WO1996011861A1 - Article anti-oxygene pour emballages - Google Patents

Article anti-oxygene pour emballages Download PDF

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Publication number
WO1996011861A1
WO1996011861A1 PCT/US1995/012639 US9512639W WO9611861A1 WO 1996011861 A1 WO1996011861 A1 WO 1996011861A1 US 9512639 W US9512639 W US 9512639W WO 9611861 A1 WO9611861 A1 WO 9611861A1
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WO
WIPO (PCT)
Prior art keywords
oxygen scavenging
ribbon
article
oxygen
heat sealable
Prior art date
Application number
PCT/US1995/012639
Other languages
English (en)
Inventor
Ta Yen Ching
Original Assignee
Chevron Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Chemical Company filed Critical Chevron Chemical Company
Priority to MX9702634A priority Critical patent/MX9702634A/es
Priority to AU37617/95A priority patent/AU699050B2/en
Priority to CA002201738A priority patent/CA2201738C/fr
Publication of WO1996011861A1 publication Critical patent/WO1996011861A1/fr

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Classifications

    • 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
    • B65D81/267—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 the absorber being in sheet form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B—MAKING CONTAINERS OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31B50/00—Making rigid or semi-rigid containers, e.g. boxes or cartons
    • B31B50/74—Auxiliary operations
    • B31B50/81—Forming or attaching accessories, e.g. opening devices, closures or tear strings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • An improved oxygen scavenging system for use in a variety of packaging environments particularly food and beverage-containing products and packages involves the use of an oxygen scavenging ribbon.
  • oxygen scavengers within a cavity of the package is one form of active packaging.
  • oxygen scavengers are in the form of sachets which contain a composition which scavenges the oxygen through oxidation reactions.
  • One sachet contains iron-based compositions which oxidize to their ferric states.
  • Another type of sachet contains unsaturated fatty acid salts on a particulate adsorbent. See U.S. Patent No. 4,908,151.
  • Yet another sachet contains metal/polyamide complex. See U.S. Patent No. 5,194,478.
  • sachets are the need for additional packaging operations to add the sachet to each package.
  • a further disadvantage arising from the iron-based sachets is that certain atmospheric conditions (e.g., high humidity, low C0 2 level) in the package are sometimes required in order for scavenging to occur at an adequate rate. Further, the sachets can present a danger to consumers if accidentally ingested.
  • Another means for regulating the exposure to oxygen involves incorporating an oxygen scavenger into the packaging structure itself. A more uniform scavenging effect throughout the package is achieved by incorporating the scavenging material in the package itself instead of adding a separate scavenger structure (e.g., a sachet) to the package.
  • incorporating the oxygen scavenger into the package structure provides a means of intercepting and scavenging oxygen as it permeates the walls of the package (herein referred to as an "active oxygen barrier") , thereby maintaining the lowest possible oxygen level in the package.
  • active oxygen barrier a means of intercepting and scavenging oxygen as it permeates the walls of the package.
  • One attempt to prepare an oxygen-scavenging wall involves the incorporation of inorganic powders and/or salts. See U.S. Patent Nos. 5,153,038, 5,116,660, 5,143,769, and 5,089,323.
  • incorporation of these powders and/or salts cause degradation of the wall's transparency and mechanical properties such as tear strength.
  • these compounds can lead to processing difficulties, especially when fabricating thin films and multilayer constructions.
  • Such polymers when made into walls or layers and/or articles exhibit a number of drawbacks however.
  • Third, the optical appearance and the gloss of the surface of the article can be reduced as pitting and molecular decomposition takes place near or at the surface.
  • the accessibility of the triggering means e.g., UV light or corona discharge may be difficult, particularly in certain environments such as printed bags.
  • EP 0 507 207 discloses an oxygen-scavenging composition comprising an ethylenically unsaturated hydrocarbon and a transition metal catalyst.
  • This patent states that ethylenically unsaturated compounds such as squalene, dehydrated castor oil, and 1,2- polybutadiene are useful oxygen scavenging compositions, and ethylenically saturated compounds such as polyethylene and ethylene copolymers are used as diluents.
  • additives such as squalene, castor oil, or other such unsaturated hydrocarbons typically have an oily texture, which can introduce problems, e.g., poor adhesion, in multilayer film construction, and this texture is particularly undesirable for certain applications such as wrapping meat for sale in retail grocery stores. Further, these additives are of a size that introduces problems in terms of migration. Finally, polymer chains which are ethylenically unsaturated would be expected to either cross-link and become brittle or to degrade upon scavenging oxygen, weakening the wall of the package in either case.
  • an oxygen scavenger is an integral part of a packaging film structure. That is, in packaging film manufacturing, warehouse storage, as well as in designing triggering mechanisms for activating the oxygen removal processes, there are many limitations relating to preset, customer and/or structurally specific film processing and distribution conditions, which limitations make the design of a flexible system difficult, if not impossible. These limitations include extrusion temperature, coextrusion layers, film cooling speed, color printing, on line activation, duration of film storage, storage temperatures, and the like. Accordingly, the need still exists for alternative oxygen scavenging system in which can achieve some or all of the same advantages as that associated with coextruding but without the disadvantages.
  • an oxygen scavenging ribbon provides a flexibility, i.e., it can be effectively employed in a variety of environments, and can solve a number of problems traditionally associated with oxygen scavenging techniques.
  • this invention relates to an oxygen scavenging ribbon which comprises a heat sealable polymeric resin on at least the outer surface thereof and an oxygen scavenging material.
  • this ribbon upon oxidation of this oxygen scavenging material, does not release significant amounts of byproducts which are (i) odorous and/or (ii) not GRAS food additives.
  • this ribbon can be, for example, a multi-layer film structure in which the oxygen scavenging material is located in and encompassed by a outer layer comprising the heat sealable polymer and an polymeric selective barrier layer which is intermediate the two.
  • the ribbon can have a tubular shape, also with a multilayer design.
  • the present invention relates to articles such as flexible barrier packaging, e.g., bags, and rigid barrier packaging, e.g., bottles and boxes, which include this oxygen scavenging ribbon as well as methods for making the ribbons and the articles.
  • articles such as flexible barrier packaging, e.g., bags, and rigid barrier packaging, e.g., bottles and boxes, which include this oxygen scavenging ribbon as well as methods for making the ribbons and the articles.
  • Figures 3 and 4 illustrate two techniques for producing packages which employ an oxygen scavenging ribbon of the present invention
  • compositions are employed which are effective to scavenge oxygen.
  • scavenge means to absorb, deplete, or react with oxygen so that substantial amounts of oxygen does not return to the environment from which it is absorbed, depleted, or reacted.
  • oxygen scavenging material the present invention refers to a material that is capable of scavenging at least " 0.5 cc 0 2 /gram of oxygen scavenging material/day/atm.
  • the material is capable of scavenging at least about 1, and more preferably at least about 5, cc Oj/gram of oxygen scavenging material/day/atm.
  • oxygen scavenging materials are employed in the form of a ribbon structure which ribbon is introduced into the desired oxygen scavenging environment.
  • the following discussions relating to certain preferred embodiments of the invention focus on a one piece ribbon arrangement which includes the oxygen scavenging material, it is also within the purview of the present invention to employ a two piece ribbon structure which comprises a plurality of "patches," each of which include an oxygen scavenging material, on a "support tape".
  • the ribbon can be employed largely in the same manner as those ribbons of the preferred embodiment with the exception that the patches are transferred from the support tape to the package surface and then sealed, for example, by heat sealing and/or an adhesive.
  • the shape of these patches is not critical and can include circular or strips, e.g, the shape of adhesive bandages.
  • the ribbon preferably has a shape which is substantially longitudinal, i.e., its length is substantially longer than its width. This allows it to be more effectively produced in rolls and then introduced into a variety of packaging systems by way of a continuous operation. However, to the extent it can be effectively incorporated into processing systems in the manner discussed below, the exact shape is not critical to the present invention.
  • the ribbon preferably has a thickness of 0.5 to 10 mil, more preferably 2-3 mil, although the thickness also is not critical to the invention.
  • the ribbon comprises at least two materials, a heat sealable polymer which, as will be seen, allows the ribbon to be effectively employed and maintained in a variety of packaging systems and an oxygen scavenging material.
  • the relationship between these two components varies depending on the nature of the oxygen scavenger and will become clear with respect to the following discussion relating to the oxygen scavenging materials employed in the present invention.
  • the particular oxygen scavenging material is not critical to the present invention, however, as will be apparent to those skilled in the art, the choice of a particular oxygen scavenging material will influence the exact structure of the resulting ribbon.
  • the present invention typically involves the use of organic oxygen scavenging materials which are recognized in the art.
  • the organic oxygen scavenging material may be an organic compound such as squalene or dehydrated caster oil as disclosed in EP 0 507 207, which is incorporated by reference in its entirety herein. This organic compound may be blended with a polymer carrier, which itself may or may not scavenge oxygen.
  • the organic oxygen scavenging material may be layer laminated to another layer such as a polymeric selective barrier layer and/or a heat sealable layer which arrangements are discussed in detail below.
  • the organic oxygen scavenging material may be coated onto a polymer layer or onto a multilayer structure, in which case the organic oxygen scavenging material normally forms its own layer.
  • the organic scavenging material is typically a polymer having oxidizable sites in the polymer and containing a catalyst such as a transition metal salt that assists initiation of oxidation of the oxidizable sites.
  • a catalyst such as a transition metal salt that assists initiation of oxidation of the oxidizable sites.
  • polymers having oxidizable sites include polybutadiene, disclosed in U.S. Pat. No. 5,211,875; poly(meta-xylenediamine- adipic acid) (also known as MXD-6) , disclosed in U.S. Pat. Nos. 5,021,515 and 5,049,624, each of which is incorporated by reference in its entirety herein for all purposes.
  • this invention can also comprise the use of a polymeric material which functions as a selective barrier to certain oxidation products but not to oxygen (also called a polymeric selective barrier layer herein) .
  • a polymeric selective barrier layer herein
  • the oxidation products in question are often odorous and/or considered not generally recognized as safe (GRAS) food additives by the FDA. These oxidation products result from oxidation of the particular organic oxygen scavenging material utilized.
  • Examples of these oxidation products include carboxylic acids, such as acetic, propionic, butyric, and valeric acids; aldehydes, such as acetaldehyde; ketones, such as acetone and methyl ethyl ketone; esters, such as methyl formate; and other compounds such as isophthalic acid, isophthalic amide, and 1,6- hexanoic diacid.
  • carboxylic acids such as acetic, propionic, butyric, and valeric acids
  • aldehydes such as acetaldehyde
  • ketones such as acetone and methyl ethyl ketone
  • esters such as methyl formate
  • other compounds such as isophthalic acid, isophthalic amide, and 1,6- hexanoic diacid.
  • a polymeric layer functions as a barrier when it completely blocks an oxidation product or when it impedes migration of an oxidation product to an extent that the amount of oxidation product found in the enclosed volume after 5 days at 49°C produces slight to no odor in the case of odorous compounds or is within a U.S. Food and Drug Administration guideline for extractives in the case of compounds which are not generally regarded as safe. See 21 C.F.R. ⁇ 170-199 and Recommendations for Chemistry Data for Indirect Food Additive Petitions, published by the U.S. Food and Drug Administration, Sep. 1988, Version 1.2, Mar. 1993, each of which is incorporated in its entirety herein.
  • the polymeric selective barrier layer does not necessarily impede migration of all oxidation products. For example, it is not necessary that the polymeric selective barrier layer impedes migration of oxidation products such as carbon dioxide, water or compounds affirmed,as GRAS. Therefore, these oxidation products may migrate through the polymeric selective barrier layer to the extent recognized as safe by the FDA. Also, the polymeric selective barrier layer may impede migration of many but not all of the oxidation products whose migration is to be impeded.
  • a layer is considered to be a polymeric selective barrier layer when it prevents at least about half of the number and/or amount of oxidation products having a boiling point of at least about 75°C from passing through the polymeric selective barrier layer from the layer carrying the organic oxygen scavenging material.
  • the polymeric selective barrier layer also permits oxygen to migrate through it to contact the layer carrying an organic oxygen scavenging material.
  • the polymeric selective barrier layer permits enough oxygen to migrate through it such that the effective oxygen scavenging rate from the packaged volume for the composition of this invention (i.e., oxygen scavenging layer with polymeric selective barrier layer present) is at least about 0.1 cc 0 2 /gm of organic oxygen scavenging material/day/atm.
  • the polymeric selective barrier layer allows enough oxygen to migrate through it from the packaged volume such that the oxygen scavenging rate for the oxygen scavenging layer is at least about 1, and more preferably, about 5 cc 0 2 /gm of organic oxygen scavenging material/day/atm.
  • the polymeric selective barrier layer has an oxygen transmission rate (OTR) of at least about 1 cc 0 2 /100 in. 2 polymeric selective barrier layer 1 mil/day/atm. , as measured by ASTM D-3985, which is incorporated by reference in its entirety herein.
  • OTR oxygen transmission rate
  • the OTR is at least about 5, and more preferably, at least about 10, cc 0 2 /100 in. 2 polymeric selective barrier layer 1 mil/day/atm.
  • T g glass transition temperature
  • ASTM D-3418 ASTM D-3418
  • ASTM D-3418 ASTM D-3418
  • the use temperature of that polymer is the highest temperature to which the polymeric selective barrier layer is exposed after orienting the polymer.
  • the use temperature in this case may be encountered at any time after which the polymer has been oriented, such as during film processing, during lamination or during the time that the oriented polymer is to function as a selective barrier.
  • the use temperature is the highest temperature to which the polymeric selective barrier layer is exposed after this subsequent orientation of the polymer layer.
  • polymeric layers that have been oriented are effective polymeric selective barrier layers.
  • oriented polyethylene terephthalate (OPET) oriented polyethylene terephthalate
  • BOPET biaxially oriented polyethylene terephthalate
  • nylon-6 are each effective polymeric selective barrier layers to many of the oxidation products of polymeric oxygen scavenging material.
  • the use temperature in this case may be encountered at any time after which the polymer has been oriented, such as during film processing, during lamination or during the time that the oriented polymer is to function as a selective barrier.
  • the use temperature is the highest temperature to which the polymeric selective barrier layer is exposed after this subsequent orientation of the polymer layer.
  • the use temperature in this case may be encountered at any time after which the polymer has been oriented, such as during film processing, during lamination or during the time that the oriented polymer is to function as a selective barrier.
  • the use temperature is the highest temperature to which the polymeric selective barrier layer is exposed after this subsequent orientation of the polymer layer.
  • the use temperature is the temperature to which the composition of this invention is exposed while the composition is scavenging oxygen from the packaged volume and protecting the contents (ex. food) of the container into which the composition of this invention has been incorporated.
  • the use temperature would be the highest temperature that the meat package would encounter while the composition of this invention was scavenging oxygen to protect the meat from the oxygen.
  • polymers having particular crystalline and/or ordered structures as indicated by the T f , by the polymer crystallinity, and/or by the fact that the polymer has been oriented, provide channels within the polymer having dimensions that selectively block the diffusion of some larger molecules, such as odorous or extractive oxidation products, yet permit smaller molecules such as oxygen to pass through the polymer.
  • This theory is supplied only for the purpose of helping to explain why certain polymers are effective as polymeric selective barrier layers and is not limiting of the scope of this invention.
  • the T g of the polymeric selective barrier layer is at least about 40°C.
  • the T g of the polymeric selective barrier layer is at least about 50°C, and more preferably the T g of the polymeric selective barrier layer is at least about 60°C.
  • Solubility of the oxidation products in the polymeric selective barrier layer also can be a factor in determining whether a selected polymer will act as a polymeric selective barrier layer. If an oxidation product is very soluble in a polymer, it is likely to migrate through the polymer, and therefore the polymer would not be useful as a polymeric selective barrier layer. An oxidation product that is soluble in a polymer can change the T g of the polymer. As a result, a polymer having a T g sufficient to block oxidation products may have its T g reduced by an oxidation product to a level that the polymer cannot be used as a polymeric selective barrier layer.
  • a polymer may be an effective polymeric selective barrier layer in some applications, such as where the food product contained within the package is consumed shortly after packaging, but may not be an effective polymeric selective barrier layer in other situations, such as where the food product is expected to have a shelf-life of many years.
  • a polymeric selective barrier layer may contain plasticizers such as phthalate esters and/or polyethylene glycols.
  • a polymeric selective barrier layer may be a blend of polymers, such as a compatibilized blend including PET or nylon-6 which is then oriented.
  • the polymeric selective barrier layer may be modified for example, with fillers such as calcium carbonate and/or Tio 2 .
  • the polymeric selective barrier layer may also be a "multi-layer" construction in which any one layer alone does not necessarily qualify as a polymeric selective barrier layer, but together the multi-layer construction is a polymeric selective barrier layer.
  • the polymeric selective barrier layer is an oriented layer such as OPET or oriented nylon
  • the polymeric selective barrier layer may be oriented prior to it being co-laminated with the layer carrying an organic oxygen scavenging material.
  • an unoriented polymeric selective barrier layer may be coextruded with the layer carrying an organic oxygen scavenging material, and this multi-layer structure may then be oriented.
  • the ribbon comprises an arrangement in which the oxygen scavenging material is covered, and preferably completely encompassed by a polymeric selective barrier layer.
  • the heat sealable polymer is then introduced as the outside layer of the ribbon, preferably completely encompassing the barrier layer thereby forming an arrangement as in Figure 1.
  • Suitable heat sealing materials for use in the present invention are those heat sealable resins recognized in the art and can include ionomers and terpolymers such as ethylene-vinyl acetate, ethylene- methyl acrylate, low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , ethylene-sodium acrylate, ethylene-zinc acetate, ethylene-acrylic acid- sodium acrylate, and ethylene-acrylic acid-zinc acetate.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • ethylene-sodium acrylate ethylene-zinc acetate
  • ethylene-acrylic acid- sodium acrylate ethylene-acrylic acid-zinc acetate
  • the amount of the components employed are clearly dependent upon the particular application, i.e., the size of the packaging, the materials being packaged, the amount of oxygen that must be removed, and the like, and as such are readily determinable by those skilled in the art.
  • the dimensions can vary but the total weight is typically about 0.1-25 g, with the selective barrier layer having a thickness of about 0.1-5 mil, and a heat seal layer of 0.1 to 10 mil. Moreover, for a preferred 2-3 g ribbon, the capacity of 0 2 absorption is from 10-500 cc/ribbon.
  • oxygen scavenging ribbons can be produced by means well recognized in the art.
  • the above multilayered ribbon can be produced by suitable means such as multi-layer casting.
  • the casting can be performed such that the outer layers have a greater width that the inner layer and thus, complete encompass the inner layer.
  • the ribbon can be in the form of a long "tube" produced by art recognized techniques , e.g., blown film extrusion.
  • the ribbon structure can be a multi-layer structure having an outer heat sealable layer, followed by a barrier layer, the oxygen scavenging material containing layer, and another optional, inner layer also comprising the heat sealable polymeric material. See, for example, the cross-section of a tube illustrated by Figure 2.
  • oxygen scavenging material involves the use of oxygen scavenging powders traditionally employed within sachets such as "Ageless", an oxygen scavenging powder available from Mitsubishi Gas Chemical Co.
  • these powders which upon oxidation do not give off the undesirable products discussed above, can be blended directly into a suitable heat sealable resin and then extruded or otherwise formed into the desired ribbon shape.
  • suitable resins for use in this embodiment of the invention include Chevron LLDPE-6335 thermoplastic resin and Chevron EMAC® SP-2207 resin.
  • the powder is introduced in an amount of 5 to 80 % by weight, preferably about 20 % by weight.
  • the present invention can include additives which would not adversely effect the oxygen scavenging ability of the ribbon. Examples of such additives include color indicators, i.e., materials introduced into the ribbon which will effectively change the color of the ribbon upon oxidation of the oxygen scavenger.
  • the present invention relates to articles including oxygen-sensitive products, e.g., food packages and the like, containing the oxygen scavenging ribbons according to the present invention.
  • the ribbons can be introduced into rigid barrier packaging such as bottles or boxes, flexible barrier packaging such as bags, or tray containers such as polystyrene thermal storage trays.
  • FIGS 3 and 4 Two examples of suitable means for introducing a film into the particular environment are provided by Figures 3 and 4.
  • the ribbon is separately introduced into the packaging system prior to heat sealing of the package.
  • the particular technique is not critical and can include a variety of art-recognized systems which would allow for the separate introduction of the ribbons into the packaging.
  • a roll of the ribbon is triggered off line from the packaging film material and then fed continuously into the film line during the packaging process. The ribbon is then cut and sealed with the film material itself.
  • oxygen scavenging ribbons has a number of advantages over traditional scavenging techniques including separate storage of the film and thus greater control over the shelf life of the ribbon, the ability to introduce a single ribbon into very different types of packaging materials and in differing amounts to satisfy different packaging needs, the ability to employ triggering/activation means which are separate from and will not influence the structure of the packaging material itself, the ability to seal the ribbon at two separate locations within the packaging material so as to substantially reduce or eliminate any accidental ingestion of the antioxidant material.
  • the present invention is capable of being tailored for the individual needs of a particular package. For example, in the food environment, different foods can have different optimal oxygen scavenging demands.
  • the present invention allows for these differences to be considered, for example, the size of the ribbon can be altered, without altering the packaging, e.g., box or bag, size. Such flexibility can significantly increase the cost efficiency of a packaging system.
  • the present invention provides this flexibility while at the same time solving many of the problems present within existing scavenging technologies.
  • Example 1 Production of oxygen scavenging ribbon by multi-layer casting
  • a 4 inch wide, 3 mil thick oxygen scavenging ribbon with an "ABCBA" structure is prepared in Randcastle mini-extruder by coextrusion of (A) a Chevron EMAC® SP-2207 heat seal adhesive resin, (B) an Allied Signal Nylon 6 resin, and (C) an MXD-6 nylon containing 1000 ppm of cobalt ion oxygen scavenging compound.
  • A a Chevron EMAC® SP-2207 heat seal adhesive resin
  • B an Allied Signal Nylon 6 resin
  • C an MXD-6 nylon containing 1000 ppm of cobalt ion oxygen scavenging compound.
  • Example 2 Production of oxygen scavenging ribbon by blown film extrusion
  • a tubular ribbon structure as illustrated by Figure 2 is made by 4 layer blown film process with the outer film, 1, being EMAC® resin, followed by a barrier layer, 2, Nylon 6, an oxygen scavenging material layer, 3, comprising MXD-6, and another optional inner layer, 4, of EMAC® resin.
  • This tube shape ribbon can be used just as the flat ribbon for sealing into flexible bags or rigid trays.
  • Example 3 Production of thermoplastic ribbon filled with "Ageless" oxygen scavenging powder
  • a Chevron LLDPE-6335 thermoplastic resin filled with 20 weight % of Ageless oxygen scavenging powder under anaerobic condition is extruded into a single layer 2 mil film which is immediately stored in nitrogen.
  • Example 4 Incorporation of oxygen scavenging ribbon into flexible barrier food packaging
  • a 4 inch wide, 3 mil thick oxygen scavenging ribbon, 5, produced in accordance with Example 1 is triggered by a suitable means to activate oxygen scavenging capability, and is then fed along with the packaging film, 6, into a vertical fill food packaging machine, 7. After the food loading, it is sealed, 8, and die-cut, 9, along with the package to give structure 10.
  • Example 5 Incorporation of oxygen scavenging ribbon into rigid barrier food packaging
  • a 2 inch wide, 2 mil thick layer oxygen scavenging ribbon, 11, produced in accordance with Example 2 is fed along with a lidding film, 12.
  • the ribbon is optionally triggered/activated by a suitable means, 15, e.g., a UV or corona discharge, before being introduced into a lidding packaging machine, 13.
  • the lidding film is a barrier layer has a composition of HDPE/EMAC® resin/EVOH/EVA and the resulting food package, 14, containing the ribbon is provided.

Abstract

La présente invention concerne un ruban anti-oxygène constitué d'une résine thermosoudable et d'une substance anti-oxygène. Lors de l'oxydation de la substance anti-oxygène, ce ruban ne dégage pas de quantité significative de sous-produits odorants et/ou d'additifs alimentaires qui ne sont pas généralement reconnus inoffensifs (non 'G.R.A.S.'). Ce ruban peut se présenter sous différentes formes y compris un article moulé multicouche ou un tube en film soufflé. Ce ruban permet une grande souplesse d'utilisation pour l'élimination de l'oxygène à l'intérieur des atmosphères des emballages.
PCT/US1995/012639 1994-10-12 1995-10-11 Article anti-oxygene pour emballages WO1996011861A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
MX9702634A MX9702634A (es) 1994-10-12 1995-10-11 Articulo eliminador de oxigeno para uso en empaques.
AU37617/95A AU699050B2 (en) 1994-10-12 1995-10-11 Oxygen scavenging article for use in packages
CA002201738A CA2201738C (fr) 1994-10-12 1995-10-11 Article anti-oxygene pour emballages

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32172894A 1994-10-12 1994-10-12
US08/321,728 1994-10-12

Publications (1)

Publication Number Publication Date
WO1996011861A1 true WO1996011861A1 (fr) 1996-04-25

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PCT/US1995/012639 WO1996011861A1 (fr) 1994-10-12 1995-10-11 Article anti-oxygene pour emballages

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AU (1) AU699050B2 (fr)
CA (1) CA2201738C (fr)
MX (1) MX9702634A (fr)
WO (1) WO1996011861A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2825689A1 (fr) * 2001-06-08 2002-12-13 Cebal Utilisation de substances absorbant l'oxygene dans la fabrication de tubes souples
WO2004028261A1 (fr) * 2002-09-27 2004-04-08 Nestec S.A. Arome de cafe stabilise ne contenant pas de stabilisateur
US6960362B2 (en) 2001-03-23 2005-11-01 Nestec S.A. Stabilized aroma-providing components and foodstuffs containing same
US7060315B2 (en) 2001-03-23 2006-06-13 Nestec S.A. Aroma-containing components
EP1676790A1 (fr) * 2005-01-04 2006-07-05 Yuanmei Yang Absorbeur d'oxygène avec indicateur de niveau d'oxygène
US8349382B2 (en) 1999-05-18 2013-01-08 Nestec S.A. Method for dispensing a liquid beverage concentrate
WO2013119972A1 (fr) 2012-02-10 2013-08-15 Multisorb Technologies, Inc. Film comprenant des régions d'absorption d'oxygène
WO2021030265A1 (fr) * 2019-08-14 2021-02-18 Csp Technologies, Inc. Procédés et appareil pour couper et placer un film sur des substrats d'emballage

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DE2020622A1 (de) * 1970-04-28 1971-11-11 Josef Schmitter Kg Diesel Und Verfahren und Vorrichtung zur Herstellung von Verpackungsmaterial fuer feuchtigkeitsempfindliches Gut
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GB2207439A (en) * 1987-07-27 1989-02-01 Metal Box Plc Improvements in and relating to packaging
EP0402217A1 (fr) * 1989-06-08 1990-12-12 Gringoire-Brossard S.A. Film multicouches pour la fabrication d'emballages contenant des produits alimentaires
WO1991013556A1 (fr) * 1990-03-12 1991-09-19 Yhtyneet Paperitehtaat Oy Matiere de conditionnement supprimant l'oxygene d'un emballage et procede de production
EP0466515A2 (fr) * 1990-07-13 1992-01-15 Toray Industries, Inc. Absorbeur d'oxygène

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FR2025430A1 (fr) * 1968-12-05 1970-09-11 Sulzer Ag
FR2040254A1 (fr) * 1969-04-26 1971-01-22 Yasuda Shigeyuki
DE2020622A1 (de) * 1970-04-28 1971-11-11 Josef Schmitter Kg Diesel Und Verfahren und Vorrichtung zur Herstellung von Verpackungsmaterial fuer feuchtigkeitsempfindliches Gut
US4536409A (en) * 1981-01-23 1985-08-20 American Can Company Oxygen scavenger
GB2207439A (en) * 1987-07-27 1989-02-01 Metal Box Plc Improvements in and relating to packaging
EP0402217A1 (fr) * 1989-06-08 1990-12-12 Gringoire-Brossard S.A. Film multicouches pour la fabrication d'emballages contenant des produits alimentaires
WO1991013556A1 (fr) * 1990-03-12 1991-09-19 Yhtyneet Paperitehtaat Oy Matiere de conditionnement supprimant l'oxygene d'un emballage et procede de production
EP0466515A2 (fr) * 1990-07-13 1992-01-15 Toray Industries, Inc. Absorbeur d'oxygène

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8349382B2 (en) 1999-05-18 2013-01-08 Nestec S.A. Method for dispensing a liquid beverage concentrate
US7060315B2 (en) 2001-03-23 2006-06-13 Nestec S.A. Aroma-containing components
US6960362B2 (en) 2001-03-23 2005-11-01 Nestec S.A. Stabilized aroma-providing components and foodstuffs containing same
US7056545B2 (en) 2001-03-23 2006-06-06 Nestec S.A. Stabilization of aroma-providing components
FR2825689A1 (fr) * 2001-06-08 2002-12-13 Cebal Utilisation de substances absorbant l'oxygene dans la fabrication de tubes souples
WO2002100733A1 (fr) * 2001-06-08 2002-12-19 Cebal Sa Utilisation de substances absorbant l'oxygene dans la fabrication de tubes souples
WO2004028261A1 (fr) * 2002-09-27 2004-04-08 Nestec S.A. Arome de cafe stabilise ne contenant pas de stabilisateur
US7056546B2 (en) 2002-09-27 2006-06-06 Nestec S.A. Stabilizer-free stabilized coffee aroma
EP1676790A1 (fr) * 2005-01-04 2006-07-05 Yuanmei Yang Absorbeur d'oxygène avec indicateur de niveau d'oxygène
WO2013119972A1 (fr) 2012-02-10 2013-08-15 Multisorb Technologies, Inc. Film comprenant des régions d'absorption d'oxygène
EP2812262A4 (fr) * 2012-02-10 2015-11-25 Multisorb Tech Inc Film comprenant des régions d'absorption d'oxygène
US9340326B2 (en) 2012-02-10 2016-05-17 Multisorb Technologies, Inc. Film with oxygen absorbing regions
US9604758B2 (en) 2012-02-10 2017-03-28 Multisorb Technologies, Inc. Film with oxygen absorbing regions
WO2021030265A1 (fr) * 2019-08-14 2021-02-18 Csp Technologies, Inc. Procédés et appareil pour couper et placer un film sur des substrats d'emballage

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MX9702634A (es) 1997-07-31
CA2201738C (fr) 2003-12-16
CA2201738A1 (fr) 1996-04-25
AU3761795A (en) 1996-05-06

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