WO2004052646A1 - Biologisch abbaubare mehrschichtfolie - Google Patents

Biologisch abbaubare mehrschichtfolie Download PDF

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Publication number
WO2004052646A1
WO2004052646A1 PCT/DE2003/004157 DE0304157W WO2004052646A1 WO 2004052646 A1 WO2004052646 A1 WO 2004052646A1 DE 0304157 W DE0304157 W DE 0304157W WO 2004052646 A1 WO2004052646 A1 WO 2004052646A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
polyester
film according
starch
blend
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/DE2003/004157
Other languages
German (de)
English (en)
French (fr)
Inventor
Werner Berger
Frits Pieter Eduard Anton De Jong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Biop Biopolymer Technologies AG
Original Assignee
Biop Biopolymer Technologies AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Biop Biopolymer Technologies AG filed Critical Biop Biopolymer Technologies AG
Priority to ES03812564T priority Critical patent/ES2385020T3/es
Priority to CA2543306A priority patent/CA2543306C/en
Priority to US10/538,020 priority patent/US20070042207A1/en
Priority to AU2003296535A priority patent/AU2003296535A1/en
Priority to JP2004557811A priority patent/JP4619127B2/ja
Priority to AT03812564T priority patent/ATE549158T1/de
Priority to EP03812564A priority patent/EP1581388B1/de
Publication of WO2004052646A1 publication Critical patent/WO2004052646A1/de
Priority to NO20052785A priority patent/NO20052785L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2003/00—Use of starch or derivatives as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/20—Starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • the invention relates to a biodegradable multilayer film with an adjustable barrier effect against oxygen (O 2 ), nitrogen (N 2 ), carbon dioxide (CO 2 ) and water vapor for use in the packaging sector, in particular for foodstuffs or in agriculture, and a method for their manufacture.
  • Packaging materials for fruits and vegetables must also take into account the natural breathing and maturation process of these products with controlled oxygen and water vapor permeation.
  • Blend production mixing the materials and extrusion into one layer.
  • the prerequisites for good performance properties of the film are comparable melting points and viscosities of the components during extrusion or coextrusion. These parameters should be as close as possible to one another or can be approximated to one another by additives such as phase or adhesion promoters or other additives.
  • foils made of synthetic materials are mostly used for packaging foils in the food sector. These often consist of polyvinyl chloride or polyvinylidene chloride.
  • multilayer films made from alternative, chlorine-free materials such as. B. polyamide, polyethylene, polyvinyl alcohol used. In order to meet the criterion of low gas permeability, some of them are also coated with aluminum or silicon compounds.
  • thermoplastic starch is obtained, for example, by processing with glycerin and water (WO9005161). In order to use thermoplastic starch as processable and usable materials, it must be processed as a blend with other materials in a melt (DE 199 38 672 and DE 100 62 848). Such blends consisting of starch and thermoplastic polymers are also known from DE 195 13 237 A1 and DE 969212557 T2.
  • WO 02/059198 A1 describes a mixture of polydihydroxydiacid with defined molecular weight and melting points and polylactate.
  • the mixture can also contain starch.
  • WO 9001043 discloses aliphatic polyesters (polyhydroxycarboxylic acids) which can be laminated in solution on prefabricated films made of hydrophilic polymers, such as starch. The solvents are evaporated after the coating process.
  • EP 0616569 B1 describes a laminated film based on starch, in which the laminate layer consists of natural or synthetic waxes or a mixture of waxes.
  • EP 1195401 A1 also describes a laminated film in which the laminate layer is described as being selectively permeable to CO 2 and is based on poly (4-methylpentene-1).
  • EP 0495950 describes the production of laminated films in which a hydrophobic polymer is evaporated onto a hydrophilic starch film.
  • starch acetate has to be prepared in a complex manner.
  • EP 0647184 B1 describes a multilayer film composed of a moisture-sensitive polymer and thermally sensitive polymers and other components.
  • WO 03/035753 A1 (published May 1, 2003) describes compositions in the form of a film consisting of the components, destructurized starch and polyhydroxyalkanoate copolymer (PHA) with a defined structure of at least 2 randomly repeating monomer units. This mixture is used, inter alia, to produce a laminar film in which at least one layer is built up from this mixture.
  • Tomka describes the production of a multilayer film by coextrusion, consisting of thermoplastic processable starch with a polyethylene or polypropylene layer and an adhesion promoter to improve the adhesion between the layers.
  • DE 4116404 A1 describes a polymer mixture and points out the possibility of using it to produce a water-resistant three-layer film by coextrusion.
  • a blend of thermoplastic starch (TPS), polyolefin and a polyethylene-acrylate-MSA copolymer is proposed for the outer layers of this film and a thermoplastic starch for the middle layer.
  • TPS thermoplastic starch
  • the water resistance can be improved even further by adding borax, magnesium sulfate and calcium carbonate.
  • EP 0537657 B1 describes a process for producing multilayer films from TPS or a blend with TPS and polyolefins (polyethylene, polypropylene) using phase or adhesion promoters in the form of a block copolymer.
  • EP 0479964 and US 6,242,102 each describe a multilayer film consisting of thermoplastically processable starch, which contains at least 20% by weight of an additive and a further layer of a polyolefin or a polymer blend of starch and polyolefin.
  • coating variants silicon monoxide coating and the application of alkylsiloxanes are also mentioned.
  • the basic material of these last-mentioned multilayer films is made of biodegradable starch, but disadvantageously all of these films contain polyolefins, such as. B. polyethylene or polypropylene, or other non-biodegradable substances.
  • Starch blend must be less than 1%.
  • the TPS used must be dried down from a water content of approx. 18% to less than 1%.
  • the object of the present invention is to provide a multilayer film for use in packaging which
  • the object is achieved by a multilayer film obtainable by coextrusion, which is composed of at least a.) A starch blend layer consisting of a modified thermoplastic starch blend and b.) A polyester layer consisting of a biodegradable polyester.
  • the film consists of at least two layers. It preferably consists of an inner layer which is surrounded by two outer layers.
  • the layers Due to the manufacturing process, in which the materials for all layers are melted and the layers are simultaneously formed by coextrusion, the layers are fused across the entire interaction area and are physically inseparable.
  • the materials of the individual layers are selected or adapted to one another by additives so that they have comparable viscosity and melting properties.
  • the modified thermoplastic starch blend preferably consists of the following components:
  • plasticizer preferably glycerin
  • the water content acts as an additional plasticizer.
  • the modified starch blend is mainly responsible for the oxygen barrier effect, by varying the thickness of this layer and the starch content, the gas permeability can be adjusted.
  • the polyester in the modified starch blend is preferably composed of dihydroxy compounds and dicarboxylic acids as monomers.
  • the polyester is particularly preferably a randomly aliphatic-aromatic copolyester made from the monomers butanediol, adipic acid and terephthalic acid or a purely aliphatic polyester made from the monomers
  • the proportion of terephthalic acid must not exceed 30% to ensure biodegradability.
  • such a polyester is also, for example, a polylactide or a blend of a polylactide and another polyester or a
  • the starch blend layer contains no polyester of the following type: polyhydroxyalkanoate copolymer consisting of at least 2 randomly repeating monomer units, a first monomer having the structure (I):
  • R2 represents a C3 to C19 alkyl or C3 to C19 alkenyl radical, or the second monomer has the structure (III):
  • the two outer layers and the polyester component in the starch blend can be formed from the same polyester material or different polyester materials or in each case a mixture of polyester materials.
  • the polyester that forms the outer layers is primarily responsible for the barrier effect against water vapor.
  • the water vapor permeability can thus be adjusted by varying the thickness of the outer layers.
  • Compatibility promoters or phase promoters are preferably polymeric components which each contain block-arranged hydrophilic and hydrophobic groups.
  • the compatibilizer contains a saponified polyvinyl acetate (DE 19750846).
  • other compatibility agents such as “Lotader”, CDT-Chemie, “Novatec”, Mitsubishi Chemicals, Japan, “Surleyn”, DuPont, USA, or “Lonly”, MitsuiToatsu, Japan, can also be used.
  • Polymers with reactive groups such as epoxy or acid anhydride groups, which react with the starch during the processing step, can also be used as compatibilizers (EP 0596437 B2).
  • Migrate compatibility agent in the phase boundary layer and thus increase liability.
  • Processing aids which can be used include erucic acid amide (e.g. Loxamide E from Cognis), stearic acid (Edenor L2SM from Cognis), glycerol monostearate (Edenor GMS 50/2 from Cognis).
  • erucic acid amide e.g. Loxamide E from Cognis
  • stearic acid e.g. stearic acid
  • glycerol monostearate glycerol monostearate
  • the total thickness of the film is preferably 10 ⁇ m to 300 ⁇ m.
  • An outer layer is preferably between 1 ⁇ m and 100 ⁇ m thick.
  • the thickness of the inner layer is preferably between 5 ⁇ m and 250 ⁇ m.
  • the inner layer is preferably 2 times up to 10 times thicker than an outer layer.
  • the film according to the invention is distinguished by the following advantageous properties: good tear strength, good stretch properties,
  • the multilayer film is produced by a coextrusion process in which at least one a.) Layer each consists of a modified thermoplastic
  • the process according to the invention is characterized in that materials with particularly coordinated melting and viscosity properties are selected for the structure of the layers, and in that the high-glare layer contains over 1% to 10% water.
  • the materials preferably have a viscosity with an MFI value between 4 g to 10 g per 10 min at 130 ° C. and 10 kg load or 5 g to 40 g per 10 min at 160 ° C. and 10 kg load.
  • the modified thermoplastic starch blend is passed over a barrier screw with a cross-hole mixing part and melt filter.
  • the temperature of the starch blend must not exceed 160 ° C, since otherwise bound water evaporates, the starch is broken down and the phase stability of the blend is disturbed.
  • a step gradient is preferably run in the extruder, so that a temperature between 100 ° C. and 130 ° C. is maintained for the starch blend component.
  • the starch blend is first melted at around 110 ° C., then heated to 130 ° C., cooled to 125 ° C. and again heated to 135 ° C. for extrusion.
  • the temperature in the extruder is preferably kept between 120 ° C and 140 ° C.
  • the polyester is first melted at around 120 ° C., then heated to 150 ° C., cooled to 140 ° C. and kept at this temperature until it is extruded.
  • temperatures of 150 ° C to 190 ° C are necessary.
  • the modified starch blend in the process according to the invention can contain up to 8% to 10% water without the water evaporating during processing and bubbles forming.
  • the materials from which the layers are built do not have to be dried before processing.
  • the film is preferably inflated in a ratio of 1: 3 to 1: 5.
  • the inflation ratio relates to the ratio of the diameter of the nozzle in the blow head and the film width at the end of the process.
  • the film is particularly surprising, despite the high water content of the starch material, due to its good stretchability.
  • the films can be stretched monoaxially or biaxially at a ratio of 1: 3 to 1: 5. There is no phase separation between starch blend and
  • polyester components of the layers are preferably in a ratio of up to 1: 5, preferably up to
  • Stretching can take place in a temperature range from 30 ° C to 70 ° C.
  • the stretching is preferably carried out at a temperature between 40 ° C. to
  • Stretching advantageously increases and reduces the tensile strength
  • the invention also includes the use of the multilayer film according to the invention for packaging, in particular for food.
  • the following products are used to build up the polyester or high-glare layer:
  • Ecoflex FBX 7011 BASF, Ludwigshafen, is a statistically aliphatic-aromatic copolyester made from the monomers butanediol, adipic acid and terephthalic acid.
  • the proportion of terephthalic acid is less than 30%.
  • PLA 4042 D Cargill Dow LLC, USA, is a polylactide.
  • BlOPar ® 9345 BIOP Biopolymer Technologies AG, Dresden, is a starch blend consisting of starch, compatibilizers, glycerin, processing aids and a variable proportion of a polyester.
  • BlOPar ® 9345/15 contains: approx. 40% to 50% starch
  • BlOPar ® 9345/31 contains 50% EcoFlex FBX 7011 (MFI 10).
  • BlOPar ® 9345/30 contains 40% EcoFlex FBX 7011 (MFI 10).
  • BlOPar ® 9712/23 contains 30% EcoFlex FBX 7011 (MFI 10).
  • BlOPar ® 9713/24 contains 20% EcoFlex FBX 7011 (MFI 10).
  • Ecoflex (3/10) denotes a blend of 50% Ecoflex FBX 7011 (MFI 10) and 50% Ecoflex FBX 7011 (MFI 3).
  • the production of a three-layer film of the ABA type is described, the outer and inner layer (A) being built up from the biodegradable polyester Ecoflex FBX 7011 and the middle layer (B) from the starch blend BlOPar ® 9345-30 or BlOPar ® 9345-15 , The production takes place with a Coex-3 layer blown film line from Windmöller & Hölscher of the type Varex ® ; Optifil Plus; Filmatic-K double winder.
  • This system is equipped with the following components: • Extruder A, Varex ® 60.30 D for the outer layer Ecoflex FBX 7011,
  • a film width of 1,530 mm and film thickness of 40 ⁇ m is achieved with the following parameters:
  • Blow head temperature 130 ° C
  • the description describes the production of a three-layer film of the ABA type with a layer composition analogous to exemplary embodiment 2, with the difference that the production is carried out on a film blown film line from the company Kuehne, machine no. 2002-140312-0100; KFB 45 - 70 - 1,600 BC.
  • This system is equipped with the following components:
  • a film width of 880 mm to 1000 mm and film thickness of 30 ⁇ m is achieved with the following parameters: - Total material throughput: 125 kg / h at
  • Blow head temperature 130 ° C
  • This system is equipped with the following components:
  • a film width of 450 mm to 800 mm and film thickness of 30 ⁇ m to 50 ⁇ m is achieved with the following parameters:
  • the table below compares the mechanical properties of three-layer films of the ABA type, which are produced analogously to Example 4, as a function of the composition of the starch blend used for the middle layer B (variation in polyester content).
  • the biodegradable polyester Ecoflex (3/10) was used for the outer and inner layers A.
  • the films each have a mass ratio between the layers A: B: A of 10:80:10 and a total thickness of 50 ⁇ m.
  • the mechanical properties can be significantly influenced, for example, by the polyester content in the starch blend.
  • a polyester layer was used, which consists of the components Ecoflex
  • the starch blend Biopar 9345/30 was used for the middle layer.
  • the films each have a mass ratio between the layers A: B: A of 15:70:15 and a total thickness of 50 ⁇ m.
  • Embodiment 7 By varying the composition of the polyester components in the layers surrounding the starch blend, the mechanical properties can be significantly improved.
  • composition of the starch blend used for the middle layer B (lines 2, 3 and 5),
  • the three-layer films of type ABA listed in the 4th to 8th line consist of an inner and outer layer A Ecoflex (3/10) *.
  • the composition of the starch blend used for the middle layer B is given in the table (for further information on the product compositions see embodiment 1).
  • the three-layer films each have a mass ratio between the layers A: B: A of 10:80:10.
  • the film listed on the 5th line contains 4% Kronus. Dye in the starch blend layer, the starch blend is otherwise identical to that from lines 3 and 4.
  • the film listed in the 6th line is constructed like the one from line 4 with a higher thickness.
  • composition and production of the film in line 7 corresponds to that from line 6 with the difference that the film was stretched at 60 ° C. in a ratio of 1: 3.
  • Three-layer films of the ABA type which are produced analogously to embodiment 4, are compared as a function of the ratio of the layer thicknesses between the inner, middle and outer layers.
  • the starch blend Biopar 9345/30 was used for the middle layer.
  • the foils each have a total thickness of 50 ⁇ m.
  • Column 1 shows the mass ratio between layers A: B: A as the mass for the ratio of the layer thicknesses.
  • Embodiment 9 By varying the mass ratios of the layers, the tensile strength and tear propagation resistance are significantly improved, while the elongation at break remains surprisingly constant.
  • the biodegradable polyester Ecoflex (3/10) was used for the outer and inner layer A.
  • the films each have a mass ratio between the layers A: B: A of 11:78:11 (lines 1 and 2) and 10:80:10 (lines 3 and 4).
  • Embodiment 2 (lines 1 and 2): 0.8 mm
  • Embodiment 3 (lines 3 and 4): 1.0 mm
  • Embodiment 10 is a diagrammatic representation of Embodiment 10:
  • Type ABA which is produced analogously to embodiment 2, and the influence of a subsequent stretching of the film on the mechanical properties of the film are shown.
  • the biodegradable polyester Ecoflex (3/10) was used for the outer and inner layer A and the starch blend for the middle layer
  • the starting film was at a take-off speed of 11.3 m each
  • the stretching was carried out monoaxially at 60 ° C. and with a stretching ratio of 1: 3.
  • Example 11 Subsequent stretching significantly improves the tensile strength of the film.
  • Embodiment 12 is a diagrammatic representation of Embodiment 12
  • the description describes the production of a three-layer film of type ABC, the outer layer (A) made of the biodegradable polyester Ecoflex FBX 7011, the middle layer (B) made of the starch blend BlOPar ® 9345-30 and the inner layer made of the polylactide PLA 4042 D is built up.

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PCT/DE2003/004157 2002-12-09 2003-12-09 Biologisch abbaubare mehrschichtfolie Ceased WO2004052646A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
ES03812564T ES2385020T3 (es) 2002-12-09 2003-12-09 Película de capas múltiples biodegradable
CA2543306A CA2543306C (en) 2002-12-09 2003-12-09 Biodegradable multi-layer film
US10/538,020 US20070042207A1 (en) 2002-12-09 2003-12-09 Biodegradable multi-layer film
AU2003296535A AU2003296535A1 (en) 2002-12-09 2003-12-09 Biodegradable multi-layer film
JP2004557811A JP4619127B2 (ja) 2002-12-09 2003-12-09 生分解性多層フィルム
AT03812564T ATE549158T1 (de) 2002-12-09 2003-12-09 Biologisch abbaubare mehrschichtfolie
EP03812564A EP1581388B1 (de) 2002-12-09 2003-12-09 Biologisch abbaubare mehrschichtfolie
NO20052785A NO20052785L (no) 2002-12-09 2005-06-09 Bionedbrytbar flersjiktsfilm

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DE2002158227 DE10258227A1 (de) 2002-12-09 2002-12-09 Biologisch abbaubare Mehrschichtfolie

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FR2881985A1 (fr) * 2005-02-11 2006-08-18 A P C A Assemblee Permanente D Materiau multicouches au moins partiellement biodegradable et procede de fabrication correspondant
WO2007060137A3 (de) * 2005-11-23 2007-10-11 Treofan Germany Gmbh & Co Kg Pla-folie mit guten antistatischen eigenschaften
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WO2020008029A1 (fr) 2018-07-06 2020-01-09 Carbiolice Matiere plastique à haute teneur en pla comprenant un ester de citrate
WO2020008030A1 (fr) 2018-07-06 2020-01-09 Carbiolice Matiere plastique à haute teneur en pla comprenant des oligomeres d'acide lactique
WO2020193770A1 (fr) 2019-03-28 2020-10-01 Carbiolice Article multicouche enzyme
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CN110016215A (zh) * 2019-04-12 2019-07-16 南昌航空大学 一种淀粉/聚乳酸复合材料制备的方法
WO2021005205A1 (fr) 2019-07-10 2021-01-14 Carbiolice Matiere plastique à haute teneur en pla comprenant du ppgdge
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JP4619127B2 (ja) 2011-01-26
JP2006508830A (ja) 2006-03-16
AU2003296535A1 (en) 2004-06-30
CA2543306C (en) 2013-07-23
NO20052785L (no) 2005-09-05
ATE549158T1 (de) 2012-03-15
EP1581388B1 (de) 2012-03-14
CN1723123A (zh) 2006-01-18
EP1581388A1 (de) 2005-10-05
EP2399738A1 (de) 2011-12-28
CA2543306A1 (en) 2004-06-24
NO20052785D0 (no) 2005-06-09
ES2385020T3 (es) 2012-07-17
PT1581388E (pt) 2012-06-18
DE10258227A1 (de) 2004-07-15
US20070042207A1 (en) 2007-02-22

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