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US20130146600A1 - Seal Capable of Generating Molecular Hydrogen and Suitable for Closing a Container and for Scavenging Oxygen - Google Patents

Seal Capable of Generating Molecular Hydrogen and Suitable for Closing a Container and for Scavenging Oxygen Download PDF

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Publication number
US20130146600A1
US20130146600A1 US13/808,219 US201113808219A US2013146600A1 US 20130146600 A1 US20130146600 A1 US 20130146600A1 US 201113808219 A US201113808219 A US 201113808219A US 2013146600 A1 US2013146600 A1 US 2013146600A1
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US
United States
Prior art keywords
seal
container
liner
molecular hydrogen
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/808,219
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English (en)
Inventor
Hilde Krikor
Alain Dessaint
Luc Verheyen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Plastipak BAWT SARL
Original Assignee
La Seda de Barcelona SA
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 La Seda de Barcelona SA filed Critical La Seda de Barcelona SA
Assigned to LA SEDA DE BARCELONA S.A. reassignment LA SEDA DE BARCELONA S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Dessaint, Alain, KRIKOR, HILDE, VERHEYEN, LUC
Publication of US20130146600A1 publication Critical patent/US20130146600A1/en
Assigned to PLASTIPAK BAWT, S.A.R.L. reassignment PLASTIPAK BAWT, S.A.R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LA SEDA DE BARCELONA S.A
Abandoned legal-status Critical Current

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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
    • B65D53/00—Sealing or packing elements; Sealings formed by liquid or plastics material
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B2/708—Preservation of foods or foodstuffs, in general 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
    • A23B2/712—Preservation of foods or foodstuffs, in general 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
    • A23B2/717—Oxygen absorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B65D51/00—Closures not otherwise provided for
    • B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
    • B65D51/244—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes provided with oxygen absorbers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B5/00—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2581/00—Seals; Sealing equipment; Gaskets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a novel seal that is capable of generating molecular hydrogen from a chemical reaction with water, and that can be used for closing a container and for scavenging oxygen.
  • the container can be used for storing any oxygen-sensitive substance that can be altered by oxygen, and in particular a food substance or a beverage such as for example juice, beer, wine, . . . .
  • Aromatic polyester resins and in particular polyethylene terephthalate (PET), are widely used in the packaging industry for making various types containers for storing any substance, and in particular for storing food substance or a beverage.
  • PET polyethylene terephthalate
  • PET has a number of valuable properties for packaging, but lacks sufficient gas barrier properties for many applications.
  • PET alone is not appropriate for packaging oxygen-sensitive food and beverage products such as beer, fruit juices, some carbonated soft drinks, etc. . . . PET is also permeable to carbon dioxide, which in turn leads to a short shelf life for carbonated products, such as carbonated soft drinks, stored in PET containers.
  • a removable plastic closure cap For closing a container, it is common to use a removable plastic closure cap than can be for example removably screwed or snapped onto the container.
  • heat sealed containers especially heat sealed thermoplastic containers, for storing sensitive products, like for example dairy products (UHT milk, yoghurt, cream, . . . ) or tomato-based products.
  • the rigid opened mouth of the container is hermetically closed by heat welding a sealing foil onto a top sealing surface.
  • the heat welding operation is performed in such a way that the sealing foil hermetically closes the container and avoids, for example, any leakage of the product that is stored in the container.
  • the heat welding operation is also performed in such a way that the sealing foil is efficiently bonded with the container, but can be however peeled off manually by the final consumer for opening the container.
  • a heat weldable sealing foil generally comprises at least two laminated layers: a thermal conductive layer, and a heat weldable layer.
  • the thermal conductive layer is a metal layer having a good thermal conductivity, such as for example an aluminium layer.
  • An aluminium layer exhibits also very high gas barrier properties.
  • the use of a seal comprising an aluminium layer advantageously prevents gas transmission in or out of the container, and thereby increases the shelf life of the product stored in the container.
  • the heat weldable layer is generally made of a thermoplastic film, such as for example a polyethylene film, coated onto one face of the thermal conductive layer.
  • the heat welding operation of the sealing foil onto the container is performed by heating the sealing foil in such a way that the heat weldable layer is melted, and by mechanically pressing the heated sealing foil against the top sealing surface of the container mouth, the melted heat weldable layer being in contact with the said top sealing surface.
  • the heating of the heat weldable layer of the sealing foil can be obtained by means of different heating processes.
  • the most commonly used heating processes involve either a conductive heating of the sealing foil or an inductive heating of the sealing foil, by means notably of high frequency (HF) energy.
  • HF high frequency
  • a typical and common multilayered wall structure for a hollow rigid container is a three-layer wall: two internal and external layers made of PET, and one intermediate gas barrier layer sandwiched between the two PET layers.
  • a first known type of barrier layer is made of, or comprises, polymers that have excellent gas-barrier properties, in particular to O 2 and/or CO 2 , and is generally referred as “passive barrier layer”.
  • polymers used for making passive barrier layers homo- or copolymers of polyamides are commonly used.
  • these polyamides the so-called “MXD6” or “MXD6 nylon” (specific polyamide material manufactured by Mitsubishi Gas Chemical Company, Japan) is preferably used, i.e. a poly(m-xylyleneadipamide) produced by the polycondensation of a diamine component composed mainly of m-xylylenediamine and a dicarboxylic acid component composed mainly of adipic acid.
  • a second known type of barrier layer which has been more recently developed, is made of, or comprises, polymeric composition that has oxygen-scavenging properties, and is generally referred as “active barrier layer”.
  • active barrier layer reacts with the oxygen and “captures” the oxygen when the oxygen penetrates into the layer. Such active barrier layer is thus progressively “consumed” in use.
  • polymeric compositions used for making active barrier layer are described notably in European patent application EP-A-0 301 719 or in European patent application EP-A-0 507 207.
  • Said polymeric compositions generally comprise an oxidizable polymer and a transition metal catalyst.
  • the preferred oxidizable polymers are polyamides, and especially MXD6.
  • EP-0 507 207 one preferred oxidizable polymer is polybutadiene.
  • preferred transition metal catalysts are transition metal salts, an in particular cobalt stearate.
  • Other known metal salts used for making such composition are rhodium, manganese, copper, iron.
  • multilayered packaging articles having at least one gas barrier layer comprising a polyamide (e.g. MXD6) and a polyester (e.g. PET), very good results can be achieved in terms of shelf life of the packaged products. More especially when the barrier layer comprises a polyamide (e.g. MXD6), polyester (e.g. PET), and a catalyst such as a cobalt salt, the multilayered packaging article can be used for storing oxygen-sensitive products, such as beer, fruit juice, tomato-based products, or the like.
  • the shelf life of the packaged product widely depends of the amount of polyamide in the packaging article and of the thickness of the barrier layer.
  • gas barrier polymer like polyamide in the container wall renders the recycling of the container more difficult.
  • polyamide in particular for making a monolayer container
  • the O 2 scavenging properties are obtained by using an active substance, such as for example a hydride, that is capable of chemically reacting with water and generating molecular hydrogen, and by making said molecular hydrogen react with oxygen which may ingress the container.
  • an active substance such as for example a hydride
  • said active substance is incorporated in a plug that is positioned in a cap.
  • the active substance can however prejudicially contaminate the product stored in the container.
  • a general and main objective of the invention is to propose a novel closure that includes an active substance capable of chemically reacting with water and generating molecular hydrogen into a container.
  • a more particular objective of the invention is to propose a novel closure, that includes an active substance capable of chemically reacting with water and generating molecular hydrogen into a container, and that can be in contact with the content of the container without any risk of contamination of the said substance by the active substance.
  • a more particular objective of the invention is to propose a novel closure, that includes an active substance capable of chemically reacting with water and generating molecular hydrogen into a container, and that can be easily manufactured.
  • a more particular objective of the invention is to propose a novel active closure for a container, said closure being suitable for scavenging oxygen that may penetrate inside the container, notably through the permeable wall of the container, or oxygen that is present in the head space of the container.
  • seal of claim 1 that is adapted to be heat bonded to a container for closing an opening of the container.
  • This seal of the invention is a laminate comprising a metallic layer, a liner that is permeable to water vapour and to molecular hydrogen, and that can be heat bonded to a container, and at least an active layer, that is positioned between the metallic layer and the liner, and that is capable of chemically reacting with water and generating molecular hydrogen.
  • FIG. 1 is a view in cross-section of an example of a closure seal of the invention
  • FIG. 2 is a partial view in cross-section of a container mouth closed by the seal of FIG. 1 and by removable closure cap,
  • FIGS. 3 to 5 are schematic view in cross-section showing other possible configurations of a container mouth closed by the seal of FIG. 1 .
  • the seal 1 is a laminate made of three layers 10 , 11 , 12 that are bonded together, namely an inner active layer 11 that is sandwiched between two outer layers 10 and 12 .
  • the three layers 10 , 11 , 12 have the same shape and the shape of the laminate 1 is adapted to the shape of the container opening on which the seal is to be heat bonded.
  • the shape of the laminate 1 is for example, but not necessarily, a disk.
  • the invention is not limited to a three-layer laminate, but encompasses also laminates having more than three layers.
  • the active layer 11 is in contact with and is bonded on both faces with layers 10 and 12 .
  • This particular construction is optional and is not a limitation of the invention.
  • the invention also encompasses laminates comprising more than three bonded layers, and wherein the active layer 11 is positioned between at least two layers 10 and 12 , and is not necessarily in direct contact with these layers 10 and 12 .
  • the outer layer 10 is a metallic layer that can be heated by induction or by conduction. This layer is more preferably made of aluminium. More particularly, the outer layer 10 is for example a thin aluminium foil.
  • the inner active layer 11 is bonded on both faces with the outer layers 10 and 12 .
  • the inner active layer is capable of chemically reacting with water and generating molecular hydrogen from this reaction with water.
  • the material of the active layer 11 can be made of or can comprise any active substance forming such a hydrogen source.
  • said active substance suitable for the release of molecular hydrogen as a result of contact with water is one of the active substances described in PCT application WO2008/090354.
  • the material of the active layer 11 comprises a polymeric matrix containing the active substance which is incorporated in the polymer matrix and which is capable of chemically reacting with water and generating molecular hydrogen from this reaction with water.
  • Suitable polymeric matrix materials include but are not limited to low density polyethylene, in particular linear low density polyethylene, high density polyethylene, polypropylene, ethylene vinyl acetate, thermoplastic elastomers (TPEs), like styrenic block copolymers, polyolefin blends, elastomeric alloys, thermoplasticpolyurethanes, thermoplastic copolyester, and thermoplastic polyamides, or blend thereof.
  • TPEs thermoplastic elastomers
  • a good candidate among thermoplastic elastomer materials is a material comprising styrenic block copolymers consisting of polystyrene blocks and rubber blocks, such as for example SEBS, SEPS, SBS, SBC.
  • the ratio of the weight of active substance to matrix material may be at least 0.01, preferably at least 0.02.
  • the matrix may be a polymeric matrix and said active substance may be dispersed therein.
  • the rate of release of hydrogen is limited by either the permeation rate of water into the polymeric matrix and/or by the solubility of water in the chosen matrix.
  • selection of polymeric materials based on the permeability or solubility of water in the polymer allows one to readily control the rate of release of molecular hydrogen from any number of active substances.
  • the polymeric matrix may include at least 1 wt % of active substance, preferably at least 2 wt %.
  • the polymeric matrix may include less than 20 wt % of active substance.
  • the polymeric matrix includes 1-16 wt %, preferably 4-12 wt % of active substance.
  • the balance of material in the polymeric matrix may predominantly comprise a said polymeric material.
  • Active substances suitable for the release of molecular hydrogen as a result of contact with water are preferably the ones described in PCT application WO2008/090354.
  • said active substance may comprise a metal and/or a hydride.
  • Said metal may be selected from sodium, lithium, potassium, magnesium, zinc or aluminum.
  • a hydride may be inorganic, for example it may comprise a metal hydride or borohydride; or it may be organic.
  • active substances include but are not limited to: sodium metal, lithium metal, potassium metal, calcium metal, sodium hydride, lithium hydride, potassium hydride, calcium hydride, magnesium hydride, sodium borohydride, and lithium borohydride.
  • hydrolysis catalysts and/or agents in the polymeric matrix can be used.
  • the rate of hydrolysis of silicon hydrides may be enhanced by the use of hydroxide or fluoride ions, transition metal salts, or noble metal catalysts.
  • the active substance may also be the polymeric matrix.
  • polymeric silicon hydrides such as poly(methylhydro)siloxane provide both a polymeric matrix and an active substance capable of releasing molecular hydrogen when in contact with moisture.
  • the outer layer 12 is a liner that can be heat bonded to a container.
  • the liner 12 can be a monolayer or a multilayer component.
  • the material of the liner 12 is preferably selected in order to obtain a liner 12 that:
  • the material of the liner 12 can be any polymeric material that enables to obtain characteristics (i) and (ii).
  • the materials of the liner 12 include but are not limited to low density polyethylene, in particular linear low density polyethylene, high density polyethylene, polypropylene, ethylene vinyl acetate, thermoplastic elastomers (TPEs), like styrenic block copolymers, polyolefin blends, elastomeric alloys, thermoplasticpolyurethanes, thermoplastic copolyester, and thermoplastic polyamides, polymers on methacrylateolefin base, copolymers of vinylchloride, vinylacetate and dicarbonic add, or blend thereof.
  • TPEs thermoplastic elastomers
  • styrenic block copolymers polyolefin blends
  • elastomeric alloys thermoplasticpolyurethanes
  • thermoplastic copolyester thermoplastic copolyester
  • thermoplastic polyamides polymers on methacrylateole
  • FIG. 2 Heat-Sealed Container
  • FIG. 2 shows a container C having a rigid plastic neck or mouth 2 terminated by an opening 2 b .
  • This top opening 2 b is knowingly used for filling the container with a product and/or for pouring the product outside the container.
  • This opening 2 b is surrounded by a circumferential top sealing surface 2 a .
  • a seal 1 like the one previously described in reference to FIG. 1 is heat bonded to the container C in order to hermetically close the container opening 2 b . More particularly, in the embodiment of FIG. 2 , the liner 12 of the seal 1 is heat bonded to the top sealing surface 2 a of the container C, on the whole periphery of the opening 2 b.
  • a removable closure cap 3 is also fitted onto the container C for closing the opening 2 b .
  • the closure cap 3 is screwed on the container neck 2 .
  • the closure cap 3 can be snapped on the container neck 2 .
  • the neck or mouth 2 of the container is preferably rigid and at least the neck or mouth 2 of the container is made of plastic material.
  • suitable plastic materials for the neck or mouth 2 of the container C may comprise polyester (including but not limited to PET), polyetheresters, polyesteramides, polyurethanes, polyimides, polyureas, polyamideimides, polyamides, polycarbonates, polyphenyleneoxide, phenoxy resins, epoxy resins, polyolefins (including but not limited to polypropylene and polyethylene), polyacrylates, polystyrene, polyvinyls (including but not limited to polyvinyl chloride)) and combinations thereof.
  • the container body can be for example any plastic container or any cardboard container.
  • the container can be for example a bottle-shaped container, a flask, a jar, a tube, a bag, a pouch.
  • the container body can be rigid, semi rigid or flexible.
  • the body of containers contemplated in the present invention may be either of a monolayer or a multilayer construction.
  • Suitable materials which may be used as a layer or part of one or more layers in either monolayer or multilayer containers include polyester (including but not limited to PET), polyetheresters, polyesteramides, polyurethanes, polyimides, polyureas, polyamideimides, polyamides, polycarbonates, polyphenyleneoxide, phenoxy resins, epoxy resins, polyolefins (including but not limited to polypropylene and polyethylene), polyacrylates, polystyrene, polyvinyls (including but not limited to polyvinyl chloride)) and combinations thereof. All of the aforementioned polymers may be in any desired combination thereof.
  • the container C can be manufactured by using any method known in the art, including but not limited to injection moulding, injection blow moulding (IBM), injection stretch-blow moulding (ISBM), extrusion blow moulding, thermoforming, rotational moulding, folding.
  • IBM injection blow moulding
  • ISBM injection stretch-blow moulding
  • extrusion blow moulding thermoforming
  • rotational moulding folding.
  • the process for heat bonding the seal 1 onto the container C is known in the art, and can be any known thermo-sealing process or induction-sealing process.
  • the outer layer 10 is heated by conduction and the seal is mechanically pressed against the top sealing surface 2 a .
  • the heat is thus transferred to the liner 12 which melts and is heat bonded to the top sealing surface 2 a of the container on the whole periphery of the opening 2 b.
  • the outer layer 10 is heated by induction, for example by using HF energy, and the seal is mechanically pressed against the top sealing surface 2 a .
  • the heat is thus transferred to the liner 12 which melts and is heat bonded to the top sealing surface 2 a of the container on the whole periphery of the opening 2 b.
  • the heat welding operation is performed in such a way that the liner 12 seal is efficiently bonded with the container, but can be however peeled off manually by the final consumer for opening the container.
  • the liner 12 is facing the inside IN of the container C, and forms a protective barrier that prevents the product stored in the container from contacting the active layer 11 and that prevents the active substance (H 2 generator) of the active layer 11 from migrating into the container.
  • This layer 12 also limits the ingress of water in contact with the active layer 11 , and thereby enables to obtain a controlled release of molecular hydrogen by the active layer 11 over a prolonged period of time.
  • a three-layer laminate constituted by three films or sheets of suitable material and corresponding respectively to the layers 10 , 11 , 12 , is formed by thermal bonding and this laminate is then cut or punched in order to form the seal 1 .
  • a laminate made of two layers 11 and 12 is prepared by co-extrusion; this co-extruded two-layer laminate is then laminated with the metallic layer 10 in order to for a three-layer laminate, which is then cut or punched in order to form the seal 1 .
  • a suitable adhesive is for example a polyester with isocyanate, cross-linked with a polyol to get polyurethane.
  • the liner 12 avoids any contact between the active layer 11 and the product stored in the container C.
  • the water vapour contained in the head space of container penetrates through the liner 12 and enters in contact with the active layer 11 .
  • the active substance of the active layer 11 produces molecular hydrogen that migrates through the liner 12 and penetrates in the container head space.
  • This molecular hydrogen combines with oxygen which may have entered in the container through its permeable wall.
  • This oxygen scavenging reaction can be catalysed by a catalyst incorporated in the closure cap 3 and/or in the container wall and/or in the container neck.
  • a large number of catalysts are known to catalyze the reaction of hydrogen with oxygen, including many transition metals, metal borides (such as nickel boride), metal carbides (such as titanium carbide), metal nitrides (such as titanium nitride), and transition metal salts and complexes.
  • Group VIII metals are particularly efficacious. Of the Group VIII metals, palladium and platinum are especially preferred because of their low toxicity and extreme efficiency in catalyzing the conversion of hydrogen and oxygen to water with little or no byproduct formation.
  • the catalyst is preferably a redox catalyst.
  • the seal 1 comprises a circumferential skirt 1 a that is also heat bonded to the outer face 2 c of the neck 2 of the container C.
  • the container neck 2 does not comprise a screwing thread and the container opening 2 b is closed only by the seal 1 .
  • the seal 1 has been deformed by mechanical pressure in order to form a recess 4 .
  • a central part of the seal 1 is thus positioned inside the container neck 2 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Wood Science & Technology (AREA)
  • Closures For Containers (AREA)
  • Packages (AREA)
  • Laminated Bodies (AREA)
US13/808,219 2010-07-06 2011-07-05 Seal Capable of Generating Molecular Hydrogen and Suitable for Closing a Container and for Scavenging Oxygen Abandoned US20130146600A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10168596A EP2404753A1 (fr) 2010-07-06 2010-07-06 Joint capable de générer de l'hydrogène moléculaire et adapté à la fermeture d'un conteneur et désoxygénant
EP10168596.4 2010-07-06
PCT/EP2011/061309 WO2012004261A1 (fr) 2010-07-06 2011-07-05 Scellement apte à générer de l'hydrogène moléculaire et pouvant refermer un récipient et extraire de l'oxygène

Publications (1)

Publication Number Publication Date
US20130146600A1 true US20130146600A1 (en) 2013-06-13

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Application Number Title Priority Date Filing Date
US13/808,219 Abandoned US20130146600A1 (en) 2010-07-06 2011-07-05 Seal Capable of Generating Molecular Hydrogen and Suitable for Closing a Container and for Scavenging Oxygen

Country Status (4)

Country Link
US (1) US20130146600A1 (fr)
EP (1) EP2404753A1 (fr)
JP (1) JP2013537500A (fr)
WO (1) WO2012004261A1 (fr)

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US20230166893A1 (en) * 2021-11-30 2023-06-01 Owens-Brockway Glass Container Inc. Package, container, closure assembly, and closure components

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US8496885B2 (en) 2010-03-12 2013-07-30 Amcor Limited Container having oxygen scavenging system
MX343088B (es) 2010-06-25 2016-10-24 Amcor Ltd Sistema de depuración de oxígeno para un recipiente.
JP4756102B1 (ja) * 2010-10-25 2011-08-24 ミズ株式会社 生体適用液への選択的水素添加器具
US8802207B2 (en) 2012-08-01 2014-08-12 Graham Packaging Company, L.P. In-situ polymerized polymer-platinum group metal nanoparticle blends and oxygen scavenging containers made therefrom
US9428292B2 (en) 2013-03-13 2016-08-30 Silgan White Cap LLC Fluid injection system and method for supporting container walls
US10011609B2 (en) 2013-11-14 2018-07-03 Cadila Healthcare Limited Heterocyclic compounds
JP6348330B2 (ja) * 2014-04-22 2018-06-27 株式会社テックコーポレーション 水素放出器、水素ガス供給方法及び水素放出システム
JP7096049B2 (ja) * 2018-04-06 2022-07-05 東洋アルミニウム株式会社 水素発生材料及びその製造方法
JP6671454B1 (ja) * 2018-12-28 2020-03-25 ユニ・チャーム株式会社 ドリップシート
JP7325242B2 (ja) * 2019-06-18 2023-08-14 ユニ・チャーム株式会社 食品用容器
CN112142002B (zh) * 2020-09-30 2022-03-11 中国人民解放军63653部队 一种铝碱反应可控的制氢系统
WO2022163376A1 (fr) * 2021-01-29 2022-08-04 バイオコーク技研株式会社 Feuille de génération d'hydrogène, rouleau, matériau d'emballage, et procédé de fabrication de feuille de génération d'hydrogène

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US20230166893A1 (en) * 2021-11-30 2023-06-01 Owens-Brockway Glass Container Inc. Package, container, closure assembly, and closure components
US11919687B2 (en) * 2021-11-30 2024-03-05 Owens-Brockway Glass Container Inc. Package, container, closure assembly, and closure components
CN114291418A (zh) * 2021-12-20 2022-04-08 岱纳包装（太仓）有限公司 一种防伪环保型润滑油瓶盖及润滑油瓶

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JP2013537500A (ja) 2013-10-03
WO2012004261A1 (fr) 2012-01-12

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