US20150329266A1 - Methods of making oxygen scavenging articles containing moisture - Google Patents
Methods of making oxygen scavenging articles containing moisture Download PDFInfo
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- US20150329266A1 US20150329266A1 US14/811,373 US201514811373A US2015329266A1 US 20150329266 A1 US20150329266 A1 US 20150329266A1 US 201514811373 A US201514811373 A US 201514811373A US 2015329266 A1 US2015329266 A1 US 2015329266A1
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- oxygen scavenging
- oxygen
- film
- liquid
- stretched
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
- B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
- B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
- B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
- A23L3/3427—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O in which an absorbent is placed or used
- A23L3/3436—Oxygen absorbent
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
Definitions
- This disclosure relates to oxygen scavenging articles. More specifically, the disclosure relates to oxygen scavenging materials containing moisture and systems for and methods of making such articles
- Flexible food packaging materials such as used to form a plastic pouch usually require good oxygen barrier properties in order to prevent microbial growth and preserve the freshness of the food. This need can be exemplified by packages such as those for beef jerky, sausages, and processed meats, among others.
- a sachet containing an oxygen scavenger is commonly used in these type food pouches to absorb the head space oxygen and to absorb any oxygen permeating through the package wall.
- Sachets have been used for some time in ready-to-serve food packages, but they have potential disadvantages and limitations. For example, sachets are generally comingled with the food product, and thus may be accidentally ingested. Sachets also are susceptible to accidental piercing or cutting, which can lead to contamination of the food product. And, sachets are not aesthetically pleasing. In addition, sachets are not generally suited for use in packaging liquid products requiring oxygen scavenging.
- Extruded articles containing oxygen scavengers in the form of film, tape, ribbon or strands are known and may be advantageous in some packaging applications due to their powder-free construction and integral, usually one-piece format.
- such articles are generally not preferable in low-moisture applications, such as in packaging coffee, because there is insufficient ambient moisture to facilitate absorption of oxygen by the iron.
- U.S. Pat. No. 5,896,994, issued Apr. 27, 1999 to WR Grace for “Sealed Articles,” relates to an oxygen scavenging film strip disposed in a tray package containing oxygen sensitive articles.
- an oxygen scavenger suitable for operating at a water activity of 0.4 or lower, for example, as in connection with food products such as powdery coffee and dry infant food powder.
- a water activity of 0.4 or lower for example, as in connection with food products such as powdery coffee and dry infant food powder.
- oxygen may deteriorate aroma or flavor due to oxidation.
- the present invention remedies the foregoing needs in the art by providing an improved oxygen scavenging material containing water that can be readily formed for inclusion in myriad packaging applications.
- a method of making an oxygen scavenging material includes stretching an oxygen scavenging material in at least one axial direction to form pores in the material and wetting the stretched material with a liquid such that the pores in the material retain a portion of the liquid.
- the method may also include drying the stretched material after wetting to remove any moisture remaining on the surface.
- a system for manufacturing an oxygen scavenging material includes a supply of oxygen scavenging material, a tool for stretching the supply of oxygen scavenging material in at least one axial direction, and a water supply for wetting the stretched oxygen scavenging material.
- the system includes a dryer for drying the stretched material after wetting to remove moisture remaining on the surface.
- an oxygen scavenger in yet another aspect of the disclosure, includes a stretched oxygen scavenging film having a plurality of pores therein; and a liquid retained in the pores.
- FIG. 1 is a flow chart illustrating a method of making a polymeric fabricated oxygen scavenger including moisture.
- FIG. 2 is a schematic representation of a system for creating an oxygen scavenging film containing moisture according to one embodiment of the invention.
- FIG. 3 is a schematic representation of a system for creating an oxygen scavenging film containing moisture according to another embodiment of the invention.
- FIG. 4 is a schematic representation of a multi-cavity die-cut and dispensing apparatus which may be used in embodiments of the invention.
- FIG. 1 describes a manufacturing process 110 according to an embodiment of the invention.
- a supply of an oxygen scavenging material is provided.
- the oxygen scavenging material can be provided in many forms including but not limited to film, ribbon, and tape, and may be either in a packaged form for presentment, such as on a spool, or as a continuous web from machinery forming the material, such as an extruder, mold, or the like.
- the oxygen scavenging material may comprise any number of compositions.
- it includes an iron-based oxygen scavenger, an inorganic salt such as NaCl which forms an electrolyte in water, and a moisture absorber such as activated carbon, silica gel, molecular sieve, or clay.
- the oxygen scavenging material also optionally includes mineral particles such as calcium carbonate as a pore former or a source of initiation of cavitation.
- the oxygen scavenging material is formed as a ribbon, tape or film, it also includes a polymer such as polypropylene, polyethylene, or polylactic acid.
- the provided oxygen scavenging material is stretched to form pores therein.
- the oxygen scavenging material is stretched axially in one or more directions, resulting in the desired pore formation.
- the film or sheet of oxygen-scavenging material can be uniaxially stretched using conventional machine directional orientation tools. It can also be biaxially stretched by machine directional orientation and transverse directional orientation tools to create voids or pores through deformation of pore formers.
- the draws ratio defined as the ratio of the stretch length divided by the un-stretched length, can range from 1 to 100.
- the suitable draw ratio can be experimentally determined to create porosity for the particular formulation chosen.
- the pore or void size can range from submicron to a few millimeter.
- the pores are preferably evenly distributed across the articles. They can be isolated or interconnected. They can be any shapes such as spherical, rectangular, triangular or multi-surfaced space.
- the pores can also be reticulated structure in which the open space is connected by fibrillated polymer structure such as that commonly seen in filter papers or filtration membranes. Pores can also be cavitation or voids as initiated by deformation around the included particles such as calcium carbonate or talc.
- the characteristics of the pores such as their morphology, shape, size and number, the liquid retention properties of the material can be controlled.
- pores are voids formed by stretching, pores may be naturally occurring in the oxygen scavenging material, even without stretching. Pores are broadly understood to be any free volume in the oxygen scavenging material that is capable of retaining a liquid, as will be described in more detail below.
- the stretched and porous material is then moistened in step 116 .
- the moisturizer may be any liquid, but in one preferred embodiment is water.
- Other liquids used in the invention may include water and alcohol mixtures, glycerin, water and glycerin mixtures, and solutions including water, such as electrolytic solutions.
- the moisturizing may be done by spraying, perhaps as a vapor, the liquid onto the stretched and porous material or by introducing the material to a bath containing the liquid.
- the porous material When the porous material is moistened, the pores retain some of that moisture, even if the material is subsequently dried to remove surface moisture.
- the stretched, porous, moistened material is subsequently cut in step 118 to form oxygen scavenging articles. Each of the articles is placed in a container requiring oxygen absorption in step 120 .
- the articles formed according to the process of FIG. 1 can be selectively manufactured to any number of specifications and for any number of uses.
- the oxygen scavenging article may be fabricated in the form of a packet, a ribbon, a strand, a ring, a flat film, a sheet, a label, or an insert for use in a coffee package, e.g., a single-serve cup, such as a K-cup, bag, or container, to absorb residual oxygen in the package.
- the articles could be formed as lid stocks or sealing layers.
- the oxygen scavenging fabricated article is fabricated in the form of a packet, a ribbon, a strand, a ring, a flat film, a sheet, a label, or an insert stored with infant food to absorb residual oxygen in the infant food package.
- the invention is particularly useful in these applications because there is very little, if any, moisture in packages containing coffee and infant food.
- the oxygen scavenger already contains moisture, so it will absorb oxygen under these circumstances.
- the manufacturing process described with reference to FIG. 1 also can be altered to provide desired results.
- the porosity of the material can be varied, which in turn varies the amount of moisture retained by the material.
- the amount of moisture will have a direct impact on the rate of absorption of the oxygen scavenging article.
- the oxygen scavenging composition may be made according to many formulations, which can lead to varied performance results.
- the composition includes a polymer, an oxygen scavenger, a salt, a moisture absorber, and a pore former. Additional components, such as surfactants also may be included.
- Polymers useful for making the oxygen scavenging articles can include common polyolefins such as low density polyethylene, high density polyethylene, polypropylene, polystyrene, high-impact polystyrene, polycarbonate, polymethylmethacrylate and their derivatives or copolymers. They also may include sustainable or biodegradable polymers, which generally include all common polymers generated from renewable resources and biodegradable polymers, such as polylactic acid copolymers, starch-based polymers such as thermoplastics starch, polyhydroxyalkanoates, and polyhydroxybutyrate . Other biodegradable polymers may be petroleum-based polymers such as polyethylene oxide or polyvinyl alcohol.
- the oxygen scavenger generally includes an iron powder. More specifically, the reduced iron powder preferably has 1-200 um mean particle size, more preferably 5-50 um mean particle size and most preferably 10-40 um mean particle size.
- the iron can be mixed with salt or a combination of different electrolytic and acidifying components.
- the iron particles can also be coated with salt.
- the combination and relative fraction of activating electrolytic and acidifying components coated onto the iron particles can be selected according to the teachings of U.S. Pat. No. 6,899,822, US Pat. applications 2005/0205841 and 2007/020456, incorporated herein by reference.
- the coating technique is preferably a dry coating process as described in the references above.
- the salt can be any inorganic salt such as sodium-, potassium- or calcium-based ionic compounds that are soluble in water. Typical examples include NaCl, KCl, Na 2 HPO 4 and others. A mixture of separate electrolytic and acidifying salt components can be advantageously used in the formulation as described in prior art.
- the oxygen absorbing composition preferably also includes a moisture absorber, such as silica gel, activated carbon, molecular sieve, another sorbent material, or a combination thereof.
- a moisture absorber such as silica gel, activated carbon, molecular sieve, another sorbent material, or a combination thereof.
- a mixture of the materials may include activated carbon and silica gel in a 50/50 mixture.
- the total loading can range from 2-80 wt %, preferably 5-60%, and more preferably 10-50%.
- a pore former can also be used in the invention to promote formation of voids or pores during the stretching step.
- the pore former may be, for example, CaCO 3 , talc, Mg(OH) 2 , or some other mineral particle.
- the loading can range from 10-70%, and preferably from 20-50%.
- pore formers can be compounded separately with resin as master batches and fed into the extruder forming the polymeric oxygen scavenger.
- stretching of the oxygen scavenging material facilitates creation of micro-mechanical deformations around inorganic particles, such as around the pore former.
- Surfactants also may be used in mixtures used to create the oxygen scavenger material.
- Some such surfactants useful for treating resin pellets or coated iron powders in order to maximize dispersion include lubricants such as mineral oil, fatty acids such as stearic acid, and low molecular weight compounds such as waxes.
- a smaller size of composite oxygen scavenging particles (limited by small particle sizes producing significant light scattering and haze in films), comprising all necessary components for efficient oxidation, produces oxygen scavenging films with higher effective reactivity with permeating oxygen and allows for a more efficient design of barrier structures.
- barrier film reactivity is in some instances advantageously improved by multilayer structural designs where the oxygen scavenging layer such as made according to the foregoing mixtures forms the middle layer of a three-layer structure made from the same matrix resin.
- the specific optimal layer thickness ratios depend on the overall film thickness and the oxidation kinetics of the activated scavenger.
- the three-layer film structure preferably has a layer ratio in the range of 49/2/49 and 1/98/1, with an optimum ratio, depending on the design target (such as the rate of headspace oxygen absorption) may be about 40/20/40.
- the iron is preferably located in the middle of the three layers.
- the outer layers may be any known oxygen permeable construction.
- Films to be used as labels, laminates or inserts for a pouch may consist of single or multilayer structure with the coated iron uniformly distributed in the film or in the chosen layer(s).
- the coated iron is preferably located in the middle of the structure. It can be located adjacent to the external layer to facilitate absorption.
- a layered structure according to the invention may include an absorptive layer including iron disposed on a backing or substrate, such as a PET substrate.
- the substrate may be chosen for its aesthetics, for example, because it may be more readily printed on or has an otherwise more desirable surface characteristic.
- the substrate also may be chosen for its barrier properties or for its ability to act as a removable layer, such as when the oxygen scavenger is an adhesive label. Handling may also dictate the use and structure of the barrier layer.
- FIG. 2 is a schematic representation of a system 200 for forming oxygen scavenging articles using a process similar to that described in connection with FIG. 1 .
- the system 200 generally includes a supply 210 of an oxygen-absorbing polymeric material 212 .
- the supply 210 is a spool 211 about which the material 212 is disposed.
- the material 212 may be provided directly from the machine making the material, such as an extruder or mold.
- the material 212 is provided as a continuous web fed from the spool 211 through a conveyance path.
- a stretching tool 214 which, as noted above, may be a conventional MDO or TDO tool.
- the material 212 is delivered, for example, with the assistance of rollers 216 , proximate a moisturizer 218 .
- the moisturizer 218 provides a liquid 220 to the material 212 .
- additional moisturizers could be present and placed in a multitude of locations, including beneath the material 212 .
- the material 212 is conveyed to a cutter 222 that cuts the material 212 into a plurality of discrete oxygen scavenging articles 224 .
- the oxygen scavenging articles 224 may be ready for use after cutting, or they may undergo further processing.
- the articles 224 may be placed on a conveyor 226 , driven by a series of rollers 228 , to be presented to a dryer 230 for removing surface water.
- the conveyor 226 preferably transports the articles 224 for direct packaging into a container in which oxygen is undesirable, or to a staging area, such as a bag, having limited oxygen. Once wet, the articles 224 are active, so it is important to maintain them in a low-to-no oxygen environment until use.
- FIG. 3 shows a system 300 slightly different from the system of FIG. 2 .
- a continuous web of oxygen scavenging material 312 is provided on a supply 310 , which is a spool 311 in the illustrated embodiment.
- the oxygen scavenging material is fed, by a series of rollers 316 or the like, to a moisturizing bath 318 containing a liquid 320 .
- the web of material is conveyed through the bath 318 while submerged in the liquid 320 to allow pores in the material or the material itself, e.g. by way of the silica gel or similar moisture retaining material, to retain some of the liquid 320 .
- the film may be required to be left in the bath 318 for a (relatively longer) time sufficient to allow the liquid to permeate the oxygen scavenging material 312 and occupy pores therein.
- the web may be stretched prior to wetting using an MDO or a TDO machine, as in the embodiment described in connection with FIG. 2 .
- the material used in these embodiments may be a single layer or a multi-layer, as described above.
- the moistened material 312 is subsequently subjected to a dryer 330 to remove surface liquid remaining after the bath 318 . Once dried, the material 312 is cut by a cutter 322 to form discrete oxygen scavenging articles 324 . After moistening, the oxygen scavenging material 312 is active, so the articles 324 are preferably quickly cut and placed in a subsequently-sealed container 350 .
- the container 350 may be the container of ultimate use for the product, or may be an interim container that is preferably oxygen-free so as to maintain efficacy of the article 324 .
- the wetted material may be a single layer, having a structure like that described above or some similar structure, or may have multiple layers.
- the composition of the oxygen absorbing layer may be adjusted to achieve desired performance. For example, when the material is not to be stretched, additional silica gel or other similar water retention material may be incorporated with the pore former being reduced, even to the point of elimination. Similarly, the number of pores can be varied by including more or less of the pore former. Pore size can also be increased by additional stretching of the material.
- FIG. 4 is a schematic representation of the system in which the cutter 322 is a die cutter that forms the discrete oxygen scavenging articles 324 as circular discs from the moisture-retaining material 312 . As shown, a row of oxygen scavenging discs may be formed at the same time, and, although only one container 350 is shown, a plurality of containers 350 preferably are arranged, each for receipt of one of the articles 324 .
- the inventor also has conducted an experiment including aspects of the above-described disclosure, which is described as follows:
- a 15-mil film that contains an oxygen scavenger formulation was prepared by extruding a mixture of polypropylene, a modifier, iron, talc, and silica gel.
- the polypropylene was a homopolymer commercially available as Dow H110-02N.
- the modifier was a propylene-based elastomer commercially available from ExxonMobil as VistamaxxTM VM6102, which can be used with polypropylene to enhance its performance in certain applications, such as in forming films.
- the iron was an iron and salt combination made according to the teachings of U.S. Patent Application Publication No. 2010/0255231 to Chau et al. for oxygen scavenging films, the disclosure of which is hereby incorporated by reference.
- the talc was a commercially available talc sold by Luzinac as Jetfill 700 and the silica gel was a commercially available silica gel having a 5 micron average particle size.
- the mixture was extruded in a twin screw extruder at an average temperature of 250° C. for the extruder and die to form a 5-inch wide 15 mil thick sheet.
- the sheet was collected on a winder.
- One-inch-wide samples were cut from the sheet and subsequently stretched using an Instron tensile tester at l/min strain rate to approximately 300% elongation, creating porosity or voids in the samples.
- the films appeared to show some stress-whitening and opaqueness after stretching.
- the film stripes were subsequently immersed in water for 30 min and, in this experimental process, blot-dried briefly to remove the surface water.
- the wetted sample was found to have a water activity of approximately 0.7, different from the 0.4 of the unstretched, non-wetted film.
- the samples were cut into one- to two-inch pieces and weighted to achieve approximately 3.5 gm for both the as-extruded and stretched pieces. These cut pieces were tested for oxygen scavenging performance using a pouch test. More specifically, the cut samples were sealed in a high gas barrier bag and the bag was injected with 300 cc of O 2 /N 2 mixture to achieve a starting oxygen level of approximately 4.7-5%. The oxygen absorption rate was measured using a MOCON PacCheck Model 450 Head Space Analyzer at various times at room temperature. The oxygen absorbed by the samples at these times is shown in Table-1. The data showed that the stretched and stress-whitened samples had higher absorption rate than the un-stretched, control film, despite both being wetted.
Abstract
An extruded or molded article containing iron based oxygen scavenger, electrolytes, activated carbon, silica gel, or other water absorbing media, and optionally pore formers, is subjected to deformation to create voids or porosity, and subjected to water spraying or dipping to obtain a water activity of 0.4 or higher. The article is placed in a container or package containing oxygen sensitive articles.
Description
- 1. Technical Field
- This disclosure relates to oxygen scavenging articles. More specifically, the disclosure relates to oxygen scavenging materials containing moisture and systems for and methods of making such articles
- 2. Description of Related Art
- Flexible food packaging materials such as used to form a plastic pouch usually require good oxygen barrier properties in order to prevent microbial growth and preserve the freshness of the food. This need can be exemplified by packages such as those for beef jerky, sausages, and processed meats, among others. A sachet containing an oxygen scavenger is commonly used in these type food pouches to absorb the head space oxygen and to absorb any oxygen permeating through the package wall. Sachets have been used for some time in ready-to-serve food packages, but they have potential disadvantages and limitations. For example, sachets are generally comingled with the food product, and thus may be accidentally ingested. Sachets also are susceptible to accidental piercing or cutting, which can lead to contamination of the food product. And, sachets are not aesthetically pleasing. In addition, sachets are not generally suited for use in packaging liquid products requiring oxygen scavenging.
- As one conventional alternative to using sachets, it is known to purge the ambient air from a container and backfill the container with an inert gas, such as nitrogen. However, this process is costly and does not account for migration of oxygen into the package, for example, after sealing the package.
- Extruded articles containing oxygen scavengers in the form of film, tape, ribbon or strands are known and may be advantageous in some packaging applications due to their powder-free construction and integral, usually one-piece format. However, such articles are generally not preferable in low-moisture applications, such as in packaging coffee, because there is insufficient ambient moisture to facilitate absorption of oxygen by the iron.
- The following are documents identified by the inventor as relating generally to oxygen scavenging:
- U.S. Pat. No. 5,896,994, issued Apr. 27, 1999 to WR Grace for “Sealed Articles,” relates to an oxygen scavenging film strip disposed in a tray package containing oxygen sensitive articles.
- U.S. Pat. No. 4,769,175, issued Sep. 6, 1988 to Mitsubishi Gas for “Sheet Like Oxygen Scavenging Agent,” describes mixtures of fiber, iron powder, water, and electrolyte formed into a sheet-like product using a paper making process.
- U.S. Pat. No. 4,317,742, issued Mar. 2, 1982 to Teijin for an “Oxygen Scavenging Composition, Heat-Generating Composition, And Heat-Generating Structure,” teaches a heat generating composition capable of scavenging oxygen.
- In view of the above-described deficiencies in the art, and shortcomings of the just-listed patents, there is a need in the art for an oxygen scavenger made from a film, tape or ribbon that contains a certain amount of moisture. There also is a need in the art for an oxygen scavenger having an adjustable amount of moisture therein, for example, such that the rate of oxygen scavenging in the container or package is controllable.
- There also is a need in the art for an oxygen scavenging article that does not occupy large spaces, is functional and is easy to dispense.
- There also is a need in the art for an oxygen scavenger suitable for operating at a water activity of 0.4 or lower, for example, as in connection with food products such as powdery coffee and dry infant food powder. Of noted interest, for example, it is desirable to preserve coffee aroma or flavor for single serving ready-to-brew cups that are approximately 30 cc or larger in volume. In a small food package, oxygen may deteriorate aroma or flavor due to oxidation.
- There also is a need in the art for a non-leachable oxygen scavenger, which will not change the taste of the articles with which the scavenger is packaged.
- There also is a need in the art for a solution to one or more of the aforementioned products that is a sustainable solution using materials of renewable resources and biodegradable in nature.
- There also is a need in the art for an improved method of making an oxygen scavenger such as that described above.
- The present invention remedies the foregoing needs in the art by providing an improved oxygen scavenging material containing water that can be readily formed for inclusion in myriad packaging applications.
- In one aspect of the disclosure, a method of making an oxygen scavenging material includes stretching an oxygen scavenging material in at least one axial direction to form pores in the material and wetting the stretched material with a liquid such that the pores in the material retain a portion of the liquid.
- The method may also include drying the stretched material after wetting to remove any moisture remaining on the surface.
- In another aspect of the disclosure, a system for manufacturing an oxygen scavenging material includes a supply of oxygen scavenging material, a tool for stretching the supply of oxygen scavenging material in at least one axial direction, and a water supply for wetting the stretched oxygen scavenging material.
- In another aspect, the system includes a dryer for drying the stretched material after wetting to remove moisture remaining on the surface.
- In yet another aspect of the disclosure, an oxygen scavenger includes a stretched oxygen scavenging film having a plurality of pores therein; and a liquid retained in the pores.
- These and other aspects and features of the invention will be appreciated from the following disclosure and attached figures, in which preferred embodiment s of the invention are described and illustrated.
-
FIG. 1 is a flow chart illustrating a method of making a polymeric fabricated oxygen scavenger including moisture. -
FIG. 2 is a schematic representation of a system for creating an oxygen scavenging film containing moisture according to one embodiment of the invention. -
FIG. 3 is a schematic representation of a system for creating an oxygen scavenging film containing moisture according to another embodiment of the invention. -
FIG. 4 is a schematic representation of a multi-cavity die-cut and dispensing apparatus which may be used in embodiments of the invention. - As noted above, the disclosure relates generally to a method of making polymeric fabricated articles containing oxygen scavengers and moisture.
FIG. 1 describes amanufacturing process 110 according to an embodiment of the invention. Instep 112 of the process, a supply of an oxygen scavenging material is provided. The oxygen scavenging material can be provided in many forms including but not limited to film, ribbon, and tape, and may be either in a packaged form for presentment, such as on a spool, or as a continuous web from machinery forming the material, such as an extruder, mold, or the like. - The oxygen scavenging material may comprise any number of compositions. In one embodiment it includes an iron-based oxygen scavenger, an inorganic salt such as NaCl which forms an electrolyte in water, and a moisture absorber such as activated carbon, silica gel, molecular sieve, or clay. The oxygen scavenging material also optionally includes mineral particles such as calcium carbonate as a pore former or a source of initiation of cavitation. When the oxygen scavenging material is formed as a ribbon, tape or film, it also includes a polymer such as polypropylene, polyethylene, or polylactic acid. Those of ordinary skill in the art, when enlightened by this disclosure will understand that other compositions of oxygen scavenging materials will be readily compatible with the process, systems and articles described herein.
- In
step 114, the provided oxygen scavenging material is stretched to form pores therein. In one embodiment, the oxygen scavenging material is stretched axially in one or more directions, resulting in the desired pore formation. For example, the film or sheet of oxygen-scavenging material can be uniaxially stretched using conventional machine directional orientation tools. It can also be biaxially stretched by machine directional orientation and transverse directional orientation tools to create voids or pores through deformation of pore formers. The draws ratio, defined as the ratio of the stretch length divided by the un-stretched length, can range from 1 to 100. The suitable draw ratio can be experimentally determined to create porosity for the particular formulation chosen. The pore or void size can range from submicron to a few millimeter. It is preferably ranging from 0.1 to 500 micron, more preferably ranging from 0.5 to 50 micron. The pores are preferably evenly distributed across the articles. They can be isolated or interconnected. They can be any shapes such as spherical, rectangular, triangular or multi-surfaced space. The pores can also be reticulated structure in which the open space is connected by fibrillated polymer structure such as that commonly seen in filter papers or filtration membranes. Pores can also be cavitation or voids as initiated by deformation around the included particles such as calcium carbonate or talc. By varying the characteristics of the pores, such as their morphology, shape, size and number, the liquid retention properties of the material can be controlled. Although as just described in connection with the embodiment illustrated inFIG. 1 the pores are voids formed by stretching, pores may be naturally occurring in the oxygen scavenging material, even without stretching. Pores are broadly understood to be any free volume in the oxygen scavenging material that is capable of retaining a liquid, as will be described in more detail below. - In the embodiment of
FIG. 1 , the stretched and porous material is then moistened instep 116. The moisturizer may be any liquid, but in one preferred embodiment is water. Other liquids used in the invention may include water and alcohol mixtures, glycerin, water and glycerin mixtures, and solutions including water, such as electrolytic solutions. The moisturizing may be done by spraying, perhaps as a vapor, the liquid onto the stretched and porous material or by introducing the material to a bath containing the liquid. - When the porous material is moistened, the pores retain some of that moisture, even if the material is subsequently dried to remove surface moisture. The stretched, porous, moistened material is subsequently cut in
step 118 to form oxygen scavenging articles. Each of the articles is placed in a container requiring oxygen absorption in step 120. - The articles formed according to the process of
FIG. 1 can be selectively manufactured to any number of specifications and for any number of uses. For example, the oxygen scavenging article may be fabricated in the form of a packet, a ribbon, a strand, a ring, a flat film, a sheet, a label, or an insert for use in a coffee package, e.g., a single-serve cup, such as a K-cup, bag, or container, to absorb residual oxygen in the package. In other embodiments, the articles could be formed as lid stocks or sealing layers. - In another embodiment, the oxygen scavenging fabricated article is fabricated in the form of a packet, a ribbon, a strand, a ring, a flat film, a sheet, a label, or an insert stored with infant food to absorb residual oxygen in the infant food package.
- In fact, the invention is particularly useful in these applications because there is very little, if any, moisture in packages containing coffee and infant food. The oxygen scavenger already contains moisture, so it will absorb oxygen under these circumstances.
- The manufacturing process described with reference to
FIG. 1 also can be altered to provide desired results. For example, by controlling the amount of stretching, the porosity of the material can be varied, which in turn varies the amount of moisture retained by the material. The amount of moisture will have a direct impact on the rate of absorption of the oxygen scavenging article. - Moreover, and as noted above, the oxygen scavenging composition may be made according to many formulations, which can lead to varied performance results. In one embodiment, the composition includes a polymer, an oxygen scavenger, a salt, a moisture absorber, and a pore former. Additional components, such as surfactants also may be included.
- Polymers useful for making the oxygen scavenging articles can include common polyolefins such as low density polyethylene, high density polyethylene, polypropylene, polystyrene, high-impact polystyrene, polycarbonate, polymethylmethacrylate and their derivatives or copolymers. They also may include sustainable or biodegradable polymers, which generally include all common polymers generated from renewable resources and biodegradable polymers, such as polylactic acid copolymers, starch-based polymers such as thermoplastics starch, polyhydroxyalkanoates, and polyhydroxybutyrate . Other biodegradable polymers may be petroleum-based polymers such as polyethylene oxide or polyvinyl alcohol.
- The oxygen scavenger generally includes an iron powder. More specifically, the reduced iron powder preferably has 1-200 um mean particle size, more preferably 5-50 um mean particle size and most preferably 10-40 um mean particle size. The iron can be mixed with salt or a combination of different electrolytic and acidifying components. The iron particles can also be coated with salt. The combination and relative fraction of activating electrolytic and acidifying components coated onto the iron particles can be selected according to the teachings of U.S. Pat. No. 6,899,822, US Pat. applications 2005/0205841 and 2007/020456, incorporated herein by reference. The coating technique is preferably a dry coating process as described in the references above.
- The salt can be any inorganic salt such as sodium-, potassium- or calcium-based ionic compounds that are soluble in water. Typical examples include NaCl, KCl, Na2HPO4 and others. A mixture of separate electrolytic and acidifying salt components can be advantageously used in the formulation as described in prior art.
- The oxygen absorbing composition preferably also includes a moisture absorber, such as silica gel, activated carbon, molecular sieve, another sorbent material, or a combination thereof. For example, a mixture of the materials may include activated carbon and silica gel in a 50/50 mixture. The total loading can range from 2-80 wt %, preferably 5-60%, and more preferably 10-50%.
- A pore former can also be used in the invention to promote formation of voids or pores during the stretching step. The pore former may be, for example, CaCO3, talc, Mg(OH)2 , or some other mineral particle. The loading can range from 10-70%, and preferably from 20-50%. Typically, pore formers can be compounded separately with resin as master batches and fed into the extruder forming the polymeric oxygen scavenger. When a material containing a pore former is used, stretching of the oxygen scavenging material facilitates creation of micro-mechanical deformations around inorganic particles, such as around the pore former.
- Surfactants also may be used in mixtures used to create the oxygen scavenger material. Some such surfactants useful for treating resin pellets or coated iron powders in order to maximize dispersion include lubricants such as mineral oil, fatty acids such as stearic acid, and low molecular weight compounds such as waxes.
- Fillers, modifiers, or other materials generally known in the polymer film-making art, such as elastomers, coloring agents, or the like, also may be incorporated into the oxygen scavenging material.
- A smaller size of composite oxygen scavenging particles (limited by small particle sizes producing significant light scattering and haze in films), comprising all necessary components for efficient oxidation, produces oxygen scavenging films with higher effective reactivity with permeating oxygen and allows for a more efficient design of barrier structures.
- In addition, while mixtures according to the foregoing disclosure may be formed into a single layer film, barrier film reactivity is in some instances advantageously improved by multilayer structural designs where the oxygen scavenging layer such as made according to the foregoing mixtures forms the middle layer of a three-layer structure made from the same matrix resin. The specific optimal layer thickness ratios depend on the overall film thickness and the oxidation kinetics of the activated scavenger.
- The three-layer film structure preferably has a layer ratio in the range of 49/2/49 and 1/98/1, with an optimum ratio, depending on the design target (such as the rate of headspace oxygen absorption) may be about 40/20/40. The iron is preferably located in the middle of the three layers. The outer layers may be any known oxygen permeable construction.
- Films to be used as labels, laminates or inserts for a pouch may consist of single or multilayer structure with the coated iron uniformly distributed in the film or in the chosen layer(s). For a multilayer structure, the coated iron is preferably located in the middle of the structure. It can be located adjacent to the external layer to facilitate absorption. In other embodiments, a layered structure according to the invention may include an absorptive layer including iron disposed on a backing or substrate, such as a PET substrate. The substrate may be chosen for its aesthetics, for example, because it may be more readily printed on or has an otherwise more desirable surface characteristic. The substrate also may be chosen for its barrier properties or for its ability to act as a removable layer, such as when the oxygen scavenger is an adhesive label. Handling may also dictate the use and structure of the barrier layer.
-
FIG. 2 is a schematic representation of asystem 200 for forming oxygen scavenging articles using a process similar to that described in connection withFIG. 1 . Thesystem 200 generally includes asupply 210 of an oxygen-absorbingpolymeric material 212. In the illustration, thesupply 210 is aspool 211 about which thematerial 212 is disposed. In other embodiments, thematerial 212 may be provided directly from the machine making the material, such as an extruder or mold. - In
FIG. 2 , thematerial 212 is provided as a continuous web fed from thespool 211 through a conveyance path. First, the material is acted upon by a stretchingtool 214, which, as noted above, may be a conventional MDO or TDO tool. Once stretched thematerial 212 is delivered, for example, with the assistance ofrollers 216, proximate amoisturizer 218. Themoisturizer 218 provides a liquid 220 to thematerial 212. Although only one moisturizer is shown inFIG. 2 , disposed above thematerial 212 for moisturizing a top surface of the material, additional moisturizers could be present and placed in a multitude of locations, including beneath thematerial 212. - Once moisturized, the
material 212 is conveyed to acutter 222 that cuts thematerial 212 into a plurality of discreteoxygen scavenging articles 224. Theoxygen scavenging articles 224 may be ready for use after cutting, or they may undergo further processing. For example, as shown inFIG. 2 , thearticles 224 may be placed on aconveyor 226, driven by a series ofrollers 228, to be presented to adryer 230 for removing surface water. Theconveyor 226 preferably transports thearticles 224 for direct packaging into a container in which oxygen is undesirable, or to a staging area, such as a bag, having limited oxygen. Once wet, thearticles 224 are active, so it is important to maintain them in a low-to-no oxygen environment until use. -
FIG. 3 shows asystem 300 slightly different from the system ofFIG. 2 . InFIG. 3 , a continuous web ofoxygen scavenging material 312 is provided on asupply 310, which is aspool 311 in the illustrated embodiment. In this embodiment there is no stretcher and the oxygen scavenging material is fed, by a series ofrollers 316 or the like, to amoisturizing bath 318 containing a liquid 320. The web of material is conveyed through thebath 318 while submerged in the liquid 320 to allow pores in the material or the material itself, e.g. by way of the silica gel or similar moisture retaining material, to retain some of the liquid 320. Because the material is not stretched in the illustrated embodiment, the film may be required to be left in thebath 318 for a (relatively longer) time sufficient to allow the liquid to permeate theoxygen scavenging material 312 and occupy pores therein. In another embodiment the web may be stretched prior to wetting using an MDO or a TDO machine, as in the embodiment described in connection withFIG. 2 . Whether stretched or not, the material used in these embodiments may be a single layer or a multi-layer, as described above. - The moistened
material 312 is subsequently subjected to adryer 330 to remove surface liquid remaining after thebath 318. Once dried, thematerial 312 is cut by acutter 322 to form discreteoxygen scavenging articles 324. After moistening, theoxygen scavenging material 312 is active, so thearticles 324 are preferably quickly cut and placed in a subsequently-sealedcontainer 350. Thecontainer 350 may be the container of ultimate use for the product, or may be an interim container that is preferably oxygen-free so as to maintain efficacy of thearticle 324. Again, the wetted material may be a single layer, having a structure like that described above or some similar structure, or may have multiple layers. - Whether the material used is stretched or not, and whether a single or multiple layers are used, the composition of the oxygen absorbing layer may be adjusted to achieve desired performance. For example, when the material is not to be stretched, additional silica gel or other similar water retention material may be incorporated with the pore former being reduced, even to the point of elimination. Similarly, the number of pores can be varied by including more or less of the pore former. Pore size can also be increased by additional stretching of the material.
-
FIG. 4 is a schematic representation of the system in which thecutter 322 is a die cutter that forms the discreteoxygen scavenging articles 324 as circular discs from the moisture-retainingmaterial 312. As shown, a row of oxygen scavenging discs may be formed at the same time, and, although only onecontainer 350 is shown, a plurality ofcontainers 350 preferably are arranged, each for receipt of one of thearticles 324. - The inventor also has conducted an experiment including aspects of the above-described disclosure, which is described as follows:
- A 15-mil film that contains an oxygen scavenger formulation was prepared by extruding a mixture of polypropylene, a modifier, iron, talc, and silica gel. The polypropylene was a homopolymer commercially available as Dow H110-02N. The modifier was a propylene-based elastomer commercially available from ExxonMobil as Vistamaxx™ VM6102, which can be used with polypropylene to enhance its performance in certain applications, such as in forming films. The iron was an iron and salt combination made according to the teachings of U.S. Patent Application Publication No. 2010/0255231 to Chau et al. for oxygen scavenging films, the disclosure of which is hereby incorporated by reference. The talc was a commercially available talc sold by Luzinac as Jetfill 700 and the silica gel was a commercially available silica gel having a 5 micron average particle size. The weight ratio for the mixture was polypropylene/Vistamaxx/iron/talc/silica gel=25/25/10/30/10.
- The mixture was extruded in a twin screw extruder at an average temperature of 250° C. for the extruder and die to form a 5-inch wide 15 mil thick sheet. The sheet was collected on a winder. One-inch-wide samples were cut from the sheet and subsequently stretched using an Instron tensile tester at l/min strain rate to approximately 300% elongation, creating porosity or voids in the samples. The films appeared to show some stress-whitening and opaqueness after stretching. The film stripes were subsequently immersed in water for 30 min and, in this experimental process, blot-dried briefly to remove the surface water. The wetted sample was found to have a water activity of approximately 0.7, different from the 0.4 of the unstretched, non-wetted film.
- The samples were cut into one- to two-inch pieces and weighted to achieve approximately 3.5 gm for both the as-extruded and stretched pieces. These cut pieces were tested for oxygen scavenging performance using a pouch test. More specifically, the cut samples were sealed in a high gas barrier bag and the bag was injected with 300 cc of O2/N2 mixture to achieve a starting oxygen level of approximately 4.7-5%. The oxygen absorption rate was measured using a MOCON PacCheck Model 450 Head Space Analyzer at various times at room temperature. The oxygen absorbed by the samples at these times is shown in Table-1. The data showed that the stretched and stress-whitened samples had higher absorption rate than the un-stretched, control film, despite both being wetted.
-
TABLE 1 Oxygen absorption for the stretched films containing sorbents and oxygen scavenger Film thickness Time O2 absorbed Sample mil hrs cc/gm of film As extruded 14.5 0 0 14.5 1.04 24 1.69 48 2.64 Stretched 13 0 0 14.5 1.71 24 2.55 48 3.49 - The foregoing embodiments of the present invention are provided as exemplary embodiments and are presently best modes for carrying out the invention. Modifications of these embodiments will be readily apparent to those of ordinary skill in the art. The invention is not intended to be limited by the foregoing embodiments, but instead is intended to be limited only by the appended claims.
Claims (18)
1.-25. (canceled)
26. An oxygen scavenging material made by:
stretching a film containing an oxygen scavenger to obtain a stretched film; and
wetting the stretched film with a liquid such that pores in the material retain a portion of the liquid.
27. The oxygen scavenging material of claim 26 , wherein the film containing the oxygen scavenger comprises the oxygen scavenger, salt, as moisture absorber, and a polymer.
28. The oxygen scavenging material of claim 26 , wherein the film containing the oxygen scavenger comprises a bonding agent.
29. The oxygen scavenging material of claim 26 , wherein the film containing the oxygen scavenger comprises a pore former.
30. The oxygen scavenging material of claim 26 , wherein the film is extruded from a mixture of the oxygen scavenger, a salt, a moisture absorber, and a polymer.
31. A sachet formed using the oxygen scavenging material of claim 26 .
32. An oxygen scavenging article formed using the oxygen scavenging material of claim 26 .
33. The oxygen scavenging article of claim 32 , formed as a packet, a ribbon, a strand, a ring, a flat film, a sheet, a label, an insert, lid stock, or a sealing layer.
34. The oxygen scavenging material of claim 26 , wherein the liquid is water.
35. The oxygen scavenging material of claim 26 , wherein the liquid comprises an alcohol and water mixture, glycerin, a glycerin and water mixture or an electrolytic solution
36. An oxygen scavenging article comprising:
a stretched oxygen scavenging film having a plurality of axially-extending pores formed by stretching the oxygen scavenging film; and
a liquid retained in the axially-extending pores.
37. The oxygen scavenging article of claim 36 , wherein each of the plurality of pores is sized generally between about 0.1 micron and 500 micron across.
38. The oxygen scavenging article of claim 36 , wherein the liquid is water.
39. The oxygen scavenging article of claim 36 , wherein the stretched oxygen scavenging film comprises a polymer, an oxygen scavenger, a moisture absorber, and a salt.
40. The oxygen scavenging article of claim 36 , further comprising at least one of a pore former and a bonding agent.
41. The oxygen scavenging article of claim 36 , wherein the oxygen scavenger is one of a packet, a ribbon, a strand, a ring, a flat film, a sheet, a label, an insert, lid stock, or a sealing layer.
42. The oxygen scavenging material of claim 26 , wherein the liquid comprises an alcohol and water mixture, glycerin, a glycerin and water mixture or an electrolytic solution
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US14/811,373 US20150329266A1 (en) | 2011-09-22 | 2015-07-28 | Methods of making oxygen scavenging articles containing moisture |
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US13/240,594 US9107442B2 (en) | 2011-09-22 | 2011-09-22 | Methods of making oxygen scavenging articles containing moisture |
US14/811,373 US20150329266A1 (en) | 2011-09-22 | 2015-07-28 | Methods of making oxygen scavenging articles containing moisture |
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US14/811,373 Abandoned US20150329266A1 (en) | 2011-09-22 | 2015-07-28 | Methods of making oxygen scavenging articles containing moisture |
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DE2964337D1 (en) | 1978-02-24 | 1983-01-27 | Teijin Ltd | Oxygen scavenger composition, heat-generating composition and structure, and their use as an oxygen scavenger or generator of heat |
KR890002855B1 (en) | 1985-06-26 | 1989-08-05 | 미쯔비시 가스 가가구 가부시기가이샤 | Sheet-type deoxide material |
DE68914102T2 (en) | 1988-11-24 | 1994-07-07 | Sumitomo Chemical Co | Oxygen-absorbing thermoplastic synthetic resin film. |
JPH03202150A (en) | 1989-12-28 | 1991-09-03 | Toagosei Chem Ind Co Ltd | Preparation of oxygen absorbent |
EP0547761B1 (en) | 1991-11-13 | 1995-08-02 | Mitsubishi Gas Chemical Company, Inc. | Oxygen absorber and method for producing same |
US6248690B1 (en) | 1992-05-26 | 2001-06-19 | Multisorb Technologies, Inc. | Oxygen absorber |
NZ272780A (en) | 1994-08-23 | 1998-02-26 | Grace W R & Co | Food package comprising an oxygen-sensitive article enclosed in polymeric film |
DE69909902T2 (en) | 1998-06-03 | 2004-05-06 | Mitsubishi Gas Chemical Co., Inc. | Oxygen absorbing composition, oxygen absorbing resin and preservation method |
US6899822B2 (en) | 2002-11-18 | 2005-05-31 | Multisorb Technologies, Inc. | Oxygen-absorbing composition |
KR100743930B1 (en) | 2003-09-10 | 2007-07-30 | 도꾸리쯔교세이호진상교기쥬쯔소고겡뀨죠 | Oxygen scavenger and method for production thereof |
US7951419B2 (en) | 2005-07-21 | 2011-05-31 | Multisorb Technologies, Inc. | Dry-coated oxygen-scavenging particles and methods of making them |
US20110177742A1 (en) | 2008-07-09 | 2011-07-21 | Filip Frederix | Functional sheet |
JP5188407B2 (en) | 2009-01-23 | 2013-04-24 | 三菱樹脂株式会社 | Biaxially stretched polyamide laminated film and method for producing the same |
US20100255231A1 (en) | 2009-04-01 | 2010-10-07 | Multisorb Technologies, Inc. | Oxygen scavenging films |
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2011
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