WO2007140538A1 - Bouchon de récipient - Google Patents

Bouchon de récipient Download PDF

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Publication number
WO2007140538A1
WO2007140538A1 PCT/AU2007/000803 AU2007000803W WO2007140538A1 WO 2007140538 A1 WO2007140538 A1 WO 2007140538A1 AU 2007000803 W AU2007000803 W AU 2007000803W WO 2007140538 A1 WO2007140538 A1 WO 2007140538A1
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WO
WIPO (PCT)
Prior art keywords
closure
container
polymer composition
starch
barrier
Prior art date
Application number
PCT/AU2007/000803
Other languages
English (en)
Inventor
Rulande Henderson
Kishan Khemani
Nicholas John Mccaffrey
Original Assignee
Plantic Technologies Ltd
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
Priority claimed from AU2006903095A external-priority patent/AU2006903095A0/en
Application filed by Plantic Technologies Ltd filed Critical Plantic Technologies Ltd
Publication of WO2007140538A1 publication Critical patent/WO2007140538A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/10—Oxidised starch
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • This invention relates to closures for containers including tubes, bottles and jars.
  • the closures are particularly useful in preventing transfer of gases such as water vapour, carbon dioxide, oxygen and nitrogen into and out of bottles and jars. This is important in the packaging of solid and liquid foodstuffs and particularly important in the packaging of foodstuffs which can lose their characteristics and become unusable through loss of gases (such as carbonated drinks) or need to be kept dry and inaccessible to, for example, moisture ingress
  • Closures for containers are effective barriers if the closures can both be adequately sealed onto a container after the container is filled, and can be subsequently opened easily by a consumer.
  • closures Most materials commonly used to form closures are however very poor at stopping gas transfer into and out of packaging. Thus, although the closure may be sealed onto the container gas transfer occurs through the material itself.
  • the commodity plastics such as polyethylene terephthalate (PET), polypropylene (PP), polyvinyl chloride (PVC) and polyethylene (PE) all have some barrier properties against the ingress or egress of O 2 and H 2 O. These barrier properties are usually proportional to the thickness of the barrier layer but are not sufficient to prevent gas transfer over long periods and were thus unsatisfactory for ensuring products have long shelf lives. There was therefore a need for materials with better barrier properties than common consumer plastic packaging. Over the last thirty years industry has developed the use of barrier layers. These layers are used to stop the transfer of gases such as water vapour, O 2 , CO 2 and N 2 into and out of food and beverages.
  • the first successful high performance barrier material was polyvinylidene chloride (PVDC).
  • EVOH ethylene vinyl alcohol copolymer
  • nylons e.g. MXD6
  • nitriles nitriles
  • the present invention provides a sustainable, renewable and biodegradable material for use as a barrier layer in container closures.
  • container closures There are three main types of container closures that use barrier layers; plug seals, membranes and cap seals.
  • Plug seals are used most commonly in respect of bottles and are made from injection moulded plastic.
  • the plug friction fits within the inside walls of a bottle, thus sealing the bottle preventing ingress or egress of gases.
  • to minimise gas exchange not only must the plug form a seal with the bottle but the material forming the plug must prevent or minimise gas transmission.
  • Traditionally plugs have been formed of plastics with limited abilities to prevent gas transmission. These plastics are however not biodegradable. When the container is opened the plug is discarded adding to landfill and environmental waste.
  • This invention provides a plug which can be formed to friction fit within a container, limits gas transmission and is biodegradable. Membranes are used to seal the necks of tubes, larger bottles and jars, often in cases where plugs are not suitable.
  • the membrane formed of a material which limits gas transmission (often plastic), is sealed to the rim of the container thereby preventing gas ingress or egress.
  • Membranes are often composed of multiple layers as the barrier layer is not capable of sealing to the rim of the container. Again, when the consumer opens the container the membrane is discarded which adds to landfill.
  • This invention provides a membrane that can be formed of a single layer, is easy to manufacture and is biodegradable.
  • Cap seals are a disc like seal located in the inside top of plastic or metal bottle caps.
  • the seals may be formed from single or multiple layers of material.
  • EVA Ethylene vinyl acetate
  • EVA seals are known to have a relatively high gas transmission rate, which presents a particular problem when the container to be sealed contains a carbonated beverage.
  • a particular carbon dioxide gas pressure must be maintained in the container.
  • Carbonated beverages have a limited shelf life due, at least in part, to the gas transmission properties of the EVA seal.
  • oxygen can enter the container through the EVA seal degrading the product. This can also be particularly problematic in the case of beer and other fermented beverages.
  • Multiple layer seals have been used to inhibit gas transfer to and from containers.
  • One example of a multiple layer seals has a gas barrier layer of ethylene vinyl alcohol copolymer ("EVOH") sandwiched between layers of EVA. These seals are formed by co-extrusion process to prevent the gas barrier layer from being exposed to moisture. Seals of this type are generally expensive and did not perform well.
  • EVOH ethylene vinyl alcohol copolymer
  • This invention provides such a seal and method for making the seal that results in a closure that is more impervious to gas transfer, is biodegradable and is easily manufactured. It has also become attractive in recent years for food and beverage manufacturers to use the closures as a means of advertising and promoting products by printing on the closures. However, most of the materials from which the closures are made are not suitable for printing. In order to print on the closures it has thus been necessary either to emboss rather than print or to add a further layer to the closure and print on that layer. Embossing is expensive, further complicates the manufacturing process and can reduce the effectiveness of the closure. Including additional layers in the closure adds to the cost and difficulty of manufacture.
  • the present invention provides a biodegradable gas barrier layer material which can be printed upon, avoiding the need for additional layers or embossing.
  • a closure for sealing a container comprising a biodegradable polymer composition including on a dry basis: a) from 30 to 90% by weight of starch; b) from 0.1 to 15% by weight of a water soluble polymer selected from polyvinyl alcohol, polyvinylacetate, and copolymers of ethylene and vinyl alcohol which have a melting point compatible with the molten state of the starch component; and c) from 5 to 45% by weight of one or more plasticisers having a molecular weight in the range of 18 - 6000, more preferably 50-2500 and more preferably still 75 - 400 and desirably selected from the group consisting of water, sorbitol, glycerol, maltitol, xylitol, mannitol, erythritol, glycerol trioleate, tributyl citrate, acetyl tri-ethyl citrate, glyceryl tri
  • the closure is located in the cap of a container and wherein the cap is in contact with the container such that the closure contacts and seals the container and the polymer acts as a barrier to the transmission of gases into and out of the container.
  • the biodegradable polymer composition comprises from 40 to 80% starch, from 5 to 15% water soluble polymer and from 10 to 30% plasticiser.
  • the biodegradable polymer composition comprises from 55 to 70% starch, from 10 to 15% water soluble polymer and from 15 to 25% plasticiser.
  • the biodegradable polymer composition comprises from 60 to 65% starch, from 12 to 13% water soluble polymer such as PVOH and from 20 to 21 % plasticiser (made up of 0 to 1 % PEO, 0 to 1 % PEG, 2 to 6% glycerol, 0 to 5% maltitol, 10 to 13% sorbitol) and 0 to 4% of other substances such as processing aids.
  • the starch is a high amylose starch and/or a modified starch selected from starches modified by acid or enzymatic hydrolysis, oxidation or by reaction with a hydroxyl alkyl group, acetate or a dicarboxylic acid anhydride or a grafting polymer.
  • the plasticiser is preferably a non re-crystallising plasticiser. At drying temperatures of 130°C glycerol may be released with any water present. It has also been found that some plasticisers migrate or bloom. In both cases, an optimum outcome is not achieved.
  • the plasticiser is selected from the group consisting of one or more of water, maltitol, xylitoi, glycerol and erythritol.
  • the polymer compositions may also include on a dry basis from up to 2.5 % by weight of a C 8- 22 fatty acid or salt. They may also optionally include up to 3% of emulsifier having a hydrophilic lipophilic balance (HLB) value between 1 and 22. They may also optionally include up to 10% of clay minerals.
  • HLB hydrophilic lipophilic balance
  • additives and fillers may also be included in the polymeric compositions.
  • additives may include other processing aids than those already identified, extenders, epoxidised oils, humectants, fillers, pigments, thermal stabilisers and antioxidants against discolouration and degradation, antimicrobial agents, UV/light stabilisers, lubricating agents, flame retardant, nanoparticles and antiblocking agents.
  • a preferred filler is talc.
  • the closure can be either water soluble or not water soluble.
  • the polymer composition forms a barrier layer along side at least one upper layer of a second polymer composition. More preferably the polymer composition forms a barrier layer along side at least one lower layer of a third polymer composition. Even more preferably, the upper layer is LDPE or EVA and the lower layer is HDPE or PP.
  • the closure is formed by the extrusion of said polymer composition into a sheet, the cutting of a disc from said sheet and injection moulding at least one upper layer and at least one lower layer around said disc, forming the closure.
  • polymeric compositions are suitable for extruding, co extruding, compression moulding, insert-moulding, or casting thin films for use alone or as part of a laminate structure.
  • Other processing methods may also be used including co injection or injection moulding possibly followed by blow moulding
  • injection-blow-moulding and injection-stretch-blow-moulding extruding or co extruding shapes including tubes for blow moulding (extrusion-blow-moulding), and extruded or co-extruded and/or laminated sheet for subsequent thermoforming.
  • Maltitol is found to be a particularly effective plasticiser when high processing temperatures are used in co-injection and co-extrusion processes.
  • the gas barrier properties of the polymer of this invention will, it is anticipated, outperform starch-based prior art compositions and current common non-biodegradable commercial barrier materials at elevated humidities.
  • the films formed from the polymers of the invention have excellent oxygen barrier properties in particular having an oxygen permeability coefficient, for example, below 0.1 cm 3 mm/m 2 day atm at relative humidities up to 60% RH and below 0.7 cm 3 mm/m 2 day atm atm at relative humidities up to 90% RH.
  • the films formed form the compositions of the invention further have a carbon dioxide permeability coefficient below 0.5 cm 3 mm/m 2 day atm at relative humidities up to 60% RH and below 0.9 cm 3 mm/m 2 day atm at relative humidities up to 90% RH.
  • the films formed from the compositions may be laminated with other packaging polymers such as PET, PE, (BO)PP, LDPE and polylactic acid, and other polymers which are poor barriers to the transmission of gasses, by co- extrusion, co-injection moulding, film blowing or thermal lamination techniques.
  • packaging polymers such as PET, PE, (BO)PP, LDPE and polylactic acid, and other polymers which are poor barriers to the transmission of gasses, by co- extrusion, co-injection moulding, film blowing or thermal lamination techniques.
  • Adhesion is excellent with polar materials such as PET, whereas for adhesion with non-polar materials such as PP common tie layer resins are indicated.
  • Suitable tie layer materials include grafted polymers based on PP, EVA, LDPE or LLDPE. It is also found that the polymer compositions of the invention when formed into films can be used as a base to which marketing, sales and promotional materials such as temporary and permanent printing can be applied which may lead to an increase their adoption by the packaging industry, particularly that directed at retail consumer products.
  • the printing can be applied directly to the material or applied to a barrier film which is then applied to the membrane, seal or plug.
  • the material may also be used in an in-mould labelling or in-mould decoration process to apply a barrier film to the surface of an injection moulded part, or to produce a printed or decorated part in a single injection moulding shot.
  • the substrate for the in-moulding decoration process may be either conventional plastic, or a biodegradable polymer.
  • the film may also be used as an insert in an injection moulding process to produce a barrier layer encapsulated within an injection moulded component, such as a seal for carbonated beverages.
  • the barrier film of this invention is biodegradable and water soluble it is suitable for use with recyclable plastics.
  • it is suitable for use with PET because it dissolves in the washing process used in the recycling of
  • PET It is suitable for use with PLA because it is compostable and will biodegrade at least as fast as PLA.
  • a co-extruded or monolayer film of the polymer composition including on a dry basis: a) from 30 to 90% by weight of starch; b) from 0.1 to 15% by weight of a water soluble polymer selected from polyvinyl alcohol, polyvinylacetate, and copolymers of ethylene and vinyl alcohol which have a melting point compatible with the molten state of the starch component; and
  • plasticisers having a molecular weight in the range of 18 - 6000, more preferably 50-2500 and more preferably still 75 - 400 and desirably selected from the group consisting of water, sorbitol, glycerol, maltitol, xylitol, mannitol, erythritol, glycerol trioleate, tributyl citrate, acetyl tri-ethyl citrate, glyceryl triacetate, 2,2,4-trimethyl-1 ,3-pentanediol diisobutyrate, polyethylene oxide, ethylene glycol, diethylene glycol or polyethylene glycol, polyglycerol
  • Figure 1 is a graph showing the comparative gas performance of the polymer composition according to one embodiment of the invention.
  • the amount of starch, modified and/or unmodified, in the composition is limited by the required addition levels of all the other components: it makes up the balance.
  • the starch may be derived from wheat, maize, potato, rice, oat, arrowroot, tapioca, sago and pea sources.
  • One preferred source is maize (corn) starch.
  • Unmodified starch is a cheap biodegradable raw material from renewable resources that may contribute to the barrier properties of the final product and is therefore highly attractive for this application. However, its use is limited by the occurrence of retrogradation (crystallisation resulting in brittleness), limited optical clarity of the resulting formed products, limited film-forming properties and limited elasticity for stretching.
  • One preferred concentration range for unmodified starch as a fraction of the total amount of starch is 0 to 50% although levels up to 90% may be possible.
  • Preferred levels of starch are 40 to 80%, more preferably 55 to 70% and even more preferably 60 to 65%.
  • modified starch is present, the upper limit is largely determined by its cost. This component may contribute structural benefits to the resulting material, including good film-forming properties, good optical properties, and resistance to retrogradation. Retrogradation and crystallisation of starch may relate to one of the most important practical problems with starch based plastics, as they have a tendency to become brittle over time, analogous to the staling process in baked goods.
  • Typical modified starches include those having an hydroxyalkyl C 2 - 6 group or starch modified by reaction with a dicarboxylic acid anhydride.
  • One preferred modified starch is high amylose hydroxypropylated starch.
  • Other modified starches can be hydroxyethyl or hydroxybutyl substituted to form hydroxyether substitutions.
  • Acetates or anhydrides such acetic, maleic, phthalic or octenyl succinic anhydride can be used to produce modified starches which are ester derivatives.
  • the degree of substitution [the average number of hydroxyl groups in a unit that are substituted] is preferably 0.05 to 2. If modified starch is used, one preferred starch is a high amylose maize (corn) starch, more preferably a hydroxypropylated high amylose starch.
  • the minimum level of hydroxypropylation in this product is 3.0%, more preferably above 6.0%. Typical values are 6.1 to 6.9%.
  • this starch For cost saving reasons and for property optimisation reasons it is possible to substitute part of this starch with: i) higher or lower levels of hydroxypropylation; ii) a higher level of unmodified starch. This may be possible if the level of hydroxypropylation of the modified starch is increased; iii) a starch modified with acetate or octenyl succinic anhydride (OSA), which has a higher degree of hydrophobicity.
  • OSA octenyl succinic anhydride
  • the addition of this modified starch increases water resistance with increasing degree of substitution. This is relevant when the films formed from the polymers of the invention are incorporated as a barrier layer in packaging applications containing fluids, as the relative humidity in these situations may be up to 90%.
  • the acetyl linkages in the OSA starch ensure that the material retains biodegradability upon access to water and a biologically active environment; or iv) a starch co-polymer, preferably consisting of a styrene butadiene grafted with starch. This material improves impact resistance of the product.
  • the polymer component b) of the composition is preferably compatible with starch, water soluble and has a melting point compatible with the processing temperature/s of the starch or starches selected.
  • Polyvinyl alcohol is one preferred polymer but polymers of ethylene-vinyl alcohol, ethylene vinyl acetate, vinyl acetate or blends with polyvinyl alcohol may also be used.
  • the selected polymer should preferably not be water soluble at room temperature conditions.
  • PVOH offers a combination of excellent film forming and binder characteristics, good elasticity and aids processing of starch-based formulations. PVOH is produced by the hydrolysis of polyvinylacetate which is made by the polymerisation of vinyl acetate monomer.
  • the fully hydrolysed grades contain few, if any, residual acetate groups; while partially hydrolysed grades retain some of the residual acetate groups.
  • Fully hydrolysed grades dissolve in hot (90° C) water, and remain in solution when cooled to room temperature.
  • Preferred grades of PVOH include those having weight average molecular weight in the range 50,000 - 500,000. The higher molecular weight grade PVOH appears to improve impact resistance and to reduce water sensitivity. Increasing the level of PVOH significantly increases elongation at break and decreases Young's modulus. Film forming may become difficult below 6%. Therefore, a preferred concentration range for thin film barrier material is 4 to 15% and the preferred concentration range for barrier materials to be applied in injection-blow moulded bottles is 4% to 15%. Further preferred levels of water soluble polymer are 10 to 15%, and even more preferably 12 to 13%.
  • a range of plasticisers and humectants are useful in the compositions of the invention in order to aid processing and to control and stabilise the mechanical properties of the barrier material, and in particular in reducing dependency on moisture content and relative humidity.
  • the desired plasticiser content depends primarily on the required processing behaviour during the (co)- extrusion or (co)-injection moulding process and subsequent thermoforming, blowing or stretching processes as well as on the required mechanical properties of the end product. Cost and the purpose to which the film is to be put such as, for example, for use in food packaging are important issues in choosing the appropriate plasticiser.
  • the plasticiser plays a triple role: it provides suitable rheology for the extrusion compounding process and for the lamination process, it positively affects the mechanical properties of the product and it may act as an anti-retrogradation or anti-crystallising agent.
  • Preferred plasticisers are those having a molecular weight in the range of 50 - 6000, more preferably 50 - 2500 and more preferably still 100 - 400 and which are desirably selected from the group consisting of sorbitol, glycerol, maltitol, xylitol, mannitol, erythritol, glycerol trioleate, tributyl citrate, acetyl tri-ethyl citrate, glyceryl triacetate, 2,2,4-trimethyl- 1 ,3-pentanediol diisobutyrate, polyethylene oxide, ethylene glycol, diethylene glycol or polyethylene glycol.
  • the plasticiser is non crystallising
  • plasticiser content is 10-40% depending on the particular application and co-extrusion or lamination process. Further preferred levels of plasticiser are 10 to 30%, more preferably 15 to 25% and even more preferably 20 to 21 %.
  • Sorbitol and xylitol function also as particularly good humectants.
  • Glycerol helps dissolve the PVOH during processing.
  • Some polyols (sorbitol and glycerol in particular) may exhibit migration to the surface of the film where either an opaque crystalline film may form in the case of sorbitol, or an oily film in the case of glycerol. Blending various polyols inhibits this effect to varying degrees. It is known that the polyol may have a synergistic effect with salt resulting in enhanced mechanical properties.
  • PEG compounds may be used as emulsifying agents, plasticisers or humectants.
  • Polyethylene oxide and polyethylene glycol alternately or together may also provide an increased water resistance, to prevent swelling which may result in delamination in multi-layer structures (MLS).
  • MLS multi-layer structures
  • plasticisers more commonly used in the PVC industry may also be suitable including tributyl citrate, 2,2,4 trimethyl-1 ,3-pentanediol diisobutyrate, and acetyl tri-ethyl citrate.
  • a humectant or water binding agent or gelling agent may be used to act as a (co)plasticiser.
  • Suitable examples are carrageenan, xanthan gum, gum arabic, guar gum, gelatine, sucrose or glucose.
  • Biopolymers such as carrageenan, typically used in food products as thickeners and partially soluble in cold water but fully soluble in hot water may be suitable for tailoring mechanical properties. By binding water these components may have a significant plasticising function.
  • Gelatine may be added to improve the mechanical properties and reduce moisture sensitivity.
  • Xanthan Gum has a high water holding capacity and also acts as an emulsifier and in starch compositions has an anti-retrogradation effect.
  • Gum Arabic may also be used as a texturiser and film former, and the hydrophilic carbohydrate and hydrophobic protein enable its hydrocolloid emulsification and stabilisation properties. Guar gum has similar anticrystallisation effects in starch compositions. Another suitable humectant is glyceryl triacetate.
  • Plasticisation and humectant effects may also be obtained or enhanced with salts such as sodium chloride and sodium hydroxide.
  • salts such as sodium chloride and sodium hydroxide.
  • Potassium salt, potassium acetate, calcium oxide and sodium iodide are also suitable.
  • Calcium salt improves the rigidity and size stability of extruded starch materials, and may furthermore be used in combination with carrageenan to assist gelling.
  • Fatty acids and fatty acid salts such as stearic acid may also be used as a lubricating agent in the composition because it has shown better compatibility with starches than for example waxes.
  • Stearic acid is hydrophobic and may therefore improve moisture sensitivity of the starch-based material.
  • salts such as calcium stearate may be used.
  • the degree of saturation of the fatty acid portion of the emulsifier limits its ability to perform as required with more saturated fatty acids being preferred.
  • Stearic acid is particularly useful as a processing aid, however in the presence of PEO or PEG it may not be necessary.
  • Preferred levels of stearic acid are 0.1 % to 5%.
  • Sodium and potassium salts of stearic acid may also be used.
  • Sulfiting agents are added to many foods to prevent enzymatic and non-enzymatic browning and act in the compositions of the invention as antioxidants or reducing agents. Sulfites inhibit non-enzymatic browning by reacting with carbonyl intermediates, thereby preventing their further reaction to form brown pigments.
  • Citric acid often in conjunction with ascorbic acid or sodium bisulfite, has long been used as a chemical inhibitor of enzymic browning.
  • One preferred concentration of potassium bisulfite for applications where browning is undesirable may up to 2%, possibly in conjunction with up to 2% ascorbic acid.
  • thermal stabilisers such as Vitamin E or hindered phenols in amounts of up to 2% by weight are suitable.
  • the emulsifier is preferably a food grade emulsifier.
  • the selection of the emulsifier is based on its HLB value.
  • Preferred emulsifiers are selected from food grade emulsifiers with HLB numbers between 1 and 22 and include propylene glycol monostearate, glycerol monoleate, glycerol trioleate, glycerol monostearate, acetylated monoglycerides (stearate), sorbitan monooleate, propylene glycol monolaurate, sorbitan monostearate, calcium stearoxyl-2-lactylate, glycerol monolaurate, sorbitan monopalmitate, soy lecithin, diacetylated tartaric acid esters of monoglycerides, sodium stearoyl lactylate, sorbitan monolaurate. Sodium stearoyl lactylate and glycerol monostearate are commonly used in starch systems. Table A
  • HLB Hydrophobic / Hydrophilic Balance
  • Glycerol monostearate is a lipophilic, non-ionic surfactant, which is particularly suitable for this application as it has a defoaming effect and anti- retrogradation effect in starch compositions. Glycerol monostearate added at levels ranging from 1-1.5% acts as an emulsifier to stabilise mechanical properties and increase homogeneity of the blend. Sodium stearoyl lactylate at
  • 0.25% to 1.5% may be added to a plasticiser system to stabilise mechanical properties and increase homogeneity of the blend.
  • Combinations of glycerol monostearate and sodium stearoyl lactylate result in faster stabilisation of properties.
  • the HLB value follows the additive rule and is preferably of the order of 4 to 10 for a suitable mixture of SSL and GMS.
  • Water is added for the purpose of "gelatinising” (also called destructurising or melting) the starch into a polymeric gel structure. Water also may act like a plasticiser in the end-product in that it softens the material or reduces the modulus.
  • the moisture content of the barrier material may vary at water activities or relative humidities (RH) below 30% or superior to 75%. In many barrier film and barrier bottle applications, the local relative humidity to which the barrier material is exposed may reach values of up to 90%. For stable mechanical, lamination, and barrier properties and for ease of processing at all temperatures, non-volatile plasticisers are preferred. Therefore some or all of the water may be dried off during or after the compounding stage and/or in the feeding stage of the subsequent injection moulding or film forming.
  • Fillers which may be incorporated into the film forming compositions include calcium carbonate, kaolin, clay, titanium dioxide, talc, natural and synthetic fibres and may be selected according to the purpose of the composition.
  • Clay minerals can also be added to improve the melt processability of the polymer and also improves the tensile strength and translucency so that higher starch contents are viable and acceptable biodegradable polymers can be produced at an acceptable cost.
  • the clay may be any compatible clay with a large surface area, a large aspect ratio and an appropriate platelet thickness.
  • a preferred clay is montmorillonite [MMT]. Montmorillonite (MMT) has a high surface area (about 750m 2 /g), a large aspect ratio (greater than 50), and platelet thickness of 1 ⁇ A.
  • the clay is usually treated to make it compatible with the polymers.
  • the inorganic surface of the clay is modified by organic treatments to make the platelet more compatible with the polymer.
  • Ammonium or phosphonium salts can also be used to make the clay platelets compatible.
  • starch content of the polymer blend increases the clay, and the treatment made to the clay, needs to be varied to ensure that the intercalating chemicals added to the clay are more compatible to starch than polyester.
  • the clay modifiers may include chemicals with a hydrophilic and cationic part which is clay compatible and another part that is hydrophilic and H-bond active such as a carboxylic group that is starch compatible. They clay is preferably used in sufficient quantity to produce an exfoliated or nanocomposite structure where the clay layers are completely interspaced with polymer. This structure retards crystal formation so that blended material is amorphous which results in transparency and improved elongation to break and acceptable tensile strength properties.
  • MMT differs from more commonly used fillers such as talc and mica because this layered silicate can be dispersed into individual layers only 1 ⁇ A thick.
  • tactoids When MMT is blended into a polymer and the layers do not separate they are referred to as tactoids. Intercalation occurs when a small amount of polymer moves into the gallery spacing between the clay platelets, causing separations less than 2 ⁇ A to 3 ⁇ A. Exfoliation occurs with basal spacing of 8 ⁇ A to 100A or more.
  • a well-dispersed nanocomposite consists of exfoliated platelets distributed homogeneously throughout the polymer. It is generally believed that maximum benefits are achieved when the platelets are uniformly dispersed, due to the potential of the fully exfoliated surface area.
  • the membrane for sealing a container is a thin sheet of material shaped to fit the lip of a bottle or the like.
  • the membrane can be monolayer or multilayer.
  • For a monolayer membrane the polymer composition is extruded into a sheet 30 to 250 microns thick. Promotional or advertising material is printed onto the sheet. Discs the same size as the lip of the bottle to be sealed are then cut from the sheet using conventional methods.
  • the shape cut from the sheet can be sized so as to fit over the lip of the bottle or the like with an overhang in at least one area to form a handle for the user to grip when peeling the membrane from the container.
  • To apply the membrane to the container the container is filled and the membrane is attached to the lip of the container.
  • the membrane can be applied to the container using conventional adhesives.
  • the membrane can be applied by placing the membrane over the container lip, wetting that part of the membrane in contact with the container and applying pressure.
  • the polymer composition can be extruded into a sheet and attached to sheets of other material, including materials which are poor barriers to the transmission of gasses, using conventional methods as described above.
  • the multilayer sheet can be obtained by co- extruding the polymer composition with other products. Once the multilayer sheet is obtained the sheet can be printed upon and cut out as described above for monolayer sheets.
  • the membrane can also be applied to the container in the same manner as monolayer membranes. However, it should be noted that the membrane can only be attached to the container by wetting if the bottom layer is the polymer composition and that care must be taken in the selection of the bottom layer as some materials cannot be readily attached to containers using adhesives.
  • the membrane When the consumer wishes to remove the membrane this is achieved by peeling or tearing the membrane from the container, exposing the product within. The membrane is then disposed of. Where the membrane is monolayer or is combined with other materials which are recyclable or biodegradable the membrane can be recycled or will biodegrade. In the case of monolayer membranes the membrane can also be removed by wetting the membrane and allowing it to dissolve. This would be a preferred method of removal for products which would not be harmed by small amounts of water but which may be messy or harmful to the user if touched, such as paints and adhesives.
  • the membranes described above could also be formed by injection moulding (or in the case of a multilayer membrane co-injection moulding) in the desired shape using conventional methods. Where the membrane is injection moulded printing could be applied to the membrane during the injection moulding process. Plugs
  • Plugs for sealing a container are moulded to precise specifications in order to ensure a friction fit within the neck of the container.
  • Plugs are usually thicker than membranes and are shaped so as to be manually removable by a user.
  • plugs can be monolayer or multilayer.
  • the polymer composition is injection moulded or blow moulded to the shape of the container. Printing is applied to the plug during the moulding process in the conventional manner.
  • the plug is fitted within the neck, preventing ingress or egress of gases.
  • Multilayer plugs are formed by co-injection moulding or co-blow moulding the polymer composition with other compositions, including compositions which are poor barriers to the transmission of gasses. Again, printing can be applied to the plug in the conventional manner during moulding.
  • plugs can be formed by extruding the polymer into a sheet and then thermoforming the sheet to form a plug (or in the case of a multilayer plug co-extruding the sheet or extruding separate sheets which are subsequently attached together in the conventional manner).
  • the plug In use the plug is fitted into the neck of the container once the container is filled. To access the contents of the container the plug is manually removed by the user. Depending upon the contents of the container, the plug can then be discarded or replaced to protect the remaining contents of the container. In the later case the plug is discarded once the entire contents of the container are used.
  • the plug can be recycled or will biodegrade.
  • the plug can also be removed by wetting the plug and allowing it to dissolve. This would be a preferred method of removal for products which would not be harmed by small amounts of water but which may be messy or harmful to the user if touched, such as paints and adhesives.
  • Cap seals fit within the cap of a bottle or the like. They function to seal the container and prevent gas transmission which would otherwise occur through the cap.
  • the seal can be monolayer or multilayer and is sized so as to fit exactly inside the cap.
  • the seal can be formed by injection moulding to the desired shape or extruding the polymer into a sheet and then cutting the seals from the sheet using conventional methods. Where the seals are formed using injection moulding promotional materials can be printed on the seals during injection moulding. Where the seals are formed from an extruded sheet printing on the seal can take place either before or after the seals are cut from the sheet.
  • Multilayer seals can also be formed by injection moulding.
  • the polymer composition can be co-injection moulded with other compositions, including compositions which are poor barriers to the transmission of gasses, to form the seal.
  • Printing can be placed on the polymer composition layer of the seal during the injection moulding process using conventional methods.
  • the multilayer seals can also be formed by forming a multilayer sheet and cutting the seals from the sheet.
  • the multilayer sheet can be formed by co-extrusion or by extruding sheets separately and then attaching sheets of various materials to form the multilayer sheet. Again, printing on the sheets can be undertaken either before or after the seals are cut from the sheet in the conventional manner.
  • a further method of forming the multilayer seal is by extruding the polymer composition into a sheet, printing on the sheet and cutting discs from the sheet. The discs are then placed into an appropriate injection mould and other compositions, including compositions which are poor barriers to the transmission of gasses, are injection moulded around the disc to form the seal.
  • Other compositions which may be particularly useful in this application include materials which form a soft compounded seal (such as LDPE or EVA) and closure shell materials (such as HDPE or PP).
  • the seal is fitted inside the cap to act as a gas barrier.
  • the cap is screwed down onto the container so as to bring the seal into contact with the container, sealing the container and preventing gas transfer.
  • the cap is screwed in the other direction forcing the seal out of contact with the container.
  • the polymer composition of this invention may be formed from starch polymer compositions of the formulae set out in table 1.
  • the permeability to oxygen of selected common packaging materials and barrier films for packaging purposes is provided as a means of comparison in table 2.
  • the permeability to carbon dioxide of selected common packaging materials and barrier films for packaging purposes is provided as a means of comparison in table 3.
  • the main components contributing to the barrier performance of the compositions of this invention are starch and PVOH.
  • the polyol plasticisers also contribute to the barrier properties. Synergistic effects of the components, as well as any complexes that may be formed by these components in the extrusion process, may assist in significantly enhancing the oxygen barrier of the polymeric material of this invention. Table 3
  • the material is manufactured by means of extrusion compounding, using Co- or counter-rotating twin screw or selected design single screw extruders.
  • the preferred process is twin screw co-rotating compounding.
  • Water may be added to the process (by means of liquid injection together with the plasticisers) dependent on the level and nature of other plasticisers. Removal of water may be carried out by means of convective drying, contact heating, IR heating, vacuum drying, or microwave drying for the extrudate strands, a centrifuge and a fluidised bed for granulate, or barrel venting or a combination of these.
  • Granulate may be obtained by means of underwater pelletising, die face cutting or strand cooling and cutting.
  • the composition may be injection moulded using conventional screw driven or injection driven processes with hot or cold runner systems.
  • the compositions of this invention have been designed to be compatible with PET for co-injection moulding at elevated temperatures.
  • the compositions of this invention have also been designed to be compatible with other polymers like PP, HDPE, LDPE, PLA and biopolymers for co-injection moulding. It is expected that the compositions of this invention will be successfully co-injection moulded on an industry standard preform co-injection machine.
  • the cold half of the preform mould it is expected will be standard design.
  • the hot half may be of special design.
  • the two materials can be conveyed in separate manifolds, and combined in the nozzle to form an annular flow pattern.
  • each manifold There may be separate temperature control of each manifold, with good thermal separation.
  • the nozzle is the only part of the manifold system where both material streams must be at the same temperature. This temperature is typically around 250-280 0 C to suit the requirements of PET. Similar temperatures suit the requirements of PP, HDPE, LDPE, PLA and biopolymers.
  • Materials may be dried as required in standard industry de-humidifying driers.
  • compositions of this invention may be readily blown into plugs or seals on conventional stretch blow moulding lines.
  • Preform temperatures may be in the range 100 to 120 0 C, and a blow moulding pressures of 35 to 45 bar are likely to be used.
  • Adhesion with PET is expected to be excellent due to the polar nature of the barrier material having a surface tension of >50 dynes/cm and due to the lack of crystallinity-related shrinkage.
  • Adhesion with PP, HDPE, LDPE, PLA and biopolymers is also expected to be excellent.
  • a barrier layer typically makes up about 5-20% of the total layer thickness of the multilayer structure. Therefore its mechanical properties will contribute somewhat to the mechanical properties of the final product. Where the mechanical properties of the barrier material are lower, some compensation may be required by slightly increasing the wall thickness of the container, but never by more than the barrier layer thickness, hence 10% increase at the most, offset by the advantage of excellent barrier properties at a cost saving compared to conventional barrier materials. Also important is the elongation behaviour as in the blowing process stretching occurs. This stretching occurs in heated form, and the barrier layer is supported by the matrix.
  • the mechanical properties of barrier materials according to the invention are compared to commercial materials for injection stretch blow moulding in Table 4.
  • the polymer composition of the invention may also be used as a single layer product, with printing and varnishes.
  • the resulting films could be thin, for membranes and seals, or thick, for thermofoiming applications, as this material is also ideally suited for thermoforming processing.
  • formulations of this invention are suitable for extrusion casting of thin films. Those skilled in the art would be able to select suitable plasticiser levels to obtain the required melt strength and mechanical properties for the required application.
  • Selected formulations of this invention were cast into monolayer thin films using a 90mm single screw extruder at throughput rates of 70-200 kg/h through a 1050 mm wide sheet die with barrel temperatures ranging from 90-200 0 C.
  • Haul off ratios of order 10-30 were used with roll speeds ranging from 10-50m/min, resulting in some to strong mono-axial orientation.
  • compositions used in this invention are cold sealable and heat sealable.
  • the polymer composition of the invention can be co-extruded into a laminate or combined with conventional film polymers (e.g. biaxially oriented PP) in a separate lamination step.
  • the other materials may be any suitable packaging polymer such as polypropylene (PP) polyethylene (PE) or low density polyethylene (LDPE), or biodegradable polymers such as polylactic acid (PLA) or other polyesters.
  • PP polypropylene
  • PE polyethylene
  • LDPE low density polyethylene
  • PLA polylactic acid
  • the polymer composition of this invention is preferably used as the middle layer in a three layer laminate or a 5 to 7-layer product if additional tie layers and protective coatings are deemed necessary.
  • Adhesion of the films of the invention is excellent with polar materials such as PET, whereas for adhesion with non-polar materials such as BO-PP common tie layer resins are indicated.
  • Suitable tie layer materials include grafted polymers based on PP, EVA,
  • LDPE or LLDPE For adhesion to PP Orevac PPC from Atofina is suitable for clear applications and Orevac 18729 or 18910 from Atofina for opaque applications.
  • Other suitable tie layers include EVA copolymers, acrylic copolymers and terpolymers, ionomers, metallocene PE, ethylene acrylic ester terpolymers and ethylene vinyl acetate terpolymers.
  • Anhydride modified polymers (such as DuPont Bynel CXA50E662) are also suitable for dry formulations of this invention.
  • the barrier material is inherently antistatic, and may be printed or coated with all standard printing techniques.
  • the adhesion with inks and coatings is excellent for solvent based inks, as determined with the tape peel test.
  • the tear propagation resistance is (ASTM D 1938) 200-400 Nm and the kinetic coefficient of friction (ASTM D 1434) is 0.1-0.3.
  • this polymer composition can be co-extruded into blown film, using similar tie layer principles if required.
  • composition of the invention may be injection moulded using conventional screw driven or injection driven processes with hot or cold runner systems.
  • a polymer composition was prepared comprising 63.95% starch, 11.71 % sorbitol, 12.54% PVOH, 1.65% stearic acid, 1.07% GMS, 0.28% stearoyl sodium lactylate, 0.68% PEO, 0.26% PEG, 5.00% glycerol and 3.29% maltitol.
  • the composition was injection moulded according to conventional methods into a circular mould having a diameter of 26.5mm and a wall thickness of 0.3mm (a sample mould of equivalent size to the mould for a cap seal).
  • the film gate on the injector was 3mm in width and 0.1 mm thick and the plastifying extruder was 45mm thick.
  • the injection moulding was carried out at various temperatures for the purpose of assessing the resulting product.
  • the main problem in achieving a satisfactory injection was the narrowness of the film gate and the thickness of the extruder, making it difficult to fill the cavity.
  • the thickness of the injector was increased to 0.2mm and the plastifying extruder was narrowed to 18mm for Test 6 and a satisfactory result was achieved.
  • Table 6 shows that compositions of the invention can be used to form cap seals by injection moulding.
  • a polymer composition was prepared comprising 63.95% starch, 11.71 % sorbitol, 12.54% PVOH, 1.65% stearic acid, 1.07% GMS, 0.28% stearoyl sodium lactylate, 0.68% PEO, 0.26% PEG, 5.00% glycerol and 3.29% maltitol.
  • the composition was extruded using conventional methods into a sheet 150-250 microns thick. Promotional logos were printed onto the sheet using conventional methods. Discs 20mm in diameter were cut from the sheet using a punch of appropriate size. The discs are printed and punched immediately so as to minimise shrinkage due to humidity changes. The discs were then stacked in transport tubes. The transport tubes were sealed to prevent humidity changes and thus warping of the discs. The discs were then stored for a period of 3 weeks before being tested for changes in shape. No significant shape changes were observed.
  • a disc was then selected and placed into an injection mould.
  • a composition comprising a soft compound seal material and a closure shell was then co-injection moulded around the disc. The disc was enclosed within the injection moulded material.
  • compositions of this invention are unique among barrier materials in that they offer better barrier properties than the most commonly used materials (e.g. MXD6, EVOH etc) at a significantly lower costs, allowing for cost savings both in terms of the thickness of the layer and the price of the compound. They also allow printing to the barrier material removing the need for further layers reducing costs and simplifying manufacturing.
  • the water solubility of the compositions offers excellent recyclability to the matrix materials with which this barrier is combined. If used as a single-layer structure, this material is furthermore compostable and biodegradable and will disintegrate and biodegrade as litter at environmental temperatures. These unique properties are due to the combination of compounds in the formula.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Bouchon servant à fermer hermétiquement un récipient, le bouchon comprenant une composition de polymère biodégradable comprenant, sur une base sèche, (a) de 30 à 90 % en poids d'amidon, (b) de 0,1 à 15 % en poids d'un polymère soluble dans l'eau sélectionné parmi l'alcool polyvinylique, l'acétate de polyvinyle et des copolymères de l'éthylène et de l'alcool vinylique qui ont un point de fusion compatible avec l'état fondu du composant amidon et (c) de 5 à 45 % en poids d'un ou de plusieurs plastifiants ayant un poids moléculaire compris dans la plage de 18-6000, de façon plus particulièrement préférable de 50-2500 et de façon encore plus particulièrement préférable de 75-400 et de préférence sélectionnés dans le groupe constitué de l'eau, du sorbitol, du glycérol, du maltitol, du xylitol, du mannitol, de l'érythritol, du trioléate de glycérol, du citrate de tributyle, de l'acétylcitrate de triéthyle, du triacétate de glycéryle, du diisobutyrate de 2,2,4-triméthyl-1,3-pentanediol, du polyoxyde d'éthylène, de l'éthylèneglycol, du diéthylèneglycol ou du polyéthylèneglycol, du polyglycérol, le polymère servant de barrière à la transmission de gaz vers et en dehors du récipient.
PCT/AU2007/000803 2006-06-07 2007-06-07 Bouchon de récipient WO2007140538A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2006903095 2006-06-07
AU2006903095A AU2006903095A0 (en) 2006-06-07 Container closure

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WO2007140538A1 true WO2007140538A1 (fr) 2007-12-13

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WO (1) WO2007140538A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010008751A1 (fr) * 2008-06-24 2010-01-21 S.D. Warren Company Compositions de liant à base d'amidon à plusieurs composants
US20120138613A1 (en) * 2009-05-15 2012-06-07 Ellery West Pinch Top Closure System
WO2013090973A1 (fr) 2011-12-22 2013-06-27 Plantic Technologies Limited Films multi-couches
US20180118906A1 (en) * 2016-10-27 2018-05-03 Monosol, Llc Water-Soluble Film with Low Coefficient of Friction
WO2020017968A1 (fr) * 2018-07-19 2020-01-23 Huhtamaki Molded Fiber Technology B.V. Unité d'emballage alimentaire biodégradable et compostable obtenue à partir d'un matériau de pâte moulé ou en flocons à multicouche stratifié, et procédé de fabrication d'une telle unité d'emballage alimentaire
NL2022734B1 (en) * 2018-07-19 2020-01-29 Huhtamaki Molded Fiber Tech Bv Biodegradable and compostable food packaging unit from a moulded or fluff pulp material with a laminated multi-layer, and method for manufacturing such food packaging unit
EP4101886A4 (fr) * 2020-02-03 2024-04-03 Plantic Tech Ltd Composition de résine

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006042364A1 (fr) * 2004-10-18 2006-04-27 Plantic Technologies Ltd Film barrière

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006042364A1 (fr) * 2004-10-18 2006-04-27 Plantic Technologies Ltd Film barrière

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010008751A1 (fr) * 2008-06-24 2010-01-21 S.D. Warren Company Compositions de liant à base d'amidon à plusieurs composants
US20120138613A1 (en) * 2009-05-15 2012-06-07 Ellery West Pinch Top Closure System
US8881927B2 (en) * 2009-05-15 2014-11-11 Ellery West Pinch top closure system
WO2013090973A1 (fr) 2011-12-22 2013-06-27 Plantic Technologies Limited Films multi-couches
EP2794425A4 (fr) * 2011-12-22 2015-08-26 Plantic Technologies Ltd Films multi-couches
US10894392B2 (en) 2011-12-22 2021-01-19 Plantic Technologies Limited Multilayer films
US11590738B2 (en) 2011-12-22 2023-02-28 Plantic Technologies Limited Multilayer films
US20180118906A1 (en) * 2016-10-27 2018-05-03 Monosol, Llc Water-Soluble Film with Low Coefficient of Friction
WO2020017968A1 (fr) * 2018-07-19 2020-01-23 Huhtamaki Molded Fiber Technology B.V. Unité d'emballage alimentaire biodégradable et compostable obtenue à partir d'un matériau de pâte moulé ou en flocons à multicouche stratifié, et procédé de fabrication d'une telle unité d'emballage alimentaire
NL2022734B1 (en) * 2018-07-19 2020-01-29 Huhtamaki Molded Fiber Tech Bv Biodegradable and compostable food packaging unit from a moulded or fluff pulp material with a laminated multi-layer, and method for manufacturing such food packaging unit
CN112469862A (zh) * 2018-07-19 2021-03-09 普乐模塑纤维技术私人有限责任公司 具有层压的多层件的由模制浆料或绒毛浆料制成的可生物降解和可堆肥的食物包装单元及制造这种食物包装单元的方法
EP4101886A4 (fr) * 2020-02-03 2024-04-03 Plantic Tech Ltd Composition de résine

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