 10 mbar.
- the cavity was then filled with product, leaving about 1 ⁇ 2-1 inch head space, and the package was sealed with the capping web made in Example 7 at 180° C. with a dwell or sealing time of about 2.0 second.
- a total heating seal plate was used, but in typical practice a perimeter sealing plate may be used.
- the packaged meat was placed in an AlkarTM oven set to 190° F. for six hours.
- the package was removed and frozen in a freezer. No venting or rupture of the seal occurred.
- the package was taken from the freezer and placed in a conventional oven set to 250° F. for reheat. After 30 minutes in the oven, the package spontaneously opened by venting through a tiny vent and continued to be heated under partial steam in a bubble with a raised top web for a total of 90 minutes reheat time.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Food Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
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Priority Applications (1)
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US13/822,886 US20130236612A1 (en) | 2010-09-14 | 2011-09-13 | Thermoformable Copolyester Laminate |
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US38265810P | 2010-09-14 | 2010-09-14 | |
US13/822,886 US20130236612A1 (en) | 2010-09-14 | 2011-09-13 | Thermoformable Copolyester Laminate |
PCT/US2011/051346 WO2012037087A1 (en) | 2010-09-14 | 2011-09-13 | Thermoformable copolyester laminate |
Related Parent Applications (1)
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PCT/US2011/051346 A-371-Of-International WO2012037087A1 (en) | 2010-09-14 | 2011-09-13 | Thermoformable copolyester laminate |
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US15/980,843 Division US10954054B2 (en) | 2010-09-14 | 2018-05-16 | Thermoformable copolyester laminate |
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US15/980,843 Active US10954054B2 (en) | 2010-09-14 | 2018-05-16 | Thermoformable copolyester laminate |
US17/206,357 Pending US20210292076A1 (en) | 2010-09-14 | 2021-03-19 | Thermoformable copolyester laminate |
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US15/980,843 Active US10954054B2 (en) | 2010-09-14 | 2018-05-16 | Thermoformable copolyester laminate |
US17/206,357 Pending US20210292076A1 (en) | 2010-09-14 | 2021-03-19 | Thermoformable copolyester laminate |
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US (3) | US20130236612A1 (de) |
EP (1) | EP2616241A1 (de) |
JP (1) | JP6027004B2 (de) |
KR (1) | KR101937231B1 (de) |
CN (1) | CN103153619B (de) |
BR (1) | BR112013005947A2 (de) |
MX (1) | MX2013002695A (de) |
WO (1) | WO2012037087A1 (de) |
Cited By (6)
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US20130196099A1 (en) * | 2012-01-31 | 2013-08-01 | Dai Nippon Printing Co., Ltd. | Packaging material for boil/retort treatment and pouch |
US10954054B2 (en) | 2010-09-14 | 2021-03-23 | Dupont Teijin Films U.S. Limited Partnership | Thermoformable copolyester laminate |
US11298927B2 (en) * | 2016-07-27 | 2022-04-12 | Toyobo Co., Ltd. | White polyester film, laminate, and packaging bag |
US11427688B2 (en) * | 2017-04-17 | 2022-08-30 | Eastman Chemical Company | Copolyesters plasticized with polymeric plasticizer |
US11683977B2 (en) | 2017-11-30 | 2023-06-20 | 3M Innovative Properties Company | Substrate including a self-supporting tri-layer stack |
US11707925B2 (en) | 2016-03-18 | 2023-07-25 | Toyobo Co., Ltd. | Polyester film, laminate, and package |
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EP2955128A1 (de) * | 2014-06-11 | 2015-12-16 | Cryovac, Inc. | Doppelte ofenfähige Pakete für verderbliche Nahrungsmittelprodukte |
EP3645419A1 (de) * | 2017-06-29 | 2020-05-06 | Cryovac, LLC | Verwendung von zweifach ofentauglichen polyesterfolien in wärmeformungsverpackungsanwendungen und daraus erhaltene, zweifach ofentaugliche wärmegeformte verpackungen |
DE102018112817A1 (de) | 2018-05-29 | 2019-12-05 | Klöckner Pentaplast Gmbh | Transparente Polymerfolie mit Verfärbungskompensation |
WO2020016757A1 (en) * | 2018-07-19 | 2020-01-23 | 3M Innovative Properties Company | Conformable shielding film |
DE102018215422A1 (de) * | 2018-09-11 | 2020-03-12 | Mitsubishi Polyester Film Gmbh | Heißsiegelbare Polyesterfolie für die Herstellung von Menüschalen, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP2023551656A (ja) | 2020-11-18 | 2023-12-12 | クロックナー、ペンタプラスト、オブ、アメリカ、インコーポレイテッド | 熱成形包装およびその形成方法 |
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Also Published As
Publication number | Publication date |
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MX2013002695A (es) | 2013-06-07 |
BR112013005947A2 (pt) | 2016-05-31 |
EP2616241A1 (de) | 2013-07-24 |
WO2012037087A1 (en) | 2012-03-22 |
JP6027004B2 (ja) | 2016-11-16 |
CN103153619A (zh) | 2013-06-12 |
US20180257842A1 (en) | 2018-09-13 |
KR20130113456A (ko) | 2013-10-15 |
CN103153619B (zh) | 2015-11-25 |
US10954054B2 (en) | 2021-03-23 |
KR101937231B1 (ko) | 2019-01-10 |
JP2013543453A (ja) | 2013-12-05 |
US20210292076A1 (en) | 2021-09-23 |
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