WO2015100211A1 - Composition composite servant à former des constructions barrières - Google Patents

Composition composite servant à former des constructions barrières Download PDF

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Publication number
WO2015100211A1
WO2015100211A1 PCT/US2014/071821 US2014071821W WO2015100211A1 WO 2015100211 A1 WO2015100211 A1 WO 2015100211A1 US 2014071821 W US2014071821 W US 2014071821W WO 2015100211 A1 WO2015100211 A1 WO 2015100211A1
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Prior art keywords
composite composition
polymer
functional filler
ethylene
barrier
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PCT/US2014/071821
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English (en)
Inventor
Sergio TORRES-GINER
Jose-Luis Feijoo
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A. Schulman, Inc.
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Publication of WO2015100211A1 publication Critical patent/WO2015100211A1/fr

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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08L23/06—Polyethene
    • 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
    • C08L23/08—Copolymers of ethene
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Definitions

  • the present subject matter relates generally to barrier constructions.
  • the present subject matter relates to a composite material comprising a binder material containing a lamellar filler used to make barrier constructions for use in packaging and containers, and related methods.
  • Barrier applications are typically found in food and pharmaceutical industries where product shelf life is often directly linked to gas permeability. High gas barrier properties are frequently needed to ensure that the flavor and the quality of the food are well preserved for an extended period of time.
  • plastic fuel tanks with appropriate barrier properties allow manufacturers to comply with strict international fuel vapor emission regulations. Enhancing barrier properties in building and construction applications can improve insulation as well as protect the environment against leakage.
  • barrier constructions that are resistant to migration of organic solvents increase agricultural production yields, while minimizing the use of agrochemicals.
  • oxygen barrier resins such as ethylene vinyl alcohol (EVOH), polyesters, and polyamides
  • OTR oxygen transmission rate
  • the role of oxygen barrier resins is to delay the ingress of oxygen, i.e. an agent responsible for a number of deterioration processes.
  • the excellent barrier properties of some oxygen barrier resins derive from a high degree of crystallinity and the presence of hydroxyl groups in the polymer structure which result in both high intermolecular and intramolecular cohesive energy and a low fractional free volume between the polymer chains available for the mass exchange of low molecular weight substances.
  • oxygen barrier resins can be adversely affected by high humidity and are liable to undergo an increase of oxygen permeability under a highly humid atmosphere. This deterioration derives from a plasticization effect, i.e. increase of the fractional free volume of the polymer and decrease of the mechanical integrity.
  • oxygen barrier structures that are subjected to high humidity environments are conventionally adapted to retain their oxygen barrier property by including a protective layer, such as of a polyolefin, having low water absorption characteristics.
  • a protective layer such as of a polyolefin
  • Protective layers also habitually called structural layers, not only can offer mechanical support and thermal stability, but also offer decreased water vapor transmission rate (WVTR) through the structures.
  • WVTR water vapor transmission rate
  • the oxygen barrier resin which is typically EVOH, is sandwiched between at least two symmetric or asymmetric protective layers.
  • these packages or containers can be subjected to a retort process in which the molded package/container is exposed to excessive moisture (in the form of steam) at elevated temperatures, i.e. above 100°C.
  • excessive moisture in the form of steam
  • diffusion of water vapor increases exponentially with temperature increase due to the greater mobility of the polymer chains and with the increase of the free volume of the polymer at higher temperatures.
  • retort shock This effect is called “retort shock” and it leads to a lowering of the effectiveness of the oxygen barrier resin in retarding oxygen permeation during a certain period of time.
  • plastic Film and Sheeting 1988, 4, 63-71 Tsai, B.C.; Jenkins, B.J. J.
  • the oxygen barrier properties of retortable packages containing an EVOH barrier layer was initially reduced by two orders of magnitude when these containers were subjected to steam or pressurized water thermal processing. During long term storage (>200 days) the barrier was partially recovered (e.g. by a factor of ten).
  • the present invention describes a novel composite composition to form barrier constructions.
  • the use of this composite composition induces restriction of diffusion of gases, e.g., water and oxygen, in polymeric materials as well as allows faster recovery of the oxygen barrier property from moisture after retort in multilayer packaging structures.
  • the present subject matter provides a composite composition used in forming a barrier construction.
  • the composite composition comprises a functional filler dispersed in a binder resin.
  • the function filler comprises lamellar particles with a median size Dsa of the particles from about 0.5 microns to about 5 microns, and an aspect ratio higher than about 2.8, and a specific surface area greater than about 10 m 2 /g.
  • the binder resin comprises a thermoplastic polymer.
  • the present subject matter provides a method of using a composite composition for forming a barrier construction.
  • the method comprises mixing the functional filler with a binder resin to form a composite composition.
  • the method further comprises adding the composite composition to a polymer matrix to form a polymer composite.
  • the method also comprises incorporating the polymer composite in the barrier construction.
  • the functional filler comprises lamellar particles with a median size of the particles Dsofrom about 0.5 microns to about 5 microns, and aspect ratio higher than about 2.8, and a specific surface area greater than about 10 m 2 /g.
  • the binder resin comprises a thermoplastic polymer.
  • the present subject matter allows for a high degree of dispersion of the functional filler having certain size characteristics in the polymer matrix, thereby providing a significant decrease in the gas permeability of barrier constructions including the highly dispersed functional filler, when compared to barrier constructions not including the functional filler so highly dispersed.
  • Figure 1A is a schematic, exploded perspective view of a barrier construction in accordance with the present subject matter for use as a retort food packaging and detailed views of the layers.
  • Figure 1B is a schematic, exploded perspective view of a barrier construction in accordance with the present subject matter for use as a plastic fuel tank and detailed views of the layers.
  • Figure 2 is an SEM micrograph of functional filler particles in accordance with the present subject matter.
  • Figure 3 is an SEM micrograph of functional filler particles intercalated with a binder resin in accordance with the present subject matter.
  • Figure 4 is an SEM micrograph of functional filler particles exfoliated in a polymer matrix in accordance with the present subject matter.
  • the present invention provides a composite composition that is used in forming a barrier construction.
  • the composite composition includes a pristine (i.e., non-organically modified) filler and a binder polymer.
  • the present subject matter also provides a method for obtaining a high barrier construction used in containers and packaging products.
  • the composite composition is directly used to form barrier constructions having reduced permeability, e.g. to oxygen and water.
  • the composite composition is incorporated as a masterbatch into a polymer matrix to form a polymer composite at from about 1 weight percent (wt%) to about 99 wt% of the masterbatch to the polymer matrix.
  • the polymer matrix can comprise any thermoplastic resin.
  • the methods include using the above-mentioned barrier construction in single- and multilayer structures for packaging and containers.
  • the composite composition can be used in a monolayer or in a multilayer, including the protective layer(s), the barrier layers(s), the tie layer(s), any other internal layer(s) and/or any external layer(s).
  • the composite composition is used to generate a barrier construction that protects gas sensitive materials, for example, in food packaging.
  • the composite composition can also be applied to generate a barrier construction that reduces gas emissions, for example, in plastic fuel tanks.
  • binder is understood to mean an uncompacted particulate product in which the particles are free to move in relation to each other, as well as a densified product where the particles or certain particles are temporarily bound in agglomerates.
  • Median size Dso is understood to mean a size such that 50% of the particles by weight have a measurement in the largest dimension, less than the said size; "cutoff size Dgs'is understood to mean a size such that 95% by weight of the particles have a measurement in the largest dimension less than the said size; “cutoff size Doe” is understood to mean a size such that 98% by weight of the particles have a measurement in the largest dimension less than the said size.
  • the size consists of the diameter.
  • Specific surface area is understood to mean the area of the surface of the particles of the powder with respect to unit mass, determined according to the BET method by the quantity of argon adsorbed on the surface of the said particles so as to form a monomoiecular layer completely covering the said surface (measurement according to the BET method, AFNOR standard X 11-621 and 622).
  • the "!amellarity index” characterizes the shape of the particle, and more particularly its flatness (large dimension/thickness).
  • “High lamellarity” is understood to mean a powder of which the lamellarity index is high and in particular greater or much greater than 2.8. The particle size and lamellarity parameters are assumed to be measured on the elementary particles of which the powder consists.
  • talc is understood either to mean the hydrated magnesium silicate mineral, or the mineral chlorite (hydrated magnesium aluminium silicate), or a mixture of the two, associated optionally with other minerals (dolomite, etc.) or furthermore a mineral substance derived from talc and having similar properties.
  • the composite composition comprises functional filler and binder resin and is used for making a barrier construction.
  • the functional filler material that can be used includes mineral powder, in particular a talc, kaolin or mica powder, and is characterized by a particle size distribution such that the median size of the particles Dso lies substantially between about 0.5 and about 5 microns, the cutoff size D95 is less than 10 microns, and the cutoff size Dge is less than 20 microns.
  • the filler has a high aspect ratio (HAR) with a lamellarity index of greater than about 2.8, more often great than about 4.0, and a specific surface area (BET) greater than about 10 m 2 /g, or in another embodiment, greater than about 20 m 2 /g.
  • HAR high aspect ratio
  • BET specific surface area
  • the filler is lamellar and has a particle size Dsofrom about 0.1 pm to about 10 pm, more often between about 0.5 pm and about 2.0 pm. In one embodiment, the filler particles have a Dso particle size not a less than about 0.1 microns.
  • the filler has only one particle morphology. That is, the particles do not comprise more than one set of particles and do not arise from distinct populations of particles that can be characterized as having significantly different particle morphology. In this embodiment, the particles do not have substantially different particles characteristics, but are considered to be a single set of particles with a unimodal size distribution.
  • the particulate filler in this embodiment will produce a plot of number of particles versus the particular size characteristic (i.e. largest dimension, thickness, aspect ratio, etc.) having one peak.
  • the filler is non-organically modified, such that the filler is in its pristine form.
  • the filler comprises talc for example
  • the surface of talc filler is predominantly hydrophilic and has not been organically modified.
  • the filler readily mixes into a hydrophilic binder polymer, such as an acrylic polymer or maleic anhydride modified or grafted polymer, to form a composite composition for use as a masterbatch or a ready-to-use compound.
  • the previous composite composition is introduced into a polymer matrix, and the hydrophilic filler readily disperses therein, whether the matrix resin is hydrophilic or hydrophobic.
  • the filler is included from about 1 wt% to about 99 wt% of the polymer matrix, and in another aspect from about 10 wt% to about 90 wt% of the polymer matrix.
  • Talc fillers are obtained from macro-crystalline minerals with a pronounced lamellar character. Such minerals contain crystals, which appear as lamellae, and that are larger in comparison to micro-crystalline talc which has natural crystals of a smaller size.
  • the talc comprises magnesium silicates or chlorites, or a mixture of both, optionally mixed with other minerals having similar properties.
  • the lamellar fillers may be surface treated in order to influence their physical behavior, for example to reduce the tendency to agglomerate. Additional fillers may be added, such as for example mica, kaolin, in particular calcined kaolin, provided they have the appropriate shape and size characteristics as discussed for the talc particles.
  • the talc constitutes at least 50% of the mineral filler content, or at least 75%, or talc is the only lamellar filler used.
  • characteristics of the mineral lamellar fillers is such that the lamellarity index is maintained at a level of at least about 3 after incorporation into the binder resin and/or polymer matrix by the process according to the invention.
  • the filler can comprise, in one embodiment, talc at about 94 wt%, chlorite at about 5 wt%, and dolomite at about 1 wt%, and has a loss of ignition at 1050°C of about 5.8 wt%.
  • the filler has a whiteness (Minolta CR300, illuminant D65/2") Y of about 87; a BET (DIN ISO 9277) of about 22 m 2 /g; density (ISO 787/10) of about 2.7 g/cm 3 ; tapped bulk density (ISO 787/11) of about 0.7 g/cm 3 , hardness (Mohs' scale) of about 1; and moisture content at 105°C (ISO 787/2) of about 0.5%.
  • An example of an appropriate filler is Mistron HAR® talc from Imerys, Inc.
  • Another examples of filler are Luzenac HAR® W92 and Luzenac HAR® T84 from Imerys, Inc.
  • Figure 2 shows suitable HAR particles useful in the present subject matter.
  • Figure 2 is a Scanning Electron Microscopy (SEM) micrograph of Mistron HAR® talc as purchased from Imerys Inc., at 2,000 times magnification with a white scale marker of 10 m. From Figure 2, it can be seen that this is a lamellar type mineral in large agglomerates of several microns, which consist of a stacks of individual talc particles.
  • SEM Scanning Electron Microscopy
  • the present subject matter includes dispersing the filler particles in a binder resin in order to make a composite composition to be used as a ready-to-use compound or a masterbatch used for properly dispersing the filler particles in a polymer matrix, e.g. a polyolefin.
  • the binder resin comprises a thermoplastic polymer.
  • the polymer used in the composite composition comprises a thermoplastic.
  • thermoplastics provide for suitable intercalation for the above described filler particles. Accordingly, the agglomerated particles shown in Figure 2, are flaked apart and are highly exfoliated in the binder resin as depicted in Figure 3. In this way, the particles attain a high degree of dispersion when added to the polymer matrix, and thus provide greater barrier properties to permeants, such as oxygen and water.
  • thermoplastic as the binder resin further allows for mixing of the filler particles into the binder resin by melt compounding techniques. Mixing, dispersing, and intercalation of the filler in the binder resin can be accomplished using an extruder.
  • the filler particles are added to the binder resin in dry form, i.e. with no intentionally added carrier liquid, such as water, solvents, or other liquid vehicles.
  • the binder polymer is also free of intentionally added water, solvent, or other vehicle for the filler or masterbatch.
  • thermoplastic resin While any appropriate thermoplastic resin may be used in forming the composite composition, it is preferred that the polymer is selected from the group consisting of polyolefins, ethylene methylacrylate copolymers, polyvinyl acetates, polyethylene terephthalate (PET), polystyrene (PS), styrene butadiene copolymers, poly(methyl methacrylate) (PMMA), polyimide, polycarbonate (PC), acrylonitrile butadiene styrene (ABS), styrene acrylonitrile, styrene block copolymers, polyacrylonitriles, ethylene vinyl alcohol (EVOH) copolymers, polyamides, thermoplastic polyurethane (TPU), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), thermoplastic elastomers (TPEs), biodegradable polymers and mixtures thereof.
  • Polyolefins are particularly preferred.
  • the thermoplastic resin is selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene (PP), maleic anhydride- modified and -grafted polyethylenes (PE-g-MAH), maleic anhydride-modified and - grafted polypropyienes (PP-g-MAH), ethylene methacrylate (EMA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), ethylene vinyl acetate (EVA), their copolymers, their terpolymers, and their blends thereof.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • PE-g-MAH maleic anhydride- modified and -grafted polyethylenes
  • PP-g-MAH maleic anhydride-modified and - grafted polypropyienes
  • EMA ethylene methacryl
  • additives may be introduced in the composite composition according to the invention.
  • additives include well known additives in thermoplastic compositions, such as thermoplastic elastomers, coupling agents, reactive components, antiblock additives, slip aids, antifog agents, antistatic agents, antioxidants and light stabilizers, colorants, processing aids, antimicrobials, acid scavengers, fluidity enhancers, viscosity modifiers, impact modifiers, and the like.
  • such other additives do not constitute more than 10% by weight of the total masterbatch, preferably not more than 5% by weight.
  • Complementary active barrier additives may be also combined in the composite composition according to the invention. These include on one hand desiccators such as calcium oxide (CaO) and zeolites, and on the other, oxygen scavengers such as unsaturated hydrocarbons and reducing components, e.g. ascorbic acid. In one aspect, such other additives do not constitute more than 20% by weight of the total masterbatch, preferably not more than 10% by weight.
  • desiccators such as calcium oxide (CaO) and zeolites
  • oxygen scavengers such as unsaturated hydrocarbons and reducing components, e.g. ascorbic acid.
  • such other additives do not constitute more than 20% by weight of the total masterbatch, preferably not more than 10% by weight.
  • passive fillers to be used in the present invention are not particularly limited to the above, and include inorganic fillers, such as silica, diatomaceous earth, alumina, zinc white, magnesium oxide, calcium sulfite, calcium sulfate, calcium silicate, glass powders, glass fibers (inclusive of silane-treated glass fibers), asbestos, gypsum fibers, and the like.
  • inorganic fillers such as silica, diatomaceous earth, alumina, zinc white, magnesium oxide, calcium sulfite, calcium sulfate, calcium silicate, glass powders, glass fibers (inclusive of silane-treated glass fibers), asbestos, gypsum fibers, and the like.
  • the masterbatch composition if free of water and free of fully water-soluble polymers such as polyvinyl alcohol (PVOH).
  • PVOH polyvinyl alcohol
  • the present subject matter provides polymer matrix compositions selected from any type of thermoplastic, charged with specific mineral lamellar fillers, which are worked through a particular masterbatch and introduced into the polymer matrix, in order to obtain a barrier construction, which brings together a reduction in gas permeability, in packaging materials and containers.
  • the composite composition can be used as a masterbatch in order to disperse the filler into the polymer matrix.
  • the composite composition obtained from dilution of the masterbatch into a polymer matrix can then be used in creating barrier constructions.
  • the composite composition can be used in a tie layer in a multilayer construction, or can itself be used in a barrier layer in a single- or multilayer construction for packaging materials and containers.
  • the composite composition is presented in at least one layer of the resultant barrier construction.
  • the adhesive layer acts to bond the oxygen barrier layer to the polyolefin protective layer and also acts as the barrier layer.
  • Typical examples of this multilayer construction in food packaging comprise polypropylene as the protective layer and EVOH as the oxygen barrier layer, as shown in Figure 1A.
  • Typical examples of this multilayer structure in plastic fuel tanks comprise HDPE as the protective layer and EVOH as the oxygen barrier layer, as shown in Figure 1B, and may also include a regrind or foam layer as shown.
  • the polymer matrix can be a hydrophilic or hydrophobic polymer, or combinations of both, as long as the masterbatch can be sufficiently mixed therein to properly disperse the filler and to attain a desired level of barrier properties. If the polymer composite is used as an adhesive, the polymer composite should be compatible (showing adhesion) both with the oxygen-barrier layer and the protective or structural layer(s) in multilayer barrier constructions.
  • suitable material for the polymer matrix also include polar group- containing modified polyolefins obtained by graft modifying polyethylene (PE- g-MAH), graft modifying polypropylene (PP-g-MAH), or ethylene vinyl acetate copolymer with unsaturated carboxylic acids, or unsaturated polycarboxylic acids or anhydrides thereof; ethylene vinyl acetate (EVA) and saponification products thereof; ethylene methacrylate (EMA), ethylene ethyl acrylate (EEA), ethylene butyl acrylate (EBA), ionomers obtained by cross-linking such copolymers with metallic ions; and block copolymers of styrene with butadiene.
  • EMA ethylene methacrylate
  • EAA ethylene ethyl acrylate
  • EBA ethylene butyl acrylate
  • ionomers obtained by cross-linking such copolymers with metallic ions
  • the polymer matrix resin comprises a thermoplastic polyolefin.
  • the thermoplastic polyolefin comprises polypropylene. This is to be used as the main ingredient when making the masterbatch and can also be used as the sole or main material for making the ready-to-use compositions.
  • polypropylene for use as the matrix, we mean homopolymers as well as copolymers, when obtained by any polymerization process, using any catalyst, whether modified or not, alone or in mixture, formulated or not.
  • polypropylenes are the result of polymerization of propylene with itself, or where copolymers are concerned, with itself and other olefinic co-monomers, having a preferred chain-length of 2 to 12 carbon atoms, thus including for example ethylene, butylene, isopropylene, isobutylene, pentylene, hexylene, decylene and dodecylene, provided the propylene segment of the copolymer is present in an important quantity compared to the other co-monomers, preferably more than 50% by weight, more preferably at least 65%, most preferably at least 75% by weight based on the total weight of copolymer.
  • Particularly useful polypropylene materials for use as the matrix include homopolymers of propylene, copolymers of propylene with ethylene, such as ethylene-alpha-olefin, including polypropylenes of high crystallinity.
  • the density of the preferred polypropylenes is in the range of 0.850 to 0.905 g/cm 3 when measured according to ASTM 1505.
  • the polypropylenes have a melt flow rate of from about 1-100 g/10 minutes when measured according to ASTM 01238, at 2.16 kg and 230°C, or can be in the range of from about 5-55 g/10 minutes, or from about 25-100 g/10 minutes.
  • Mixtures of polypropylenes can be used, such as different homopolymers, different copolymers or mixtures of homopolymers and copolymers of polypropylene. It will be understood that the present subject matter includes the use of mixtures of polypropylenes with other polyolefin homo- or copolymers which are compatible with, or have been made compatible with the polypropylenes, for example via grafting or through the use of agents acting as compatibilizers. In one aspect of using these mixtures, the polypropylenes remain a majority component of the matrix, being present at more than about 70 wt%, or more than about 80 wt% of the mixture. Partial cross-linking of such mixtures may take place.
  • the polyolefins of the polymer matrix may be virgin materials or may be materials used out of recycling activities, such as polypropylene materials which already have certain fillers present. Recycled materials may result from rejects during production, production stoppages, or materials which are retrieved from recycled or scrapped products, such as automobiles, packaging etc.
  • the masterbatch is introduced into the polymer matrix at a ratio by weight of the masterbatch to the matrix polymer of from 99:1 to 1:99.
  • the film is continuous in that it has no perforations or pores which extend through the thickness of the film.
  • the film preferably is not dissolved, solubilized, or otherwise damaged by water or other polar solvent since the film of the present subject matter may be exposed to water during retort processes.
  • the heat shrinkable film may be coated with hydrophobic or water repellent lacquer or other agents including, but not limited to polyvinylidene chloride, acrylates, polyurethane, epoxy resins, silicones, polytetrafluoroethylene (for example, TeflonTM from DuPont, USA), polyvinyl fluoride (for example, Tedlar, a registered mark of DuPont, USA), THV (a polymer of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride) (for example, Dyneon THV, a registered mark of 3M, USA), etc.
  • lacquer or other agents including, but not limited to polyvinylidene chloride, acrylates, polyurethane, epoxy resins, silicones, polytetrafluoroethylene (for example, TeflonTM from DuPont, USA), polyvinyl fluoride (for example, Tedlar, a registered mark of DuPont, USA), TH
  • the polyolefin component in the film may also advantageously contain various additives as is generally known in the art.
  • the films of the present subject matter can include other layers or treatments for specific intended uses and include printing receptive layers or treatments, hydrophobic layers or treatments, additional laminated heat shrinkable film layers, or the like. Examples include priming, printing, hydrophobic treatments, etc.
  • Oxygen Barrier Layer
  • the multilayer construction includes an oxygen barrier layer.
  • the oxygen barrier layer can comprise any material or composition that is capable of reducing OTR through the construction as desired for a particular application. Examples of the material for this layer include ethylene vinyl alcohol (EVOH) copolymers, polyamides, polyvinyl alcohol, modification products and mixtures thereof.
  • EVOH ethylene vinyl alcohol
  • the oxygen barrier layer can also be made of multiple extruded layers of the same or different barrier materials.
  • the multilayer construction includes a protective layer.
  • the protective layer can comprise any material or composition that is capable of protecting the other layers of the construction from environmental exposure, such as moisture, light, abrasion, or the like as desired for a particular application.
  • Examples of the material use in the protective layer include homo and copolymers from the family of polypropylene resins, polystyrene and rubber modified polystyrene, linear and branched polyethylene regardless of the resin density (for example high-density of density above 0.94, medium-density polyethylene of density above 0.92 to 0.94, and low-density and linear low density polyethylene of density 0.92 and below), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonates, acrylonitrile-styrene-butadiene copolymer, modification products and mixtures thereof.
  • the polymer used for the protective layer is not limited however, and for example, nylon (polyamide) can also be used in this application.
  • the material used in the protective layer or layers is a random or block copolymer of ethylene and propylene.
  • the present invention is also directed to a single or multilayer barrier construction made using the composite composition disclosed herein.
  • the barrier construction can be a container, or a portion thereof, that at least partially separates a gas sensitive material from a gas containing environment.
  • a container of this nature may generally comprise a lid and a body, where the body is constructed of a floor and walls and the lid sits over an opening in the container.
  • the lid or the body can be constructed of the barrier construction disclosed herein, or metal, or any suitable barrier material.
  • the container comprises a muitilayered barrier of polyolefin/oxygen barrier resin/polyolefin adhered together with adhesive layers comprising the composite composition disclosed herein.
  • the container of the invention can be manufactured by thermoforming of the muitilayered barrier.
  • Thermoforming of polyolefins for example, is well known.
  • a sheet of the polyolefin is formed or shaped by heating the sheet above the softening temperature of the polyolefin, fitting the sheet along the contours of a mold with pressure supplied by vacuum or other force, and removing the shaped article from the mold after cooling below its softening point.
  • thermoforming involves heating of a thermoplastic film or laminate and forming the film or laminate into a desired shape for holding a product to be inserted.
  • This sheet of a film or laminate is usually referred to as a forming web.
  • Various systems and devices are used in a thermoforming process, often accompanied by vacuum-assist and plug- assist components to provide the proper forming of the forming web into a predetermined shape.
  • a packaging container according to the present invention may therefore comprise a container formed by deforming a multilayer sheet as described above according to a thermoforming method, and a lid made of a resin or of a metal, or of another suitable barrier material and adapted for sealing the holding container.
  • the container can also be formed by other methods, for example and not limited to, co-injection molding, co-extrusion blow molding, laminated sheet thermoforming, and any other method known to one skilled in the art.
  • FIG. 1A depicts an example of a multilayer structure, extensively used in retort food packaging, based on polypropylene as the protective layer and EVOH as the oxygen barrier layer.
  • the composite composition is incorporated in the adhesive layer that bonds the two protective layers to the oxygen barrier layer.
  • Figure 1 B shows a coextruded 6-layer structure used to contain fuel in industrial and automotive tanks.
  • the barrier layers are sandwiched between the protective layers that comprise high density polyethylene (HDPE) and which remain exposed to the environment outside and inside the container.
  • a regrind or foam is included, which is generally used for cost savings and to reduce the weight of the construction.
  • EVOH is used as the oxygen barrier layer and a standard adhesive bonds the layers.
  • the HAR filler is melt compounded with the thermoplastic binder resin in a suitable melt mixing compounder.
  • a mixing compounder used for the experiments detailed below is a ZSK-40 intermeshing co- rotating twin-screw extruder from CoperionTM.
  • the ZSK series is based on a building- block principle.
  • mixing of components, residence time of resin, as well as point of addition of components can be easily modified by changing screw design, barrel design and processing parameters.
  • Similar machines are also provided by other twin- screw compounder manufacturers like Werner Pfieiderer, Leistritz, Maris, Berstorff, etc., which can be operated either in the co-rotating or the counter-rotating mode.
  • the screws of the above mentioned ZSK compounder are 40 mm in diameter. Suitable screw diameters for twin-screw extruders range, but are not limited, from 16 to 135 mm.
  • This compounder is provided with a main feed hopper through which resins are fed, while additives might be fed using one of the feeders of the main hopper or using one or more of the side feeders.
  • the HAR filler is added to the thermoplastic binder through the side feeder in order to ensure intercalation of the filler through proper viscous mixing and to ensure a high degree of dispersion for the filler through the polymer matrix, as well as to control the thermal history.
  • the thermoplastic binder is fed using the main feed hopper, and is followed by the addition of the HAR filler through the downstream side feeder.
  • the HAR filler, together with any optional additives, and the thermoplastic binder are premixed and fed using the main feed hopper.
  • This method is particularly suitable if there is only one feeding port available, and also there are limitations on the screw design.
  • the HAR filler together with any optional addenda, is melt blended with the thermoplastic binder of the invention using any suitable melt mixing device such as a single-screw compounders (also including reciprocating extruders such as Buss), batch-mixers such as Bambury and Farrel Continuous Mixer, roll mills, etc.
  • a single-screw compounders also including reciprocating extruders such as Buss
  • batch-mixers such as Bambury and Farrel Continuous Mixer, roll mills, etc.
  • any optional additives described in the present invention can be incorporated using the main feed hopper and/or one or more side feeder(s).
  • reactive extrusion with liquids is the modification, functionalization or grafting of maleic anhydride (MAH) with polyethylene and polypropylene in the case of the HAR filler is incorporated into the tie layer.
  • MAH maleic anhydride
  • the form of the composite composition is not particularly limited and can be in a pellet particulate form, in a melt or softened form; dissolved in a solvent, or in other forms that can be used to adequately disperse the filler in a polymer matrix.
  • the invention is also directed to a method for protecting a gas sensitive substance, such as a foodstuff, comprising the step of enclosing the material in a package.
  • the package comprises a single or multilayer film structure according to any of the embodiments that are described herein, or a film structure as described above.
  • the multilayer structure comprises a layer of an oxygen barrier material and two protective layers, wherein one of the two protective layers is bonded on either side of the oxygen barrier layer, in a face-to-face relationship such that the protective layers are co-extensive with the oxygen barrier layer.
  • the protective layers are bonded to the oxygen barrier layer using an adhesive composition comprising the filler material as disclosed herein, wherein the filler material is introduced to the adhesive composition in the form of a masterbatch as described herein.
  • the oxygen barrier layer material is selected from the group consisting of ethylene vinyl alcohol (EVOH) copolymers, polyamide, polyvinyl alcohol (PVOH), modification products thereof, and mixtures thereof.
  • EVOH ethylene vinyl alcohol
  • PVOH polyvinyl alcohol
  • the invention is also directed to a process for protecting an oxygen or moisture sensitive material comprising the steps of providing oxygen or moisture sensitive material, enclosing the material in a container, wherein the container comprises a structure according to any of the film structures or the multilayer film structures disclosed herein.
  • the invention is also directed to a process for protecting an oxygen or moisture sensitive material comprising the steps of providing an oxygen or moisture sensitive material, enclosing the material in a container, wherein the container walls, lid, or both, are partially or totally constructed of a structure according to any of the film structures or the multilayer film structures disclosed herein.
  • Example 1 Composite Composition
  • Example 1 illustrates the formation of a composite composition in accordance with the present subject matter.
  • Mineral powders used as the functional filler and which are intended to be incorporated in thermoplastic materials for barrier properties are preferred to be fine lamellar powders.
  • the HAR filler used in the following example is Mistron® HAR talc from Imerys.
  • Figure 2 shows the Mistron® HAR particles as received.
  • this filler is a lamellar type mineral and it is presented in a form of large agglomerates of several microns that consists of a stack of a plurality of elementary leaves.
  • Figure 2 is an SEM micrograph taken at 2,000 times magnification with a white scale marker of 10 pm.
  • Elvaloy® AC 1125 from DuPont which comprises 25 wt% of acrylate, was used as the binder resin.
  • This thermoplastic material when used, is a copolymer of ethylene and methyl acrylate, henceforth to be referred to as EMA.
  • the masterbatch composition was compounded in a ZSK-40 intermeshing co- rotating twin-screw extruder from CooperionTM using following temperature profile settings: Feed Zone 120 °C, Second Zone 13P °C, Third Zone 130 °C, Fourth Zone 130 °C, Fifth Zone 130 *C and Die Zone 140 e C.
  • the present composite composition was in an amount of 40 wt% of HAR filler in EMA.
  • the HAR talc surface is sufficiently chemically compatible with the EMA polymer chains and the polymer can break the energy barrier to enter between the interlayer spaces, binding the inorganic particles to the polymer resin in an intercalated or exfoliated structure.
  • talc agglomerates as originally received thereby form into lamellar structures that are mainly ultrathin, i.e., structures having submicron measurements in at least one dimension, e.g. in thickness. This is depicted in Figure 3, showing the agglomerated particles from Figure 2, having been intercalated by a binder resin.
  • Example 2 illustrates the use of the composite composition as a masterbatch in a polymer matrix in order to obtain a polymer composite in accordance with the present subject matter.
  • the composite composition was used as a masterbatch to obtain a polymer composite using polypropylene as the polymer matrix.
  • this was diluted at 12 wt% in Basell Moplen® RP210G, which is a random copolymer polypropylene with a Melt Flow Rate of 1.8 g/10 min (230°C, 2.16 Kg) and density of 0.9 g/cm 3 , using a Collin E30M single-screw extruder.
  • Rotor speed was set at 40 rpm, with a barrel length diameter of 30 and a flat die exit of 300 mm.
  • the profile of temperatures was set accordingly to provide a melt temperature of 210°C.
  • the cooling temperature of the mandrels was fixed at 40°C and this performed a relation of stretching of 7.2%.
  • Resultant composite films presented ca. 160 pm of thickness.
  • Figure 4 shows the resultant polymer composite using the composite composition according to the present invention. This indicates that the ultrathin lamellar structures contained in the masterbatch were effectively dispersed and exfoliated into the polypropylene matrix. The ultrathin particles are also seen to be preferably oriented to the flow direction, i.e. extrusion direction. These lamellar structures act as functional fillers because they are impermeable and have appropriate large aspect ratios that alter the diffusion pathway of gas-penetrant molecules, forcing them to follow a longer and more tortuous pathway in order to diffuse through the film.
  • Figure 4 is an SEM micrograph taken at 2,500 times magnification with a white scale marker of 10 pm.
  • Example 3 illustrates the advantages and benefits of the composite composition of the present invention used as a water barrier construction in a single layer polyolefin film when compared to the same polyolefin film without the present invention.
  • equivalent polymer composites were produced using the same process conditions described in Example 2, but employed other commercial nano-sized clays or nanoclays not having the size characteristics as described herein.
  • the other nanoclays used were Cloisitel 16®, which is a natural bentonite, Cloisite 20®, which is a modified bentonite with bis(hydrogenated tallow alkyl)dimethyl quaternary ammonium salt, both from BYK Additives & Instruments; and Bentone® EW CE, which is a natural montmorillonite, from Elementis Specialties, Inc.
  • the istron® HAR talc sample which is used in the composite composition according to the present invention, provided the lowest amount of water uptake compared to the unfilled sample and other composite films containing different filler material.
  • Example 4 illustrates the use of the composite composition as a ready- to-use compound in a single structure in flexible packaging in order to obtain an oxygen-barrier film in accordance with the present subject matter.
  • the HAR filler used in the following example is Mistron® HAR talc from Imerys (see Figure 2).
  • Basell Clyrell® EC2340 a heterophasic polypropylene copolymer specially designed for film applications, was used as the binder resin.
  • This polypropylene has a Melt Flow Rate of 6.5 g/10 min (230°C, 2. 6Kg) and density of 0.9 g/cm 3 .
  • the composite composition was compounded in a ZSK-24 intermeshing co-rotating twin-screw extruder from CooperionTM using following temperature profile settings: Feed Zone 180 °C, Second Zone 220 °C, Third Zone 220 "C, Fourth Zone 210 °C, Fifth Zone 200 °C and Die Zone 190 °C.
  • the present composite composition compromised 20 wt% of HAR filler in polypropylene.
  • a single film of approximately 150 pm was obtained using a Collin E30M single-screw extruder, using previous process conditions described in Example 2.
  • a film made of pure polypropylene polymer was similarly obtained as a control.
  • Oxygen Transmission Rate was measured using OXTRAN 2/20 equipment based on ASTM 03985 (23°C and 0% HR). The amount of oxygen gas that passes through the films over a 20-h period was recorded and resultant values are gathered in Table 1. This shows a reduction, of over 50%, in the oxygen permeability for the polypropylene films containing the HAR fillers.
  • Example 5 Oxygen barrier properties in injection-molded trays
  • Example 5 illustrates the use of the composite composition as a masterbatch in a single structure in rigid packaging in order to obtain an oxygen-barrier food trays in accordance with the present subject matter.
  • the HAR filler used in the following example is Mistron® HAR talc from Imerys (see Figure 2).
  • Baseli Moplen® HP648U a polypropylene homopolymer specially designed for injection molding applications, was used as the binder resin. This polypropylene has a Melt Flow Rate of 75 g/ 0 min (230°C, 2.16Kg) and density of 0.9 g/cm 3 .
  • the composite composition was compounded in a ZSK-25 intermeshing co-rotating twin-screw extruder from CooperionTM using same profile temperature settings of Example 4.
  • the present composite composition a masterbatch, compromised 50 wt% of HAR filler in polypropylene that was incorporated through the side feeder.
  • Bondyram® 1101 from Polyram a maleic anhydride modified PP (PP-g- MAH), was incorporated as a coupling agent for the polypropylene and the HAR filler.
  • This functionalized homo-polypropylene has a Melt Flow Index of 150 g/10 min (190°C, 2.16Kg) and density of 0.9 g/cm 3 . Table 2 below summarizes the present masterbatch composition.
  • Oxygen Transmission Rate was measured in duplicate, in same conditions as in Example 4.
  • Graph 2 shows OTR reduction (%) for the two measures (OTR1 and OTR2) as a function of the HAR filler content, after masterbatch dilution, for the injection-molded polypropylene composites. As it can be seen from the graph there is a continuous reduction with growing content of the composite composition.
  • Example 6 illustrates the use of the composite composition as a ready- to-use compound in the tie layer of a multilayer structure based on polyethylene/tie layer/EVOH/tie layer/polyethylene in order to obtain an oxygen-barrier film improved for retort applications in accordance with the present subject matter.
  • the HAR filler used in the following example is Luzenac HAR® T84 talc from Imerys.
  • Bondyram® 4108 from Polyram a maleic anhydride modified linear low density polyethylene (LLDPE-g-MAH) was employed as the polymer binder.
  • This functionalized polyethylene has a Melt Flow Index of 1.5 g/10 min (190°C, 2.16 Kg) and density of 0.92 g/cm 3 .
  • Linear low density polyethylene ExxonMobilTM LLDPE LL 1002YB with a Melt Flow Index of 2 g/10 min (190°C, 2.16Kg) and density of 0.92 g/cm 3 was used as the structural layer for the multilayer film.
  • Ethylene vinyl alcohol copolymer (EVOH) SoamolTM DC3203RB with 32 mol% ethylene content, Melt Flow Rate of 3.8 g/10 min (210°C, 2.16Kg) and density of 1.19 g/cm 3 was used as the oxygen-barrier resin in the multilayer film.
  • the composite composition was compounded in a ZSK-24 intermeshing co-rotating twin-screw extruder from CooperionTM using following temperature profile settings: Feed Zone 160°C, Second Zone 200°C, Third Zone 200°C, Fourth Zone 190 e C, Fifth Zone 180°C and Die Zone 170°C.
  • the present composite composition compromised 25 wt% of HAR filler in the LLDPE-g-MAH.
  • a multilayer film of ca. 110 - 120 ⁇ was obtained using a cast line of Dr. Collin 5 layers (EX A - 30mm, Ex B - 25mm, Ex C - 25mm) to produce following extructure: polyethylene/tie layer/EVOH/tie layer/polyethylene.
  • the tie layer accounted for about 10% of the total thickness, i.e. 6 microns each layer. This performed as an adhesive layer to tie the two structural external polyethylene layers to the oxygen-barrier layer EVOH.
  • a multilayer film made of pure Bondyram® 4108 as the tie layer resin was obtained in same conditions as a control.
  • Example 7 illustrates the use of the masterbatch in a multilayer structure of low density polyethylene (LDPE) in order to improve oxygen barrier properties obtain of a blown film in accordance with the present subject matter.
  • LDPE low density polyethylene
  • the HAR filler used in the following example is Luzenac® HAR W92 talc from Imerys.
  • Riblene FM 34 F from Polimeri was selected as the binder resin, which is a LDPE resin for blown film applications and is suitable for thin packaging film purposes.
  • This polyethylene has a Melt Flow Index of 3.5 g/10 min (190°C, 2.16Kg) and a density of 0.924 g/cm 3 .
  • Bondyram® 4108 from Polyram a maleic anhydride modified LLDPE, was incorporated into the formulation as a coupling agent for the polyethylene and the HAR filler. Table 4 below summarizes the present masterbatch Table 4. Masterbatch composition
  • the above masterbatch was diluted at 50 wt% in SABIC® LDPE 2201 TH00, which is a LDPE resin for blown films and is suitable for thin packaging film purposes.
  • This polyethylene has a Melt Flow Index of 0.85 g/10 min (190°C, 2.16Kg) and a density of 0.922 g/cm 3 .
  • a multilayer (3-layer) film of approximately 100 Mm was produced on a Kiefel IBC blown film line of 200 kg h, die size of 200 mm, die gap of 0.8 mm, blow-up ratio (BUR) 1:3, and melt temperatures of 150°C - 170°C.
  • the composite composition was incorporated as an internal layer of 40 pm thickness sandwiched between two 30- pm layers of pure LDPE.
  • a similar monolayer 100-pm thick film made of pure LDPE was produced as a control.
  • Oxygen Transmission Rate was measured in same conditions as in Example 4. Table 4 gathers the obtained results.

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Abstract

Cette invention concerne une composition composite servant à former une construction barrière pour les matériaux sensibles aux gaz et les procédés qui lui sont associés. La composition composite selon l'invention contient des particules de charge fonctionnelles ayant des caractéristiques de tailles spécifiques, à base de particules minérales hydrophiles lamellaires ultraminces ayant un rapport d'aspect élevé et une importante surface spécifique, et une résine liante, ladite résine liante contenant un polymère thermoplastique. Elle peut être introduite sous forme de mélange maître dans une matrice polymère pour former un composite polymère. La charge fonctionnelle se disperse à un degré élevé dans la matrice polymère et fournit des propriétés barrières accrues. Le composite polymère, ou la composition composite en soi, peut être utilisé dans une construction barrière pour réduire les taux de transmission des gaz dans des matériaux et des récipients d'emballage.
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CN107049481A (zh) * 2015-12-17 2017-08-18 毕达哥拉斯医疗有限公司 经腔的电极导管
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WO2019075001A1 (fr) * 2017-10-10 2019-04-18 A. Schulman, Inc. Produits polymères ayant une morphologie de type couche formés à partir de mélanges maîtres
CN111718578A (zh) * 2020-06-30 2020-09-29 重庆科聚孚工程塑料有限责任公司 一种乙醇汽油油箱用聚酰胺6复合材料及其制备方法
CN113999514A (zh) * 2020-07-27 2022-02-01 万华化学集团股份有限公司 一种分散相形态可控的聚氨酯组合物及其制备方法和应用
CN113999514B (zh) * 2020-07-27 2023-04-28 万华化学集团股份有限公司 一种分散相形态可控的聚氨酯组合物及其制备方法和应用
CN112519359A (zh) * 2020-11-05 2021-03-19 江西春光新材料科技股份有限公司 一种高阻隔复合硬片及其制备方法
CN112358688A (zh) * 2020-11-23 2021-02-12 上海金发科技发展有限公司 一种疏水玻纤增强聚丙烯复合物及其制备方法

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