US20070117919A1 - Heat sealable polyvinyl chloride films - Google Patents
Heat sealable polyvinyl chloride films Download PDFInfo
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- US20070117919A1 US20070117919A1 US11/646,034 US64603406A US2007117919A1 US 20070117919 A1 US20070117919 A1 US 20070117919A1 US 64603406 A US64603406 A US 64603406A US 2007117919 A1 US2007117919 A1 US 2007117919A1
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- film
- weight
- seal
- resin composition
- pvc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
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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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
- Y10T428/1393—Multilayer [continuous layer]
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Definitions
- This invention relates to packaging films for fresh meat and vegetable produce and, in particular, a packaging film that is heat sealable, heat shrinkable and has a controlled gas permeability rate.
- Optically transparent films useful for covering food product containers and packaging food products are ideally formulated to provide consumers with a clear view of the packaged food product while maintaining its appearance and freshness.
- Films with oxygen transmission rate (OTR) control properties extend the shelf life of refrigerated freshly cut produce and fresh meat since the presence of either too much or too little oxygen in the package lowers shelf life.
- OTR oxygen transmission rate
- In the packaging of lettuce excessive oxygen in the package results in enzymatic browning of cut surfaces of the lettuce.
- insufficient oxygen in the package results in lettuce spoilage caused by anaerobiosis.
- fresh meat packaging permits delivery of sufficient oxygen to the myoglobin contained within the meat to maintain its natural red color and thus achieve the fresh looking product preferred by consumers.
- Packaging films made from polyvinyl chloride (PVC) and plasticizer have been used to wrap red meat and produce.
- PVC films provide a sparkling clear view of the packaged product, and, when formulated with plasticizers, exhibit cling and stretch properties.
- Conventional PVC packaging films have difficulty forming hermetic seals because PVC has a narrow sealing range. The precision required to seal conventional PVC films is too high for manufacturing with conventional packaging equipment.
- Packaging films made from olefinic materials can be formulated to control OTR, to seal to themselves and to be heat shrinkable at lower temperatures than conventional PVC films.
- films of olefinic materials are susceptible to surface moisture buildup in the form of small beads that obscure a consumer's view of the product contained in the package. Reducing fog (surface moisture buildup) in olefinic films by adding standard anti-fog agents has been largely unsuccessful. Anti-fog agents are difficult to contain on the film surface because they tend to wash off. Anti-fog agents also interfere with other film surface properties of the olefinic film making it difficult to print and seal.
- films for applications such as contact packaging for bottles or base films for pharmaceutical packaging have used blends of conventional PVC, meaning non-crosslinked PVC resin, and conventional PVC/VA, meaning non-crosslinked PVC/VA resin.
- conventional PVC/VA meaning non-crosslinked PVC/VA resin.
- U.S. Pat. No. 6,265,041 discloses a film for use as a cover sheet in pharmaceutical packaging. The disclosed film comprises between 1-80% by weight of a PVC resin and 20-99% by weight of a PVC/VA resin.
- U.S. Pat. No. 4,264,010 discloses a shrink wrap film for contact packaging products, such as a large bottle for carbonated beverages. The disclosed film comprises PVC and 5 to 20 parts by weight PVC/VA.
- the disclosed films comprise PVC/VA and PVC, these films require no controlled OTR and contain only small amounts of plasticizer.
- the amount of plasticizer is less than 2% by weight of the resin portion of the film.
- U.S. Pat. No. 6,265,041 discloses examples of film containing ESO, a plasticizer, in amounts ranging from 1.5 parts by weight out of 114.5 parts of resin composition to about 2.0 parts by weight out of 113 parts of resin composition. Stated in percentages by weight, these amounts range from 1.3% by weight of the resin composition to 1.8% by weight of the resin composition.
- the amount of plasticizer ranges from 11 to 17 weight parts out of 119.7 parts to 141.7 parts. Stated in percentage by weight, the amount of plasticizer in these examples ranges from about 9% to about 12% by weight of the film.
- One embodiment of the film comprises a blend of vinyl chloride homopolymer (hereinafter referred to as PVC) and copolymer of vinyl chloride and vinyl acetate (hereinafter referred to as PVC/VA).
- PVC/VA is sometimes referred to as poly(vinyl chloride-co vinyl acetate).
- the embodiment comprises about 18% by weight PVC/VA.
- the embodiment further comprises at least about 15% by weight plasticizer.
- a homogenous blend of these components was achieved by following the blending steps described in more detail below.
- Such a film has several properties beneficial for food packaging film.
- the film has a broad heat sealing temperature range that allows the film to be sealed on equipment capable of forming hermetic seals.
- the film can form a welded, hermetic seal at temperatures ranging from about 200° F. sealing time typically ranges up to about 1000 milliseconds.
- This embodiment is further capable of sealing over a heat sealing window that is sufficiently broad so that the film may be sealed on conventional packaging equipment.
- the film has an OTR of about 500 cc/100 in 2 /24 hours or greater, which is desirable for food packaging.
- the film may be either biaxially oriented or uniaxially oriented, depending on the desired shrink properties. When exposed to temperatures ranging from about 180° F. to about 350° F., the film will heat shrink.
- FIG. 1 is a graph of hot tack seal strength of sample film of Example 1 and Comparative Example 1, measured 250 ms following seal formation.
- FIG. 2 is a graph of hot tack seal strength of sample films of Example 1 and Comparative Example 1, measured 500 ms following seal formation.
- FIG. 3 is a graph of hot tack seal strength of sample films of Example 2 and Comparative Example 1, measured 250 ms following seal formation.
- FIG. 4 is a graph of hot tack seal strength of sample films of Example 2 and Comparative Example 1, measured 500 ms following seal formation.
- FIG. 5 is a graph of hot tack seal strength of sample films of Example 2 and Example 3, measured 250 ms following seal formation.
- FIG. 6 is a graph of hot tack seal strength of sample films of Example 2 and Example 3, measured 500 ms following seal formation.
- FIG. 7 is a graph of hot tack seal strength of sample of Example 4 and Comparative Example 2, measured 250 ms following seal formation.
- FIG. 8 is a graph of hot tack seal strength of sample of Example 4 and Comparative Example 2, measured 500 ms following seal formation.
- the film comprises a blend of two polyvinyl chloride resins: vinyl chloride homopolymer and copolymer of vinyl chloride and vinyl acetate.
- PVC/VA is sometimes referred to as poly(vinyl chloride-co vinyl acetate).
- the embodiment comprises about 18% by weight PVC/VA.
- the embodiment further comprises at least about 15% by weight plasticizer. A homogenous blend of these components was achieved by following the blending steps described in more detail below.
- Such a film has several properties beneficial for food packaging film.
- the film has a broad heat sealing temperature range that allows the film to be sealed on equipment capable of forming hermetic seals, such as an OSSID 500E wrapping machine.
- the film can form a hermetic seal at temperatures ranging from about 200° F. to about 400° F. on conventional packaging equipment. Sealing time typically ranges from about 500 to about 1000 milliseconds.
- the film is capable of forming a welded heat seal at temperatures ranging from about 320° F. to about 400° F.
- a welded seal is a seal with strength greater than the tear strength of the film, so that the film will tear before the seal separates.
- comprising a homogenous blend of PVC, PVC/VA and at least 15% by weight plasticizer has a broad heat sealing window, as discussed in greater detail below.
- the film of this embodiment has an OTR of about 500 cc/100 in 2 /24 hours or greater, which is desirable for food packaging.
- the film may be either biaxially oriented or uniaxially oriented, depending on the desired shrink properties. When exposed to temperatures ranging from about 180° F. to about 350° F., the film will heat shrink.
- PVC refers to vinyl chloride homopolymer.
- PVC refers to polymers formed by conventional PVC-forming processes and does not include crosslinked vinyl chloride polymers, such as those disclosed in U.S. Pat. No. 5,210,141.
- Suitable examples of PVC include those resins available from Shintech under product numbers 1150 and 1300; those resins available from Georgia Gulf under the tradename PVC 2095; those resins available from OxyVinyls under the product numbers 240, 450, and 455; and those resins available from ESSO under the product numbers 369 and 469.
- PVC/VA comprises PVC copolymerized with vinyl acetate and has a melting temperature of less than about 200° F.
- PVC/VA refers to polymers obtained by conventional polymerization processes and does not include cross-linked polymers.
- the amount of vinyl acetate monomer incorporated into the PVC/VA copolymer ranges between about 5% to about 15%.
- the amount of vinyl acetate monomer incorporated into the PVC/VA copolymer ranges from about 10% to about 13%.
- Suitable examples of PVC/VA include the following: those resins available from Occidental Chemical Cop.
- Oxychem Oxy 6338 those resins available from Formosa Plastics Formolon under product numbers 171C, 168 and 113; and those resins available from Vinnolit GmbH & Co. of Germany under the tradename Vinnolit S, product numbers 3060/10 and 3157/11.
- the amount of PVC/VA in the film affects the sealing properties of the film.
- One embodiment of the film comprises PVC/VA in an amount ranging between about 1% to about 30% by weight of the film. Stated otherwise, the amount of PVC/VA incorporated in the film is about 1 to about 30 weight parts, based on 100 weight parts of resin composition.
- Resin composition refers to the total PVC, PVC/VA, plasticizer, and other film additives discussed below. Percentage by weight is used below to describe the components of the film, however, one skilled in the art would understand that these percentages may also represent weight parts out of 100 weight parts resin composition.
- the resin composition may be only a portion of a film that contains additional components, such as particulate fillers. Alternatively, a film may include only the resin compositions disclosed.
- each component discussed above refers to its percentage by weight of the resin composition (including resins, plasticizer and additives), whether stated as a percentage by weight of a film or a percentage by weight of a resin composition, and may not represent the percentage by weight of the entire film, if other components, such as particulate fillers, are added.
- the film comprises PVC/VA in an amount ranging from about 5% to about 20% by weight of the resin composition or film. In yet another embodiment, the amount of PVC/VA ranges from about 10% to about 20% by weight of the resin composition. In still another embodiment, the amount of PVC/VA ranges from about 17% to about 20% by weight of the resin composition.
- the PVC and PVC/VA resins are highly plasticized to provide a film with flexibility and elasticity.
- the film comprises plasticizer in an amount greater than about 15% by weight of the resin composition.
- the film comprises plasticizer in an amount ranging from about 15% to about 40% by weight of the resin composition.
- the film comprises plasticizer in an amount ranging from about 15% to about 35% by resin composition weight.
- the film comprises plasticizer in an amount ranging from about 15% to about 30% by weight of the resin composition.
- the film comprises a blend of plasticizers.
- Suitable plasticizers for use in the film include di(2ethylhexyl)adipate (DEHA) and epoxidized soybean oil (ESO). ESO acts both as a plasticizer and a stabilizer.
- the film may comprise DEHA in an amount ranging from about 18% to about 25% by weight of the resin composition and ESO in an amount ranging from about 4% to about 10% by weight of the resin composition.
- DEHA include the following: those available from Sunoco under the product number PX-238; those available from Eastman under the tradename Kodaflex DOA; and those available from Solutia under the tradename DOA.
- ESO examples include the following: those available from Acme-Hardesty under the tradename Jenkinol, product number 680M; those available from Crompton Corporation under the tradename Drapex, product number 6.8; those available from Ferro Corporation under the tradename Plascheck, product number 775; those available from Atofina under the tradename Vikoflex, product number 7170; and those available from CP Hall under the tradename Paraplex G-62.
- the amount of plasticizer incorporated into the film and the film's thickness control the OTR of the film.
- the plasticizer may be increased.
- the film has an OTR of about 815 cc/100 in 2 /24 hours. OTR rates for specific examples are discussed in the examples section below.
- the film has an OTR of about 792 cc/100 in 2 /24 hours.
- the thickness of the film may also be adjusted to affect OTR.
- the film has an OTR of at least about 500 cc/100 in 2 /24 hours.
- the OTR of this film will increase by twice if the gauge of the film is reduced by half and the OTR will decrease by half if the gauge of the film is doubled.
- an embodiment with an OTR of 500 cc/100 in 2 /24 hours at 1 mil would be expected to have an OTR of at least about 1000 cc/100 in 2 /24 hours at a thickness of 0.5 mil.
- a film of the same composition would be expected to have an OTR of at least about 125 cc/100 in 2 /24 hours at a thickness of 3 mils.
- the film may also comprise additives such as stabilizer, antifog, lubricant, slip agent and antiblock.
- stabilizers include tris-nonylphenyl phosphite (“TNPP”) , and a blend of calcium and zinc fatty acid soaps (“Ca/Zn”) .
- TNPP include the following: those available from Witco under the tradename Mark C; those available from Dover Chemical under the tradename Doverphos; those available from Huntsman Chemical under the tradename Weston TNPP; and those available from Uniroyal under the tradenames Wytox 312 and Naugard P.
- CaZn examples include: those available from Cognis under the tradename Stabiol VCZ-2200, those available from Akzo Nobel under the tradename Interstab, product numbers CZL-720 and CZ-11; those available from Ferro Corp under the tradename Thermocheck, product numbers 760X and 760; those available from Blatchford under the tradename Chemstab R6100; and those available from Witco under the tradename Mark 152.
- the film comprises stabilizer in an amount up to about 2% by weight of the resin composition. In another embodiment, the film comprises stabilizer in an amount ranging from about 0.4% to about 2% by weight of the composition.
- Suitable examples of antifog include: glycerol mono-oleate, such as those available from American Ingredients under the tradename Pationic, product numbers 1530 and 1087 and from Crompton under the tradename Atmer 400; sorbitan mono-oleate, such as those available from CIBA Specialty Chemical (“CIBA”) under the tradename Atmer 105; sorbitan mono-laurate such as those available from CIBA Specialty Chemical (“CIBA”) under the tradename Atmer 100; sorbitan mono-stearate such as those available from CIBA under the tradename Atmer 103; poly-oxy-ethylene (20) sorbitan mono-oleate such as those available from CIBA Specialty Chemical (“CIBA”) under the tradename Atmer 116, from Witco under the tradenames Flo-Mo-SMO 20 and Witconol 2722, from Lonza under the tradename Glycosperse 0-20, and from Specialty Ind.
- CIBA CIBA Specialt
- the film comprises antifog in an amount up to about 3% by weight of the resin composition. In another embodiment, the film comprises antifog in an amount ranging from about 0.8% to about 3.5% by weight of the resin composition.
- Suitable examples of lubricant include stearic acid, such as stearic acid available from Crompton under the tradenames Hystrene 5016, Emersol 136 and Hystrene 5016 and from Acme Hardesty under the tradename 6ORGSA; lauric acid; palmetic acid; and polyethylene wax; such as the waxes available from Allied Signal under the product numbers AC629A and AC316A and from Texas Eastman under the tradename Epolene E-14P.
- the film comprises lubricant in an amount ranging from about 0.1% to about 0.6% by weight of the resin composition.
- slip agent examples include ethylene bis-oleamide and erucamide slip.
- ethylene bis-oleamide examples include: those available from Crompton under the tradename Kemamide W-20; those available from Croda under the tradename Crodaflex EBO; those available from Morton International under the tradename Advawax 240; and those available from Lonza under the tradename Glycolub VL.
- erucamide slip examples include those available from Crompton under the tradename Kemamide E.
- the film contains slip in an amount sufficient to enable the film to shrink around a package without becoming caught on the edge of the package when the film shrinks.
- the film comprises slip agent in an amount ranging from about 0.05% to about 0.6% by weight.
- the film comprises slip agent in an amount ranging from about 0.1% to about 0.5% by weight.
- antiblock examples include: silica antiblock such as those available from Crosfield under the tradename Gasil 144; silica aerogel, such as those available from Grace/Davison under the tradename Syloid 74; and zeospheres, also known as clay microbeads, such as those available from 3M under the product number W210.
- the antiblock is present in an amount up to about 0.6% by weight of the resin composition.
- the film may be a single layer film.
- one or more layers of the resin compositions described herein may be included in a film with layers of other compositions.
- the embodiments of the film discussed above may be formed by blending PVC homopolymer resin and all additive ingredients in a high intensity mixer, such as a Henschel mixer.
- a high intensity mixer such as a Henschel mixer.
- suitable mixers include Papenmeier mixers and Welex mixers.
- the action of the mixer drives the temperature of the PVC polymer resin particles by shear and friction to a point at which the particles swell and retain by adsorption the plasticizers, the other liquid additives, solid additives with lower melt points coating the particles and other solid additives dispersed among the PVC resin particles.
- the PVC resin particles will form a granular free flowing powder called a dry blend.
- PVC/VA resin is also added during this blending cycle, in which it also adsorbs a share of plasticizers, stabilizers and other additives, and all ingredients become evenly dispersed.
- the blend is dropped into a holding and cooling blender at a temperature which is high enough to permit even adsorption of additives among the PVC resin particles and lower than the point at which the resin particles begin to melt or agglomerate into clumps.
- Suitable holding and cooling blenders include Ribbon Blenders and High Intensity Henschel Cooler.
- the PVC/VA resin softens and begins to melt at a much lower temperature than the PVC homopolymer resin. As a result the maximum or drop temperature for blending highly plasticized PVC and PVC/VA is lower than a blend PVC homopolymer and plasticizer alone.
- a lower maximum temperature prevents the PVC/VA resin particles from partially melting and agglomerating into clumps, and allowing the plasticizers and other additives to be uniformly adsorbed into the resin particles.
- PVC/VA resin, PVC resin and plasticizer, in the amounts described above can be blended into a homogenous mixture at maximum temperatures less than about 195° F.
- the resins and plasticizer, in the amounts described above can be blended into a homogenous mixtures at maximum temperatures less than about 190° F.
- the resins and plasticizer, in the amounts described above can be blended into a homogenous mixtures at maximum temperatures less than about 185° F.
- the PVC, plasticizer, and PVC/VA are blended into a homogeneous mixture at maximum temperatures ranging from 183° F. to about 187° F.
- a homogenous mixture of PVC/VA and PVC refers to a blend in which all materials are evenly distributed, so that a film formed from the blend is smooth and uniform, without gels or lumps.
- the finished granular powder blend may be melted and extruded directly into film using a single screw extruder.
- the powder may be melted and extruded into pellets with a suitable extruder.
- the pellets are melted and extruded into film by blown or cast film extrusion method, using a single screw extruder.
- the secondary step of making the powder blend into pellets gives extra mixing to disperse the PVC/VA resin more completely into the film structure.
- the film may be irradiated to crosslink polymers in the film.
- the film is oriented.
- the film is oriented in the machine direction in an amount ranging from about 50% to about 400% of its original length. When exposed to temperatures ranging from about 180° F. to about 200° F., the oriented film will shrink less than about 60% of its original length.
- the film is biaxially oriented, about 50% to about 400% of its original length in both the machine direction and the transverse direction. When exposed to temperatures ranging from about 180° F. to about 200° F., the film will heat shrink less than 80% in the machine and transverse directions.
- the biaxially oriented film will heat shrink between about 30% to about 50% in both the machine and transverse directions.
- the film may be biaxially oriented with a double bubble method. Alternatively, the film may be biaxially oriented using a tenter frame and a machine direction orienter.
- the embodiments discussed above provide good OTR, with an OTR of at least 500 cc/100 inches/24 hours for a film with a thickness of about 1 mil. Also, as discussed above, the OTR can be controlled by varying the amount of plasticizer in the film.
- the embodiments discussed above are also capable of forming a welded heat seal on conventional packaging equipment, such as an OSSID 500E. Heat seals are permanent bonds between layers of film by the application of pressure and heat over a specified period of time, the dwell time. A heat seal is generally formed by causing the film surfaces to melt and flow together. Unlike other polymer film structures, plasticized PVC does not have a sharp or well defined melt point, but goes through progressive softening levels. PVC is an amorphous non-crystalline polymer, and with the addition of relatively large amounts of plasticizer and other additives, forms a rubbery state.
- PVC films may form three types of heat seals: cling seals, heat tack (or peel) seals and welded seals, the first two of which are false seals.
- the true heat seal is called a welded seal, and is defined by being as strong or stronger than the surrounding film.
- a welded seal has a strength equivalent to or greater than the film's tear strength.
- the inventive film has a broad heat sealing window over which the film can form a welded seal.
- a broad heat sealing window permits manufacturing equipment to overshoot the sealing temperature to provide a complete seal without burning the films.
- the heat sealing window is the difference between the temperature at which the film begins to form a welded seal and the temperature at which the film begins to burn through. Burn through means that the film separates and forms holes or begins to disintegrate in response to heat.
- the heat sealing window is determined by the amount of PVC/VA included in the film. Additives can also affect the heat sealing window and the sealing temperatures of the films. For example, in an embodiment of the film comprising 61% PVC, 28% plasticizer and 12% PVC/VA, the film begins to seal at 313° F.
- the heat sealing window is 85° F. More examples and their heat sealing ranges are discussed below.
- the film is capable of forming a welded heat seal above about 320° F. and has a heat sealing window greater than about 20° F. In another embodiment the film has a heat seal window greater than 30° F. In yet another embodiment, the heat sealing window is greater than 40° F.
- the heat sealing temperature range refers the range of temperatures over which the film may form a welded heat seal. For example, for a film with a heat sealing range of 40° F., if the film begins to seal at 300° F., the film will be able to seal at temperatures up to 340° F.
- seals may be formed at low temperatures, such as delaminating seals and cling seals.
- Delaminating seals appear to be welded, but can be worked loose or can be separated by hand peeling at the interface between the sealed layers.
- Cling seals are the result of a film's cling or electrostatic attraction and also stress relaxation (dead fold) properties as the surfaces wet together.
- Cling seals are more easily loosened or separated than the delaminating seal during package handling or transportation.
- Cling seals are also easily separated by hand, and are affected by moisture.
- a cling seal may occur at room temperature with sufficient pressure and time.
- Hot tack refers to the strength of the seal immediately following sealing and before the seal has fully cooled.
- film used to wrap food products on a tray is oriented and is heat shrinkable. When the film is heat sealed around a product, the film will shrink somewhat in response to the heat used to seal the film. If the film does not have sufficient hot tack seal strength, the seal can come apart in response to shrinking immediately upon heat sealing.
- the wrapped product proceeds to a heat shrinking tunnel just after the film is heat sealed. As a result, the seal may not have cooled completely before the film heat shrinks around the product.
- Good hot tack seal strength helps keep the seal intact when the film heat shrinks following formation of the heat seal.
- the film forms a seal with a hot tack seal strength of at least 60 grams/mil over a broad range of temperatures.
- Seal strength is expressed in grams/mil (also referred to as g/mil or grams force per mil of thickness) or grams/in (also referred to as g/in or grams force per inch) in the description above and in the examples below.
- the film is described in detail below, but the invention is not limited by these examples.
- the PVC and PVC/VA if included, were blended in a high intensity blender with plasticizers and any other additives.
- the resulting powder was extruded into pellets and the pellets were extruded into film, forming film samples. Sealing properties, tear strength and OTR were measured for Examples 1-3.
- hot tack seal strength of the sample films were tested by sealing at temperatures ranging from 220° F. to 350° F.
- the sample films were sealed in a fin seal with sealing jaws at 60 psi of pressure with a dwell time of 1000 milliseconds or 500 milliseconds, as specified below.
- the hot tack seal strengths for each sealing temperature were measured at 500 milliseconds or 250 milliseconds following seal formation. Note that seal strengths of less than 20 g/in can be caused by cling between the film and may not be the result of heat sealing.
- the sample films of Example 1 comprise: 54.84% by weight PVC, 12.46% by weight PVC/VA, and 28.27% by weight plasticizer.
- the films of Example 1 further comprise minor amounts of additives: 1.47% by weight stabilizer, 2.02% by weight antifog, 0.24% by weight slip, 0.1% by weight lubricant, 0.17% by weight slip, and 0.44% by weight antiblock.
- Example 1 A film of Example 1 was formed with a gauge of 1 mil. The film was tested for OTR and for heat sealing characteristics. The film had an OTR of 1025.9 cc/100 in 2 /24 hours. The film formed a welded seal, beginning at a temperature of 328° F. and a burn through temperature of 421° F., providing a 93° F. heat sealing window.
- the sample films of Comparative Example 1 comprise: 68.51% by weight PVC, 0% PVC/VA, and 28.09% by weight plasticizer.
- the Comparative Example 1 film samples further comprise minor amounts of additives: 2.06% by weight stabilizer, 1.16% by weight antifog, 0.18% by weight lubricant and 0.14% by weight slip.
- FIG. 1 shows the hot tack seal strength over seal temperature for samples of Example 1 and Comparative Example 1, measured 250 milliseconds following release of the sealing jaws.
- FIG. 2 shows seal strengths over seal temperature, measured 500 millisecond following release of the sealing jaws.
- the film was sealed with a dwell time of 500 milliseconds.
- Table A shows the data from this testing for Example 1
- Table B shows the results of testing.
- Table C shows the results of testing.
- films for packaging fresh produce should be capable of sealing along a temperature range that is sufficiently broad to allow conventional heat sealing equipment to create a reliable seal that will remain intact when the film heat shrinks as a result of heat sealing and proceeds into a heat shrinking tunnel immediately following sealing.
- the film of Example 1 a blend of plasticized PVC and PVC/VA copolymer
- the film of Example 1 also achieves hot tack seal strengths over 60 g/in at temperatures ranging from 280° F. to 320° F.
- the sample films of Example 2 comprise: 54.92% by weight PVC; 12.48% PVC/VA; and 28.31% by weight plasticizer.
- the sample films further comprise minor amounts of additives: 1.47% by weight of stabilizer; 2.02% by weight antifog; 0.33% by weight slip; 0.17% by weight lubricant; and 0.30% by weight antiblock.
- Example 2 A film of Example 2 was formed with a gauge of I mil. The film was tested for OTR and for heat sealing characteristics. The film had an OTR of 904 cc/100 in 2 /24 hours. The film formed a welded seal beginning at a temperature of 313° F. and a burn through temperature of 398° F., providing an 85° F. heat sealing window.
- Example 2 Three samples of Example 2 were tested for hot tack seal strength. The data from this testing is shown in Tables E-F.
- FIG. 3 is a graph of the hot tack heat seal data 250 ms following sealing as shown in Table E (Example 2) and Table C (Comparative Example 1).
- FIG. 4 is a graph of hot tack heat seal 500 ms following sealing, as shown in Table F (Example 2) Table D (Comparative Example 1).
- Example 2 provides higher tack seal strength than Comparative Example 1 over a broad temperature range.
- Example 2 sample films comprise the composition disclosed above.
- Example 3 sample films comprise: 61.16% by weight PVC, 6.24% PVC/VA, 28.31% by weight plasticizer.
- the films of Example 3 further comprise minor amounts of additives: 1.48% by weight stabilizer, 2.02% by weight stabilizer, 0.33% by weight slip, 0.17% by weight lubricant, and 0.30% by weight antiblock.
- Example 3 A film of Example 3 was formed with a gauge of 1 mil. The film was tested for OTR and for heat sealing characteristics. The film had a OTR of 818.8 cc/100 in 2 /24 hours. The film formed a welded seal, beginning at a temperature of 356° and a burn through temperature of 416°, providing a 60° F. heat sealing window.
- Table E above and Table G below show hot tack heat seal strengths for Examples 2 and 3 over different sealing temperatures, measured 250 milliseconds following heat sealing.
- Table F above and Table H below show heat seal strengths for Examples 2 and 3 from sealing at temperatures ranging from 220° F. to 350° F.
- FIG. 5 is a graph of the data in Tables E and G and
- FIG. 6 is a graph of the data in Tables F and H.
- the films of Example 3 comprise 6.24% by weight PVC/VA and the films of Example 2 comprise 12.48% by weight PVC/VA. As shown in FIGS. 5 and 6, both Examples 2 and 3 provide films with broad heat sealing temperature ranges and good hot tack seal strength.
- the sample films of Example 4 comprise: 55.87% by weight PVC, 10.00 PVC/VA, and 18.99% by weight plasticizer.
- the films of Example 4 further comprise minor amounts of additives: 1.56% by weight stabilizer; 0.96% antifog; 0.12% by weight slip, 0.23% lubricant; and 2.27% by weight antiblock.
- the sample films of Comparative Example 2 comprise: 68.06% by weight of PVC; 0% by weight of PVC/VA; and 26.24% by weight of plasticizer.
- the films of Example 5 further comprise additives: 1.48% by weight stabilizer; 1.23% by weight of antifog; 0.13% by weight of slip; 0.24% by weight lubricant; and 2.46% by weight antiblock.
- Example 4 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 1 14 18 27 30 37 69 53 64 53 65 64 80 113 67 Seal (g/in) Sample 2 23 18 37 32 57 37 57 41 60 65 60 110 88 83 Seal (g/in) Sample 3 25 21 27 41 42 50 48 67 51 51 103 94 80 80 Seal (g/in) Avg. 21 19 30 34 45 52 53 57 55 60 76 95 94 77 Seal (g/in)
- Example 4 has a broader heat seal range than Comparative Example 2.
- Example 4 also provides good hot tack seal strengths over a wide range of sealing temperatures.
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Abstract
Description
- This application is a continuation of U.S. application Ser. No. 10/429,054, filed May 2, 2003, currently pending, which is a continuation-in-part of U.S. application Ser. No. 09/715,874 titled Polymer Composite Packaging Film for Fresh Meat and Vegetable produce, currently pending. The disclosure of U.S. application Ser. Nos. 09/715,874 and 10/429,054 is hereby incorporated by reference.
- [Not Applicable]
- [Not Applicable]
- This invention relates to packaging films for fresh meat and vegetable produce and, in particular, a packaging film that is heat sealable, heat shrinkable and has a controlled gas permeability rate.
- Optically transparent films useful for covering food product containers and packaging food products are ideally formulated to provide consumers with a clear view of the packaged food product while maintaining its appearance and freshness. Films with oxygen transmission rate (OTR) control properties extend the shelf life of refrigerated freshly cut produce and fresh meat since the presence of either too much or too little oxygen in the package lowers shelf life. For example, in the packaging of lettuce, excessive oxygen in the package results in enzymatic browning of cut surfaces of the lettuce. On the other hand, insufficient oxygen in the package results in lettuce spoilage caused by anaerobiosis. Similarly, fresh meat packaging permits delivery of sufficient oxygen to the myoglobin contained within the meat to maintain its natural red color and thus achieve the fresh looking product preferred by consumers.
- Packaging films made from polyvinyl chloride (PVC) and plasticizer have been used to wrap red meat and produce. PVC films provide a sparkling clear view of the packaged product, and, when formulated with plasticizers, exhibit cling and stretch properties. However, it is often desirable to wrap the food product on a tray, heat seal the film around the tray and heat shrink the film. Conventional PVC packaging films have difficulty forming hermetic seals because PVC has a narrow sealing range. The precision required to seal conventional PVC films is too high for manufacturing with conventional packaging equipment.
- Packaging films made from olefinic materials can be formulated to control OTR, to seal to themselves and to be heat shrinkable at lower temperatures than conventional PVC films. However, films of olefinic materials are susceptible to surface moisture buildup in the form of small beads that obscure a consumer's view of the product contained in the package. Reducing fog (surface moisture buildup) in olefinic films by adding standard anti-fog agents has been largely unsuccessful. Anti-fog agents are difficult to contain on the film surface because they tend to wash off. Anti-fog agents also interfere with other film surface properties of the olefinic film making it difficult to print and seal.
- In other packaging technology areas, films for applications such as contact packaging for bottles or base films for pharmaceutical packaging have used blends of conventional PVC, meaning non-crosslinked PVC resin, and conventional PVC/VA, meaning non-crosslinked PVC/VA resin. For example, U.S. Pat. No. 6,265,041 discloses a film for use as a cover sheet in pharmaceutical packaging. The disclosed film comprises between 1-80% by weight of a PVC resin and 20-99% by weight of a PVC/VA resin. U.S. Pat. No. 4,264,010 discloses a shrink wrap film for contact packaging products, such as a large bottle for carbonated beverages. The disclosed film comprises PVC and 5 to 20 parts by weight PVC/VA.
- While the disclosed films comprise PVC/VA and PVC, these films require no controlled OTR and contain only small amounts of plasticizer. For example, in the film disclosed in U.S. Pat. No. 6,265,041, the amount of plasticizer is less than 2% by weight of the resin portion of the film. U.S. Pat. No. 6,265,041 discloses examples of film containing ESO, a plasticizer, in amounts ranging from 1.5 parts by weight out of 114.5 parts of resin composition to about 2.0 parts by weight out of 113 parts of resin composition. Stated in percentages by weight, these amounts range from 1.3% by weight of the resin composition to 1.8% by weight of the resin composition.
- For the examples of films with PVC and PVC/VA blends disclosed in U.S. Pat. No. 4,264,010, the amount of plasticizer ranges from 11 to 17 weight parts out of 119.7 parts to 141.7 parts. Stated in percentage by weight, the amount of plasticizer in these examples ranges from about 9% to about 12% by weight of the film.
- While homogenous blends of conventional PVC and conventional PVC/VA may have been achieved with these low levels of plasticizer, it has generally been believed that blending highly plasticized PVC with a copolymer such as PVC/VA was too difficult to manufacture commercially. PVC resins are typically blended with a high speed impeller, which creates heat by friction. PVC/VA fuses at a lower temperature than PVC, so PVC/VA will tend to agglomerate and fuse together at the temperatures required to blend PVC. If the PVC/VA forms agglomerates, the PVC/VA agglomerate may discolor when exposed to heat during processing, forming black impurities in any film formed from the blend.
- It would be desirable, therefore, to have available a film that is optically transparent and has a controllable OTR. A film that is heat shrinkable and that may be hermetically sealed to itself by conventional packaging equipment is also needed.
- One embodiment of the film comprises a blend of vinyl chloride homopolymer (hereinafter referred to as PVC) and copolymer of vinyl chloride and vinyl acetate (hereinafter referred to as PVC/VA). PVC/VA is sometimes referred to as poly(vinyl chloride-co vinyl acetate). The embodiment comprises about 18% by weight PVC/VA. The embodiment further comprises at least about 15% by weight plasticizer. A homogenous blend of these components was achieved by following the blending steps described in more detail below.
- Such a film has several properties beneficial for food packaging film. The film has a broad heat sealing temperature range that allows the film to be sealed on equipment capable of forming hermetic seals. Depending on the particular composition, the film can form a welded, hermetic seal at temperatures ranging from about 200° F. sealing time typically ranges up to about 1000 milliseconds.
- This embodiment is further capable of sealing over a heat sealing window that is sufficiently broad so that the film may be sealed on conventional packaging equipment. In addition, the film has an OTR of about 500 cc/100 in2/24 hours or greater, which is desirable for food packaging. During processing the film may be either biaxially oriented or uniaxially oriented, depending on the desired shrink properties. When exposed to temperatures ranging from about 180° F. to about 350° F., the film will heat shrink.
- Additional aspects and advantages of this invention will be apparent from the following detailed description of specific embodiments, which proceeds with reference to the accompanying drawings.
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FIG. 1 is a graph of hot tack seal strength of sample film of Example 1 and Comparative Example 1, measured 250 ms following seal formation. -
FIG. 2 is a graph of hot tack seal strength of sample films of Example 1 and Comparative Example 1, measured 500 ms following seal formation. -
FIG. 3 is a graph of hot tack seal strength of sample films of Example 2 and Comparative Example 1, measured 250 ms following seal formation. -
FIG. 4 is a graph of hot tack seal strength of sample films of Example 2 and Comparative Example 1, measured 500 ms following seal formation. -
FIG. 5 is a graph of hot tack seal strength of sample films of Example 2 and Example 3, measured 250 ms following seal formation. -
FIG. 6 is a graph of hot tack seal strength of sample films of Example 2 and Example 3, measured 500 ms following seal formation. -
FIG. 7 is a graph of hot tack seal strength of sample of Example 4 and Comparative Example 2, measured 250 ms following seal formation. -
FIG. 8 is a graph of hot tack seal strength of sample of Example 4 and Comparative Example 2, measured 500 ms following seal formation. - In one embodiment, the film comprises a blend of two polyvinyl chloride resins: vinyl chloride homopolymer and copolymer of vinyl chloride and vinyl acetate. PVC/VA is sometimes referred to as poly(vinyl chloride-co vinyl acetate). The embodiment comprises about 18% by weight PVC/VA. The embodiment further comprises at least about 15% by weight plasticizer. A homogenous blend of these components was achieved by following the blending steps described in more detail below.
- Such a film has several properties beneficial for food packaging film. The film has a broad heat sealing temperature range that allows the film to be sealed on equipment capable of forming hermetic seals, such as an OSSID 500E wrapping machine. Depending on the particular composition, the film can form a hermetic seal at temperatures ranging from about 200° F. to about 400° F. on conventional packaging equipment. Sealing time typically ranges from about 500 to about 1000 milliseconds.
- In one embodiment, the film is capable of forming a welded heat seal at temperatures ranging from about 320° F. to about 400° F. A welded seal is a seal with strength greater than the tear strength of the film, so that the film will tear before the seal separates. In the embodiment discussed above, comprising a homogenous blend of PVC, PVC/VA and at least 15% by weight plasticizer, has a broad heat sealing window, as discussed in greater detail below.
- The film of this embodiment has an OTR of about 500 cc/100 in2/24 hours or greater, which is desirable for food packaging. During processing the film may be either biaxially oriented or uniaxially oriented, depending on the desired shrink properties. When exposed to temperatures ranging from about 180° F. to about 350° F., the film will heat shrink.
- As mentioned above, PVC refers to vinyl chloride homopolymer. As used herein, PVC refers to polymers formed by conventional PVC-forming processes and does not include crosslinked vinyl chloride polymers, such as those disclosed in U.S. Pat. No. 5,210,141. Suitable examples of PVC include those resins available from Shintech under product numbers 1150 and 1300; those resins available from Georgia Gulf under the tradename PVC 2095; those resins available from OxyVinyls under the
product numbers 240, 450, and 455; and those resins available from ESSO under the product numbers 369 and 469. - PVC/VA comprises PVC copolymerized with vinyl acetate and has a melting temperature of less than about 200° F. As used herein, PVC/VA refers to polymers obtained by conventional polymerization processes and does not include cross-linked polymers. In one embodiment, the amount of vinyl acetate monomer incorporated into the PVC/VA copolymer ranges between about 5% to about 15%. In another embodiment, the amount of vinyl acetate monomer incorporated into the PVC/VA copolymer ranges from about 10% to about 13%. Suitable examples of PVC/VA include the following: those resins available from Occidental Chemical Cop. under the tradename Oxychem Oxy 6338; those resins available from Formosa Plastics Formolon under product numbers 171C, 168 and 113; and those resins available from Vinnolit GmbH & Co. of Germany under the tradename Vinnolit S, product numbers 3060/10 and 3157/11.
- As discussed in more detail below, the amount of PVC/VA in the film affects the sealing properties of the film. One embodiment of the film comprises PVC/VA in an amount ranging between about 1% to about 30% by weight of the film. Stated otherwise, the amount of PVC/VA incorporated in the film is about 1 to about 30 weight parts, based on 100 weight parts of resin composition.
- Resin composition, as used herein, refers to the total PVC, PVC/VA, plasticizer, and other film additives discussed below. Percentage by weight is used below to describe the components of the film, however, one skilled in the art would understand that these percentages may also represent weight parts out of 100 weight parts resin composition. The resin composition may be only a portion of a film that contains additional components, such as particulate fillers. Alternatively, a film may include only the resin compositions disclosed. The amounts of each component discussed above refer to its percentage by weight of the resin composition (including resins, plasticizer and additives), whether stated as a percentage by weight of a film or a percentage by weight of a resin composition, and may not represent the percentage by weight of the entire film, if other components, such as particulate fillers, are added.
- Referring to another embodiment, the film comprises PVC/VA in an amount ranging from about 5% to about 20% by weight of the resin composition or film. In yet another embodiment, the amount of PVC/VA ranges from about 10% to about 20% by weight of the resin composition. In still another embodiment, the amount of PVC/VA ranges from about 17% to about 20% by weight of the resin composition.
- The PVC and PVC/VA resins are highly plasticized to provide a film with flexibility and elasticity. In one embodiment, the film comprises plasticizer in an amount greater than about 15% by weight of the resin composition. In another embodiment, the film comprises plasticizer in an amount ranging from about 15% to about 40% by weight of the resin composition. In another embodiment, the film comprises plasticizer in an amount ranging from about 15% to about 35% by resin composition weight. In yet another embodiment, the film comprises plasticizer in an amount ranging from about 15% to about 30% by weight of the resin composition. In one embodiment, the film comprises a blend of plasticizers.
- Suitable plasticizers for use in the film include di(2ethylhexyl)adipate (DEHA) and epoxidized soybean oil (ESO). ESO acts both as a plasticizer and a stabilizer. For example, the film may comprise DEHA in an amount ranging from about 18% to about 25% by weight of the resin composition and ESO in an amount ranging from about 4% to about 10% by weight of the resin composition. Examples of DEHA include the following: those available from Sunoco under the product number PX-238; those available from Eastman under the tradename Kodaflex DOA; and those available from Solutia under the tradename DOA. Examples of ESO include the following: those available from Acme-Hardesty under the tradename Jenkinol, product number 680M; those available from Crompton Corporation under the tradename Drapex, product number 6.8; those available from Ferro Corporation under the tradename Plascheck, product number 775; those available from Atofina under the tradename Vikoflex, product number 7170; and those available from CP Hall under the tradename Paraplex G-62.
- The amount of plasticizer incorporated into the film and the film's thickness control the OTR of the film. As the amount of plasticizer increases and the gauge of the film decreases, the breathability of the film increases. Therefore, if a higher OTR is desired, the plasticizer may be increased. For example, in an embodiment containing plasticizer in an amount of about 26% by weight of the resin composition and a gauge of about 1 mil, the film has an OTR of about 815 cc/100 in2/24 hours. OTR rates for specific examples are discussed in the examples section below. In another embodiment containing plasticizer in an amount of about 23% and a gauge of about 1 mil, the film has an OTR of about 792 cc/100 in2/24 hours. The thickness of the film may also be adjusted to affect OTR. In one embodiment, comprising at least about 15% plasticizer and a thickness of 1 mil, the film has an OTR of at least about 500 cc/100 in2/24 hours. The OTR of this film will increase by twice if the gauge of the film is reduced by half and the OTR will decrease by half if the gauge of the film is doubled. Thus an embodiment with an OTR of 500 cc/100 in2/24 hours at 1 mil would be expected to have an OTR of at least about 1000 cc/100 in2/24 hours at a thickness of 0.5 mil. Similarly, an embodiment, that at 1.0 mil has an OTR of 500 cc/100 in2/24 hours, would be expected to have an OTR of at least about 250 cc/100 in2/24 hours at a thickness of 2 mils. A film of the same composition would be expected to have an OTR of at least about 125 cc/100 in2/24 hours at a thickness of 3 mils.
- The film may also comprise additives such as stabilizer, antifog, lubricant, slip agent and antiblock. Suitable examples of stabilizers include tris-nonylphenyl phosphite (“TNPP”) , and a blend of calcium and zinc fatty acid soaps (“Ca/Zn”) . Examples of TNPP include the following: those available from Witco under the tradename Mark C; those available from Dover Chemical under the tradename Doverphos; those available from Huntsman Chemical under the tradename Weston TNPP; and those available from Uniroyal under the tradenames Wytox 312 and Naugard P. Examples of CaZn include: those available from Cognis under the tradename Stabiol VCZ-2200, those available from Akzo Nobel under the tradename Interstab, product numbers CZL-720 and CZ-11; those available from Ferro Corp under the tradename Thermocheck, product numbers 760X and 760; those available from Blatchford under the tradename Chemstab R6100; and those available from Witco under the tradename Mark 152. In one embodiment, the film comprises stabilizer in an amount up to about 2% by weight of the resin composition. In another embodiment, the film comprises stabilizer in an amount ranging from about 0.4% to about 2% by weight of the composition.
- Suitable examples of antifog include: glycerol mono-oleate, such as those available from American Ingredients under the tradename Pationic, product numbers 1530 and 1087 and from Crompton under the tradename Atmer 400; sorbitan mono-oleate, such as those available from CIBA Specialty Chemical (“CIBA”) under the tradename Atmer 105; sorbitan mono-laurate such as those available from CIBA Specialty Chemical (“CIBA”) under the
tradename Atmer 100; sorbitan mono-stearate such as those available from CIBA under the tradename Atmer 103; poly-oxy-ethylene (20) sorbitan mono-oleate such as those available from CIBA Specialty Chemical (“CIBA”) under the tradename Atmer 116, from Witco under the tradenames Flo-Mo-SMO 20 and Witconol 2722, from Lonza under the tradename Glycosperse 0-20, and from Specialty Ind. Chem. under thetradename Polysorbac 80; and ethoxylated nonylphenol, such as those available from Huntsman Chemical under the tradename Surfonic N-60. In one embodiment, the film comprises antifog in an amount up to about 3% by weight of the resin composition. In another embodiment, the film comprises antifog in an amount ranging from about 0.8% to about 3.5% by weight of the resin composition. - Suitable examples of lubricant include stearic acid, such as stearic acid available from Crompton under the tradenames Hystrene 5016, Emersol 136 and Hystrene 5016 and from Acme Hardesty under the tradename 6ORGSA; lauric acid; palmetic acid; and polyethylene wax; such as the waxes available from Allied Signal under the product numbers AC629A and AC316A and from Texas Eastman under the tradename Epolene E-14P. In one embodiment, the film comprises lubricant in an amount ranging from about 0.1% to about 0.6% by weight of the resin composition.
- Suitable examples of slip agent include ethylene bis-oleamide and erucamide slip. Examples of ethylene bis-oleamide include: those available from Crompton under the tradename Kemamide W-20; those available from Croda under the tradename Crodaflex EBO; those available from Morton International under the
tradename Advawax 240; and those available from Lonza under the tradename Glycolub VL. Examples of erucamide slip include those available from Crompton under the tradename Kemamide E. In one embodiment, the film contains slip in an amount sufficient to enable the film to shrink around a package without becoming caught on the edge of the package when the film shrinks. In one embodiment, the film comprises slip agent in an amount ranging from about 0.05% to about 0.6% by weight. In another embodiment, the film comprises slip agent in an amount ranging from about 0.1% to about 0.5% by weight. - Suitable examples of antiblock include: silica antiblock such as those available from Crosfield under the tradename Gasil 144; silica aerogel, such as those available from Grace/Davison under the tradename Syloid 74; and zeospheres, also known as clay microbeads, such as those available from 3M under the product number W210. In one embodiment, the antiblock is present in an amount up to about 0.6% by weight of the resin composition.
- The film may be a single layer film. Alternatively, one or more layers of the resin compositions described herein may be included in a film with layers of other compositions.
- The embodiments of the film discussed above may be formed by blending PVC homopolymer resin and all additive ingredients in a high intensity mixer, such as a Henschel mixer. Other suitable mixers include Papenmeier mixers and Welex mixers. The action of the mixer drives the temperature of the PVC polymer resin particles by shear and friction to a point at which the particles swell and retain by adsorption the plasticizers, the other liquid additives, solid additives with lower melt points coating the particles and other solid additives dispersed among the PVC resin particles. The PVC resin particles will form a granular free flowing powder called a dry blend. PVC/VA resin is also added during this blending cycle, in which it also adsorbs a share of plasticizers, stabilizers and other additives, and all ingredients become evenly dispersed.
- The blend is dropped into a holding and cooling blender at a temperature which is high enough to permit even adsorption of additives among the PVC resin particles and lower than the point at which the resin particles begin to melt or agglomerate into clumps. Suitable holding and cooling blenders include Ribbon Blenders and High Intensity Henschel Cooler. The PVC/VA resin softens and begins to melt at a much lower temperature than the PVC homopolymer resin. As a result the maximum or drop temperature for blending highly plasticized PVC and PVC/VA is lower than a blend PVC homopolymer and plasticizer alone. A lower maximum temperature prevents the PVC/VA resin particles from partially melting and agglomerating into clumps, and allowing the plasticizers and other additives to be uniformly adsorbed into the resin particles. PVC/VA resin, PVC resin and plasticizer, in the amounts described above, can be blended into a homogenous mixture at maximum temperatures less than about 195° F. In another embodiment, the resins and plasticizer, in the amounts described above, can be blended into a homogenous mixtures at maximum temperatures less than about 190° F. In another embodiment, the resins and plasticizer, in the amounts described above, can be blended into a homogenous mixtures at maximum temperatures less than about 185° F. In another embodiment, the PVC, plasticizer, and PVC/VA are blended into a homogeneous mixture at maximum temperatures ranging from 183° F. to about 187° F. As used herein, a homogenous mixture of PVC/VA and PVC refers to a blend in which all materials are evenly distributed, so that a film formed from the blend is smooth and uniform, without gels or lumps.
- The finished granular powder blend may be melted and extruded directly into film using a single screw extruder. Alternatively, the powder may be melted and extruded into pellets with a suitable extruder. The pellets are melted and extruded into film by blown or cast film extrusion method, using a single screw extruder. The secondary step of making the powder blend into pellets gives extra mixing to disperse the PVC/VA resin more completely into the film structure. Following extrusion, the film may be irradiated to crosslink polymers in the film.
- Following formation of the film, the film is oriented. In one embodiment, the film is oriented in the machine direction in an amount ranging from about 50% to about 400% of its original length. When exposed to temperatures ranging from about 180° F. to about 200° F., the oriented film will shrink less than about 60% of its original length. In one embodiment, the film is biaxially oriented, about 50% to about 400% of its original length in both the machine direction and the transverse direction. When exposed to temperatures ranging from about 180° F. to about 200° F., the film will heat shrink less than 80% in the machine and transverse directions. In one embodiment, the biaxially oriented film will heat shrink between about 30% to about 50% in both the machine and transverse directions. The film may be biaxially oriented with a double bubble method. Alternatively, the film may be biaxially oriented using a tenter frame and a machine direction orienter.
- The embodiments discussed above provide good OTR, with an OTR of at least 500 cc/100 inches/24 hours for a film with a thickness of about 1 mil. Also, as discussed above, the OTR can be controlled by varying the amount of plasticizer in the film. The embodiments discussed above are also capable of forming a welded heat seal on conventional packaging equipment, such as an OSSID 500E. Heat seals are permanent bonds between layers of film by the application of pressure and heat over a specified period of time, the dwell time. A heat seal is generally formed by causing the film surfaces to melt and flow together. Unlike other polymer film structures, plasticized PVC does not have a sharp or well defined melt point, but goes through progressive softening levels. PVC is an amorphous non-crystalline polymer, and with the addition of relatively large amounts of plasticizer and other additives, forms a rubbery state.
- Additionally, the embodiments described above are capable of forming welded seal at a wide temperature window. PVC films may form three types of heat seals: cling seals, heat tack (or peel) seals and welded seals, the first two of which are false seals. The true heat seal is called a welded seal, and is defined by being as strong or stronger than the surrounding film. When attempting to separate the layers of a welded seal, the adjacent film tears before the seal itself. Thus a welded seal has a strength equivalent to or greater than the film's tear strength.
- As mentioned above, in one embodiment the inventive film has a broad heat sealing window over which the film can form a welded seal. A broad heat sealing window permits manufacturing equipment to overshoot the sealing temperature to provide a complete seal without burning the films. The heat sealing window is the difference between the temperature at which the film begins to form a welded seal and the temperature at which the film begins to burn through. Burn through means that the film separates and forms holes or begins to disintegrate in response to heat. The heat sealing window is determined by the amount of PVC/VA included in the film. Additives can also affect the heat sealing window and the sealing temperatures of the films. For example, in an embodiment of the film comprising 61% PVC, 28% plasticizer and 12% PVC/VA, the film begins to seal at 313° F. and begins to burn through when exposed to temperatures of about 398° F. The difference between the beginning sealing temperature, 313° F., and the bum through temperature, about 398° F., is the heat sealing range. For this embodiment, the heat sealing window is 85° F. More examples and their heat sealing ranges are discussed below.
- In one embodiment, the film is capable of forming a welded heat seal above about 320° F. and has a heat sealing window greater than about 20° F. In another embodiment the film has a heat seal window greater than 30° F. In yet another embodiment, the heat sealing window is greater than 40° F. The heat sealing temperature range refers the range of temperatures over which the film may form a welded heat seal. For example, for a film with a heat sealing range of 40° F., if the film begins to seal at 300° F., the film will be able to seal at temperatures up to 340° F.
- Other, less desirable, seals may be formed at low temperatures, such as delaminating seals and cling seals. Delaminating seals appear to be welded, but can be worked loose or can be separated by hand peeling at the interface between the sealed layers. Cling seals are the result of a film's cling or electrostatic attraction and also stress relaxation (dead fold) properties as the surfaces wet together. Cling seals are more easily loosened or separated than the delaminating seal during package handling or transportation. Cling seals are also easily separated by hand, and are affected by moisture. A cling seal may occur at room temperature with sufficient pressure and time.
- In addition to being capable of forming welded seals on conventional equipment, the embodiments described above have good hot tack seal strength. Hot tack refers to the strength of the seal immediately following sealing and before the seal has fully cooled. Typically, film used to wrap food products on a tray is oriented and is heat shrinkable. When the film is heat sealed around a product, the film will shrink somewhat in response to the heat used to seal the film. If the film does not have sufficient hot tack seal strength, the seal can come apart in response to shrinking immediately upon heat sealing. In addition, in a manufacturing plant, the wrapped product proceeds to a heat shrinking tunnel just after the film is heat sealed. As a result, the seal may not have cooled completely before the film heat shrinks around the product. Good hot tack seal strength helps keep the seal intact when the film heat shrinks following formation of the heat seal. In one embodiment, the film forms a seal with a hot tack seal strength of at least 60 grams/mil over a broad range of temperatures.
- Seal strength is expressed in grams/mil (also referred to as g/mil or grams force per mil of thickness) or grams/in (also referred to as g/in or grams force per inch) in the description above and in the examples below. Grams/mil may be converted into N/mm (Newtons per millimeter of thickness) by the following equation: g/mil x 0.386 =N/mm. Grams/in may be converted into N/m (Newtons per meter) by the following equation: g/inch x 0.386 =N/m.
- Specific embodiments of the film are described in detail below, but the invention is not limited by these examples. In each of the examples below, the PVC and PVC/VA, if included, were blended in a high intensity blender with plasticizers and any other additives. The resulting powder was extruded into pellets and the pellets were extruded into film, forming film samples. Sealing properties, tear strength and OTR were measured for Examples 1-3. In addition, hot tack seal strength of the sample films were tested by sealing at temperatures ranging from 220° F. to 350° F. The sample films were sealed in a fin seal with sealing jaws at 60 psi of pressure with a dwell time of 1000 milliseconds or 500 milliseconds, as specified below. The hot tack seal strengths for each sealing temperature were measured at 500 milliseconds or 250 milliseconds following seal formation. Note that seal strengths of less than 20 g/in can be caused by cling between the film and may not be the result of heat sealing.
- The sample films of Example 1 comprise: 54.84% by weight PVC, 12.46% by weight PVC/VA, and 28.27% by weight plasticizer. The films of Example 1 further comprise minor amounts of additives: 1.47% by weight stabilizer, 2.02% by weight antifog, 0.24% by weight slip, 0.1% by weight lubricant, 0.17% by weight slip, and 0.44% by weight antiblock.
- A film of Example 1 was formed with a gauge of 1 mil. The film was tested for OTR and for heat sealing characteristics. The film had an OTR of 1025.9 cc/100 in2/24 hours. The film formed a welded seal, beginning at a temperature of 328° F. and a burn through temperature of 421° F., providing a 93° F. heat sealing window.
- The sample films of Comparative Example 1 comprise: 68.51% by weight PVC, 0% PVC/VA, and 28.09% by weight plasticizer. The Comparative Example 1 film samples further comprise minor amounts of additives: 2.06% by weight stabilizer, 1.16% by weight antifog, 0.18% by weight lubricant and 0.14% by weight slip.
- Three sample films of Example 1 and Comparative Example 1 were extruded and tested by the methods discussed above.
FIG. 1 shows the hot tack seal strength over seal temperature for samples of Example 1 and Comparative Example 1, measured 250 milliseconds following release of the sealing jaws.FIG. 2 shows seal strengths over seal temperature, measured 500 millisecond following release of the sealing jaws. For the data shown in bothFIGS. 1 and 2 , the film was sealed with a dwell time of 500 milliseconds. The data from this testing for Example 1 is shown in Table A, for 250 milliseconds following sealing, and in Table B, for 500 milliseconds following sealing. For Comparative Example 1, the results of testing are shown in Table C, for 250 ms following sealing, and in Table D, for 500 ms following sealing.TABLE A (250 ms) Example 1 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 10 0 27 39 48 48 57 64 92 115 97 64 58 53 Seal (g/in) Sample 20 0 23 37 44 55 64 60 161 143 124 65 64 55 Seal (g/in) Sample 30 0 25 37 46 62 62 69 150 147 81 67 60 55 Seal (g/in) Avg. 0 0 25 38 46 55 61 64 134 135 101 65 61 54 Seal (g/in) -
TABLE B (500 ms) Example 1 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 10 0 42 65 83 79 71 78 103 269 196 106 81 69 Seal (g/in) Sample 20 0 39 67 72 81 88 73 76 267 124 117 103 65 Seal (g/in) Sample 30 0 42 65 3 129 83 83 87 170 152 111 92 90 Seal (g/in) Avg. 0 0 41 66 79 96 81 78 89 235 157 111 92 75 Seal (g/in) -
TABLE C (250 ms) Comparative Example 1 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 125 28 18 23 37 62 48 35 35 19 44 80 74 49 Seal (g/in) Sample 221 18 30 35 57 51 32 39 32 41 37 90 55 53 Seal (g/in) Sample 325 23 19 30 32 41 32 39 12 21 44 74 62 57 Seal (g/in) Avg. 24 23 22 29 42 51 37 38 26 27 42 81 64 53 Seal (g/in) -
TABLE D (500 ms) Comparative Example 1 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 142 71 41 39 60 83 57 44 35 19 44 65 129 134 Seal (g/in) Sample 230 37 51 48 64 53 30 39 48 35 34 62 197 148 Seal (g/in) Sample 339 41 39 44 41 55 44 46 11 18 35 106 201 205 Seal (g/in) Avg. 37 50 44 44 55 64 44 43 31 24 38 78 176 162 Seal (g/in) - As discussed above, films for packaging fresh produce should be capable of sealing along a temperature range that is sufficiently broad to allow conventional heat sealing equipment to create a reliable seal that will remain intact when the film heat shrinks as a result of heat sealing and proceeds into a heat shrinking tunnel immediately following sealing. As shown by the graphs in
FIGS. 1 and 2 and the data from Tables A-D, the film of Example 1 (a blend of plasticized PVC and PVC/VA copolymer) achieves greater seal strength than the film of Comparative Example 1 (PVC without PVC/VA), over sealing temperatures ranging from 240° F. to 320° F. The film of Example 1 also achieves hot tack seal strengths over 60 g/in at temperatures ranging from 280° F. to 320° F. - The sample films of Example 2 comprise: 54.92% by weight PVC; 12.48% PVC/VA; and 28.31% by weight plasticizer. The sample films further comprise minor amounts of additives: 1.47% by weight of stabilizer; 2.02% by weight antifog; 0.33% by weight slip; 0.17% by weight lubricant; and 0.30% by weight antiblock.
- A film of Example 2 was formed with a gauge of I mil. The film was tested for OTR and for heat sealing characteristics. The film had an OTR of 904 cc/100 in2/24 hours. The film formed a welded seal beginning at a temperature of 313° F. and a burn through temperature of 398° F., providing an 85° F. heat sealing window.
- Three samples of Example 2 were tested for hot tack seal strength. The data from this testing is shown in Tables E-F.
-
FIG. 3 is a graph of the hot tackheat seal data 250 ms following sealing as shown in Table E (Example 2) and Table C (Comparative Example 1).FIG. 4 is a graph of hottack heat seal 500 ms following sealing, as shown in Table F (Example 2) Table D (Comparative Example 1).TABLE E (250 ms) Example 2 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 10 0 21 28 37 48 58 60 66 64 113 92 58 51 Seal (g/in) Sample 20 0 25 30 39 48 57 65 64 118 110 85 65 55 Seal (g/in) Sample 30 0 25 21 41 46 51 69 65 83 124 71 58 53 Seal (g/in) Avg. 0 0 24 26 39 47 55 65 65 88 116 83 60 53 Seal (g/in) -
TABLE F (500 ms) Example 2 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 10 0 41 42 71 76 96 80 71 44 111 170 95 76 Seal (g/in) Sample 20 0 44 48 60 69 81 85 71 81 127 149 101 120 Seal (g/in) Sample 30 0 30 42 87 64 76 76 78 32 163 147 87 78 Seal (g/in) Avg. 0 0 38 44 73 70 84 80 73 52 134 155 94 91 Seal (g/in) - As can be seen by the data in the above tables and by FIGS. 3 and 4, Example 2 provides higher tack seal strength than Comparative Example 1 over a broad temperature range.
- Sample films of Examples 2 and 3 were formed by the steps described above. Example 2 sample films comprise the composition disclosed above. Example 3 sample films comprise: 61.16% by weight PVC, 6.24% PVC/VA, 28.31% by weight plasticizer. The films of Example 3 further comprise minor amounts of additives: 1.48% by weight stabilizer, 2.02% by weight stabilizer, 0.33% by weight slip, 0.17% by weight lubricant, and 0.30% by weight antiblock.
- A film of Example 3 was formed with a gauge of 1 mil. The film was tested for OTR and for heat sealing characteristics. The film had a OTR of 818.8 cc/100 in2/24 hours. The film formed a welded seal, beginning at a temperature of 356° and a burn through temperature of 416°, providing a 60° F. heat sealing window.
- Table E above and Table G below show hot tack heat seal strengths for Examples 2 and 3 over different sealing temperatures, measured 250 milliseconds following heat sealing. Table F above and Table H below, show heat seal strengths for Examples 2 and 3 from sealing at temperatures ranging from 220° F. to 350° F.
FIG. 5 is a graph of the data in Tables E and G andFIG. 6 is a graph of the data in Tables F and H.TABLE G (250 ms) Example 3 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 10 0 23 35 34 39 49 57 55 81 97 69 64 44 Seal (g/in) Sample 20 0 21 19 41 37 46 46 73 127 64 83 58 53 Seal (g/in) Sample 30 0 21 18 27 42 49 44 69 50 99 94 62 57 Seal (g/in) Avg. 0 0 22 24 34 39 48 49 66 86 87 82 61 51 Seal (g/in) -
TABLE H (500 ms) Example 3 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 10 0 34 55 49 60 81 74 60 53 106 170 106 80 Seal (g/in) Sample 20 0 25 37 64 64 83 76 90 48 73 134 113 126 Seal (g/in) Sample 30 0 34 28 46 62 74 81 90 34 131 166 140 103 Seal (g/in) Avg. 0 0 31 40 53 62 79 77 80 45 103 157 120 103 Seal (g/in) - As discussed above, the films of Example 3 comprise 6.24% by weight PVC/VA and the films of Example 2 comprise 12.48% by weight PVC/VA. As shown in FIGS. 5 and 6, both Examples 2 and 3 provide films with broad heat sealing temperature ranges and good hot tack seal strength.
- The sample films of Example 4 comprise: 55.87% by weight PVC, 10.00 PVC/VA, and 18.99% by weight plasticizer. The films of Example 4 further comprise minor amounts of additives: 1.56% by weight stabilizer; 0.96% antifog; 0.12% by weight slip, 0.23% lubricant; and 2.27% by weight antiblock.
- The sample films of Comparative Example 2 comprise: 68.06% by weight of PVC; 0% by weight of PVC/VA; and 26.24% by weight of plasticizer. The films of Example 5 further comprise additives: 1.48% by weight stabilizer; 1.23% by weight of antifog; 0.13% by weight of slip; 0.24% by weight lubricant; and 2.46% by weight antiblock.
- Three sample films of Example 4 and for Comparative Example 2 were tested for hot tack seal strength. The data from this testing is shown in Tables I-L.
TABLE I (500 ms) Example 4 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 114 18 27 30 37 69 53 64 53 65 64 80 113 67 Seal (g/in) Sample 223 18 37 32 57 37 57 41 60 65 60 110 88 83 Seal (g/in) Sample 325 21 27 41 42 50 48 67 51 51 103 94 80 80 Seal (g/in) Avg. 21 19 30 34 45 52 53 57 55 60 76 95 94 77 Seal (g/in) -
TABLE J (500 ms) Example 4 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 126 30 42 49 51 65 60 83 57 72 46 191 159 207 Seal (g/in) Sample 228 37 55 51 57 48 57 42 80 44 53 191 173 203 Seal (g/in) Sample 334 37 37 67 57 71 53 72 42 67 74 205 218 179 Seal (g/in) Avg. 29 35 45 56 55 61 57 66 60 61 58 196 183 196 Seal (g/in) -
TABLE K (500 ms) Comparative Example 2 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 14 5 12 16 21 28 35 44 71 34 51 42 83 80 Seal (g/in) Sample 29 11 9 14 28 25 30 55 48 46 51 53 49 74 Seal (g/in) Sample 34 9 12 18 16 18 41 35 46 41 39 55 64 69 Seal (g/in) Avg. 6 8 11 16 22 24 35 45 55 40 47 50 65 74 Seal (g/in) -
TABLE L (500 ms) Comparative Example 2 Seal Temperature (° F.) 220 230 240 250 260 270 280 290 300 310 320 330 340 350 Sample 112 16 27 30 34 41 60 55 58 51 60 34 71 147 Seal (g/in) Sample 218 19 21 30 37 42 49 51 58 48 57 42 51 150 Seal (g/in) Sample 312 21 21 35 37 48 51 50 62 41 58 41 57 141 Seal (g/in) Avg. 14 19 23 32 36 44 53 52 59 50 58 39 60 146 Seal (g/in) - Similar to the results seen in
FIGS. 1-2 for Example 1 and Comparative Example 1, Example 4 has a broader heat seal range than Comparative Example 2. Example 4 also provides good hot tack seal strengths over a wide range of sealing temperatures. - It will be obvious to those having skill in the art that many changes may be made to the details of the above-described embodiments without departing from the underlying principles of the invention. The scope of the present invention should, therefore, be determined only by the following claims.
Claims (20)
Priority Applications (1)
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US11/646,034 US20070117919A1 (en) | 2000-11-17 | 2006-12-27 | Heat sealable polyvinyl chloride films |
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US71587400A | 2000-11-17 | 2000-11-17 | |
US10/429,054 US7175903B1 (en) | 2000-11-17 | 2003-05-02 | Heat sealable polyvinyl chloride films |
US11/646,034 US20070117919A1 (en) | 2000-11-17 | 2006-12-27 | Heat sealable polyvinyl chloride films |
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US10/429,054 Continuation US7175903B1 (en) | 2000-11-17 | 2003-05-02 | Heat sealable polyvinyl chloride films |
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US11/646,034 Abandoned US20070117919A1 (en) | 2000-11-17 | 2006-12-27 | Heat sealable polyvinyl chloride films |
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Cited By (1)
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US10526190B2 (en) | 2015-04-17 | 2020-01-07 | Ds Smith Plastics Limited | Multilayer film used with flexible packaging |
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US7175903B1 (en) * | 2000-11-17 | 2007-02-13 | Pliant Corporation | Heat sealable polyvinyl chloride films |
US20150122841A1 (en) * | 2013-11-06 | 2015-05-07 | The Procter & Gamble Company | Easy to empty flexible containers |
CN109880253B (en) * | 2019-02-15 | 2020-11-10 | 嘉兴新安包装材料有限公司 | PVC (polyvinyl chloride) heat shrinkable film and preparation method thereof |
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US6514606B2 (en) * | 1998-09-30 | 2003-02-04 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet for skin adhesion and first-aid adhesive plaster using the same |
US6627274B1 (en) * | 1998-12-03 | 2003-09-30 | Sporos Sa | Multilayer heat shrinkable film |
US6787220B2 (en) * | 1999-12-15 | 2004-09-07 | Vector Europe Nv | Multilayer heat shrinkable film |
US6706820B2 (en) * | 2000-08-21 | 2004-03-16 | Showa Denko K.K. | Vinyl chloride resin composition |
US7175903B1 (en) * | 2000-11-17 | 2007-02-13 | Pliant Corporation | Heat sealable polyvinyl chloride films |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US10526190B2 (en) | 2015-04-17 | 2020-01-07 | Ds Smith Plastics Limited | Multilayer film used with flexible packaging |
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US7175903B1 (en) | 2007-02-13 |
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