Classifications

• • 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
• • 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
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/738—Thermoformability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • 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
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • 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]
  • Y10T428/31652—Of asbestos
  • Y10T428/31663—As siloxane, silicone or silane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31928—Ester, halide or nitrile of addition polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31935—Ester, halide or nitrile of addition polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

• This invention relates to a gas permeable film suitable for use in food packaging.
• This invention particularly relates to improved packaging structures for perishable food products. DESCRIPTION OF THE RELATED ART Perishable food products are subject to contamination when exposed to microbial organisms such as bacteria, molds and the like. Contamination can result in accelerated spoilage, toxin formation and other harmful effects.
• Packaging such perishable goods in gas impermeable materials such as foil, coated paperboard and oxygen barrier films can provide a barrier to microbial contamination.
• anaerobic organisms such as C. botulinum, which produces a potent toxin that is the causative agent of botulism, thrive in oxygen-depleted atmospheres.
• Gas impermeable materials such as foil, paperboard and oxygen barrier films are not suitable to package goods highly susceptible to botulin toxin formation.
• Vacuum packaging is a process used to protect perishable items from deterioration wherein a vacuum is applied to a package to actively remove air to conform the packaging film to the shape of the content prior to sealing the package.
• Skin packaging is a known technique where goods are tightly packaged within a wrapping material and where substantially all of the atmospheric air is excluded. Vacuum skin packaging is a combination of the two packaging processes. However, conventional packaging of this type excludes oxygen and therefore does not inhibit the growth of C.
• U.S. Patent Numbers 4,685,274; 4,840,271 ; 5,025,61 1 ; 5,103,618 and 5,115,624 describe packages, methods, and apparatuses for packaging perishable goods.
• U.S. Pat. App. Pub. 2003/0198715 A1 discloses films and packages of highly neutralized blends of organic acids and ethylene acid copolymers having good oxygen permeability.
• the present invention is a monolithic film obtained from a blend comprising: (a) one or more aliphatic organic acids or salts thereof having fewer than 36 carbon atoms;
• E/X/Y copolymer ethylene acid copolymer
• E is derived from ethylene
• X is derived from at least one C3 to Cs ⁇ , ⁇ - ethylenically unsaturated carboxylic acid
• Y is derived from a comonomer selected from alkyl acrylates and alkyl methacrylates, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of said E/X/Y copolymers, wherein X is from about 3 to about 30 weight % of said E/X/Y copolymer, and Y is from 0 to about 35 weight % of said E/X/Y copolymer, and wherein greater than 70% of all the total acid moieties from (a) plus (b) are neutralized to the corresponding metal salts; and
• At least one additional polymer or polymer combination selected from the group consisting of: (1) ethylene-containing homopolymers and/or copolymer; (2) silicone-containing polymer.
• the present invention is a multilayered film comprising at least one layer of film that is obtained from a blend comprising: (a) one or more aliphatic organic acids or salts thereof having fewer than 36 carbon atoms;
• E/X/Y copolymer wherein E is derived from ethylene, X is derived from at least one C3 to C ⁇ ⁇ , ⁇ -ethylenically unsaturated carboxylic acid (ethylene acid copolymer), and Y is derived from a comonomer selected from alkyl acrylates and alkyl methacrylates, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of said E/X/Y copolymers, wherein X is from about 3 to about 30 weight % of said E/X/Y copolymer, and Y is from 0 to about 35 weight % of said E/X/Y copolymer, and wherein greater than 70% of all the total acid moieties from (a) plus (b) are neutralized to the corresponding metal salts; and
• At least one additional polymer or polymer combination selected from the group consisting of: (1) ethylene-containing homopolymers and/or copolymer; (2) silicone-containing polymer.
• the present invention is a multilayered film comprising:
• E/X/Y copolymer wherein E is derived from ethylene, X is derived from at least one C3 to Cs ⁇ , ⁇ -ethylenically unsaturated carboxylic acid (ethylene acid copolymer), and Y is derived from a comonomer selected from alkyl acrylates and alkyl methacrylates, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of said E/X/Y copolymers, wherein X is from about 3 to about 30 weight % of said E/X/Y copolymer, and Y is from 0 to about 35 weight % of said E/X/Y copolymer, and wherein greater than 70% of all the total acid moieties from (a) plus
• E is derived from ethylene
• X is derived from at least one C3 to Cs ⁇ , ⁇ -ethylenically unsaturated carb
• the present invention is a multilayered film comprising:
• E/X/Y copolymer wherein E is derived from ethylene, X is derived from at least one C3 to Cs ⁇ , ⁇ -ethylenically unsaturated carboxylic acid (ethylene acid copolymer), and Y is derived from a comonomer selected from alkyl acrylates and alkyl methacrylates, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of said E/X/Y copolymers, wherein X is from about 3 to about 30 weight % of said E/X/Y copolymer, and Y is from 0 to about 35 weight % of said E/X/Y copolymer, and wherein greater than 70% of all the total acid moieties from (a) plus (b) are neutralized to the corresponding metal salts; and
• At least one additional polymer or polymer combination selected from the group consisting of: (1) ethylene-containing homopolymers and/or copolymer; (2) silicone-containing polymer and (ii) at least a second polymeric layer consisting essentially of at least one ethylene-containing copolymer or at least one silicon-containing polymer or copolymer.
• the present invention is a package comprising a film obtained from a blend comprising: (a) one or more aliphatic organic acids or salts thereof having fewer than 36 carbon atoms; (b) at least one EIXIY copolymer wherein E is derived from ethylene, X is derived from at least one C3 to Cs ⁇ , ⁇ -ethylenically unsaturated carboxylic acid (ethylene acid copolymer), and Y is derived from a comonomer selected from alkyl acrylates and alkyl methacrylates, wherein the alkyl groups have from 1 to 8 carbon atoms, or ionomers of said E/X/Y copolymers, wherein X is from about 3 to about 30 weight % of said EIKfY copolymer, and Y is from 0 to about 35 weight % of said E/X/Y copolymer, and wherein greater than 70% of all the total acid moieties from (a) plus (b) are
• the present invention provides an improvement in the OPV of previously described films obtained from ethylene acid copolymer/organic acid blends. It has been discovered that there can be a synergistic effect when an ethylene-containing copolymer (that is neither an ethylene acid copolymer nor an ionomer) is blended with a neutralized acid copolymer/organic acid blend, particularly with respect to the OPV. It has been found that inclusion of the ethylene-containing copolymer can improve OPV even though the level of E/X/Y terpolymer is reduced.
• a blend comprising a neutralized copolymer of ethylene and an ⁇ , ⁇ - ethylenically unsaturated carboxylic acid/organic acid blend with an ethylene-containing copolymer can provide OTR of greater than 10,000 cc/m 2 /24 hr.
• the ethylene copolymer blends of the present invention provide good moisture barrier properties, and show improved processibility relative to similar blends wherein the ethylene- containing copolymer is absent.
• blended compositions provide films and or film structures having a combination of improved oxygen permeability, good formability and structural strength and can be useful in wrapping food products requiring breathable films such as case ready meat, fish, sausage, fresh produce, and the like.
• the phrases “inside face”, “inside layer”, or “innermost” layer refers to the face or layer of a film or packaging web that is in contact with the packaged goods
• the phrase “outside face” or “outer layer” refers to the face of a film or packaging web not in direct contact with the packaged article and which provides the exterior surface of the package after it is formed.
• Perishable goods that can be packaged according to this invention include meat, fish, poultry or fresh vegetables, as well as other perishable goods.
• Films as described herein provide a combination of high oxygen permeability and low moisture permeability. Such films are particularly well suited for packaging perishable food products subject to spoiling in an anaerobic atmosphere, and/or deteriorating due to dehydration, or otherwise require O 2 breathability to maintain freshness and the appearance of freshness.
• Organic Acids and Salts are particularly well suited for packaging perishable food products subject to spoiling in an anaerobic atmosphere, and/or deteriorating due to dehydration, or otherwise require O 2 breathability to maintain freshness and the appearance of freshness.
• the organic acids employed in the present invention are aliphatic, mono-functional (saturated, unsaturated, or multi-unsaturated) organic acids, particularly those having fewer than 36 carbon atoms. Also salts of these organic acids may be employed.
• the organic acid salts are preferably magnesium or calcium salts, however other salts can be used as long as the concentration of other salts does not negate the property of oxygen permeability in a film of the present invention.
• Other salts can be any of the alkaline earth metals, including the barium or strontium salts, for example.
• organic acids (and salts) While it may be useful for the organic acids (and salts) to have a low volatility when being melt-blended with acid copolymer or ionomer, it has been discovered that volatility is not a limiting factor when neutralizing the blend to high levels, particularly near to or at 100%. As such, organic acids with lower carbon content can be used in the practice of the present invention. It can be preferred, however, that the organic acid (or salt) be non-volatile and non-migratory. By non-volatile, it is meant that they do not volatilize in the range of temperatures useful for melt blending the acid copolymer as described herein. By non-migratory, it is meant that the organic acid does not bloom to the surface of the polymer under normal storage conditions (ambient temperatures).
• acids as described herein effectively modify the ionic morphology and/or remove ethylene crystallinity from ethylene/C ⁇ .g ⁇ , ⁇ -ethylenically unsaturated carboxylic acid copolymers or ionomers thereof.
• Particularly useful organic acids include acids having from four to 34 carbons, more preferred are CQ to
• Organic acids useful in the practice of the present invention include, but are not limited to, caproic acid, caprylic acid, capric acid, palmitic acid; lauric acid, stearic acid, isostearic acid, behenic acid, erucic acid, oleic acid, and linoleic acid and their mixtures. More preferably, the naturally derived organic fatty acids such as palmitic, stearic, oleic, behenic, and mixtures thereof can be conveniently employed. Saturated organic acids can be preferred for the purpose of reducing organoleptic properties of the films. Stearic acid can be preferred.
• Saturated, branched organic acids can be particularly preferred to provide greater oxygen permeability.
• branched saturated acids particularly preferred is isostearic acid.
• mixtures of any of the organic acids contemplated herein can provide properties that can be expected or anticipated from the properties of the individual organic acid components.
• Optional antioxidant additives can be useful in modifying the organoleptic properties (e.g. reducing odor or taste) of the blends of organic acid and ethylene copolymers used in this invention.
• Antioxidants may be preferred when the organic acid is unsaturated.
• Antioxidants are available under the trade name Irganox as from Ciba Geigy Inc. Tarrytown, New York.
• phenolic antioxidants such as IRGANOX E201, CAS Number 10191-41-0
• IRGANOX 1010 is another antioxidant suitable for use in this invention.
• this invention provides packages and packaged food products wherein the blends of (a), (b) and (c), as defined above, further comprise an antioxidant.
• Acid copolymers used in the present invention to make ionomers are preferably "direct" acid copolymers. They are preferably alpha olefin, particularly ethylene, C3..8 ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, particularly acrylic and methacrylic acid, copolymers. They may optionally contain a third monomer that can disrupt the crystallinity.
• the acid copolymers can be described as EJXIY copolymers where E is ethylene, X is the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, and Y is a comonomer. X is present in from 3 to 35 (preferably from 4 to 25, more preferably from 5 to 20) weight % of the polymer, and Y is present in from 0 to 35 weight %, preferably from 1 to 35 weight, more preferably from 4 to 25 of the polymer. Notable are E/X dipolymers, wherein Y is 0 weight % of the E/X/Y copolymer.
• Suitable third comonomers are monomers selected from alkyl acrylate, and alkyl methacrylate, wherein the alkyl groups have from 1 to 8 carbon atoms.
• Preferred alkyl acrylate, and alkyl methacrylates are those wherein the alkyl groups have from 1 to 4 carbon atoms, and more preferred are those wherein the alkyl groups have from 3 to 4 carbon atoms.
• the ethylene acid copolymers with high levels of acid (X) are difficult to prepare in continuous polymerizers because of monomer- polymer phase separation. This difficulty can be avoided by use of "co- solvent technology" as described in U.S. Patent No. 5,028,674 or by employing somewhat higher pressures than those at which copolymers with lower acid levels can be prepared.
• Specific acid copolymers include, but are not limited to: ethylene/(meth)acrylic acid dipolymers; ethylene/(meth)acrylic acid/n-butyl (meth)acrylate terpolymers; ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate terpolymers; ethylene/(meth)acrylic acid/methyl (meth)acrylate terpolymers; and ethylene/ (meth)acrylic acid/ethyl (meth)acrylate terpolymers.
• (Meth)acrylic acid as used herein is shorthand notation, and shall be taken to mean “methacrylic acid and/or acrylic acid", that is, methacrylic acid alone, acrylic acid alone, or the combination of both. lonomers useful herein can either be “modified” or "unmodified” ionomers. Unmodified melt processible ionomers (that is, melt processible ionomers that are not blended with an organic acid component) used in this invention are obtained from acid copolymers by neutralization of same. They include partially neutralized acid copolymers, particularly ethylene/(meth)acrylic acid copolymers.
• the unmodified ionomers may be neutralized to any level that does not result in an intractable (that is, not melt processible) polymer without useful physical properties.
• lonomers blended with the organic acids described herein (modified ionomers) can be neutralized to any level, particularly levels higher than 70%.
• high levels of neutralization can be obtained by adding the stoichiometric amount of a cation source calculated to neutralize the target amount of acid moieties in the acid copolymer and organic acid(s) in the blend (hereinafter referred to as "% nominal neutralization" or “nominally neutralized”).
• % nominal neutralization or "nominally neutralized”
• the ionomers useful herein consist essentially of calcium and/or magnesium-neutralized ionomers.
• Calcium and/or magnesium ionomeric compositions are preferred for restriction of moisture in addition to high oxygen permeability, but other cations can be present, so long as the concentration of said other cations does not rise to the level wherein the oxygen permeability of the resultant films is decreased below about 10,000 (cc/m 2 )(day)(atm).
• Other cations useful in making the highly oxygen permeable blends of this invention include lithium, sodium, potassium, or zinc, or combinations of such cations. In some instances it can be found that use of calcium can be preferred over the use of magnesium, or vice versa.
• Fattv Acid Modified lonomer Blends are preferred for restriction of moisture in addition to high oxygen permeability, but other cations can be present, so long as the concentration of said other cations does not rise to the level wherein the oxygen permeability of the resultant films is decreased below about 10,000 (cc/m
• Components (a) and (b) of the blends described herein can be neutralized according to the following procedure: (1) melt-blending ethylene ⁇ , ⁇ -ethylenically unsaturated 63.8 carboxylic acid copolymer(s) and/or ionomer(s) thereof with one or more aliphatic, mono-functional, saturated or unsaturated organic acids having less than 36 carbon atoms or salts of the organic acids, and concurrently or subsequently; (2) adding a sufficient amount of a cation source to increase the level of neutralization of all the acid moieties (including those in the acid copolymer and in the organic acid) to greater than about 70%, preferably greater than about 80%, more preferably greater than about 90%, and even more preferably from about 91 % to about 100%, with the caveat that the ionomer component is melt processible when it is blended with the aliphatic organic acid in step (1).
• Neutralization of the organic acid can be done to any specific level within the ranges described herein, notwithstanding the specifically defined end- points enumerated herein.
• neutralization to any level taught or claimed herein is within the teachings provided here or in the prior art.
• the aliphatic, mono-functional, saturated or unsaturated organic acids having less than 36 carbon atoms or salts of the organic acids are present in a range of from about 5 to about 150 parts, alternatively, from about 25 to about 80 parts per hundred (pph) by weight of the ethylene ⁇ , ⁇ -ethylenically unsaturated 63.3 carboxylic acid copolymer(s) or ionomer(s) thereof.
• Neutralization of acid copolymers and organic acids in this manner can be preferred. Neutralization of the acid copolymers can be also accomplished using a diluent as the copolymer and organic acid are neutralized. Care should be taken when neutralizing copolymers of the present invention so that there is no loss of desirable properties or difficulties in processing the copolymers.
• an acid copolymer blended with organic acid(s) can be neutralized to over 80%, preferably 90%, more preferably to about 100% or to 100% nominal neutralization without losing melt processibility as can occur with acid copolymers, not of this invention, that are neutralized to greater than 80%.
• the acid copolymer(s) or unmodified, melt-processible ionomer(s) can be melt-blended with the organic acid(s) or salt(s) by any suitable manner.
• the solid components can be mixed to obtain a non-homogeneous solid phase mixture of the components can be made and the components can then be melt-blended in an extruder.
• the melt-processible, acid copolymer/organic-acid-or-salt blend can be neutralized by methods known in the art.
• a Werner & Pfleiderer twin-screw extruder can be used to neutralize the acid copolymer and the organic acid at the same time.
• the level of organic acid that controls processibility can be determined from the teachings provided by the present invention. Generally speaking, and without being held to theory, the percent organic acid may need to be increased when higher acid levels are present in the backbone of the co- or ter-polymer in order to achieve similar melt indices for copolymers having relatively lower acid levels.
• the highly neutralized organic acids and ethylene acid copolymers (ionomers) described above are blended with at least one other polymer as component (c) which is selected from ethylene copolymers and/or homopolymers and/or silicon-containing polymers and copolymers.
• Suitable ethylene containing polymers and copolymers include polyethylene homopolymers and copolymers, including branched polyethylenes such as low density polyethylenes (LDPE), linear low density polyethylenes (LLDPE), ultra low density polyethylenes (ULDPE), very low density polyethylenes (VLDPE), metallocene polyethylenes (mPE), ethylene propylene copolymers, ethylene/propylene/diene monomer (EPDM) copolymers; and ethylene copolymers derived from copolymerization of ethylene and at least one polar comonomer selected from the group consisting of alkyl (meth)acrylate, vinyl acetate, CO, maleic acid anhydride and maleic acid derivatives.
• LDPE low density polyethylenes
• LLDPE linear low density polyethylenes
• ULDPE ultra low density polyethylenes
• VLDPE very low density polyethylenes
• mPE metallocene polyethylenes
• EPDM ethylene copolymers derived from copo
• PE Polyethylene
• Polyethylene (abbreviated PE) homopolymers and copolymers useful for the compositions described herein can be prepared by a variety of methods, for example but not limitation, the well-known Ziegler-Natta catalyst polymerization (see for example U.S. Patent Number 4,076,698 and U.S. Patent Number 3,645,992), metallocene catalyzed polymerization, Versipol catalyzed polymerization and by free radical polymerization.
• the polymerization can be conducted as solution phase processes, gas phase processes, and the like.
• the densities of polyethylenes suitable for use in the present invention range from about 0.850 g/cc to about 0.970 g/cc, preferably from about 0.850 to about 0.930, more preferably from about 0.850 to about 0.910 g/cc.
• Linear polyethylenes for use herein can incorporate alpha- olefin comonomers such as butene, hexene or octene to decrease their density to within the density range so described.
• a copolymer useful as component (c) can comprise a major portion (by weight) of a copolymer of ethylene and at least a second alpha-olefin.
• the second alpha olefin can be one selected from the group consisting of alpha-olefins having from 3 to about 20 carbon atoms, present in an amount of up to about 20% by weight of the copolymer.
• Preferred second alpha-olefins include: propylene, 1 -butene, 1 -hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, for example.
• Copolymers can be obtained by polymerization of ethylene with two or more other alpha-olefins selected from propylene, 1 -butene, 1 -hexene, 1- octene and 4-methyl-1-pentene. Also contemplated for use herein are blends of two or more of these ethylene alpha-olefin copolymers.
• the copolymer can be an ethylene/propylene elastomer comprising at least one double bond.
• Suitable ethylene-containing copolymers are commercially available from ExxonMobil (Exact® 3035) or DuPont Dow Elastomers (Engage® 8450), for example.
• metallocene polyethylene mPE
• Metallocene technology is capable of making lower density polyethylene with high flexibility and low crystallinity, with good oxygen permeability, which is a desirable property for component (c) of this invention.
• the mPE employed in films of the present invention can be any such polyethylene as generally known in the art provided the oxygen permeability is sufficiently high to afford the requisite breathability necessary for the intended film and film structure applications of interest.
• the metallocene polyethylene has a density of less than 0.91 g/cc, wherein the normalized oxygen permeation value (OPV) at 23 0 C and 50% relative humidity will be greater than about 12,400 cc- mil/m2-day atm.
• This mPE can optionally be blended with other low crystalline polyolefin or amorphous polyethylenes (such as low density polyethylene, LDPE; linear low density polyethylene, LLDPE; other mPE and the like) provided the film retains significantly high oxygen permeability.
• Metallocene technology is described in, for example, U. S. Patent Numbers 5,272,236; 5,278,272, 5,507,475, 5,264,405, and 5,240,894.
• Ethylene copolymers having small amounts of a diolefin component such as butadiene, norbornadiene, hexadiene and isoprene are also generally suitable.
• Terpolymers such as ethylene/propylene/diene monomer (EPDM) are also suitable.
• Copolymers of ethylene with polar comonomers can also be suitable in a blend of the present invention.
• Polar comonomers suitable for use in copolymers suitable herein include alkyl (meth)acrylates._ The term “(meth)acrylate” is shorthand notation for "methacrylate and/or acrylate esters”. The term “ethylene/alkyl (meth)acrylate copolymers " is shorthand notation for copolymers obtained from copolymerization of ethylene and alkyl (meth)acrylates.
• Alkyl (meth)acrylates suitable for use in the practice of the present invention are selected from alkyl (meth)acrylates comprising alkyl groups having from 1 to 8 carbon atoms.
• alkyl acrylates suitable for use herein include methyl acrylate, ethyl acrylate and butyl acrylate.
• Ethylene/methyl acrylate (EMA) is shorthand notation for a copolymer of ethylene (E) and methyl acrylate (MA).
• Ethylene/ethyl acrylate (EEA) is shorthand notation for a copolymer of ethylene and ethyl acrylate (EA).
• Ethylene/butyl acrylate (EBA) is shorthand notation for a copolymer of ethylene and butyl acrylate (BA).
• the relative amount of the alkyl (meth)acrylate comonomer incorporated into an ethylene/alkyl (meth)acrylate copolymer of the present invention can vary broadly from a few weight percent up to as high as 45 weight percent of the total copolymer or even higher.
• the alkyl group can be a methyl group or any alkyl group having up to eight carbon atoms. Most preferably, the alkyl group in the alkyl (meth)acrylate comonomer is methyl, ethyl or n-butyl.
• the alkyl (meth)acrylate comonomer has a concentration range of from 5 to 45 weight percent of the ethylene/alkyl (meth)acrylate copolymer, preferably from 10 to 35 weight %, more preferably from 10 to 28 weight %.
• the alkyl (meth)acrylate copolymer can be advantageously used in an amount ranging from about 5 to about 50 wt%.
• the (meth)acrylate copolymer is present in an amount of from about 10 to about 35 wt%. Even more preferably, the (meth)acrylate copolymer is present in an amount of from about 15 to about 30 wt%.
• component (c) of the blend is an ethylene/vinyl acetate copolymer.
• the relative amount of the vinyl acetate comonomer incorporated into ethylene/vinyl acetate copolymers can, in principle, vary broadly from a few weight percent up to as high as 40 weight percent of the total copolymer or even higher.
• the ethylene/vinyl acetate copolymer preferably has a vinyl acetate unit content of from 2 to 40% by weight, especially from 6 to 30% by weight.
• the ethylene/vinyl acetate copolymer preferably has a melt flow rate, measured in accordance with ASTM D-1238, of from about 0.1 to about 40 g/10 minutes, and especially from about 0.3 to about 30 g/10 minutes.
• the ethylene-containing copolymers useful as the third component in the blends described herein can be modified by methods well known in the art, including modification with an unsaturated carboxylic acid or its derivatives, such as maleic anhydride or maleic acid.
• a mixture of two or more different ethylene/vinyl acetate copolymers can be used in the multilayer films of the present invention in place of a single copolymer as long as the average values for the comonomer content will be within the range indicated above. Particularly useful properties may be obtained when two or more properly selected ethylene/vinyl acetate copolymers are used in blends of the present invention.
• Ethylene/alkyl acrylate copolymers can be prepared by processes well known in the polymer art using either autoclave or tubular reactors.
• the copolymerization can be run as a continuous process in an autoclave: ethylene, the alkyl acrylate, and optionally a solvent such as methanol (see U.S. Patent Number 5,028,674) are fed continuously into a stirred autoclave of the type disclosed in U.S. Patent Number 2,897,183, together with an initiator.
• Ethylene copolymers suitable for use herein can be produced by any process, including conventional processes, such as via a tubular reactor or via an autoclave, and non-conventional processes.
• Ethylene/alkyl acrylate copolymers obtained from a tubular reactor are produced at high pressure and elevated temperature in a tubular reactor or the like, wherein the inherent consequences of dissimilar reaction kinetics for the respective ethylene and alkyl acrylate comonomers is alleviated or partially compensated by the intentional introduction of the monomers along the reaction flow path within the tubular reactor.
• Such copolymers can be obtained commercially from DuPont.
• Ethylene/alkyl acrylate copolymers produced via an autoclave process can be obtained commercially from Exxon/Mobil, and/or from AtoChem, for example.
• (meth)acrylate copolymers suitable for use in the practice of the present invention can vary significantly.
• the specific melt index that is desirable can depend on the balance of properties sought from the organic acid/ethylene/alkyl (meth)acrylate copolymer blend intended to provide the desired mix of oxygen permeability and structural properties needed for a specific packaging film.
• component (c) of this invention can be a mixture of components, including mixtures various species of a particular copolymer, so long as the intended use of the blend is not compromised or negated.
• ethylene alky (meth)acrylates having various melt indices, or having different alkyl groups, for example can be utilized as a mixture to fulfill the intended function of component (c) herein.
• Silicon-containing polymers Also suitable for use as a component (c) materials are silicon- containing polymers and/or copolymers (silicon-containing polymers). Silicon-containing polymers include ethylene vinyl silane copolymers; polysiloxane; and silicone rubber, for example.
• Ethylene vinyl silane copolymers can be prepared in a high- pressure reactor by polymerizing ethylene with vinyl silane, or by extruder grafting of a polyethylene with vinyl silane. Reactor-produced copolymers are highly branched low-density materials. Graft copolymers can be prepared from any polyethylene homopolymer or copolymer, allowing for greater variety of properties. Ethylene vinyl silane copolymers can be obtained commercially from PolyOne. Polysiloxanes, such as polydimethylsiloxanes are suitable for use herein and can be obtained commercially from Akzo Nobel.
• Silicone rubbers having methyl and vinyl groups and/or combinations of methyl, vinyl phenyl and/or fluoro substituents are suitable for use herein. Silicone rubber elastomers are available from Dow Corning.
• melt-processible, highly-neutralized acid modified ionomer blends of the present invention can be produced by
• component (c) Adding an ethylene-containing polymer, and/or a silicon- containing polymer.
• the additional polymeric material of component (c) can be melt- blended with the modified acid copolymers blends of the present invention by any manner known in the art. All of the components can be blended at the same time, sequentially, and/or in order and/or any variation that can result in a blend of the present invention.
• the component (c) material can be blended in subsequent to the organic acid or salt modification (mixing and neutralization) of the acid copolymers or ionomers, that is, downstream in a continuous melt mixer, such as a single screw or twin screw extruder.
• An organic acid modified ionomer blend of the present invention can be used to prepare monolayer or multilayer film structures.
• ethylene-containing polymers or ionomers can be employed as layers in multilayer films of the present invention, with the caveat that mono- or multilayer films suitable for use in the practice of the present invention should have the requisite strength needed in the projected uses of such films, in addition to high oxygen permeability as described elsewhere in this application.
• the oxygen permeability of a multilayer film is related to the thickness and permeability of each of the layers in the following manner:
• OPV, OPV x OPV 2 where is the permeability of the package normalized to 1 mil, OPV-j is the permeability of layer 1 , OPV2 the permeability of layer 1, x-i is the fraction of the film thickness that comprises layer 1 , and X£ is the fraction of the film thickness that comprises layer 2.
• a two-layer film comprised of a standard ionomer and an organic acid modified ionomer blend composition of this invention (e.g. Ex. 3) will have the oxygen permeability values indicated:
• a highly permeable multilayer of the present invention can be obtained by combining a skin layer of a standard ionomer with a layer of organic acid modified ionomer blend.
• a two-layer film with an OPV of 10,000 cc-mil/m 2 -day can be prepared with a layer of ionomer 0.475 times the total thickness of the film and a layer of organic acid modified ionomer blend 0.525 times the total thickness.
• a three-layer structure with the same OPV can be prepared using an inner layer of organic acid modified ionomer blend 0.525 times the total thickness and two outer layers of ionomer, each 0.2375 times the total thickness.
• highly oxygen permeable films with sufficient structural properties such as formability, stiffness, and puncture resistance for packaging case ready meat, for example, could be achieved by using multilayer films as described herein.
• blends of highly neutralized ionomers, organic acids and ethylene-containing copolymers e.g. ethylene/alkyl (meth)acrylate copolymers
• ethylene-containing copolymers e.g. ethylene/alkyl (meth)acrylate copolymers
• films obtained from the organic acid modified ionomer blends of the present invention can have an oxygen permeability value (OPV, normalized to one mil thickness) of greater than 10,000 mil-cc/m 2 ⁇ day, alternatively greater than 15,000 mil-cc/m 2 ⁇ day, alternatively greater than 20,000 mil-cc/m 2 -day, alternatively greater than 25,000 mil-cc/m 2 -day, alternatively greater than 30,000 mil-cc/m 2 -day, alternatively greater than 35,000 mil-cc/m 2 -day.
• OCV oxygen permeability value
• a specific embodiment of the invention provides an oxygen permeable multilayer polymeric film comprising: (i) at least one polymeric layer consisting essentially of an organic acid modified ionomer blend composition, as defined above; and
• this embodiment comprises three polymeric layers wherein both outer layers consist essentially of the ethylene/vinyl acetate copolymer of (ii) and a middle layer consists essentially of the organic acid modified ionomer blend of (i).
• Another specific embodiment of the invention provides an oxygen permeable multilayer polymeric film comprising:
• At least one polymeric layer consisting essentially of an organic acid modified ionomer blend composition, as defined above; and (ii) at least one additional polymeric layer consisting essentially of a copolymer of ethylene and an alkyl (meth)acrylate.
• At least one polymeric layer consisting essentially of an organic acid modified ionomer blend composition, as defined above; and (ii) at least one additional polymeric layer consisting essentially of a metallocene polyethylene having a density of less than 0.91 g/cc; or a blend of a metallocene polyethylene having a density of less than 0.91 g/cc and a low density polyethylene.
• this embodiment comprises three polymeric layers wherein both outer layers consist essentially of the metallocene polyethylene or metallocene polyethylene blend of (ii) and a middle layer consists essentially of the organic acid modified ionomer blend composition of (i).
• E is derived from ethylene
• X is derived from C3 to Cs ⁇ , ⁇ -ethylenically unsaturated carboxylic acids
• Y is derived from a softening comonomer, or i
• this embodiment comprises three polymeric layers wherein both outer layers consist essentially of the ionomer of (ii) and a middle layer consists essentially of the organic acid modified ionomer blend composition of (i).
• Additional specific embodiments include films with at least three different layers, one of which consists essentially of the organic acid modified ionomer blend composition. Accordingly, a specific embodiment of the invention provides an oxygen permeable multilayer polymeric film comprising:
• At least one polymeric layer consisting essentially of an EIXfY copolymer where E is derived from ethylene, X is derived from C3 to CQ ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, and Y is derived from a comonomer, or ionomers of the EIXIY copolymers, wherein X is from about 3 to 35 weight % of the EIXIY copolymer, and Y is from 0 to about 35 weight % of the EIXIY copolymer and wherein from about 0% to about 90% of the acid is neutralized; and
• At least one additional polymeric layer consisting essentially of a metallocene polyethylene having a density of less than 0.91 g/cc; or a blend of a metallocene polyethylene having a density of less than 0.91 g/cc and a low density polyethylene.
• an oxygen permeable multilayer polymeric film comprising:
• the organic acid modified ionomer blend composition comprise an ethylene-containing polymer that is the same as that used in the at least one additional layer.
• oxygen transmission rates greater than 8,000 cc/m 2 -day, alternatively greater than 10,000 cc/m 2 -day, alternatively greater than 15,000 cc/m 2 -day, alternatively greater than 20,000 cc/m 2 -day, alternatively greater than 25,000 cc/m 2 - day, alternatively greater than 30,000 cc/m 2 -day or alternatively greater than 35,000 cc/m 2 -day.
• lonomer-3 An E/10% MAA dipolymer partially neutralized with Na, having an Ml of 1.3.
• EMA-1 An E/24% MA dipolymer, having an Ml of 2.
• EMA-2 An E/24% MA dipolymer, having an Ml of 20.
• EBA-1 An E/27% nBA dipolymer, having an Ml of 4.
• EMAA-1 An E/15 % methacrylic acid dipolymer, having an Ml of 60.
• NA-1 a neutralizing agent comprising 50 weight % of Mg(OH)2 blended in a polymer carrier comprised of an E/5% MAA dipolymer with Ml of
• NA-2 a neutralizing agent comprising 50 weight% Mg(OH)2 blended in a polymer carrier of E/nBA/AA terpolymer.
• EVA-1 An E/28 % vinyl acetate dipolymer, having an Ml of 2.
• EBAAA-1 An E/12.5 nBA/10.5 AA terpolymer, having Ml of 60
• EBAMAA-1 An E/23.5%nBA/9% MAA terpolymer, having Ml of 200.
• a coextruded two-layer film was prepared on a Brampton blown film line comprising one layer of EVA-1 , nominally 1 mil thick, and one layer, nominally 2 mil thick, comprising a blend of 95 weight % of the resin of Example 13 and 5 weight % of EMAA-1.
• the operating parameters are listed below.
• Gauge set 0.97 0.94 0.94 3.0 + .25
• Example 16 A coextruded two-layer film comprising a 1.6 mil thick layer of
• Example 3 and a 0.4 mil thick layer of Comparative Example 1 is prepared on a blown film line.
• the OTR is calculated to be 10,680 cc/m.2 day atm.
• Packages comprising two webs of the film of Example 15 and fresh salmon or flounder pieces were prepared. Pieces of fish were placed on one web of the film and a second web was placed over the fish and overlying the first web on a standard vacuum seal packaging machine. Vacuum was applied and the webs were sealed at 200 0 F with a cycle time of 15 seconds. Formability and seal strength were good to excellent.
• a package is prepared from the Example 16 film using a process similar to that used in Example 15.

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