CA2543306C - Biodegradable multi-layer film - Google Patents
Biodegradable multi-layer film Download PDFInfo
- Publication number
- CA2543306C CA2543306C CA2543306A CA2543306A CA2543306C CA 2543306 C CA2543306 C CA 2543306C CA 2543306 A CA2543306 A CA 2543306A CA 2543306 A CA2543306 A CA 2543306A CA 2543306 C CA2543306 C CA 2543306C
- Authority
- CA
- Canada
- Prior art keywords
- layer
- polyester
- layer film
- film according
- starch
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 229920002472 Starch Polymers 0.000 claims abstract description 61
- 239000008107 starch Substances 0.000 claims abstract description 61
- 235000019698 starch Nutrition 0.000 claims abstract description 61
- 229920000728 polyester Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 22
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 16
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 16
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 16
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 16
- 235000013305 food Nutrition 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000011118 polyvinyl acetate Substances 0.000 claims description 5
- 239000005022 packaging material Substances 0.000 claims description 4
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 4
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 125000001165 hydrophobic group Chemical group 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 230000004888 barrier function Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 129
- 229920005839 ecoflex® Polymers 0.000 description 47
- 238000005516 engineering process Methods 0.000 description 28
- 229920001222 biopolymer Polymers 0.000 description 26
- -1 for example Substances 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N 2-stearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 125000006545 (C1-C9) alkyl group Chemical group 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000013830 Eruca Nutrition 0.000 description 1
- 241000801434 Eruca Species 0.000 description 1
- 241001274660 Modulus Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
Classifications
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- 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
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- 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
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- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- 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
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- 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
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- 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
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- 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
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- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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.]
Abstract
The invention relates to a biodegradable multi-layer film which has a regulatable barrier effect against oxygen, nitrogen, carbon dioxide and steam and is used in the field of packaging, especially for food, or in agriculture. The invention also relates to a method for producing said film. The inventive multi-layer film can be produced by co-extrusion and is formed by at least one starch blend layer consisting of a modified thermoplastic starch blend containing between 1 % and 10 % of water, and a polyester layer consisting of a biodegradable polyester.
Description
Biodegradable Multi-Layer Film The invention relates to a biodegradable multi-layer film with an adjustable barrier effect relative to oxygen (02), nitrogen (N?), carbon dioxide (CO2), and water vapor for use in the packaging industry, in particular, for food or in agriculture, as well as a method for its manufacture.
The following requirements are usually posed on packaging materials, especially for food:
- minimal oxygen permeability (oxygen penetrability), - minimal water vapor penetrability, - excellent mechanical properties, - sealing capability, - stretching capability, - excellent processability in packaging, - inexpensive manufacture, - safe for food, - inexpensive and environmentally friendly disposal.
Packaging materials for fruits and vegetables must also be able to accommodate the natural breathing and ripening process of these products by providing a controlled oxygen and water vapor permeation.
In order to fulfill the requirements of minimal permeability for gases such as 02, N?, and CO?, in the past years mono-layer and multi-layer films on the basis of synthetic polymers have been developed.
In order to fulfill the multitude of requirements, within one film different materials and their different properties are usually combined. The combination of different materials is realized either by:
lamination: subsequent application of a laminate layer on a base layer;
- coextrusion: simultaneous production of several layers in one working step;
blend manufacture: mixing of the materials and extrusion to a layer.
Prerequisites for excellent properties of use of the film are comparable melting points and TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
viscosities of the components during extrusion or coextrusion. These parameters should be very close or can be approximated relative to one another by additives such as compatibilizers or bonding agents, or other additives.
When producing laminated films by melt coating, the requirements with regard to these parameters are not as high as for the other aforementioned methods. The lamination by solvent application is very complex and expensive. Also, the adhesion of the laminate layer on the base layer is usually insufficient.
For packaging films in the food industry, films of synthetic materials are still mostly used today.
They are often comprised of polyvinyl chloride or polyvinylidene chloride. For several years now, also multi-layer films of alternative chlorine-free materials, for example, polyamide, polyethylene, polyvinyl alcohol, have been used. In order to fulfill the criterion of minimal gas permeability, they are also partially coated with aluminum or silicon compounds.
A disadvantage is that these films on the basis of synthetic polymers are not biodegradable.
Because of the lack of environmental safety and because of the high disposal costs, it has been attempted in the last few years to replace these materials with biodegradable materials on the basis of renewable raw materials.
Materials on the basis of biodegradable polymers and renewable raw materials are described in overviews in the following publications:
J. Schroter, Biologisch abbaubare Werkstoffe (BAW), Kunststoffe 89, (1999) 4, pages 101-104;
F. Reckert, Biologisch abbaubare Kunststoffe, Kunststoffe 92 (2002) 1, pages 78-79.
Processing of these renewable biological raw materials is much more difficult than that of synthetic polymers. A reason for the difficult processability resides, for example, in the case of starch, in that it has no defined melting range and only a minimal melt stability. In order to obtain satisfactory melting properties and to become processable, the starch must be pretreated.
The following requirements are usually posed on packaging materials, especially for food:
- minimal oxygen permeability (oxygen penetrability), - minimal water vapor penetrability, - excellent mechanical properties, - sealing capability, - stretching capability, - excellent processability in packaging, - inexpensive manufacture, - safe for food, - inexpensive and environmentally friendly disposal.
Packaging materials for fruits and vegetables must also be able to accommodate the natural breathing and ripening process of these products by providing a controlled oxygen and water vapor permeation.
In order to fulfill the requirements of minimal permeability for gases such as 02, N?, and CO?, in the past years mono-layer and multi-layer films on the basis of synthetic polymers have been developed.
In order to fulfill the multitude of requirements, within one film different materials and their different properties are usually combined. The combination of different materials is realized either by:
lamination: subsequent application of a laminate layer on a base layer;
- coextrusion: simultaneous production of several layers in one working step;
blend manufacture: mixing of the materials and extrusion to a layer.
Prerequisites for excellent properties of use of the film are comparable melting points and TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
viscosities of the components during extrusion or coextrusion. These parameters should be very close or can be approximated relative to one another by additives such as compatibilizers or bonding agents, or other additives.
When producing laminated films by melt coating, the requirements with regard to these parameters are not as high as for the other aforementioned methods. The lamination by solvent application is very complex and expensive. Also, the adhesion of the laminate layer on the base layer is usually insufficient.
For packaging films in the food industry, films of synthetic materials are still mostly used today.
They are often comprised of polyvinyl chloride or polyvinylidene chloride. For several years now, also multi-layer films of alternative chlorine-free materials, for example, polyamide, polyethylene, polyvinyl alcohol, have been used. In order to fulfill the criterion of minimal gas permeability, they are also partially coated with aluminum or silicon compounds.
A disadvantage is that these films on the basis of synthetic polymers are not biodegradable.
Because of the lack of environmental safety and because of the high disposal costs, it has been attempted in the last few years to replace these materials with biodegradable materials on the basis of renewable raw materials.
Materials on the basis of biodegradable polymers and renewable raw materials are described in overviews in the following publications:
J. Schroter, Biologisch abbaubare Werkstoffe (BAW), Kunststoffe 89, (1999) 4, pages 101-104;
F. Reckert, Biologisch abbaubare Kunststoffe, Kunststoffe 92 (2002) 1, pages 78-79.
Processing of these renewable biological raw materials is much more difficult than that of synthetic polymers. A reason for the difficult processability resides, for example, in the case of starch, in that it has no defined melting range and only a minimal melt stability. In order to obtain satisfactory melting properties and to become processable, the starch must be pretreated.
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Thermoplastic starch (TPS) is obtained, for example, by processing with glycerine and water (W09005161).
In order to employ thermoplastic starch as a processable and utilizable material, it must be processed as a blend with other materials in the melt (DE 199 38 672 and DE
100 62 848). Such blends comprised of starch and thermoplastic polymers are disclosed in DE 195 13 237 Al and DE 969212557 T2.
WO 02/059198 Al discloses a mixture of polydihydroxy diacid esters, having defined molecular weight and melting points, and of polylactate. The mixture may contain starch.
Known are methods for cross-linking the starch surface which leads to improvement of the water resistance and permeation behavior (U.S. 6,242,102).
Disclosed in WO 9001043 are aliphatic polyesters (polyhydroxy carboxylic acids) that in solution can be laminated onto pre-manufactured films of hydrophilic polymers, for example, starch. In this connection, the solvents are evaporated after the coating process.
EP 0616569 B1 discloses a laminated film on the basis of starch in which the laminate layer is comprised of natural or synthetic waxes or of a mixture of waxes.
EP 1195401 Al describes also a laminated film in which the laminate layer is described as being selectively permeable for CO, and is made of poly(4-methyl pentene-1).
EP 0495950 discloses the manufacture of laminated films in which a hydrophobic polymer is vapor-deposited onto a hydrophilic starch film.
As in the case of laminated films made of synthetic materials, the disadvantages relating to a complex, expensive manufacture and lack of adhesion of the laminate layer on the base film apply to these laminates.
A high selective permeability for CO2 and excellent barrier effect relative to water vapor is
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Thermoplastic starch (TPS) is obtained, for example, by processing with glycerine and water (W09005161).
In order to employ thermoplastic starch as a processable and utilizable material, it must be processed as a blend with other materials in the melt (DE 199 38 672 and DE
100 62 848). Such blends comprised of starch and thermoplastic polymers are disclosed in DE 195 13 237 Al and DE 969212557 T2.
WO 02/059198 Al discloses a mixture of polydihydroxy diacid esters, having defined molecular weight and melting points, and of polylactate. The mixture may contain starch.
Known are methods for cross-linking the starch surface which leads to improvement of the water resistance and permeation behavior (U.S. 6,242,102).
Disclosed in WO 9001043 are aliphatic polyesters (polyhydroxy carboxylic acids) that in solution can be laminated onto pre-manufactured films of hydrophilic polymers, for example, starch. In this connection, the solvents are evaporated after the coating process.
EP 0616569 B1 discloses a laminated film on the basis of starch in which the laminate layer is comprised of natural or synthetic waxes or of a mixture of waxes.
EP 1195401 Al describes also a laminated film in which the laminate layer is described as being selectively permeable for CO, and is made of poly(4-methyl pentene-1).
EP 0495950 discloses the manufacture of laminated films in which a hydrophobic polymer is vapor-deposited onto a hydrophilic starch film.
As in the case of laminated films made of synthetic materials, the disadvantages relating to a complex, expensive manufacture and lack of adhesion of the laminate layer on the base film apply to these laminates.
A high selective permeability for CO2 and excellent barrier effect relative to water vapor is
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achieved according to DE 19613484 Al also by single-layer films of blends of starch acetate and aliphatic straight-chain or branched polycarbonates. A disadvantage is that the starch acetate must first be manufactured in a complex process.
EP 0647184 discloses a multi-layer film of a moisture-sensitive polymer and thermally sensitive polymers and additional components.
WO 03/035753 (published May 1, 2003) discloses compositions in the form of a film comprised of the components destructured starch and polyhydroxy alkanoate copolymer (PHA) with a defined structure of at least two randomly repeating monomer units. This mixture is used inter alia for producing a laminated film in which at least one layer is comprised of this mixture.
In WO 9116375, Tomka describes the manufacture by coextrusion of a multi-layer film comprised of thermoplastically processable starch with a polyethylene layer or polypropylene layer and a bonding agent for improving adhesion between the layers.
DE 4116404 discloses a polymer mixture and hints at the possibility of using it for producing 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 thermoplastic starch for the middle layer. By adding borax, magnesium sulfate, and calcium carbonate, the water resistance can be further improved.
EP 0537657 B1 discloses a method for manufacturing a multi-layer film of TPS
or a blend of TPS and polyolefins (polyethylene, polypropylene) by using compatibilizers or bonding agents in the form of a block copolymer.
EP 0479964 and U.S. 6,242,102 each disclose a multi-layer film comprised of themioplastically processable starch that contains at least 20 % by weight of an additive and an additional layer of a polyolefin or a polymer blend of starch and polyolefins. As coating variants, coating with silicon monoxide and the application of alkyl siloxanes are mentioned also.
The base material of these last mentioned multi-layer films are comprised of biodegradable
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achieved according to DE 19613484 Al also by single-layer films of blends of starch acetate and aliphatic straight-chain or branched polycarbonates. A disadvantage is that the starch acetate must first be manufactured in a complex process.
EP 0647184 discloses a multi-layer film of a moisture-sensitive polymer and thermally sensitive polymers and additional components.
WO 03/035753 (published May 1, 2003) discloses compositions in the form of a film comprised of the components destructured starch and polyhydroxy alkanoate copolymer (PHA) with a defined structure of at least two randomly repeating monomer units. This mixture is used inter alia for producing a laminated film in which at least one layer is comprised of this mixture.
In WO 9116375, Tomka describes the manufacture by coextrusion of a multi-layer film comprised of thermoplastically processable starch with a polyethylene layer or polypropylene layer and a bonding agent for improving adhesion between the layers.
DE 4116404 discloses a polymer mixture and hints at the possibility of using it for producing 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 thermoplastic starch for the middle layer. By adding borax, magnesium sulfate, and calcium carbonate, the water resistance can be further improved.
EP 0537657 B1 discloses a method for manufacturing a multi-layer film of TPS
or a blend of TPS and polyolefins (polyethylene, polypropylene) by using compatibilizers or bonding agents in the form of a block copolymer.
EP 0479964 and U.S. 6,242,102 each disclose a multi-layer film comprised of themioplastically processable starch that contains at least 20 % by weight of an additive and an additional layer of a polyolefin or a polymer blend of starch and polyolefins. As coating variants, coating with silicon monoxide and the application of alkyl siloxanes are mentioned also.
The base material of these last mentioned multi-layer films are comprised of biodegradable
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starch but, disadvantageously, all these films contain also polyolefins, for example, polyethylene or polypropylene or other materials that are not biodegradable.
The processing technology of stretching known in connection with plastic films cannot be applied easily to films of starch because as a result of the stretching process a phase separation of the starch and the other polymer phase takes place which leads to unusable films.
EP 0537657 B1 traces these bad stretching properties back to the high water contents of the known starch blends and proposes a method according to which the water contents of the employed starch blend that is permissible for coextrusion must be less than 1 %.
In order to obtain such a low water contents, the employed TPS must be dried from a water contents of approximately 18 % to one of less than 1 %. A disadvantage is that the drying process heavily stresses the material.
The object of the present intention is providing a multi-layer film for use in packaging which multi-layer film is completely biodegradable, has a minimal oxygen permeability, is stretchable, and has a defined barrier effect relative to N-), C07, and water vapor.
According to the invention, this object is solved by a multi-layer film obtainable by coextrusion, that is comprised, respectively, of at least a) one starch blend layer comprised of a modified thermoplastic starch blend and b) one polyester layer comprised of a biodegradable polyester.
The film is comprised of at least two layers. Preferably, it is comprised of an inner layer that is surrounded by two outer layers.
As a result of the manufacturing process in which the materials for all layers are melted and the layers are formed simultaneously by coextrusion, the layers are fused across the complete
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starch but, disadvantageously, all these films contain also polyolefins, for example, polyethylene or polypropylene or other materials that are not biodegradable.
The processing technology of stretching known in connection with plastic films cannot be applied easily to films of starch because as a result of the stretching process a phase separation of the starch and the other polymer phase takes place which leads to unusable films.
EP 0537657 B1 traces these bad stretching properties back to the high water contents of the known starch blends and proposes a method according to which the water contents of the employed starch blend that is permissible for coextrusion must be less than 1 %.
In order to obtain such a low water contents, the employed TPS must be dried from a water contents of approximately 18 % to one of less than 1 %. A disadvantage is that the drying process heavily stresses the material.
The object of the present intention is providing a multi-layer film for use in packaging which multi-layer film is completely biodegradable, has a minimal oxygen permeability, is stretchable, and has a defined barrier effect relative to N-), C07, and water vapor.
According to the invention, this object is solved by a multi-layer film obtainable by coextrusion, that is comprised, respectively, of at least a) one starch blend layer comprised of a modified thermoplastic starch blend and b) one polyester layer comprised of a biodegradable polyester.
The film is comprised of at least two layers. Preferably, it is comprised of an inner layer that is surrounded by two outer layers.
As a result of the manufacturing process in which the materials for all layers are melted and the layers are formed simultaneously by coextrusion, the layers are fused across the complete
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interaction surface and are physically inseparably connected to one another.
The materials of the individual layers are selected such or matched to one another by additives such that they have comparable viscosity and melting properties.
The modified thermoplastic starch blend is comprised preferably of the following components:
3010 75 %, preferably 40 to 75 %, starch 2 to 10 % water to 50 % preferably 15 to 40 %, biodegradable polyester, 5 to 20 % compatibilizer, up to 10 % plasticizer, up to 3 % processing agent.
In order to increase flowability, up to 10 % plasticizers, preferably glycerine, are admixed. The water contents acts as an additional plasticizer.
The modified starch blend is mainly responsible for the oxygen barrier effect;
by variation of the thickness of this layer and of the starch contents the gas permeability can be adjusted.
The polyester in the modified starch blend as well as the polyester employed for the outer layer is preferably composed of dihydroxy compounds and dicarboxylic acids as monomers.
The polyester is especially preferred a statistic aliphatic-aromatic copolyester that is composed of the monomers butanediol, adipic acid and terephthalic acid or a purely aliphatic polyester that is composed of the monomers butanediol, succinic acid, and adipic acid. The proportion of terephthalic acid should not surpass 30 % in order to ensure the biodegradability.
As an alternative, such a polyester can also be, for example, a polylactide or a blend of a polylactide and another polyester or a polyvinyl acetate (PVAc).
The starch blend layer contains no polyester of the following type:
polyhydroxyalkanoate copolymer comprised of at least two randomly repeating monomer units, wherein a first
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interaction surface and are physically inseparably connected to one another.
The materials of the individual layers are selected such or matched to one another by additives such that they have comparable viscosity and melting properties.
The modified thermoplastic starch blend is comprised preferably of the following components:
3010 75 %, preferably 40 to 75 %, starch 2 to 10 % water to 50 % preferably 15 to 40 %, biodegradable polyester, 5 to 20 % compatibilizer, up to 10 % plasticizer, up to 3 % processing agent.
In order to increase flowability, up to 10 % plasticizers, preferably glycerine, are admixed. The water contents acts as an additional plasticizer.
The modified starch blend is mainly responsible for the oxygen barrier effect;
by variation of the thickness of this layer and of the starch contents the gas permeability can be adjusted.
The polyester in the modified starch blend as well as the polyester employed for the outer layer is preferably composed of dihydroxy compounds and dicarboxylic acids as monomers.
The polyester is especially preferred a statistic aliphatic-aromatic copolyester that is composed of the monomers butanediol, adipic acid and terephthalic acid or a purely aliphatic polyester that is composed of the monomers butanediol, succinic acid, and adipic acid. The proportion of terephthalic acid should not surpass 30 % in order to ensure the biodegradability.
As an alternative, such a polyester can also be, for example, a polylactide or a blend of a polylactide and another polyester or a polyvinyl acetate (PVAc).
The starch blend layer contains no polyester of the following type:
polyhydroxyalkanoate copolymer comprised of at least two randomly repeating monomer units, wherein a first
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monomer has the structure (I):
-0-CH-PHOry-0-1 (1) wherein R1 is H or a C1 or C2 alkyl group, with n = 1 or 2;
wherein a second monomer has the structure (II):
(H) t.
wherein R2 is a C3 to C 1 9 alkyl or C3 to C 1 9 alkenyl group, or the second monomer has the structure (III):
-0-(CH2)m-e-wherein m is from 2 to 9.
The two outer layers and the polyester proportion in the starch blend can be composed of the same polyester material or different polyester materials or a mixture of polyester materials, respectively.
The polyester forming the outer layers is mainly responsible for the barrier effect against water vapor. By variation of the thickness of the outer layer, the water vapor permeability can be adjusted.
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monomer has the structure (I):
-0-CH-PHOry-0-1 (1) wherein R1 is H or a C1 or C2 alkyl group, with n = 1 or 2;
wherein a second monomer has the structure (II):
(H) t.
wherein R2 is a C3 to C 1 9 alkyl or C3 to C 1 9 alkenyl group, or the second monomer has the structure (III):
-0-(CH2)m-e-wherein m is from 2 to 9.
The two outer layers and the polyester proportion in the starch blend can be composed of the same polyester material or different polyester materials or a mixture of polyester materials, respectively.
The polyester forming the outer layers is mainly responsible for the barrier effect against water vapor. By variation of the thickness of the outer layer, the water vapor permeability can be adjusted.
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As the compatibilizers or phase intermediating agent preferably polymer components are used that contain hydrophilic and hydrophobic groups arranged in blocks, respectively. The compatibilizer contains especially preferred a block-saponified polyvinyl acetate (DE
19750846). Alternatively, other compatibilizers such as gLotader(0}, CDT
Chemie;
ANovatecg, Mitsubishi Chemicals, Japan; ASurleyng, DuPont, USA; or ALonly(q,), MitsuiToatsu, Japan, can be used. As compatibilizers, polymers with reactive groups such as epoxy or acid anhydride groups that react during processing with the starch can also be used (EP
0596437 B2).
Surprisingly, it was found that the effect of the compatibilizer is not only important for the stability of the blend but also for the strength of the adhesive layer between the inner and outer layers of the multi-layer film. This is based presumably on the fact that the hydrophilic and hydrophobic block segments of the compatibilizing agent migrate into the phase boundary layer and increase adhesion in this way.
Inter alia, eruca acid amide (for example, Loxamid E of the firm Cognis), stearic acid (Edenor L2SM of the firm Cognis), glycerine mono stearate (Edenor GMS 50/2 of the firm Cognis) can be used as processing agents.
Preferably, the total thickness of the film is 10 gm to 300 gm. In this connection, an outer layer preferably has a thickness between 1 1.un to 100 gm. The thickness of the inner layer is preferably between 5 gm and 250 m.
Preferably, the inner layer is two times to 10 times thicker than an outer layer.
The film according to the present intention is characterized by the following advantageous properties:
- excellent tear strength, - excellent stretching properties, - stretching capability (up to a factor of 1:5), excellent sealing capability, - complete biodegradability;
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As the compatibilizers or phase intermediating agent preferably polymer components are used that contain hydrophilic and hydrophobic groups arranged in blocks, respectively. The compatibilizer contains especially preferred a block-saponified polyvinyl acetate (DE
19750846). Alternatively, other compatibilizers such as gLotader(0}, CDT
Chemie;
ANovatecg, Mitsubishi Chemicals, Japan; ASurleyng, DuPont, USA; or ALonly(q,), MitsuiToatsu, Japan, can be used. As compatibilizers, polymers with reactive groups such as epoxy or acid anhydride groups that react during processing with the starch can also be used (EP
0596437 B2).
Surprisingly, it was found that the effect of the compatibilizer is not only important for the stability of the blend but also for the strength of the adhesive layer between the inner and outer layers of the multi-layer film. This is based presumably on the fact that the hydrophilic and hydrophobic block segments of the compatibilizing agent migrate into the phase boundary layer and increase adhesion in this way.
Inter alia, eruca acid amide (for example, Loxamid E of the firm Cognis), stearic acid (Edenor L2SM of the firm Cognis), glycerine mono stearate (Edenor GMS 50/2 of the firm Cognis) can be used as processing agents.
Preferably, the total thickness of the film is 10 gm to 300 gm. In this connection, an outer layer preferably has a thickness between 1 1.un to 100 gm. The thickness of the inner layer is preferably between 5 gm and 250 m.
Preferably, the inner layer is two times to 10 times thicker than an outer layer.
The film according to the present intention is characterized by the following advantageous properties:
- excellent tear strength, - excellent stretching properties, - stretching capability (up to a factor of 1:5), excellent sealing capability, - complete biodegradability;
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safe for food.
According to the invention, the multi-layer film is produced by a method of coextrusion in which, respectively, at least one a) layer comprised of a modified thermoplastic starch blend and b) layer comprised of a biodegradable polyester are formed simultaneously.
The method of coextrusion including the variants of blow coextrusion and wide slot extrusions are known in general. Both variants can be alternatively employed for the method according to the invention. Preferably, blow coextrusion is used.
The method according to the invention is characterized in that for the structure of the layers materials are selected that have specially matched melting and viscosity properties and in that the starch blend layer contains more than 1 % to 10 % water.
Preferably, the materials have a viscosity with an MFI value between 4 g to 10 g per 10 minutes at 130 C and 10 kg load or 5 g to 40 g per 10 minutes at 160 C and 10 kg load.
The modified thermoplastic starch blend is guided through a barrier screw having a cross hole mixing device and a melt filter.
The temperature of the starch blend should not surpass 160 C because the bonded water would otherwise evaporate, a decomposition of the starch would take place, and the phase stability of the blend would be disturbed.
The extruder is preferably operated at a stepped gradient so that for the starch blend component a temperature between 100 C and 130 C is maintained. Especially preferred, the starch blend is melted first at approximately 110 C, is then heated to 130 C, cooled to 125 C, and then heated again for extrusion to 135 C.
For producing the polyester layer, preferably the temperature in the extruder is kept between 120 C and 140 C. Especially preferred, the polyester is melted first at approximately 120 C, then
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safe for food.
According to the invention, the multi-layer film is produced by a method of coextrusion in which, respectively, at least one a) layer comprised of a modified thermoplastic starch blend and b) layer comprised of a biodegradable polyester are formed simultaneously.
The method of coextrusion including the variants of blow coextrusion and wide slot extrusions are known in general. Both variants can be alternatively employed for the method according to the invention. Preferably, blow coextrusion is used.
The method according to the invention is characterized in that for the structure of the layers materials are selected that have specially matched melting and viscosity properties and in that the starch blend layer contains more than 1 % to 10 % water.
Preferably, the materials have a viscosity with an MFI value between 4 g to 10 g per 10 minutes at 130 C and 10 kg load or 5 g to 40 g per 10 minutes at 160 C and 10 kg load.
The modified thermoplastic starch blend is guided through a barrier screw having a cross hole mixing device and a melt filter.
The temperature of the starch blend should not surpass 160 C because the bonded water would otherwise evaporate, a decomposition of the starch would take place, and the phase stability of the blend would be disturbed.
The extruder is preferably operated at a stepped gradient so that for the starch blend component a temperature between 100 C and 130 C is maintained. Especially preferred, the starch blend is melted first at approximately 110 C, is then heated to 130 C, cooled to 125 C, and then heated again for extrusion to 135 C.
For producing the polyester layer, preferably the temperature in the extruder is kept between 120 C and 140 C. Especially preferred, the polyester is melted first at approximately 120 C, then
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heated to 150 C, cooled to 140 C, and is kept at this temperature up to the step of extrusion.
When employing polylactides for the polyester layer, temperatures of 150 C to 190 C are necessary.
Surprisingly, the modified starch blend may contain in the inventive method up to 8 % to 10 %
water without the water being evaporated during processing and bubbles being formed.
Advantageously, the materials of which the layers are comprised must not be dried before processing.
During extrusion, the film is preferably blown at a ratio of 1:3 to 1:5. The blow ratio refers to the ratio of the diameter of the die in the blow head and the film width at the end of the process.
Surprisingly, for a blow ratio of 1:5 no phase separation or layer separation occurs.
The following parameters are often tightly interwoven in regard to the morphological characteristics and cannot be varied independently of one another:
type, size of the extruder, weight ratios of the components in the starch blend, - screw geometry, temperature, residence time, - shearing speed, viscosity ratio of the components under the shearing conditions, duration of shearing load, - boundary surface energy.
Surprisingly, it was found that the Na acetate residues of approximately 1.5-3.0 % by weight remaining upon manufacture of the compatibilizer act as a water binding agent in the blend and therefore do not disturb the coextrusion.
Especially surprising is that the film, despite the high water contents of the starch material,
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heated to 150 C, cooled to 140 C, and is kept at this temperature up to the step of extrusion.
When employing polylactides for the polyester layer, temperatures of 150 C to 190 C are necessary.
Surprisingly, the modified starch blend may contain in the inventive method up to 8 % to 10 %
water without the water being evaporated during processing and bubbles being formed.
Advantageously, the materials of which the layers are comprised must not be dried before processing.
During extrusion, the film is preferably blown at a ratio of 1:3 to 1:5. The blow ratio refers to the ratio of the diameter of the die in the blow head and the film width at the end of the process.
Surprisingly, for a blow ratio of 1:5 no phase separation or layer separation occurs.
The following parameters are often tightly interwoven in regard to the morphological characteristics and cannot be varied independently of one another:
type, size of the extruder, weight ratios of the components in the starch blend, - screw geometry, temperature, residence time, - shearing speed, viscosity ratio of the components under the shearing conditions, duration of shearing load, - boundary surface energy.
Surprisingly, it was found that the Na acetate residues of approximately 1.5-3.0 % by weight remaining upon manufacture of the compatibilizer act as a water binding agent in the blend and therefore do not disturb the coextrusion.
Especially surprising is that the film, despite the high water contents of the starch material,
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exhibits excellent stretching properties.
The films can be stretched at a ratio of 1:3 to 1:5 mono-axially as well as biaxially. No phase separation between the starch blend and the polyester components of the layers is observed.
Preferably, the films are stretched at a ratio up to 1:5, preferred up to 1:4.
Stretching can be carried out in a temperature range of 30 C to 70 C. Preferably, stretching is carried out at a temperature between 40 C to 60 C.
Advantageously, stretching increases the tensile strength and reduces the expansibility of the film.
The invention also includes the utilization of the multi-layer film according to the invention for packagings, in particular for food.
The invention will be explained in more detail with the aid of the following embodiments.
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exhibits excellent stretching properties.
The films can be stretched at a ratio of 1:3 to 1:5 mono-axially as well as biaxially. No phase separation between the starch blend and the polyester components of the layers is observed.
Preferably, the films are stretched at a ratio up to 1:5, preferred up to 1:4.
Stretching can be carried out in a temperature range of 30 C to 70 C. Preferably, stretching is carried out at a temperature between 40 C to 60 C.
Advantageously, stretching increases the tensile strength and reduces the expansibility of the film.
The invention also includes the utilization of the multi-layer film according to the invention for packagings, in particular for food.
The invention will be explained in more detail with the aid of the following embodiments.
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BIOPOLYMER Technologies AG
Example 1 In the following examples, the following products are used for producing the polyesters or starch blend layer.
EcoflexTM FBX 7011, BASF, Ludwigshafen, is a statistic aliphatic-aromatic copolyester composed of 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.
BIOPar7TM 9345, BIOP Biopolymer Technologies AG, Dresden, is a starch blend comprised of starch, compatibilizers, glycerine, processing agents and a variable proportion of a polyester.
BIOPar7 9345/15 contains:
approximately 40 % to 50 % starch, % to 20 % compatibilizer, 1 % to 3 % processing agent, % to 50 % EcoFlex FBX 7011 (MFI 10) 10 % glycerine.
The following starch blends are composed analogously but contain different proportions of polyester:
BIOPar7 9345/31 contains 50 % EcoFlex FBX 7011 (MFI 10) BIOPar7 9345/30 contains 40 % EcoFlex FBX 7011 (MFI 10) BIOPar7 9312/23 contains 30 % EcoFlex FBX 7011 (MFI 10) BIOPar7 9313/24 contains 20 % EcoFlex FBX 7011 (MFI 10) In the following table the viscosities and melting temperatures of the components used for the layer structure of the multi-layer films are compared.
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Example 1 In the following examples, the following products are used for producing the polyesters or starch blend layer.
EcoflexTM FBX 7011, BASF, Ludwigshafen, is a statistic aliphatic-aromatic copolyester composed of 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.
BIOPar7TM 9345, BIOP Biopolymer Technologies AG, Dresden, is a starch blend comprised of starch, compatibilizers, glycerine, processing agents and a variable proportion of a polyester.
BIOPar7 9345/15 contains:
approximately 40 % to 50 % starch, % to 20 % compatibilizer, 1 % to 3 % processing agent, % to 50 % EcoFlex FBX 7011 (MFI 10) 10 % glycerine.
The following starch blends are composed analogously but contain different proportions of polyester:
BIOPar7 9345/31 contains 50 % EcoFlex FBX 7011 (MFI 10) BIOPar7 9345/30 contains 40 % EcoFlex FBX 7011 (MFI 10) BIOPar7 9312/23 contains 30 % EcoFlex FBX 7011 (MFI 10) BIOPar7 9313/24 contains 20 % EcoFlex FBX 7011 (MFI 10) In the following table the viscosities and melting temperatures of the components used for the layer structure of the multi-layer films are compared.
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component melt viscosity MFI melt viscosity MFI melting at 130 C and at 160 C and temperature (DSC) 10.0 kg load 10.0 kg load ( C) (g/10 min) (g/10 min) Ecoflex FBX 7011 5.4 33.5 110-115 (MFI 3) Ecoflex FBX 7011 10 appr. 40 1 10-1 15 (MFI 10) BIOPar7 9345/31 9.1 18.8 BIOPar7 9345/30 8.8 18.7 BIOPar7 9345/15 8.2 18.7 BIOPar7 9712/23 4.3 9.6 BIOPar7 9713/24 1.4 5.2 Ecoflex (3/10)* 6.9 appr. 19 PLA 4042 D 3.8 200 blend of 75 % 33 Ecoflex (3/10)* and blend of 60 % 26.5 Ecoflex (3/10)* and 40 % PLA 4042 D
blend of 45 % 17.2 Ecoflex (3/10)* and 55 % PLA 4042D
*Ecoflex (3/10) defines a blend of 50 % Ecoflex FBX 7011 (MFI 10) and 50 %
Ecoflex FBX
7011 (MFI 3).
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component melt viscosity MFI melt viscosity MFI melting at 130 C and at 160 C and temperature (DSC) 10.0 kg load 10.0 kg load ( C) (g/10 min) (g/10 min) Ecoflex FBX 7011 5.4 33.5 110-115 (MFI 3) Ecoflex FBX 7011 10 appr. 40 1 10-1 15 (MFI 10) BIOPar7 9345/31 9.1 18.8 BIOPar7 9345/30 8.8 18.7 BIOPar7 9345/15 8.2 18.7 BIOPar7 9712/23 4.3 9.6 BIOPar7 9713/24 1.4 5.2 Ecoflex (3/10)* 6.9 appr. 19 PLA 4042 D 3.8 200 blend of 75 % 33 Ecoflex (3/10)* and blend of 60 % 26.5 Ecoflex (3/10)* and 40 % PLA 4042 D
blend of 45 % 17.2 Ecoflex (3/10)* and 55 % PLA 4042D
*Ecoflex (3/10) defines a blend of 50 % Ecoflex FBX 7011 (MFI 10) and 50 %
Ecoflex FBX
7011 (MFI 3).
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Example 2 Described is the manufacture of a three-layer film of the type ABA wherein the outer and inner layer (A) is comprised of a biodegradable polyester Ecoflex FBX 7011 and the middle layer (B) is comprised of the starch blend BIOPar7 9345-30 or BIOPar7 9345-15.
The manufacture is carried out with a Coex3TM layer blow film device of the firm Windmoller & Holscher of the type Varex7TM; Optifil PIUSTM, Fi1maticKTM dual winder.
This device is equipped with the following components.
- extruder A, Varex7, 60.30 D for the outer layer Ecoflex FBX 7011;
extruder B, Varex7, 90.30 D for the middle layer BIOPar7 9345-30 with an LTS
screw 37021001;
extruder C, Varex7, 60.30 D for the inner layer Ecoflex FBX 7011;
metering devices for the granular materials and conveying screws with special mixing and homogenization zones and screen changers;
a blown film die for three-layer films having a die diameter of 280 mm, a gap width of 0.8 mm A film width of 1,530 mm and film thickness of 40 [tm is achieved for the following parameters:
- total material throughput to 169.6 kg/h, - pressure outside 280 bar, middle 247 bar, inside 250 bar, and temperatures:
cylinder filter outside: - 120 - 140 - 150 - 140 - 140 - 140 C
cylinder filter middle: - 100- 120- 130- 130- 130- 125- 125- 130 C
cylinder filter inside: - 120 - 140 - 150 - 140 - 140 - 140 C
blow die temperature 130 C
- removal speed 17.7 m/min blow ratio 1:3.5 to 115.
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Example 2 Described is the manufacture of a three-layer film of the type ABA wherein the outer and inner layer (A) is comprised of a biodegradable polyester Ecoflex FBX 7011 and the middle layer (B) is comprised of the starch blend BIOPar7 9345-30 or BIOPar7 9345-15.
The manufacture is carried out with a Coex3TM layer blow film device of the firm Windmoller & Holscher of the type Varex7TM; Optifil PIUSTM, Fi1maticKTM dual winder.
This device is equipped with the following components.
- extruder A, Varex7, 60.30 D for the outer layer Ecoflex FBX 7011;
extruder B, Varex7, 90.30 D for the middle layer BIOPar7 9345-30 with an LTS
screw 37021001;
extruder C, Varex7, 60.30 D for the inner layer Ecoflex FBX 7011;
metering devices for the granular materials and conveying screws with special mixing and homogenization zones and screen changers;
a blown film die for three-layer films having a die diameter of 280 mm, a gap width of 0.8 mm A film width of 1,530 mm and film thickness of 40 [tm is achieved for the following parameters:
- total material throughput to 169.6 kg/h, - pressure outside 280 bar, middle 247 bar, inside 250 bar, and temperatures:
cylinder filter outside: - 120 - 140 - 150 - 140 - 140 - 140 C
cylinder filter middle: - 100- 120- 130- 130- 130- 125- 125- 130 C
cylinder filter inside: - 120 - 140 - 150 - 140 - 140 - 140 C
blow die temperature 130 C
- removal speed 17.7 m/min blow ratio 1:3.5 to 115.
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BIOPOLYMER Technologies AG
Example 3 Described is the manufacture of a three-layer film of the type ABA having a layer composition in analogy to Example 2 with the difference that the manufacture is performed on a layer blow film device of the firm Kuhne, machine No. 2000-140312-0100; KFB 45 - 70 -1.6000 BC.
This device is equipped with the following components:
an outer extruder K 45-24 D C for the outer layer of Ecoflex FBX 7011, -a main extruder K 70-30 D-B with barrier screw for the middle layer of BIOPar7 30, an inner extruder K 45-24 D C for the inner layer of Ecoflex FBX 7011, metering devices for the granular materials, and a blown film die for three-layer films, die diameter 220 mm, die gap 1.0 mm, and appropriate removal systems.
A film width of 880 mm to 1000 mm and film thickness of 30 [tm is achieved for the following parameters:
- total material throughput: 125 kg/h at - pressure: outside 135 bar, middle 260 bar, inside 195 bar, and - temperatures:
cylinder filter outside - 120 - 140 - 150 - 140 - 140 - 140 C, cylinder filter middle - 100 - 120 - 130 - 130 - 130 - 125 - 125 - 130 C, cylinder filter inside - 120 - 140 - 150 - 140 - 140 - 140 C, blow die temperature 130 C, - blow ratio is 1:2 to 1:4, removal speed 20 m/min.
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Example 3 Described is the manufacture of a three-layer film of the type ABA having a layer composition in analogy to Example 2 with the difference that the manufacture is performed on a layer blow film device of the firm Kuhne, machine No. 2000-140312-0100; KFB 45 - 70 -1.6000 BC.
This device is equipped with the following components:
an outer extruder K 45-24 D C for the outer layer of Ecoflex FBX 7011, -a main extruder K 70-30 D-B with barrier screw for the middle layer of BIOPar7 30, an inner extruder K 45-24 D C for the inner layer of Ecoflex FBX 7011, metering devices for the granular materials, and a blown film die for three-layer films, die diameter 220 mm, die gap 1.0 mm, and appropriate removal systems.
A film width of 880 mm to 1000 mm and film thickness of 30 [tm is achieved for the following parameters:
- total material throughput: 125 kg/h at - pressure: outside 135 bar, middle 260 bar, inside 195 bar, and - temperatures:
cylinder filter outside - 120 - 140 - 150 - 140 - 140 - 140 C, cylinder filter middle - 100 - 120 - 130 - 130 - 130 - 125 - 125 - 130 C, cylinder filter inside - 120 - 140 - 150 - 140 - 140 - 140 C, blow die temperature 130 C, - blow ratio is 1:2 to 1:4, removal speed 20 m/min.
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Example 4 Described is the manufacture of a three-layer film of the type ABA having a layer composition in analogy to example 2 with the difference that the manufacture is performed on a research device of the firm BFA Plastic GmbH, Rossdorf.
This device is equipped with the following components:
- an outer extruder BFA 30-25, LD 1:25, PE screw with mixing head for the outer layer of Ecoflex FBX 7011, - a main extruder of the type BattenfeldTM Uni-Ex 1-45-25 B, LD 1:25, with barrier screw, screw diameter 45 mm, PE screw and Maddock element for the middle layer of BIOPar7 9345-30, = an inner extruder BFA 30-25, LD 1:25, PE screw with mixing head for the inner layer of Ecoflex FBX 7011, metering devices for the granular materials in the form of ConProTM
Gravimetric Feedhoppers Type KTW G3, and a blown film die for mono-layer or 3-5 layer films, die diameter 80 mm, die gap 1.0 mm, and - appropriate removal systems.
A film width of 450 mm to 8000 mm and film thickness of 30 um to 50 p.m is achieved for the following parameters:
- total material throughput 20 kg/h at - pressure: outside 220 bar, middle 380 bar, inside 220 bar, and - temperatures:
cylinder filter outside: - 140 - 151 - 155 - 145 - 142 C
cylinder filter middle: - 110 - 140 - 140 - 135 - 135 C
cylinder filter inside: - 140 - 151 - 155 - 145 - 142 C
blow die temperature 130 C
- blow ratio 1:3.2 - removal speed 8 m/min.
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Example 4 Described is the manufacture of a three-layer film of the type ABA having a layer composition in analogy to example 2 with the difference that the manufacture is performed on a research device of the firm BFA Plastic GmbH, Rossdorf.
This device is equipped with the following components:
- an outer extruder BFA 30-25, LD 1:25, PE screw with mixing head for the outer layer of Ecoflex FBX 7011, - a main extruder of the type BattenfeldTM Uni-Ex 1-45-25 B, LD 1:25, with barrier screw, screw diameter 45 mm, PE screw and Maddock element for the middle layer of BIOPar7 9345-30, = an inner extruder BFA 30-25, LD 1:25, PE screw with mixing head for the inner layer of Ecoflex FBX 7011, metering devices for the granular materials in the form of ConProTM
Gravimetric Feedhoppers Type KTW G3, and a blown film die for mono-layer or 3-5 layer films, die diameter 80 mm, die gap 1.0 mm, and - appropriate removal systems.
A film width of 450 mm to 8000 mm and film thickness of 30 um to 50 p.m is achieved for the following parameters:
- total material throughput 20 kg/h at - pressure: outside 220 bar, middle 380 bar, inside 220 bar, and - temperatures:
cylinder filter outside: - 140 - 151 - 155 - 145 - 142 C
cylinder filter middle: - 110 - 140 - 140 - 135 - 135 C
cylinder filter inside: - 140 - 151 - 155 - 145 - 142 C
blow die temperature 130 C
- blow ratio 1:3.2 - removal speed 8 m/min.
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BIOPOLYMER Technologies AG
Example 5 In the following table the mechanical properties of three-layer films of the type ABA produced in analogy to Example 4 are compared as a function of the composition of the starch blend for the middle layer B (variation polyester components). For the outer and inner layers A the biodegradable polyester Ecoflex (3/10) was used, respectively.
The films each have a mass ratio of the layers A:B:A of 10:80:10 and a total thickness of 50 lam.
They were produced at a removal speed of 8 m per minute and a blow ratio of 1:3.2 to 1:3.3.
composition of measuring modulus tensile elongatio tear impact middle layer B direction of strengt n at tear strength strength elasticity h (%) (cN/mm (J/mm) (MPa) (MPa) Biopar extrusion 130 12.1 393 608 2.92 expansion 171 13.0 495 1184 containing 40 Ecoflex (3/10) Biopar extrusion 171 10.7 226 464 3.0 expansion 129 10.2 346 880 containing 30 Ecoflex (3/10) Biopar extrusion 222 7.1 64 272 0.8 expansion 161 6.2 82 400 containing20 % Ecoflex (3/10)
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Example 5 In the following table the mechanical properties of three-layer films of the type ABA produced in analogy to Example 4 are compared as a function of the composition of the starch blend for the middle layer B (variation polyester components). For the outer and inner layers A the biodegradable polyester Ecoflex (3/10) was used, respectively.
The films each have a mass ratio of the layers A:B:A of 10:80:10 and a total thickness of 50 lam.
They were produced at a removal speed of 8 m per minute and a blow ratio of 1:3.2 to 1:3.3.
composition of measuring modulus tensile elongatio tear impact middle layer B direction of strengt n at tear strength strength elasticity h (%) (cN/mm (J/mm) (MPa) (MPa) Biopar extrusion 130 12.1 393 608 2.92 expansion 171 13.0 495 1184 containing 40 Ecoflex (3/10) Biopar extrusion 171 10.7 226 464 3.0 expansion 129 10.2 346 880 containing 30 Ecoflex (3/10) Biopar extrusion 222 7.1 64 272 0.8 expansion 161 6.2 82 400 containing20 % Ecoflex (3/10)
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BIOPOLYMER Technologies AG
See Example 1 for product compositions.
When varying the composition of the middle layer B, the mechanical properties can be affected significantly, for example, by the polyester proportion in the starch blend.
Example 6 In the following table, the mechanical properties of three-layer films of the type ABA produced in analogy to Example 4 are compared as a function of the composition of the biodegradable polyester employed for the inner and outer layers A. For these layers a polyester was used that is comprised of the components Ecoflex (3/10) and the poly lactide PLA 4042 D.
Column 1 shows the mass proportion of the component PLA 4042 D. The rest of the polyester is comprised of Ecoflex (3/10), respectively. The starch blend Biopar 9345/30 was used for the middle layer, respectively.
The films have a mass ratio of layers A:B:A of 15:70:15 and a total thickness of 50 i_tm. They were removed at a removal speed of 8 m per minute and a blow ratio of 1:3.5.
mass measuring modulus tensile elongatio tear impact proportion of direction of strength n at tear strength strength PLA 4042 D in elasticit (MPa) (%) (cN/mm) (J/mm) the layers A
(%) (MPa) 25 extrusion 134 13.1 386 816 4.00 expansion 74 10.9 397 1344 40 extrusion 328 14.5 286 1312 8.04 expansion 123 256 2560 11.0
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See Example 1 for product compositions.
When varying the composition of the middle layer B, the mechanical properties can be affected significantly, for example, by the polyester proportion in the starch blend.
Example 6 In the following table, the mechanical properties of three-layer films of the type ABA produced in analogy to Example 4 are compared as a function of the composition of the biodegradable polyester employed for the inner and outer layers A. For these layers a polyester was used that is comprised of the components Ecoflex (3/10) and the poly lactide PLA 4042 D.
Column 1 shows the mass proportion of the component PLA 4042 D. The rest of the polyester is comprised of Ecoflex (3/10), respectively. The starch blend Biopar 9345/30 was used for the middle layer, respectively.
The films have a mass ratio of layers A:B:A of 15:70:15 and a total thickness of 50 i_tm. They were removed at a removal speed of 8 m per minute and a blow ratio of 1:3.5.
mass measuring modulus tensile elongatio tear impact proportion of direction of strength n at tear strength strength PLA 4042 D in elasticit (MPa) (%) (cN/mm) (J/mm) the layers A
(%) (MPa) 25 extrusion 134 13.1 386 816 4.00 expansion 74 10.9 397 1344 40 extrusion 328 14.5 286 1312 8.04 expansion 123 256 2560 11.0
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55 extrusion 603 16.5 238 533 10.80 expansion 190 10.0 104 2507 100 extrusion 989 20.6 60 3111 8.71 expansion 993 20.0 53 5600 By varying the composition of the polyester components in the layers that surround the starch blend, the mechanical properties can be significantly improved.
Example 7 In the following table the permeation ratios for the gases 02, N2, CO?
according to DIN 53380 and water vapor according to DIN 53122 (dated 1992) of three-layer films of the type ABA
produced in the analogy to Example 2 are compared as a function of the composition of the starch blend for the middle layer B (rows 2, 3, 5), stretching (rows 6 and 7), humidity (row 8).
composition film relative gas permeation water vapor thickne humidit (cm3/m2 x day x bar) permeation ss (um) y (%) according to DIN (g/(m2 x day) 53380 according to 02 N, CO2 1 Ecoflex FBX 70111 1600* 140 (data from BASF) 2 BIOPar7 37.7 50 40 95 (30 % Ecoflex)
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55 extrusion 603 16.5 238 533 10.80 expansion 190 10.0 104 2507 100 extrusion 989 20.6 60 3111 8.71 expansion 993 20.0 53 5600 By varying the composition of the polyester components in the layers that surround the starch blend, the mechanical properties can be significantly improved.
Example 7 In the following table the permeation ratios for the gases 02, N2, CO?
according to DIN 53380 and water vapor according to DIN 53122 (dated 1992) of three-layer films of the type ABA
produced in the analogy to Example 2 are compared as a function of the composition of the starch blend for the middle layer B (rows 2, 3, 5), stretching (rows 6 and 7), humidity (row 8).
composition film relative gas permeation water vapor thickne humidit (cm3/m2 x day x bar) permeation ss (um) y (%) according to DIN (g/(m2 x day) 53380 according to 02 N, CO2 1 Ecoflex FBX 70111 1600* 140 (data from BASF) 2 BIOPar7 37.7 50 40 95 (30 % Ecoflex)
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3 BIOPar7 9345/15 47 40 14-95 148 (40 % Ecoflex) 4 A: Ecoflex (3/10) 45 40 12 121 B: BIOPar7 A: Ecoflex (3/10) A: Ecoflex (3/10) 30 40 41 57 B: BIOPar7 9383 A: Ecoflex (3/10) 85 770 6 A: Ecoflex (3/10) 70 40 18 110 B: BIOPar7 A: Ecoflex (3/10) 7 A: Ecoflex (3/10) 35 50 128 B: BIOPar 7 A: Ecoflex (3/10) 8 A: Ecoflex (3/10) 55 0 19 95 116 B: BIOPar7 A: Ecoflex (3710)* 85 474 157 4169 For a comparison with the multi-layer films, in rows 1 and 2 and 3 data of mono-layer films made of polyester Ecoflex FBX 7011, the starch blends BIOPar7 37.7 (30 %
polyester), and BIOPar7 9345/15 (40 A polyester) are listed.
The three-layer films of the type ABA listed in rows 4 to 8 are comprised of an inner and outer layer A Ecoflex (3/10)*, respectively. The composition of the starch blend used for the middle layer B is listed in the table (more information regarding the product compositions can be taken from Example 1).
The three-layer films have a mass ratio of the layers A:B:A of 10:80:10.
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3 BIOPar7 9345/15 47 40 14-95 148 (40 % Ecoflex) 4 A: Ecoflex (3/10) 45 40 12 121 B: BIOPar7 A: Ecoflex (3/10) A: Ecoflex (3/10) 30 40 41 57 B: BIOPar7 9383 A: Ecoflex (3/10) 85 770 6 A: Ecoflex (3/10) 70 40 18 110 B: BIOPar7 A: Ecoflex (3/10) 7 A: Ecoflex (3/10) 35 50 128 B: BIOPar 7 A: Ecoflex (3/10) 8 A: Ecoflex (3/10) 55 0 19 95 116 B: BIOPar7 A: Ecoflex (3710)* 85 474 157 4169 For a comparison with the multi-layer films, in rows 1 and 2 and 3 data of mono-layer films made of polyester Ecoflex FBX 7011, the starch blends BIOPar7 37.7 (30 %
polyester), and BIOPar7 9345/15 (40 A polyester) are listed.
The three-layer films of the type ABA listed in rows 4 to 8 are comprised of an inner and outer layer A Ecoflex (3/10)*, respectively. The composition of the starch blend used for the middle layer B is listed in the table (more information regarding the product compositions can be taken from Example 1).
The three-layer films have a mass ratio of the layers A:B:A of 10:80:10.
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The film listed in row 5 contains in the starch blend layer 4 % of a coloring agent; the starch blend is otherwise identical to that of rows 3 and 4. The film listed in row 6 is of the same composition as that of row 4 but has a greater thickness.
The composition and manufacture of the films in row 7 correspond to that of row 6 with the difference that the film was stretched at 60 C at a ratio of 1:3.
When comparing the mono-layer films in rows 1 and 3, the increase of the polyester proportion leads to a strong reduction of the 02 permeation.
The coloring agent proportion of 4 % increases only the 02 permeation values and has no effect on the other measured parameters.
The mono-axial stretching increases the 02 permeation values.
In all films, the increase of permeation values for 02 and water vapor at 85 %
relative humidity relative to the values measured at 40 % is significant. Row 8 shows that with increasing humidity the permeation values increase generally, also for N2 and CO).
BIOPOLYMER Technologies AG
The film listed in row 5 contains in the starch blend layer 4 % of a coloring agent; the starch blend is otherwise identical to that of rows 3 and 4. The film listed in row 6 is of the same composition as that of row 4 but has a greater thickness.
The composition and manufacture of the films in row 7 correspond to that of row 6 with the difference that the film was stretched at 60 C at a ratio of 1:3.
When comparing the mono-layer films in rows 1 and 3, the increase of the polyester proportion leads to a strong reduction of the 02 permeation.
The coloring agent proportion of 4 % increases only the 02 permeation values and has no effect on the other measured parameters.
The mono-axial stretching increases the 02 permeation values.
In all films, the increase of permeation values for 02 and water vapor at 85 %
relative humidity relative to the values measured at 40 % is significant. Row 8 shows that with increasing humidity the permeation values increase generally, also for N2 and CO).
- 21 -Lit. TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
610POLYMER Technologies AG
Example 8 In the following table the mechanical properties of three-layer films of the type ABA produced in analogy to Example 4 are compared as a function of the ratio of the layer thickness of inner, middle and outer layers.
For the outer and inner layer A; the biodegradable polyester Ecoflex (3/10) was used, respectively. For the middle layer, the starch blend Biopar 9345/30 was used.
The films have a total thickness of 50 [nu, respectively. They were produced at a removal speed of 8 m per minute and a blow ratio of 1:3.5.
In column 1, the mass ratio of the layers A:B:A is provided as mass for the ratio of air thicknesses.
mass ratio measuring modulus of tensile elongation tear impact A:B:A direction elasticity strength at tear strength strength (MPa) (MPa) (%) (cN/mm) (J/mm) 10:80:10 extrusion 62 13.9 555 1176 3.44 expansion 64 13.1 579 1344 20:60:20 extrusion 64 15.5 587 15424 3.04 expansion 64 15.5 527 4064 25:50:25 extrusion 61 16.5 573 13984 3.24 expansion 63 15.2 534 14304 By varying the mass ratios of the layers, the tensile strength and tear strength are improved
610POLYMER Technologies AG
Example 8 In the following table the mechanical properties of three-layer films of the type ABA produced in analogy to Example 4 are compared as a function of the ratio of the layer thickness of inner, middle and outer layers.
For the outer and inner layer A; the biodegradable polyester Ecoflex (3/10) was used, respectively. For the middle layer, the starch blend Biopar 9345/30 was used.
The films have a total thickness of 50 [nu, respectively. They were produced at a removal speed of 8 m per minute and a blow ratio of 1:3.5.
In column 1, the mass ratio of the layers A:B:A is provided as mass for the ratio of air thicknesses.
mass ratio measuring modulus of tensile elongation tear impact A:B:A direction elasticity strength at tear strength strength (MPa) (MPa) (%) (cN/mm) (J/mm) 10:80:10 extrusion 62 13.9 555 1176 3.44 expansion 64 13.1 579 1344 20:60:20 extrusion 64 15.5 587 15424 3.04 expansion 64 15.5 527 4064 25:50:25 extrusion 61 16.5 573 13984 3.24 expansion 63 15.2 534 14304 By varying the mass ratios of the layers, the tensile strength and tear strength are improved
- 22 -Lit. TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
significantly while the elongation at tear surprisingly remains constant.
BIOPOLYMER Technologies AG
significantly while the elongation at tear surprisingly remains constant.
- 23 -Lit. TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
Example 9 In the following table the mechanical properties of three-layer films of the type ABA produced in analogy to Example 2 (rows 1 and 2) and in analogy to Example 3 (rows 3 and 4) are compared as a function of the die gap and the removal speed.
For the outer and -inner layer A the biodegradable polyester Ecoflex (3/10) was used, respectively. For the middle layer the starch blend Biopar 9345/15 (row 1 and 2) or Biopar 9345/30 (rows 3 and 4) are used.
The films have a mass ratio between layers A:B:A of 11:78:11 (rows 1 and 2) and 10:80:10 (rows 3 and 4).
An important parameter that differentiates the devices used in Example 2 (rows 1 and 2) and in Example 3 (rows 3 and 4) is the die gap of the blow die:
Example 2 (rows 1 and 2): 0.8 mm Example 3 (rows 3 and 4): 1.0 mm remova total blow measurin modulu tensile elongatio tear impact 1 speed thickness ratio g s of strengt n at tear strength strengt (m/min (pm) direction elasticit h (%) (cN/m h (MPa) m) (J/mm) (MPa) 1 32.0 30 1:3.4 extr.* 49 19.9 718 6044 2.60 2 17.6 50 1:3.4 extr.* 125 16.2 1085 693 4.2 3 30.3 30 1:2.5 extr.* 118 13.7 274 1013 3.2 exp.* 106 10.2 467 4213
BIOPOLYMER Technologies AG
Example 9 In the following table the mechanical properties of three-layer films of the type ABA produced in analogy to Example 2 (rows 1 and 2) and in analogy to Example 3 (rows 3 and 4) are compared as a function of the die gap and the removal speed.
For the outer and -inner layer A the biodegradable polyester Ecoflex (3/10) was used, respectively. For the middle layer the starch blend Biopar 9345/15 (row 1 and 2) or Biopar 9345/30 (rows 3 and 4) are used.
The films have a mass ratio between layers A:B:A of 11:78:11 (rows 1 and 2) and 10:80:10 (rows 3 and 4).
An important parameter that differentiates the devices used in Example 2 (rows 1 and 2) and in Example 3 (rows 3 and 4) is the die gap of the blow die:
Example 2 (rows 1 and 2): 0.8 mm Example 3 (rows 3 and 4): 1.0 mm remova total blow measurin modulu tensile elongatio tear impact 1 speed thickness ratio g s of strengt n at tear strength strengt (m/min (pm) direction elasticit h (%) (cN/m h (MPa) m) (J/mm) (MPa) 1 32.0 30 1:3.4 extr.* 49 19.9 718 6044 2.60 2 17.6 50 1:3.4 extr.* 125 16.2 1085 693 4.2 3 30.3 30 1:2.5 extr.* 118 13.7 274 1013 3.2 exp.* 106 10.2 467 4213
- 24 -Lit. TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
4 21.3 30 1:3.6 extr.* 114 11.7 361 5813 2.67 exp.* 90 10.6 446 2933 *extr. = extrusion; exp. = expansion The results show clearly that for a die gap of 0.8 mm (rows 1 and 2) in comparison to 1 mm (rows 3 and 4) significantly improved mechanical properties are obtained. A
further improvement of these properties is realized by increased removal speeds.
Example 10 In the following table the stretchability of a three-layer film of the type ABA produced in analogy to Example 2 and the effect of a subsequent stretching of the film on the mechanical properties of the film is explained.
For the outer and inner layer A, the biodegradable polyester Ecoflex (3/10) was used, respectively, and for the middle layer the starch blend Biopar 9345/15.
The starting film was produced at a removal speed of 11.3 m per minute and a blow ratio of 1:3.4.
Stretching was carried out mono-axially at 60 C at a stretching ratio of 1:3.
total stretching measuring tensile elongation tear impact thickness direction strength at tear strength strength (MPa) (%) (cN/mm) (J/mm) 70 um No extrusion 18.2 894 1067 6.03
BIOPOLYMER Technologies AG
4 21.3 30 1:3.6 extr.* 114 11.7 361 5813 2.67 exp.* 90 10.6 446 2933 *extr. = extrusion; exp. = expansion The results show clearly that for a die gap of 0.8 mm (rows 1 and 2) in comparison to 1 mm (rows 3 and 4) significantly improved mechanical properties are obtained. A
further improvement of these properties is realized by increased removal speeds.
Example 10 In the following table the stretchability of a three-layer film of the type ABA produced in analogy to Example 2 and the effect of a subsequent stretching of the film on the mechanical properties of the film is explained.
For the outer and inner layer A, the biodegradable polyester Ecoflex (3/10) was used, respectively, and for the middle layer the starch blend Biopar 9345/15.
The starting film was produced at a removal speed of 11.3 m per minute and a blow ratio of 1:3.4.
Stretching was carried out mono-axially at 60 C at a stretching ratio of 1:3.
total stretching measuring tensile elongation tear impact thickness direction strength at tear strength strength (MPa) (%) (cN/mm) (J/mm) 70 um No extrusion 18.2 894 1067 6.03
- 25 -Lit. TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
35 j.tm yes extrusion 43 to 55 442 By a subsequent stretching action, the tensile strength of the film is significantly improved.
Example 11 The manufacture of a two-layer film of the type AB is described wherein the outer layer (A) is _ comprised of a biodegradable polyester Ecoflex FBX 7011 and the inner layer (B) is comprised of the starch blend BIOPar7 9345-30.
The manufacture is realized in analogy to Example 4 with the difference that the device is equipped with only two extruders.
Example 12 The manufacture of a three-layer film of the type ABC is described wherein the outer layer (A) is comprised of the biodegradable polyester Ecoflex FBX 7011, the middle layer (B) of the starch blend BIOPar 7 9345-30, and the inner layer of the polylactide PLA 4042 D.
The manufacture is realized in analogy to Example 4 with the difference that the extruder C for the polylactide C is operated at approximately 150 C to 190 C.
BIOPOLYMER Technologies AG
35 j.tm yes extrusion 43 to 55 442 By a subsequent stretching action, the tensile strength of the film is significantly improved.
Example 11 The manufacture of a two-layer film of the type AB is described wherein the outer layer (A) is _ comprised of a biodegradable polyester Ecoflex FBX 7011 and the inner layer (B) is comprised of the starch blend BIOPar7 9345-30.
The manufacture is realized in analogy to Example 4 with the difference that the device is equipped with only two extruders.
Example 12 The manufacture of a three-layer film of the type ABC is described wherein the outer layer (A) is comprised of the biodegradable polyester Ecoflex FBX 7011, the middle layer (B) of the starch blend BIOPar 7 9345-30, and the inner layer of the polylactide PLA 4042 D.
The manufacture is realized in analogy to Example 4 with the difference that the extruder C for the polylactide C is operated at approximately 150 C to 190 C.
- 26 -Lit. TRL of PCT/DE2003/004157 - Inventor(s): Berger et al. - Assignee: BIOP
BIOPOLYMER Technologies AG
BIOPOLYMER Technologies AG
Claims (23)
1. A multi-layer film obtained by coextrusion, comprised of, respectively, at least one a) starch blend layer comprised of a modified thermoplastic starch blend comprised of the following components:
- 30 % to 75 % by weight starch, - 2 % to 10 % by weight water, - 10 % to 50 % by weight biodegradable polyester, - 5 % to 20 % by weight compatibilizer, - up to 10 % by weight plasticizer, and - up to 3 % by weight processing agent, and b) polyester layer comprised of a biodegradable polyester, wherein the starch blend layer contains no polyhydroxyalkanoate copolymer consisting of at least two randomly repeating monomer units, wherein a first monomer has the structure (I):
wherein R1 is H or a C1 or C2 alkyl group, with n = 1 or 2;
wherein a second monomer has the structure (II):
wherein R2 is a C3 to C19 alkyl or C3 to C19 alkenyl group, or the second monomer has the structure (III):
wherein m is from 2 to 9.
- 30 % to 75 % by weight starch, - 2 % to 10 % by weight water, - 10 % to 50 % by weight biodegradable polyester, - 5 % to 20 % by weight compatibilizer, - up to 10 % by weight plasticizer, and - up to 3 % by weight processing agent, and b) polyester layer comprised of a biodegradable polyester, wherein the starch blend layer contains no polyhydroxyalkanoate copolymer consisting of at least two randomly repeating monomer units, wherein a first monomer has the structure (I):
wherein R1 is H or a C1 or C2 alkyl group, with n = 1 or 2;
wherein a second monomer has the structure (II):
wherein R2 is a C3 to C19 alkyl or C3 to C19 alkenyl group, or the second monomer has the structure (III):
wherein m is from 2 to 9.
2. The multi-layer film according to claim 1, characterized in that the starch blend layer is surrounded by two polyester layers.
3. The multi-layer film according to claim 1 or 2, characterized in that the biodegradable polyester is comprised of dihydroxy compounds and dicarboxylic acids as monomers.
4. The multi-layer film according to claim 3, characterized in that the monomers are butanediol, adipic acid, and terephthalic acid; or butanediol, succinic acid, and adipic acid.
5. The multi-layer film according to claim 1 or 2, characterized in that the polyester layer comprises a polylactide; or a blend of a polylactide and another polyester; or a polyvinyl acetate.
6. The multi-layer film according to claim 1, characterized in that the compatibilizer comprises a polymer component having hydrophilic and hydrophobic groups arranged in blocks, respectively.
7. The multi-layer film according to claim 6, characterized in that the compatibilizer comprises a hydrolyzed polyvinyl acetate that is saponified in blocks.
8. The multi-layer film according to claim 1, characterized in that the plasticizer is glycerine.
9. The multi-layer film according to any one of claims 1 to 8, characterized in that the total thickness of the film is in a range of between 10 µm to 300 µm.
10. The multi-layer film according to any one of claims 1 to 9, characterized in that the thickness of the polyester layer is between 1 µm to 100 µm.
11. The multi-layer film according to any one of claims 1 to 10, characterized in that the thickness of the starch blend layer is between 5 µm to 250 µm.
12. The multi-layer film according to any one of claims 1 to 11, characterized in that the starch blend layer is two times to 10 times thicker than the polyester layer.
13. A method for manufacturing by coextrusion a multi-layer film according to claim 1, wherein, respectively, at least one a) layer of a modified thermoplastic starch blend and b) layer comprised of a biodegradable polyester is built up, wherein the materials of the starch blend layer and of the polyester layer have comparable melting and viscosity properties and wherein the starch blend layer contains more than 2 % to 10 %
by weight water.
by weight water.
14. The method according to claim 13, wherein the coextrusion is by blow extrusion.
15. The method according to claim 13 or 14, characterized in that the materials of the inner layer and of the outer layer have a viscosity of an MFI value between 4 g to 10 g per 10 minutes at 130 °C and 10 kg load or of an MFI value between 5 g to 40 g per 10 minutes at 160 °C and 10 kg load.
16. The method according to any one of claims 13 to 15, characterized in that the temperature of the starch blend is kept between 90 °C to 140°C.
17. The method according to any one of claims 13 to 16, characterized in that the temperature of the polyester is kept between 110 °C to 150 °C
or, when using polylactides for the polyester layer, is kept between 150 °C and 190 °C.
or, when using polylactides for the polyester layer, is kept between 150 °C and 190 °C.
18. The method according to any one of claims 13 to 17, characterized by a blow ratio of 1:2 to 1:5 and removal speeds of 8 m to 30 m per minute.
19. The method according to any one of claims 13 to 18, characterized in that the film is stretched after extrusion.
20. The method according to claim 19, characterized in that the film is stretched at a temperature between 40 °C and 80 °C.
21. The method according to claim 19 or 20, characterized in that the film is stretched at a ratio of up to 1:5.
22. Use of a multi-layer film according to any one of claims 1 to 12 as a packaging material.
23. Use of a multi-layer film according to any one of claims 1 to 12 as a packaging material for food.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2002158227 DE10258227A1 (en) | 2002-12-09 | 2002-12-09 | Biodegradable multilayer film |
| DE10258227.0 | 2002-12-09 | ||
| PCT/DE2003/004157 WO2004052646A1 (en) | 2002-12-09 | 2003-12-09 | Biodegradable multi-layer film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2543306A1 CA2543306A1 (en) | 2004-06-24 |
| CA2543306C true CA2543306C (en) | 2013-07-23 |
Family
ID=32477605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2543306A Expired - Lifetime CA2543306C (en) | 2002-12-09 | 2003-12-09 | Biodegradable multi-layer film |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20070042207A1 (en) |
| EP (2) | EP2399738A1 (en) |
| JP (1) | JP4619127B2 (en) |
| CN (1) | CN1723123A (en) |
| AT (1) | ATE549158T1 (en) |
| AU (1) | AU2003296535A1 (en) |
| CA (1) | CA2543306C (en) |
| DE (1) | DE10258227A1 (en) |
| ES (1) | ES2385020T3 (en) |
| NO (1) | NO20052785L (en) |
| PT (1) | PT1581388E (en) |
| WO (1) | WO2004052646A1 (en) |
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| US5500465A (en) * | 1994-03-10 | 1996-03-19 | Board Of Trustees Operating Michigan State University | Biodegradable multi-component polymeric materials based on unmodified starch-like polysaccharides |
| JPH07285192A (en) * | 1994-04-19 | 1995-10-31 | Dainippon Printing Co Ltd | Resin laminate |
| IT1272871B (en) * | 1995-01-10 | 1997-07-01 | Novamont Spa | THERMOPLASTIC COMPOSITIONS INCLUDING STARCH AND OTHER COMPONENTS OF NATURAL ORIGIN |
| JP2742892B2 (en) * | 1995-03-03 | 1998-04-22 | 日本コーンスターチ株式会社 | Esterified polyester grafted starch |
| JP3055001B2 (en) * | 1995-07-14 | 2000-06-19 | 日本コーンスターチ株式会社 | Polyester graft polymerized starch alloy |
| ATE242295T1 (en) * | 1995-04-07 | 2003-06-15 | Biotec Biolog Naturverpack | BIODEGRADABLE POLYMER BLEND |
| DE19513237A1 (en) * | 1995-04-07 | 1996-12-05 | Biotec Biolog Naturverpack | Bio-degradable polymer mixt. for adhesive, hygiene articles etc. |
| US5756194A (en) * | 1996-01-25 | 1998-05-26 | The United States Of America, As Represented By The Secretary Of Agriculture | Enhanced water resistance of starch-based materials |
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| DE19938672C2 (en) | 1999-08-06 | 2001-11-22 | Biop Biopolymer Gmbh | Process for the production of a thermoplastic polymer mixture based on starch by reactive extrusion |
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-
2002
- 2002-12-09 DE DE2002158227 patent/DE10258227A1/en not_active Withdrawn
-
2003
- 2003-12-09 US US10/538,020 patent/US20070042207A1/en not_active Abandoned
- 2003-12-09 AT AT03812564T patent/ATE549158T1/en active
- 2003-12-09 WO PCT/DE2003/004157 patent/WO2004052646A1/en active Application Filing
- 2003-12-09 ES ES03812564T patent/ES2385020T3/en not_active Expired - Lifetime
- 2003-12-09 JP JP2004557811A patent/JP4619127B2/en not_active Expired - Fee Related
- 2003-12-09 CA CA2543306A patent/CA2543306C/en not_active Expired - Lifetime
- 2003-12-09 EP EP11174359A patent/EP2399738A1/en not_active Withdrawn
- 2003-12-09 CN CNA2003801054920A patent/CN1723123A/en active Pending
- 2003-12-09 EP EP03812564A patent/EP1581388B1/en not_active Expired - Lifetime
- 2003-12-09 PT PT03812564T patent/PT1581388E/en unknown
- 2003-12-09 AU AU2003296535A patent/AU2003296535A1/en not_active Abandoned
-
2005
- 2005-06-09 NO NO20052785A patent/NO20052785L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004052646A1 (en) | 2004-06-24 |
| EP1581388A1 (en) | 2005-10-05 |
| US20070042207A1 (en) | 2007-02-22 |
| ATE549158T1 (en) | 2012-03-15 |
| JP4619127B2 (en) | 2011-01-26 |
| NO20052785D0 (en) | 2005-06-09 |
| CN1723123A (en) | 2006-01-18 |
| EP2399738A1 (en) | 2011-12-28 |
| ES2385020T3 (en) | 2012-07-17 |
| CA2543306A1 (en) | 2004-06-24 |
| PT1581388E (en) | 2012-06-18 |
| EP1581388B1 (en) | 2012-03-14 |
| JP2006508830A (en) | 2006-03-16 |
| DE10258227A1 (en) | 2004-07-15 |
| NO20052785L (en) | 2005-09-05 |
| AU2003296535A1 (en) | 2004-06-30 |
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