EP1309661A2 - Biodegradable polymeric blend - Google Patents
Biodegradable polymeric blendInfo
- Publication number
- EP1309661A2 EP1309661A2 EP01954255A EP01954255A EP1309661A2 EP 1309661 A2 EP1309661 A2 EP 1309661A2 EP 01954255 A EP01954255 A EP 01954255A EP 01954255 A EP01954255 A EP 01954255A EP 1309661 A2 EP1309661 A2 EP 1309661A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer blend
- acid
- aliphatic
- aromatic
- particular according
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 34
- 229920000728 polyester Polymers 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 17
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 16
- 150000002596 lactones Chemical class 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 229920002959 polymer blend Polymers 0.000 claims description 67
- 229920001634 Copolyester Polymers 0.000 claims description 24
- 238000004806 packaging method and process Methods 0.000 claims description 23
- 229920002472 Starch Polymers 0.000 claims description 20
- 239000008107 starch Substances 0.000 claims description 20
- 235000019698 starch Nutrition 0.000 claims description 20
- 235000013305 food Nutrition 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 aliphatic dicarboxylic acids Chemical class 0.000 claims description 10
- 235000013361 beverage Nutrition 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229920002988 biodegradable polymer Polymers 0.000 claims description 7
- 239000004621 biodegradable polymer Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 235000013410 fast food Nutrition 0.000 claims description 6
- 229940005605 valeric acid Drugs 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920002261 Corn starch Polymers 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 claims description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 239000008162 cooking oil Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000008239 natural water Substances 0.000 claims description 2
- 239000012785 packaging film Substances 0.000 claims description 2
- 229920006280 packaging film Polymers 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229920008262 Thermoplastic starch Polymers 0.000 claims 2
- 239000000155 melt Substances 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 239000004628 starch-based polymer Substances 0.000 claims 2
- 240000008042 Zea mays Species 0.000 claims 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims 1
- 235000005822 corn Nutrition 0.000 claims 1
- 239000000975 dye Substances 0.000 claims 1
- 235000021056 liquid food Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 9
- 230000005012 migration Effects 0.000 description 8
- 238000013508 migration Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 229920005839 ecoflex® Polymers 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- YNLZFQPOEWEPTM-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid;terephthalic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 YNLZFQPOEWEPTM-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000015205 orange juice Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Definitions
- the present invention relates to a biodegradable polymer blend, preferably based on renewable raw materials according to the preamble of claim 1, a method for producing a biodegradable polymer blend and uses of the polymer blend according to the invention.
- Biodegradable polymers particularly those based on renewable raw materials, are increasingly finding their way into domains to which synthetic polymers or so-called plastics are reserved. This is not least due to the fact that the properties of these polymers are constantly being improved.
- polymer materials are described, inter alia, on the basis of starch, the starch being brought into a largely crystalline form by the aid of low-molecular plasticizers, plasticizers, such as glycerol and sorbitol and other additives, so that it can be processed perfectly in a thermoplastic manner.
- plasticizers such as glycerol and sorbitol and other additives
- a number of other polymers are described as mixing partners in order to obtain improved properties.
- the additional polymers such as chemically modified cellulose, aliphatic polyesters, polymer amides, etc., have at least some of them biodegradability and are partly based on renewable raw materials.
- a major disadvantage of all of these proposed polymer mixtures lies in the fact that they contain plasticizers, plasticizers and other low molecular weight additives which can migrate out of the films, moldings etc. produced therefrom and are therefore unsuitable for a number of applications are, especially for use related to food contact.
- the problem is to create a polymer mixture that is biodegradable, for example, according to DIN 54900 and, if possible, based on renewable raw materials and that can be used in contact with food, i.e. corresponds to the regulations of the EU directives 82/711 EEC and 90/128 EEC.
- the object is achieved by means of a polymer blend according to the wording according to claim 1.
- the polymer blend according to the invention obtainable by extrusion, contains at least one copolyester with aliphatic and aromatic blocks or a so-called th partially aromatic copolyester and at least 10% of an aliphatic polyester based on one or more hydroxycarboxylic acids and / or based on lactones with a glass transition point (TG) of at least 50 ° C.
- TG glass transition point
- the polymer blend according to the invention contains no low molecular weight plasticizers or plasticizers or other low molecular weight compounds which can migrate out of films or molded articles produced from the polymer blend.
- EP 0 909 789 proposes polymer mixtures made from aliphatic and aliphatic / aromatic polyesters, but not obtainable by extrusion but by reaction of a mixture of the aforementioned components.
- DE 198 48 505 proposes partially aromatic polyesters, some of which are made up of aliphatic hydroxycarboxylic acids, such as lactic acid. Again, the resulting polymers or polymer mixtures are not blends obtainable by extrusion.
- DE 44 40 837 where polyether esters are mixed with high molecular weight hydroxycarboxylic acids such as polycaprolactone in a reaction vessel.
- DE 23 31 826 discloses thermoplastic compositions containing copolyesters with aliphatic and aromatic block units and linear aliphatic polyester resins, which, however, are not biodegradable.
- the thermoplastic compositions according to DE 23 31 826 have special electromechanical properties and in some cases include flame-retardant additives, which properties are biodegradable usually exclude.
- the polymer mixtures proposed according to the invention are obtainable by extrusion or by compounding, and not essentially by chemical reaction of the polymer components with one another.
- polyesters based on hydroxycarboxylic acids are polylactides, ie polymers based on lactic acid or derivatives of lactic acid.
- Linear polylactides are mostly used, but branched lactic acid polymers can be used, with polyfunctional acids or alcohols, for example, being used as branching agents.
- polylactides can be used which essentially consist of lactic acid or its Ci to C alkyl esters or mixtures thereof and, if appropriate, at least one aliphatic C to C 10 -
- Dicarboxylic acid and at least one C 3 - to -C 0 alkanol with three to five hydroxyl groups are available.
- those based on lactones can also be used as the aliphatic polyester, such as polycaprolactone or polymers based on hydroxybutyric acid, hydroxyvaleric acid and / or derivatives or mixtures thereof.
- Polyhydroxybutyric acid and polyhydroxybutyric acid / valeric acid copolyesters are particularly suitable.
- polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolyester (PHBV) By adding polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolyester (PHBV), an increased water vapor barrier property can be achieved in the polymer blend according to the invention.
- the reduced addition of polylactide or the omission of polylactides also results in an increased temperature resistance of moldings or foils produced from the partially aromatic polyester and PHBV to 100 ° C. or more.
- the polymer blend contains at least one partially aromatic copolyester based on aliphatic and aromatic blocks as a mixing component to the aliphatic polyester based on hydroxycarboxylic acids and / or lactones mentioned.
- the copolyester used according to the invention is produced, in addition to polyols, from aromatic or aliphatic dicarboxylic acids.
- the essential components of the biodegradable copolyester contain acid components from at least one aliphatic and / or a cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof and / or at least one aromatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof.
- the copolyester can contain at least one C 2 -C 12 -alkanediol and / or at least one C 5 - to C ⁇ -cycloalkanediol or mixtures thereof or optionally one or more components such as hydroxy compounds containing ether functions.
- the copolyester can be obtained by polycondensation of at least one diol, for example from the series 2, 1-ethanediol, 1,3-propanediol, 1, 4-butanediol and / or 1,6-hexanediol, on the other hand, with at least one aromatic dicarboxylic acid, such as terephthalic acid and optionally at least tens of an aliphatic dicarboxylic acid, such as adipic acid and / or sebacic acid.
- at least one diol for example from the series 2, 1-ethanediol, 1,3-propanediol, 1, 4-butanediol and / or 1,6-hexanediol, on the other hand, with at least one aromatic dicarboxylic acid, such as terephthalic acid and optionally at least tens of an aliphatic dicarboxylic acid, such as adipic acid and / or sebac
- the carboxylic acids with a larger number of carbon atoms can be used for the production of the copolyester according to the invention, for example with up to 30 carbon atoms.
- the ester-forming derivatives of the aliphatic or cycloaliphatic dicarboxylic acids mentioned, which can also be used, are, in particular, the di-C 1 to C 6 -alkyl esters, such as diethyl, diethyl, di-n-propyl, di-isopropyl, To name di-n-butyl ester, etc.
- Anhydrides of the dicarboxylic acids can also be used.
- the dicarboxylic acids or their ester-forming derivatives can be used individually or as mixtures of two or more thereof.
- Aromatic dicarboxylic acids to be preferably used are generally those having 8 to 12 carbon atoms and preferably those having 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2, 6-naphthoic acid and 1, 5-naphthoic acid, as well as ester-forming derivatives thereof. Anhydrides of dicarboxylic acids are also suitable ester-forming derivatives. However, aromatic dicarboxylic acids with a larger number of carbon atoms, for example up to 20 carbon atoms, can also be used.
- the aromatic dicarboxylic acids like also the aliphatic and / or cycloaliphatic dicarboxylic acids and / or their ester-forming derivatives, can be used individually or as mixtures of two or more thereof.
- Preferred diols are branched or linear alkanediols having 2 to 12 carbon atoms, preferably having 4 to 6 carbon atoms or cycloalkanediols having 5 to 10 carbon atoms.
- alkanediols examples include ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 2, 2-dimethyl-l, 3-propanediol, cyclopentanediol, 1, -cyclohexanediolmethanol, etc., to name but a few call.
- other components can be used to produce the copolyester according to the invention, such as, for example, dihydroxy compounds, such as, for example, diethylene glycol or polyethylene glycol.
- copolyesters mentioned above are only examples and can be supplemented by further possible partially aromatic copolyesters, reference being made in this connection to DE 198 49 448, in which such copolyesters described for the production of the polymer blend according to the invention are described are.
- At least the partially aromatic copolyester composed of aliphatic and aromatic polyester together with the aliphatic polyester based on hydroxycarboxylic acids and / or lactones must now be mixed in an extruder, for example in a co-rotating extruder operating in the same direction, in a temperature range of approx. 120-220 ° C.
- the temperature control depends on the starting materials used and in particular the specific melting points of the materials used. Degassing, which is common in extruders, takes place along the extruder, so that in particular during extrusion the water content in any case ⁇ 1% by weight. % is, so that foaming or the formation of bubbles in the extrudate can be avoided.
- the extrudate is cooled and usually passed through a water bath and conditioned.
- Films can now be produced from the polymer blends proposed according to the invention, such as packaging films in the food sector.
- a polylactide of at least 20% transparent films can be produced.
- partially aromatic copolyesters increased flexibility is achieved in the film, similar to films made from low-density polyethylene (LDPE). If, on the other hand, a low proportion of aromatic polyesters is used in the order of approximately 50%, the result is rather stiff films, similar to those made from high-density polyethylene (HDPE).
- HDPE high-density polyethylene
- the polymer blend proposed according to the invention can be used not only for foils, but also for applications in the injection molding field, for coatings, etc.
- the great advantage of the polymer blends according to the invention is that they are so-called plasticizer-free compounds, which are particularly useful for contact are suitable with food, ie so for food packaging.
- biodegradable e.g. according to DIN standard V 54900, i.e. they are compostable.
- suitable additives such as 20%, preferably approx. 25 - 30% of native starch can be given antistatic properties.
- the polymer blends according to the invention produced in this way are particularly suitable for applications in the electronic or electrical field where the material used in each case has to be antistatically equipped.
- the native starch used had been predried during the production of the polymer blend according to the invention and has a residual moisture content of less than about 4 to 8% water.
- Destructuring of the pre-dried starch is also ruled out under optimized conditions, such as longer residence times, screw geometry, which means that it is present in the polymer blend in a largely crystalline form, as required.
- At least 10 By using at least 10, preferably at least 20% of a polylactide, they can be made opaque to crystal clear. However, they can also be colored in any way. Films can be produced with a paper-like handle and / or paper-like creasing properties, but nevertheless these films are fat-resistant, can be embossed and / or printed, which is particularly advantageous when used in the food sector. Finally, molded articles or molded parts can be produced by deep drawing.
- Areas of application for the polymer blend according to the invention are in particular as flexible packaging in the food and non-food sector. It is primarily intended for use in so-called fast food packaging, which on the one hand has good fat resistance, but on the other hand should be compostable. It is of course additionally advantageous that the fast food packaging material produced according to the invention is produced entirely or partially on the basis of renewable raw materials.
- thermoformable film for coating food packaging such as starch or cellulose-foamed packaging (egg carton),
- An essential aspect of the polymer blends according to the invention lies in the migration values which correspond to the requirements of the EU guidelines.
- plasticizer-free compounds are possible in order to be able to provide suitable materials, in particular in the food or fast food sector.
- Global migration values of blends for example based on thermoplastic or destructurized starch, are substantially higher than the values now achieved with the polymer blends according to the invention due to the migration of the plasticizers contained, and thus mostly above the limit for use in contact with food.
- water vapor permeability is lower than has previously been possible with the starch blends known from the prior art.
- the water vapor permeability can be decisively reduced, in particular by the increased proportion of polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolymer.
- Migration test at 70 ° C, 30 min. meets the requirements for fast food (migration limit according to EU guidelines is 10 mg / dm 2 or 60 milligrams per kilogram of food)
- Polyhydroxybutyric acid / valeric acid copolyester 20% Water vapor permeability (WVTR) ⁇ 4 g / m 2 and day - measured at 23 ° C and 60% relative humidity, and
- Temperature resistance 70 - 80 ° C can be increased to over 100 ° C without adding E-copla.
- Starch is native starch, such as potato or corn starch.
- Polyester 1 terephthalic acid-butanediol-adipic acid copolyester (Ecoflex)
- Polyester 2 poly (butylene) succinate or poly (butylene) - succinate / adipate (Biomax 6929 from DuPont)
- Fillers e.g. Talc or kaolin
- B polyol ester
- C natural wax
- E-copla 6200 D from Cargill Dow Polymers Lacea H 100 J, Lacea H 100 E, Lacea H 100 PL (both from Mitsui Chemicals) and Ecopla 3000 D from Cargill were used as polylactide Dow Polymers.
- Example 11 shows a clear difference in the water vapor permeability, in Example 11, in which 19.9% of a mixture of polyhydroxybutyric acid and polyhydroxybutyric acid / valeric acid copolyester shows a significantly lower water vapor permeability.
- PLA polylactide (EcoPla 6200 D) and 44.6% polyester 1 (Ecoflex sbx) with 0.4 slipping agent (loxamide / manufacturer Cognis-Erucaklaklamid) were in a twin-screw extruder (Wemer & Pfleiderer ZSK.40) to a thermoplastic melt with a Final melting temperature of 185 ° C compounded and granulated.
- the polymer mixture thus obtained had an MFI - (g / 10 min) 190 ° C., 5 kg - of 9.5.
- a transparent film as a tube with a width of 275 mm and a wall thickness of 0.08 mm was produced from this polymer blend granulate on a Collin film blowing system.
- the film is easily printable and weldable at approx. 110 ° C. From this tube a beverage packaging in the dimensions 275 mm x 140 mm x 0.08 was produced by welding. This tubular bag packaging was infested with milk as a sensitive drink and filling material, stored in the refrigerator at 8 ° C and on storage properties both in terms of content and also tested on the packaging material.
- tubular bag packaging survived all drop tests from a height of 1 m undamaged.
- the tube bag packaging remained unchanged in its optical and physical properties after a storage time of 72 hours.
- Tubular film packaging made of polymer blend Example 29, film wall thickness 0.08 mm
- beverage packaging in the form of foil bags, produced according to Example 29, was tested with orange juice. This confirmed the good protective function for beverages of the polymer blend according to the invention as packaging means and the suitability of the material for use as beverage packaging, as a coating for beverage packaging and / or as an liner for liquid or pasty food packaging. - 21 -
- Example 29 it was possible to demonstrate impressively that the polymer blends proposed according to the invention are suitable for food packaging and in particular for packaging beverages.
- Either the tubular film packaging proposed in Example 29 can be produced from the polymer blends according to the invention, or else beverage packaging which has a cardboard reinforcement on the outside as mechanical protection and a film sleeve on the inside consisting of the polymer blend according to the invention.
- any containers using a polymer blend according to the invention for holding liquid fillings or viscous or pasty fillings, in particular for holding the above-mentioned beverage or other liquid foodstuffs, such as, for example, cooking oil.
- the so-called "slipping agent Loxiol EP 728" is a polyol partial ester from Henkel KgaA,
- Loxiol EP 728 is particularly suitable for improving the flow properties in injection molding - 22 -
- the composition was obtained by compounding in a twin-screw extruder (Werner & Pfleiderer, ZSK 40) to give a homogeneous melt at 170 ° C. melt temperature and complete degassing.
- the granules obtained have an MFI ((g / 10 min.) 190 ° C., 5 kg) of 13.7 and a residual moisture of 0.2%.
- the granulate is suitable for further processing as blown film, flat film and injection molding.
- the almost transparent films are plasticizer-free, easy to print and low-sweat.
- a polymer blend contains at least part of aromatic polyester based on aliphatic and aromatic blocks and at least one aliphatic polyester produced based on, among others, hydroxycarboxylic acids and / or lactones and / or their derivatives. Depending on the proportion of different materials, different ones can be - 23 -
- the polymer blend is at least almost free of plasticizer or free of low molecular weight components which can migrate out of films or moldings produced from the polymer blend according to the invention.
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Abstract
A biodegradable polymeric blend is provided, which can be produced by extrusion and contains at least one partly aromatic polyester, as well as aromatic and aliphatic blocks. At least 10 % w. of this polymeric blend with the partly aromatic polyester contains one aliphatic polyester based on at least one hydroxycarboxylic acid and/or at least one lactone, the glass transition temperature (TG) of the aliphatic polyester being of at least 50 DEG . This polymeric blend advantageously includes no plastifying agent and, moreover, comprises regenerating materials.
Description
Biologisch abbaubarer PolymerblendBiodegradable polymer blend
Die vorliegende Erfindung betrifft einen biologisch abbaubaren Polymerblend, vorzugsweise basierend auf nachwachsenden Rohstoffen gemäss dem Oberbegriff nach Anspruch 1, ein Verfahren zum Herstellen eines biologisch abbaubaren Poly- merblends sowie Verwendungen der erfindungsgemässen Poly- merblends .The present invention relates to a biodegradable polymer blend, preferably based on renewable raw materials according to the preamble of claim 1, a method for producing a biodegradable polymer blend and uses of the polymer blend according to the invention.
Vermehrt halten biologisch abbaubare Polymere, insbesondere auf Basis von nachwachsenden Rohstoffen, Einzug in Domänen, welchen synthetischen Polymeren oder sogenannten Kunststoffen vorbehalten sind. Dies nicht zuletzt aufgrund der Tatsache, dass die Eigenschaften dieser Polymere ständig verbessert werden. Zu verweisen ist auf eine Vielzahl von Patentdokumenten, welche sich mit Polymermischungen bzw. Po- ly erblends auf Basis von Polysacchariden, wie Stärke, Cel- lulose, PVA etc. befassen. Zu erwähnen sind u.a. mehr die folgenden Patentdokumente: DE 42 37 535, EP 409 781, EP 409 782, EP 495 950, EP 542 155, EP 575 349, EP 596 437, EP 799 335, W096/31561 und O98/0675.Biodegradable polymers, particularly those based on renewable raw materials, are increasingly finding their way into domains to which synthetic polymers or so-called plastics are reserved. This is not least due to the fact that the properties of these polymers are constantly being improved. Reference should be made to a large number of patent documents which deal with polymer mixtures or polyblends based on polysaccharides such as starch, cellulose, PVA etc. Worth mentioning include more the following patent documents: DE 42 37 535, EP 409 781, EP 409 782, EP 495 950, EP 542 155, EP 575 349, EP 596 437, EP 799 335, W096 / 31561 and O98 / 0675.
In diesen Dokumenten werden Polymerwerkstoffe u.a. auf Basis von Stärke beschrieben, wobei durch Zuhilfenahme von niedermolekularen Weichmachern, Plastifiziermitteln, wie Glycerin und Sorbitol und anderen Additiven die Stärke in eine weitgehendst kristallinfreie Form gebracht wird, damit sie thermoplastisch einwandfrei verarbeitet werden kann. Zusätzlich werden eine Reihe von weiteren Polymeren als Mischpartner beschrieben, um verbesserte Eigenschaften zu erhalten. Die zusätzlichen Polymere, wie beispielsweise chemisch modifizierte Cellulose, aliphatische Polyester, Polymeramide, etc., verfügen mindestens über eine teilweise
biologische Abbaubarkeit und basieren teilweise auf nachwachsenden Rohstoffen.In these documents, polymer materials are described, inter alia, on the basis of starch, the starch being brought into a largely crystalline form by the aid of low-molecular plasticizers, plasticizers, such as glycerol and sorbitol and other additives, so that it can be processed perfectly in a thermoplastic manner. In addition, a number of other polymers are described as mixing partners in order to obtain improved properties. The additional polymers, such as chemically modified cellulose, aliphatic polyesters, polymer amides, etc., have at least some of them biodegradability and are partly based on renewable raw materials.
Ein grosser Nachteil all dieser vorgeschlagenen Polymermischungen, beispielsweise auf Basis von Stärke, liegt in der Tatsache, dass sie Weichmacher, Plastifizier ittel und andere niedermolekulare Additive enthalten, welche aus daraus hergestellten Folien, Formkörpern etc. herausmigrieren können und so für eine Reihe von Anwendungen ungeeignet sind, wie insbesondere für Verwendung im Zusammenhang im Kontakt mit Lebensmitteln.A major disadvantage of all of these proposed polymer mixtures, for example based on starch, lies in the fact that they contain plasticizers, plasticizers and other low molecular weight additives which can migrate out of the films, moldings etc. produced therefrom and are therefore unsuitable for a number of applications are, especially for use related to food contact.
Mit anderen Worten besteht das Problem im Schaffen einer Polymermischung, welche einerseits biologisch abbaubar ist, beispielsweise nach DIN 54900 und nach Möglichkeit auf nachwachsenden Rohstoffen basiert und im Kontakt mit Le- bensmitteln verwendbar ist, d.h. den Vorschriften der EU- Richtlinien 82/711 EWG und 90/128 EWG entspricht.In other words, the problem is to create a polymer mixture that is biodegradable, for example, according to DIN 54900 and, if possible, based on renewable raw materials and that can be used in contact with food, i.e. corresponds to the regulations of the EU directives 82/711 EEC and 90/128 EEC.
Es ist daher eine Aufgabe der vorliegenden Erfindung, eine Polymermischung bzw. einen Polymerblend vorzuschlagen, welcher biologisch abbaubar ist, nach Möglichkeit auf nach- wachsenden Rohstoffen aufgebaut ist und welcher weitge- hendst weichmacherfrei ist bzw. frei von niedermolekularen Verbindungen, welche aus Formkörpern und Folien, hergestellt aus der erwähnten Polymermischung, herausmigrieren können.It is therefore an object of the present invention to propose a polymer mixture or a polymer blend which is biodegradable, if possible is based on renewable raw materials and which is largely free of plasticizers or free of low molecular weight compounds which consist of moldings and films , made from the polymer mixture mentioned, can migrate out.
Erfindungsgemäss wird die Aufgabe mittels eines Poly- merblends gemäss dem Wortlaut nach Anspruch 1 gelöst.According to the invention, the object is achieved by means of a polymer blend according to the wording according to claim 1.
Der erfindungsgemässe, mittels Extrusion erhältliche Polymerblend beinhaltet mindestens einen Copolyester mit aliphatischen und aromatischen Blöcken bzw. einen sogenann-
ten teilaromatischen Copolyester sowie mindestens 10 % eines aliphatischen Polyesters auf Basis einer oder mehrerer Hydroxycarbonsäuren und/oder auf Basis von Lactonen mit einem Glasumwandlungspunkt (TG) von mindestens 50 °C.The polymer blend according to the invention, obtainable by extrusion, contains at least one copolyester with aliphatic and aromatic blocks or a so-called th partially aromatic copolyester and at least 10% of an aliphatic polyester based on one or more hydroxycarboxylic acids and / or based on lactones with a glass transition point (TG) of at least 50 ° C.
Wesentlich dabei ist, dass der erfindungsgemässe Polymerblend keine niedermolekularen Weichmacher oder Plastifi- ziermittel enthält oder andere niedermolekulare Verbindungen, welche aus Folien oder Formkörpern, hergestellt aus dem Polymerblend, herausmigrieren können.It is essential here that the polymer blend according to the invention contains no low molecular weight plasticizers or plasticizers or other low molecular weight compounds which can migrate out of films or molded articles produced from the polymer blend.
Wohl sind aus dem Stand der Technik eine Reihe von Polymeren bzw. Polymischungen bekannt, welche ähnliche chemische Strukturen vorschlagen. So werden in der EP 0 909 789 Polymermischungen aus aliphatischen und alipha- tisch/aromatischen Polyestern vorgeschlagen, allerdings nicht erhältlich durch Extrusion, sondern durch Reaktion einer Mischung der vorgenannten Komponenten. Ähnlich werden in der DE 198 48 505 teilaromatische Polyester vorgeschlagen, welche teilweise aus aliphatischen Hydroxycarbonsäuren, wie beispielsweise Milchsäure, aufgebaut sind. Wieder- um sind die so entstehenden Polymere bzw. Polymermischungen keine mittels Extrusion erhältichen Blends . Dasselbe gilt für die DE 44 40 837, wo in einem Reaktionsgefäss Poly- etherester mit hochmolekularen Hydroxycarbonsäuren wie Po- lycaprolacton gemischt werden. Schliesslich sind aus der DE 23 31 826 thermoplastische Massen bekannt, enthaltend Copolyester mit aliphatischen und aromatischen Blockeinheiten sowie lineare aliphatische Polyesterharze, welche allerdings nicht biologisch abbaubar sind. Die thermoplastischen Massen gemäss DE 23 31 826 weisen besondere elektromechani- sehe Eigenschaften auf und umfassen teilweise flammhemmende Zusätze, welche Eigenschaften eine biologische Abbaubarkeit
in der Regel ausschliessen. Demgegenüber sind die erfin- dungsgemäss vorgeschlagenen Polymermischungen mittels Extrudieren bzw. mittels Compoundieren erhältlich, und nicht im wesentlichen durch chemische Reaktion der Polymer- komponenten untereinander.A number of polymers or polymer mixtures which propose similar chemical structures are well known from the prior art. For example, EP 0 909 789 proposes polymer mixtures made from aliphatic and aliphatic / aromatic polyesters, but not obtainable by extrusion but by reaction of a mixture of the aforementioned components. Similarly, DE 198 48 505 proposes partially aromatic polyesters, some of which are made up of aliphatic hydroxycarboxylic acids, such as lactic acid. Again, the resulting polymers or polymer mixtures are not blends obtainable by extrusion. The same applies to DE 44 40 837, where polyether esters are mixed with high molecular weight hydroxycarboxylic acids such as polycaprolactone in a reaction vessel. Finally, DE 23 31 826 discloses thermoplastic compositions containing copolyesters with aliphatic and aromatic block units and linear aliphatic polyester resins, which, however, are not biodegradable. The thermoplastic compositions according to DE 23 31 826 have special electromechanical properties and in some cases include flame-retardant additives, which properties are biodegradable usually exclude. In contrast, the polymer mixtures proposed according to the invention are obtainable by extrusion or by compounding, and not essentially by chemical reaction of the polymer components with one another.
Als Polyester auf Basis von Hydroxycarbonsäuren geeignet sind insbesondere Polylactide, d.h. Polymere auf Basis von Milchsäure bzw. Derivaten der Milchsäure. Meistens werden lineare Polylactide eingesetzt, es können aber verzweigte Milchsäurepolymerisate verwendet werden, wobei als Verzweiger beispielsweise mehrfunktionelle Säuren oder Alkohole dienen können. Beispielsweise können Polylactide verwendet werden, welche im wesentlichen aus Milchsäure oder deren Ci- bis C-Alkylester oder deren Mischungen sowie gegebe- nenfalls mindestens einer aliphatischen C- bis C10-Particularly suitable polyesters based on hydroxycarboxylic acids are polylactides, ie polymers based on lactic acid or derivatives of lactic acid. Linear polylactides are mostly used, but branched lactic acid polymers can be used, with polyfunctional acids or alcohols, for example, being used as branching agents. For example, polylactides can be used which essentially consist of lactic acid or its Ci to C alkyl esters or mixtures thereof and, if appropriate, at least one aliphatic C to C 10 -
Dicarbonsäure und mindestens einem C3- bis Cι0-Alkanol mit drei bis fünf Hydroxygruppen erhältlich sind.Dicarboxylic acid and at least one C 3 - to -C 0 alkanol with three to five hydroxyl groups are available.
Als aliphatischer Polyester können aber auch solche auf Basis von Lactonen verwendet werden, wie beispielsweise Poly- caprolacton oder Polymere auf Basis von Hydroxybuttersäure, Hydroxyvaleriansäure und/oder Derivaten oder Mischungen davon. Insbesondere geeignet sind Polyhydroxybuttersäure und Polyhydroxybuttersäure/Valeriansäure-Copolyester. Durch das Zusetzen von Polyhydroxybuttersäure oder Polyhydroxybutter- säure/Valeriansäure-Copolyester (PHBV) kann im erfindungs- gemässen Polymerblend eine erhöhte Wassserdampfbarriere- Eigenschaft erzielt werden. Durch verringerten Zusatz an Polylactid bzw. durch das Weglassen von Polylactiden ergibt sich auch eine erhöhte Temperaturbeständigkeit von Formkör- pern oder Folien, hergestellt aus dem teilaromatischen Polyester und PHBV auf 100 °C oder mehr.
Ge äss einer weiteren Ausführungsvariante ist es möglich, zusätzlich zum teilaromatischen Polyester und dem aliphatischen Polyester auf Basis Hydroxycarbonsäure (-n) und/oder Lacton(-en) native Stärke beizumengen, wodurch Folien oder Formkörper mit antistatischen Eigenschaften erhalten werden können, was insbesondere für Anwendungen im Elektro- oder Elektronikbereich von Bedeutung sein kann.However, those based on lactones can also be used as the aliphatic polyester, such as polycaprolactone or polymers based on hydroxybutyric acid, hydroxyvaleric acid and / or derivatives or mixtures thereof. Polyhydroxybutyric acid and polyhydroxybutyric acid / valeric acid copolyesters are particularly suitable. By adding polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolyester (PHBV), an increased water vapor barrier property can be achieved in the polymer blend according to the invention. The reduced addition of polylactide or the omission of polylactides also results in an increased temperature resistance of moldings or foils produced from the partially aromatic polyester and PHBV to 100 ° C. or more. According to a further embodiment variant, it is possible, in addition to the partially aromatic polyester and the aliphatic polyester based on hydroxycarboxylic acid (s) and / or lactone (s), to admix native starch, as a result of which films or moldings with antistatic properties can be obtained, which is particularly important for Applications in the electrical or electronics sector can be important.
Der Polymerblend enthält als Mischkomponente zum erwähnten aliphatischen Polyester auf Basis Hydroxycarbonsäuren und/oder Lactonen mindestens einen teilaromatischen Copolyester auf Basis aliphatischer und aromatischer Blöcke. Der erfindungsgemäss verwendete Copolyester wird nebst aus Po- lyolen aus aromatischen oder aliphatischen Dicarbonsäuren hergestellt. Der biologisch abbaubare Copolyester enthält als wesentliche Komponenten Säurekomponenten aus mindestens einer aliphatischen und/oder eine zykloaliphatischen Dicar- bonsäure oder deren esterbildenden Derivaten oder Mischungen davon und/oder mindestens eine aromatische Dicarbonsäu- re oder deren esterbildenden Derivate oder Mischungen da- von. Als Diolkomponente kann der Copolyester mindestens ein C2- Ci2-Alkandiol und/oder mindestens ein C5- bis Cχo- Cycloalkandiol oder Mischungen davon oder ggf. eine oder mehrere Komponenten, wie Etherfunktionen enthaltende Hydro- xyverbindungen enthalten.The polymer blend contains at least one partially aromatic copolyester based on aliphatic and aromatic blocks as a mixing component to the aliphatic polyester based on hydroxycarboxylic acids and / or lactones mentioned. The copolyester used according to the invention is produced, in addition to polyols, from aromatic or aliphatic dicarboxylic acids. The essential components of the biodegradable copolyester contain acid components from at least one aliphatic and / or a cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof and / or at least one aromatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof. As the diol component, the copolyester can contain at least one C 2 -C 12 -alkanediol and / or at least one C 5 - to Cχ-cycloalkanediol or mixtures thereof or optionally one or more components such as hydroxy compounds containing ether functions.
Gemäss einer Ausführungsvariante ist der Copolyester erhältlich durch Polykondensation von einerseits mindestens einem Diol beispielsweise aus der Reihe 2, 1-Ethandiol, 1,3- Propandiol, 1, 4-Butandiol und/oder 1, 6-Hexandiol mit andererseits mindestens einer aromatischen Dicarbonsäure, wie beispielsweise Terephthalsäure und gegebenenfalls mindes-
tens einer aliphatischen Dicarbonsäure, wie Adipinsäure und/oder Sebacinsäure.According to one embodiment variant, the copolyester can be obtained by polycondensation of at least one diol, for example from the series 2, 1-ethanediol, 1,3-propanediol, 1, 4-butanediol and / or 1,6-hexanediol, on the other hand, with at least one aromatic dicarboxylic acid, such as terephthalic acid and optionally at least tens of an aliphatic dicarboxylic acid, such as adipic acid and / or sebacic acid.
Prinzipiell aber können die Carbonsäuren mit einer grösse- ren Anzahl von Kohlenstoffatomen für die Herstellung des erfindungsgemässen Copolyesters verwendet werden, beispielsweise mit bis zu 30 Kohlenstoffatomen. Als esterbildende Derivate der genannten aliphatischen oder zykloa- liphatischen Dicarbonsäuren, die ebenfalls verwendbar sind, sind insbesondere die Di-Ci bis C6-Alkylester, wie Di e- thyl-, Diethyl-, Di-n-propyl-, Di-isopropyl-, Di-n- butylester, etc. zu nennen. Anhydride der Dicarbonsäuren können ebenfalls eingesetzt werden. Dabei können die Dicarbonsäuren oder deren esterbildenden Derivate einzeln oder als Gemische aus zwei oder mehr davon eingesetzt werden. Als bevorzugt zu verwendende aromatische Dicarbonsäuren sind im allgemeinen solche mit 8 - 12 Kohlenstoffatomen und vorzugsweise solche mit 8 Kohlenstoffatomen zu nennen. Bei- spielhaft erwähnt seien Terephthalsäure, Isophthalsäure, 2 , 6-Naphthoesäure und 1, 5-Naphthoesäure, sowie esterbilden- de Derivate davon. Anhydride der Dicarbonsäuren sind ebenso geeignete esterbildende Derivate. Allerdings können auch aromatische Dicarbonsäuren mit einer grösseren Anzahl an Kohlenstoffatomen, beispielsweise bis zu 20 Kohlenstoffatomen eingesetzt werden. Die aromatischen Dicarbonsäuren, wie im übrigen auch die aliphatischen und/oder zykloaliphati- schen Dicarbonsäuren und/oder deren esterbildenden Derivate können einzeln oder als Gemische aus zwei oder mehr davon eingesetzt werden. Als Diole werden bevorzugt verzweigte oder lineare Alkandiole mit 2 bis 12 Kohlenstoffatomen ver- wendet, bevorzugt mit 4 bis 6 Kohlenstoffatomen oder Zyklo- alkandiolen mit 5 bis 10 Kohlenstoffatomen. Beispiele geeigneter Alkandiole sind Ethylenglykol, 1, 2-Propandiol,
1, 3-Propandiol, 1, 2-Butandiol, 1, 4-Butandiol, 1,5- Pentandiol, 2, 2-Dimethyl-l, 3-propandiol, Cyclopentandiol, 1, -Cyclohexandiolmethanol, usw., um nur einige zu nennen. Daneben können weitere Komponenten zur Herstellung des er- findungsgemässen Copolyesters verwendet werden, wie beispielsweise Dihydroxyverbindungen, wie beispielsweise Diethylenglykol oder Polyethylenglykol.In principle, however, the carboxylic acids with a larger number of carbon atoms can be used for the production of the copolyester according to the invention, for example with up to 30 carbon atoms. The ester-forming derivatives of the aliphatic or cycloaliphatic dicarboxylic acids mentioned, which can also be used, are, in particular, the di-C 1 to C 6 -alkyl esters, such as diethyl, diethyl, di-n-propyl, di-isopropyl, To name di-n-butyl ester, etc. Anhydrides of the dicarboxylic acids can also be used. The dicarboxylic acids or their ester-forming derivatives can be used individually or as mixtures of two or more thereof. Aromatic dicarboxylic acids to be preferably used are generally those having 8 to 12 carbon atoms and preferably those having 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2, 6-naphthoic acid and 1, 5-naphthoic acid, as well as ester-forming derivatives thereof. Anhydrides of dicarboxylic acids are also suitable ester-forming derivatives. However, aromatic dicarboxylic acids with a larger number of carbon atoms, for example up to 20 carbon atoms, can also be used. The aromatic dicarboxylic acids, like also the aliphatic and / or cycloaliphatic dicarboxylic acids and / or their ester-forming derivatives, can be used individually or as mixtures of two or more thereof. Preferred diols are branched or linear alkanediols having 2 to 12 carbon atoms, preferably having 4 to 6 carbon atoms or cycloalkanediols having 5 to 10 carbon atoms. Examples of suitable alkanediols are ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1,5-pentanediol, 2, 2-dimethyl-l, 3-propanediol, cyclopentanediol, 1, -cyclohexanediolmethanol, etc., to name but a few call. In addition, other components can be used to produce the copolyester according to the invention, such as, for example, dihydroxy compounds, such as, for example, diethylene glycol or polyethylene glycol.
Generell kann gesagt werden, dass die oben angeführten Copolyester lediglich beispielshaft sind und durch weitere mögliche teilaromatische Copolyester ergänzt werden können, wobei in diesem Zusammenhang auf die DE 198 49 448 verwiesen sei, in welcher derartige für die Herstellung des er- findungsgemässen Polymerblends geeignete Copolyester beschrieben sind.In general, it can be said that the copolyesters mentioned above are only examples and can be supplemented by further possible partially aromatic copolyesters, reference being made in this connection to DE 198 49 448, in which such copolyesters described for the production of the polymer blend according to the invention are described are.
Für die Herstellung des erfindungsgemässen Polymerblends sind nun mindestens der teilaromatische Copolyester aus a- liphatischen und aromatischen Polyester zusammen mit dem aliphatischen Polyester auf Basis Hydroxycarbonsäuren und/oder Lactonen in einem Extruder, wie beispielsweise in einem gleichsinnig laufenden Zweiwellenextruder zu mischen in einem Temperaturbereich von ca. 120 - 220 °C. Die Temperaturführung richtet sich nach den verwendeten Ausgangsmaterialien und insbesondere der spezifischen Schmelzpunkte der verwendeten Materialien. Entlang dem Extruder erfolgt eine in Extrudern übliche Entgasung, so dass insbesondere beim Extrudieren der Wassergehalt auf jeden Fall < 1 Gew . % ist, so dass ein Aufschäumen oder ein Entstehen von Blasen im Extrudat vermieden werden kann. Das Extrudat wird abgekühlt und üblicherweise durch ein Wasserbad geführt und konditioniert .
Aus den erfindungsgemäss vorgeschlagenen Polymerblends können nun Folien hergestellt werden, wie beispielsweise Verpackungsfolien im Lebensmittelbereich. Insbesondere bei Verwendung von einem erhöhten Anteil eines Polylactids von mindestens 20% können klarsichtige Folien hergestellt werden. Bei Verwendung eines erhöhten Anteils an teilaromatischen Copolyestern wird eine erhöhte Flexibilität in der Folie erreicht, ähnlich Folien hergestellt aus Low- Densitypolyethylen (LDPE) . Wird hingegen ein niedriger An- teil an aromatischen Polyestern verwendet in der Grössen- ordnung von ca. 50% ergeben sich eher steife Folien, ähnlich solchen hergestellt aus High-Densitypolyethylen (HDPE) .For the production of the polymer blend according to the invention, at least the partially aromatic copolyester composed of aliphatic and aromatic polyester together with the aliphatic polyester based on hydroxycarboxylic acids and / or lactones must now be mixed in an extruder, for example in a co-rotating extruder operating in the same direction, in a temperature range of approx. 120-220 ° C. The temperature control depends on the starting materials used and in particular the specific melting points of the materials used. Degassing, which is common in extruders, takes place along the extruder, so that in particular during extrusion the water content in any case <1% by weight. % is, so that foaming or the formation of bubbles in the extrudate can be avoided. The extrudate is cooled and usually passed through a water bath and conditioned. Films can now be produced from the polymer blends proposed according to the invention, such as packaging films in the food sector. In particular when using an increased proportion of a polylactide of at least 20%, transparent films can be produced. When using an increased proportion of partially aromatic copolyesters, increased flexibility is achieved in the film, similar to films made from low-density polyethylene (LDPE). If, on the other hand, a low proportion of aromatic polyesters is used in the order of approximately 50%, the result is rather stiff films, similar to those made from high-density polyethylene (HDPE).
Selbstverständlich kann der erfindungsgemäss vorgeschlagene Polymerblend nicht nur für Folien verwendet werden, sondern auch für Anwendungen im Spritzgussbereich, für Beschichtungen, etc. Der grosse Vorteil der erfindungsgemässen Polymerblends liegt darin, dass es sich um sogenannte Weichmacher-freie Compounds handelt, welche insbesondere für den Kontakt mit Lebensmitteln geeignet sind, d.h. also für Lebensmittelverpackungen .Of course, the polymer blend proposed according to the invention can be used not only for foils, but also for applications in the injection molding field, for coatings, etc. The great advantage of the polymer blends according to the invention is that they are so-called plasticizer-free compounds, which are particularly useful for contact are suitable with food, ie so for food packaging.
Im weiteren sind sie biologisch abbaubar, beispielsweise nach der DIN-Norm V 54900, d.h. sie sind kompostierbar.Furthermore, they are biodegradable, e.g. according to DIN standard V 54900, i.e. they are compostable.
Sie sind ganz oder teilweise auf Basis nachwachsender Roh- Stoffe hergestellt.They are made entirely or in part based on renewable raw materials.
Durch die Verwendung geeigneter Additive, wie von beispielsweise 20%, vorzugsweise ca . 25 - 30% an nativer Stärke können Sie mit antistatischen Eigenschaften versehen werden. Für diese Anwendung ist es wesentlich, dass die Stärke beim Herstellen des erfindungsgemässen Polymerblends
nativ ist und die native Kornstruktur beim Herstellen des Blends weitgehendst beibehält. Mit anderen Worten liegt die Stärke auch im hergestellten Polymerblend in weitgehendst kristalliner Form vor. Die so hergestellten erfindungsge- mässen Polymerblends sind insbesondere geeignet für Anwendungen im elektronischen bzw. elektrischen Bereich, wo der jeweilig verwendete Werkstoff antistatisch ausgerüstet sein muss .Through the use of suitable additives, such as 20%, preferably approx. 25 - 30% of native starch can be given antistatic properties. For this application, it is essential that the starch when producing the polymer blend according to the invention is native and largely retains the native grain structure when producing the blend. In other words, the starch is also present in a largely crystalline form in the polymer blend produced. The polymer blends according to the invention produced in this way are particularly suitable for applications in the electronic or electrical field where the material used in each case has to be antistatically equipped.
Dies ist insbesondere dann möglich, wenn bei der Herstel- lung des erfindungsgemässen Polymerblends die zudosierte, eingesetzte native Stärke vorgetrocknet war und eine Restfeuchte von weniger als ca. 4 bis 8 % Wasser aufweist. Eine Destrukturierung der vorgetrockneten Stärke ist auch unter optimierten Bedingungen, wie längere Verweilzeit, Schne- ckengeometrie, ausgeschlossen, womit sie wie gefordert in weitgehendst kristalliner Form im Polymerblend vorliegt.This is particularly possible if the native starch used had been predried during the production of the polymer blend according to the invention and has a residual moisture content of less than about 4 to 8% water. Destructuring of the pre-dried starch is also ruled out under optimized conditions, such as longer residence times, screw geometry, which means that it is present in the polymer blend in a largely crystalline form, as required.
Für andere Beispiele von erfindungsgemäss herzustellenden Polymerblends kann es selbstverständlich von Vorteil sein, wenn die native Stärke beim Compoundieren vollständig de- strukturiert wird und somit filmbildend ist. In diesem Zusammenhang sei auf das nachfolgende Beispiel 30 verwiesen.For other examples of polymer blends to be produced according to the invention, it can of course be of advantage if the native starch is completely destroyed during compounding and is therefore film-forming. In this connection, reference is made to Example 30 below.
Durch die Verwendung von mindestens 10, vorzugsweise mindestens 20% eines Polylactides können sie opak bis glasklar transparent hergestellt werden. Sie können aber auch belie- big eingefärbt werden. Folien können mit einem papierähnlichen Griff und/oder papierähnlichen Knittereigenschaften hergestellt werden, trotzdem aber sind diese Folien fettre- sistent, können geprägt und/oder bedruckt werden, was insbesondere bei Verwendung im Lebensmittelbereich von Vorteil ist.
Schliesslich sind Formkörper bzw. Formteile mittels Tiefziehen herstellbar.By using at least 10, preferably at least 20% of a polylactide, they can be made opaque to crystal clear. However, they can also be colored in any way. Films can be produced with a paper-like handle and / or paper-like creasing properties, but nevertheless these films are fat-resistant, can be embossed and / or printed, which is particularly advantageous when used in the food sector. Finally, molded articles or molded parts can be produced by deep drawing.
Anwendungsbereiche für den erfindungsgemässen Polymerblend liegen insbesondere im Einsatz als flexible Verpackung im Lebensmittel- und Nicht-Lebensmittelbereich. Gedacht ist vor allem die Verwendung bei sogenannter Fastfood- Verpackung, welche einerseits eine gute Fettresistenz aufzuweisen hat, andererseits aber kompostierbar sein sollte. Zusätzlich vorteilhaft ist natürlich, dass das erfindungs- gemäss hergestellte Fastfood-Verpackungsmaterial ganz oder teilweise auf Basis nachwachsender Rohstoffe hergestellt ist.Areas of application for the polymer blend according to the invention are in particular as flexible packaging in the food and non-food sector. It is primarily intended for use in so-called fast food packaging, which on the one hand has good fat resistance, but on the other hand should be compostable. It is of course additionally advantageous that the fast food packaging material produced according to the invention is produced entirely or partially on the basis of renewable raw materials.
Weitere Anwendungsbeispiele sind:Further application examples are:
antistatische Verpackung für Elektronikartikel,antistatic packaging for electronic items,
- tiefgezogene Deckel für Trinkbecher,- deep-drawn lids for drinking cups,
Strohhalme,straws,
tiefziehbare Folie zur Beschichtung von Lebensmittelverpackungen, wie beispielsweise aus Stärke oder Cel- lulose-geschäumte Verpackungen (Eierkarton) ,thermoformable film for coating food packaging, such as starch or cellulose-foamed packaging (egg carton),
- Gärtnereibedarf (Pflanztöpfe, Anzuchtschale, etc.),- gardening supplies (plant pots, growing bowl, etc.),
Trägermaterial zur Anzucht von Mikroorganismen,Carrier material for the cultivation of microorganisms,
Hygienefolien,Hygiene films,
Einwickelpapier für Lebensmittel,Wrapping paper for food,
Einsatz als Blas- oder Flachfolie sowie im Spritzguss.
Ein wesentlicher Aspekt der erfindungsgemässen Polymerblends liegt in den Migrationswerten, die den Anforderungen der EU-Richtlinien entsprechen. Erstmals sind gemäss der vorliegenden Erfindung Weichermacher-freie Compounds möglich, um so geeignete Materialien, insbesondere im Food- bzw. Fastfood-Bereich zur Verfügung stellen zu können. Glo- balmigrationswerte von Blends, beispielsweise auf Basis von thermoplastischer oder destrukturierter Stärke liegen aufgrund der Migration der enthaltenen Weichmacher wesentlich über den jetzt mit den erfindungsgemässen Polymerblends erreichten Werten und damit meist über dem Limit für den Einsatz im Kontakt mit Lebensmitteln. Durch Verwendung der erfindungsgemäss vorgeschlagenen Polymerblends kann Rücksicht genommen werden auf die gesundheitliche Unbedenklichkeit der migrierenden Stoffe, da die Gesamtmigration weit unter den festgesetzten Limits liegt.Use as blown or flat film as well as in injection molding. An essential aspect of the polymer blends according to the invention lies in the migration values which correspond to the requirements of the EU guidelines. For the first time, according to the present invention, plasticizer-free compounds are possible in order to be able to provide suitable materials, in particular in the food or fast food sector. Global migration values of blends, for example based on thermoplastic or destructurized starch, are substantially higher than the values now achieved with the polymer blends according to the invention due to the migration of the plasticizers contained, and thus mostly above the limit for use in contact with food. By using the polymer blends proposed according to the invention, consideration can be given to the health safety of the migrating substances, since the overall migration is far below the stipulated limits.
Daneben ergeben sich durch Eigenschaften, wie Tiefziehfähigkeit oder Knitterfähigkeit Vorteile für den Einsatz im Fastfoodbereich. Wichtig für diesen Einsatzbereich ist auch eine geringere Wasserdampfdurchlässigkeit als dies mit den aus dem Stand der Technik bekannten Stärkeblends bisher erreicht werden konnte. Insbesondere durch den erhöhten Anteil an Polyhydroxybuttersäure bzw. Polyhydroxybuttersäu- re/Valeriansäure-Copolymer kann die Wasserdampfdurchlässig- keit entscheidend verringert werden.In addition, properties such as the ability to deep-draw or crease result in advantages for use in the fast food sector. It is also important for this area of application that the water vapor permeability is lower than has previously been possible with the starch blends known from the prior art. The water vapor permeability can be decisively reduced, in particular by the increased proportion of polyhydroxybutyric acid or polyhydroxybutyric acid / valeric acid copolymer.
Durch weitere interessante technische Eigenschaften ergeben sich weitere Anwendungsmöglichkeiten, speziell im Non- Foodbereich, z.B. durch die guten antistatischen Eigenschaften oder als Stretch-Schrumpf-Folie. Diesbezüglich sei auch auf die Reckfähigkeit von Folien, hergestellt aus den erfindungsgemässen Polymerblends, hingewiesen, wo ein Reck-
verhältniss bis zu 1:6 und mehr durchaus möglich ist. Selbstverständlich ist es möglich, dem erfindungsgemässen Polymerblend weitere Polymere, wie insbesondere und vorzugsweise biologisch abbaubare Polymere beizumengen, wie beispielsweise Cellulosederivate wie Cellulosester, Fettsäurederivate, Polyesteramide, etc. Ebenfalls können dem Polymerblend organische sowie anorganische Füllstoffe und Pigmente beigefügt werden, soweit sie für den jeweiligen Verwendungszweck geeignet sind. So ist es beispielsweise möglich, Talk, Kaolin oder Titandioxid beizufügen.Further interesting technical properties result in further application options, especially in the non-food sector, for example due to the good antistatic properties or as a stretch shrink film. In this regard, reference should also be made to the stretchability of films made from the polymer blends according to the invention, where a stretch ratio up to 1: 6 and more is quite possible. Of course, it is possible to add further polymers, such as, in particular and preferably, biodegradable polymers, such as cellulose derivatives such as cellulose esters, fatty acid derivatives, polyester amides, etc., to the polymer blend according to the invention. Organic and inorganic fillers and pigments can also be added to the polymer blend insofar as they are suitable for the particular one Are intended for use. For example, it is possible to add talc, kaolin or titanium dioxide.
Die Erfindung wird nun beispielsweise und unter Bezug auf die beigefügten Rezepturbeispiele weiter erläutert:The invention will now be further explained, for example, and with reference to the attached recipe examples:
1. Beispiel einer Rezeptur für die Herstellung eines Polymerblends für die Herstellung von glasklaren Folien:1. Example of a recipe for the production of a polymer blend for the production of crystal-clear films:
Ecoflex SBX 7000 (BASF) : 70%Ecoflex SBX 7000 (BASF): 70%
Ecopla 6200 (Cargill Dow Polymers) 30%Ecopla 6200 (Cargill Dow Polymers) 30%
Migrationsprüfung bei 70 °C, 30 min. entspricht den Anforderungen für Fastfood (Migrationslimit gemäss EU-Richtlinie beträgt 10 mg/dm2 oder 60 Milligramm pro Kilogramm Lebens- mittel)Migration test at 70 ° C, 30 min. meets the requirements for fast food (migration limit according to EU guidelines is 10 mg / dm 2 or 60 milligrams per kilogram of food)
2. Polymerblend für die Herstellung einer Folie mit guter Wasserdampf-Barriere :2. Polymer blend for the production of a film with a good water vapor barrier:
Ecoflex SBX 7000 (BASF) : 56%Ecoflex SBX 7000 (BASF): 56%
Ecopla 6200 D (Cargill Dow Polymers) : 24%, undEcopla 6200 D (Cargill Dow Polymers): 24%, and
Polyhydroxybuttersäure/Valeriansäure-Copolyester: 20%
Wasserdampfdurchlässigkeit (WVTR) < 4 g/m2 und Tag - gemessen bei 23 °C und 60% relativer Feuchtigkeit, undPolyhydroxybutyric acid / valeric acid copolyester: 20% Water vapor permeability (WVTR) <4 g / m 2 and day - measured at 23 ° C and 60% relative humidity, and
Temperaturbeständigkeit 70 - 80 °C, kann ohne Zusatz von E- copla auf über 100°C gesteigert werden.Temperature resistance 70 - 80 ° C, can be increased to over 100 ° C without adding E-copla.
3. Polymerblend für die Herstellung von Folien oder Formkörpern mit antistatischen Eigenschaften:3. Polymer blend for the production of films or moldings with antistatic properties:
Ecoflex SBX 7000 (BASF) : 63%Ecoflex SBX 7000 (BASF): 63%
Ecopla 6200 D (Cargill Dow Polymers) : 10%Ecopla 6200 D (Cargill Dow Polymers): 10%
Maisstärke 27% (32% zugegeben als native Stärke mit 12% na- türlich gebundenem Wasser,Corn starch 27% (32% added as native starch with 12% naturally bound water,
Wasser: 17%Water: 17%
Weitere Beispiele sind den nachfolgenden Tabellen zu entnehmen:
Further examples can be found in the following tables:
-14a- -14a-
- 15 -- 15 -
-16- -16-
-16a- -16a-
-17--17-
•17a- • 17a
18 -18 -
- 19 - - 19 -
Legende: Bei Stärke handelt es sich um native Stärke, wie Kartoffel- oder Maisstärke.Legend: Starch is native starch, such as potato or corn starch.
Polyester 1: Terephthalsäure-Butandiol-Adipinsäure- Copolyester (Ecoflex)Polyester 1: terephthalic acid-butanediol-adipic acid copolyester (Ecoflex)
Polyester 2: Poly (butylen) succinat oder Poly (butylen) - succinat/adipat (Biomax 6929 von DuPont)Polyester 2: poly (butylene) succinate or poly (butylene) - succinate / adipate (Biomax 6929 from DuPont)
Füllstoffe: z.B. Talk oder KaolinFillers: e.g. Talc or kaolin
Restfeuchte (4) nach dem Extruder < 1 Gew.% undResidual moisture (4) after the extruder <1% by weight and
Gleitmittel: A = Erucasäureamid B = Polyolester C = Natür- liches WachsLubricant: A = erucic acid amide B = polyol ester C = natural wax
Zusätzlicher Kommentar zu den tabellarisch angeführten Beispielen: Als Polylactid verwendet wurden unter anderem E- copla 6200 D von Cargill Dow Polymers, Lacea H 100 J, Lacea H 100 E, Lacea H 100 PL (beide von Mitsui Chemicals) sowie Ecopla 3000 D von Cargill Dow Polymers.Additional commentary on the tabulated examples: E-copla 6200 D from Cargill Dow Polymers, Lacea H 100 J, Lacea H 100 E, Lacea H 100 PL (both from Mitsui Chemicals) and Ecopla 3000 D from Cargill were used as polylactide Dow Polymers.
Insbesondere ein Vergleich der Beispiele 4 - 6 und von Beispiel 11 zeigen einen deutlichen Unterschied in der Wasserdampfdurchlässigkeit, indem Beispiel 11, bei welchem 19,9% einer Mischung aus Polyhydroxybuttersäure und Polyhydroxy- buttersäure/Valeriansäure-Copolyester eine deutlich geringere Wasserdampfdurchlässigkeit zeigt.In particular, a comparison of Examples 4-6 and Example 11 shows a clear difference in the water vapor permeability, in Example 11, in which 19.9% of a mixture of polyhydroxybutyric acid and polyhydroxybutyric acid / valeric acid copolyester shows a significantly lower water vapor permeability.
Im weiteren sei auf die Migrationswerte verwiesen, welche für einige Rezepturen ermittelt worden sind, und welche alle unter dem Migrationslimit laut Richtlinie von 10 Milli- gram pro dm2 liegen.
20Furthermore, reference is made to the migration values which have been determined for some formulations and which are all below the migration limit according to the guideline of 10 milligrams per dm 2 . 20
Beispiel Nr. 29Example No. 29
55 % PLA-Polylactid ( EcoPla 6200 D) und 44,6 % Polyester 1 (Ecoflex sbx) mit 0,4 slipping agent (Loxamid / Hersteller Cognis-Erucasäureamid) wurden im Zweiwellenextruder (Wemer&Pfleiderer ZSK.40) zu einer thermoplastischen Schmelze mit einer Schmelzendtemperatur von 185°C compoundiert und granuliert. Die so erhaltene Polymermischung hatte einen MFI - (g/10 min) 190°C, 5 kg - von 9,5. Aus diesem Polymerblendgranulat wurde auf einer Collin Folienblasanlage eine transparente Folie als Schlauch in einer Breite von 275 mm und in einer Wandstärke von 0,08 mm hergestellt. Die Folie ist leicht bedruckbar und schweissbar bei ca. 110°C. Aus diesem Schlauch wurde eine Getränkeverpackung in den Massen 275 mm x 140 mm x 0,08 durch Verschwcissen hergestellt Diese Schlauchbeutelverpackung wurde mit Milch als ein sensibles Getränk und Füllgut befällt, im Kühlschrank bei 8°C gelagert und auf Lagereigenschaften sowohl bezogen auf den Inhalt wie auch auf den Packstoff getestet.55% PLA polylactide (EcoPla 6200 D) and 44.6% polyester 1 (Ecoflex sbx) with 0.4 slipping agent (loxamide / manufacturer Cognis-Erucasäureamid) were in a twin-screw extruder (Wemer & Pfleiderer ZSK.40) to a thermoplastic melt with a Final melting temperature of 185 ° C compounded and granulated. The polymer mixture thus obtained had an MFI - (g / 10 min) 190 ° C., 5 kg - of 9.5. A transparent film as a tube with a width of 275 mm and a wall thickness of 0.08 mm was produced from this polymer blend granulate on a Collin film blowing system. The film is easily printable and weldable at approx. 110 ° C. From this tube a beverage packaging in the dimensions 275 mm x 140 mm x 0.08 was produced by welding. This tubular bag packaging was infested with milk as a sensitive drink and filling material, stored in the refrigerator at 8 ° C and on storage properties both in terms of content and also tested on the packaging material.
Ergebnisse: Die Schlauchbeutel Verpackung bleibt vollkommen dicht.Results: The tubular bag packaging remains completely sealed.
Im Kühlschrank war kein Milchgeruch nach 72 Stunden Lagerzeit zu riechen.There was no smell of milk in the refrigerator after 72 hours of storage.
Die Milch selbst blieb geruchlich und geschmacklich unverändert während derThe milk itself remained unchanged in smell and taste during the
Lagerzeit.Storage time.
Die Schlaüchbeutelverpackung überstand alle Falltests aus 1 m Höhe unbeschädigt.The tubular bag packaging survived all drop tests from a height of 1 m undamaged.
Die Schlaüchbeutelverpackung befand sich nach 72 h Lagerzeit unverändert in ihren optischen und physikalischen Eigenschaften.The tube bag packaging remained unchanged in its optical and physical properties after a storage time of 72 hours.
Tabelle:Table:
Schlauchfolienverpackung aus Polymerblend Beispiel 29, Folienwaπdstärke 0,08 mmTubular film packaging made of polymer blend Example 29, film wall thickness 0.08 mm
In einem weiteren Test wurden Getrankeverpackuπgen in Form von Folienbeuteln, hergestellt nach dem Beispiel 29, mit Orangensaft geprüft. Dabei bestätigte sich die gute Schutziunktion für Getränke des erfindungsgemäßen Polymerblends als Verpackungsmittel und die Eignung des Werkstoffes zur Verwendung als Getränkeverpackung, als Beschichtung für Getränkeverpackungen und/oder als lnliner für flüssige oder pastöse Lebensmittelverpackungen.
- 21 -In a further test, beverage packaging in the form of foil bags, produced according to Example 29, was tested with orange juice. This confirmed the good protective function for beverages of the polymer blend according to the invention as packaging means and the suitability of the material for use as beverage packaging, as a coating for beverage packaging and / or as an liner for liquid or pasty food packaging. - 21 -
Anhand von Beispiel 29 konnte eindrücklich dargelegt werden, dass die erfindungsgemäss vorgeschlagenen Polymerblends geeignet sind für Lebensmittelverpackung und insbesondere für das Verpacken von Getränken. Dabei können entweder die in Beispiel 29 vorgeschlagenen Schlauchfolienverpackungen aus den erfindungsgemässen Polymerblends hergestellt werden, oder aber Getränkeverpackungen, welche aussen als mechanischen Schutz eine Kartonverstärkung aufweisen und innen eine Folienhülle, bestehend aus dem erfin- dungsgemässen Polymerblend.Using Example 29, it was possible to demonstrate impressively that the polymer blends proposed according to the invention are suitable for food packaging and in particular for packaging beverages. Either the tubular film packaging proposed in Example 29 can be produced from the polymer blends according to the invention, or else beverage packaging which has a cardboard reinforcement on the outside as mechanical protection and a film sleeve on the inside consisting of the polymer blend according to the invention.
Allerdings ist es natürlich möglich, irgendwelche Behältnisse unter Verwendung eines erfindungsgemässen Polymerblends herzustellen für die Aufnahme von flüssigen Füllgütern bzw. viskosen oder pastösen Füllgütern, insbesondere für die Aufnahme der oben erwähnten Getränke- bzw. anderer flüssiger Lebensmittelgüter, wie beispielsweise Speiseöl.However, it is of course possible to produce any containers using a polymer blend according to the invention for holding liquid fillings or viscous or pasty fillings, in particular for holding the above-mentioned beverage or other liquid foodstuffs, such as, for example, cooking oil.
Beispiel 30:Example 30:
Eine erfindungsgemässe Polymermischung in der ZusammensetzungA polymer mixture according to the invention in the composition
15 % native Kartoffelstärke (trocken)15% native potato starch (dry)
15 % Polylactid-Ecopla 6200 D (Nature Works 6200 D)15% polylactide-Ecopla 6200 D (Nature Works 6200 D)
70 % Polyester 1-Ecoflex SBX 700070% polyester 1-Ecoflex SBX 7000
0,4 % slipping agent Loxiol EP 728 (Cognis)0.4% slipping agent Loxiol EP 728 (Cognis)
Beim sogenannten "slipping agent Loxiol EP 728" handelt es sich um einen Polyol-Partialester der Firma Henkel KgaA,The so-called "slipping agent Loxiol EP 728" is a polyol partial ester from Henkel KgaA,
Düsseldorf, COK Plastics and Coatings. Aufgrund seines polaren Charakters eignet sich Loxiol EP 728 besonders zur Verbesserung der Fliesseigenschaften bei der Spritzgussver-
- 22 -Düsseldorf, COK Plastics and Coatings. Due to its polar character, Loxiol EP 728 is particularly suitable for improving the flow properties in injection molding - 22 -
arbeitung von u.a. Polyestern. Zudem ergibt sich eine bessere Verteilung von Füllstoffen und Pigmenten in der Polymerschmelze.work of u.a. Polyesters. In addition, there is a better distribution of fillers and pigments in the polymer melt.
Die Zusammensetzung wurde erhalten durch Compoundieren im Zweiwellenextruder (Werner & Pfleiderer, ZSK 40) zu einer homogenen Schmelze bei 170 °C Schmelzetemperatur und vollständiger Entgasung. Das erhaltene Granulat hat einen MFI ((g/10 min.) 190°C, 5 kg) von 13,7 und eine Restfeuchte von 0,2 %.The composition was obtained by compounding in a twin-screw extruder (Werner & Pfleiderer, ZSK 40) to give a homogeneous melt at 170 ° C. melt temperature and complete degassing. The granules obtained have an MFI ((g / 10 min.) 190 ° C., 5 kg) of 13.7 and a residual moisture of 0.2%.
Das Granulat ist geeignet zur Weiterverarbeitung als Blasfolie, Flachfolie und Spritzguss. Die erhaltenen, fast transparenten Folien sind weichmacherfrei, leicht bedruckbar und schweissarm.The granulate is suitable for further processing as blown film, flat film and injection molding. The almost transparent films are plasticizer-free, easy to print and low-sweat.
Völlig überraschend wurde bei der mikroskopischen Untersu- chung der Folie festgestellt, dass keine granulären Strukturen der Stärke mehr vorhanden sind. Wir gehen davon aus, dass unter den optimierten Compoundierbedingungen die native Kartoffelstärke, die mit dem natürlichen Wassergehalt von ca. 18 % zudosiert wird, vollständig destrukturiert und filmbildend wird.Quite surprisingly, when the film was examined microscopically, it was found that there were no longer any granular structures of the starch. We assume that under the optimized compounding conditions, the native potato starch, which is added with the natural water content of approx. 18%, will be completely destructured and film-forming.
Die angeführten Beispiele dienen lediglich der besseren Erläuterung der vorliegenden Erfindung und diese ist keinesfalls auf die in den Beispielen verwendeten Materialien limitiert. Erfindungswesentlich ist lediglich, dass in einem Polymerblend mindestens ein Teil aromatischer Polyester enthalten ist auf Basis von aliphatischen und aromatischen Blöcken sowie mindestens ein aliphatischer Polyester, hergestellt auf Basis unter anderen von Hydroxycarbonsäuren und/oder Lactonen und/oder deren Derivaten. Je nach Anteil der verschiedenen Materialien lassen sich unterschiedliche
- 23 -The examples given serve only to better explain the present invention and this is in no way limited to the materials used in the examples. It is only essential to the invention that a polymer blend contains at least part of aromatic polyester based on aliphatic and aromatic blocks and at least one aliphatic polyester produced based on, among others, hydroxycarboxylic acids and / or lactones and / or their derivatives. Depending on the proportion of different materials, different ones can be - 23 -
Eigenschaften erzeugen, wobei es wesentlich ist, dass der Polymerblend wenigstens nahezu Weichmacher-frei ist bzw. frei von niedermolekularen Bestandteilen, welche aus Folien oder Formkörpern, hergestellt aus den erfindungsgemässen Polymerblends heraus migrieren können.
Generate properties, it being essential that the polymer blend is at least almost free of plasticizer or free of low molecular weight components which can migrate out of films or moldings produced from the polymer blend according to the invention.
Claims
1. Biologisch abbaubarer Polymerblend, erhältlich mittels Extrusion, gekennzeichnet durch mindestens eine teilaromatische Polyesterkomponente basierend auf aliphatischen und aromatischen Blöcken sowie mindestens ca. 10 Gew.% bezogen auf die Mischung mit dem teilaromatischen Polyester eines aliphatischen Polyesters auf Basis unter anderem mindestens einer Hydroxycarbonsäure und/oder mindestens eines Lactons mit einem Glasumwandlungspunkt (TG) des aliphatischen Poly- esters von höher als 50°C.1. Biodegradable polymer blend, obtainable by extrusion, characterized by at least one partially aromatic polyester component based on aliphatic and aromatic blocks and at least about 10% by weight, based on the mixture with the partially aromatic polyester of an aliphatic polyester based, inter alia, on at least one hydroxycarboxylic acid and / or at least one lactone with a glass transition point (TG) of the aliphatic polyester of higher than 50 ° C.
2. Biologisch abbaubarer Polymerblend, erhältlich durch Extrusion in einem Zweiwellenextruder.2. Biodegradable polymer blend, obtainable by extrusion in a twin-screw extruder.
3. Polymerblend, insbesondere nach einem der Ansprüche 1 oder 2, gekennzeichnet durch einen Anteil am aliphatischen Polyester von mindestens ca. 15 Gew.%, bezogen auf die Mischung mit dem teilaromatischen Polyester, vorzugsweise von mindestens ca. 20 Gew.%.3. polymer blend, in particular according to one of claims 1 or 2, characterized by a proportion of the aliphatic polyester of at least approximately 15% by weight, based on the mixture with the partially aromatic polyester, preferably of at least approximately 20% by weight.
4. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Blend mindestens ein Polylactid enthält auf Basis von Milchsäure bzw. Derivaten von Milchsäure.4. Polymer blend, in particular according to one of claims 1 to 3, characterized in that the blend contains at least one polylactide based on lactic acid or derivatives of lactic acid.
5. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 3, gekennzeichnet durch mindestens einen aliphatischen Polyester auf Basis von einem oder mehreren Lactonen, wie beispielsweise Polycaprolacton.5. polymer blend, in particular according to one of claims 1 to 3, characterized by at least one aliphatic polyester based on one or more lactones, such as polycaprolactone.
6. Polymerblend, insbesondere nach einem der Ansprüche Ibis 3, gekennzeichnet durch mindestens einen aliphatischen Polyester auf Basis von Hydroxybuttersäure, Hydroxyvalerian- säure und/oder Derivaten oder Mischungen davon. - 25 -6. polymer blend, in particular according to one of claims 3, characterized by at least one aliphatic polyester based on hydroxybutyric acid, hydroxyvaleric acid and / or derivatives or mixtures thereof. - 25 -
7. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 6, gekennzeichnet durch mindestens einen teilaromatischen Copolyester auf Basis aromatischer oder aliphatischer Dicarbonsäuren und/oder deren Ester-bildenden Derivaten o- der Mischungen davon und/oder auf Basis mindestens einer aromatischen Dicarbonsäure und/oder deren Ester-bildenden Derivaten oder Mischungen davon.7. polymer blend, in particular according to one of claims 1 to 6, characterized by at least one partially aromatic copolyester based on aromatic or aliphatic dicarboxylic acids and / or their ester-forming derivatives or mixtures thereof and / or based on at least one aromatic dicarboxylic acid and / or their ester-forming derivatives or mixtures thereof.
8. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 7, gekennzeichnet durch einen teilaromatischen Copoly- ester auf Basis mindestens eines C2 - Cι2-Alkandiols und/oder mindestens eines C5 - Cι0-Cycloalkandiols oder Mischungen davon oder gegebenenfalls einer oder mehrerer Komponenten, wie Etherfunktionen enthaltenden Hydroxyverbin- dungen.8. A polymer blend, in particular according to one of claims 1 to 7, characterized by a partly aromatic copoly ester on the basis of at least one C 2 - Cι 2 alkanediol and / or at least one C 5 - Cι 0 -Cycloalkandiols or mixtures thereof or optionally one or several components, such as hydroxy compounds containing ether functions.
9. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 8, enthaltend mindestens einen Copolyester, erhältlich durch Polykondensation von einerseits mindestens einem Di- ol, beispielsweise aus der Reihe 2, 1-Ethandiol, 1,3- Propandiol, 1, 4-Butandiol und/oder 1, 6-Hexandiol mit ande- rerseits mindestens einer aromatischen Dicarbonsäure, wie beispielsweise Terephthalsäure und gegebenenfalls mindestens einer aliphatischen Dicarbonsäure, wie Adipinsäure und/oder Sebacinsäure.9. polymer blend, in particular according to one of claims 1 to 8, containing at least one copolyester, obtainable by polycondensation of on the one hand at least one diol, for example from the series 2, 1-ethanediol, 1,3-propanediol, 1, 4-butanediol and / or 1,6-hexanediol with, on the other hand, at least one aromatic dicarboxylic acid, such as, for example, terephthalic acid and optionally at least one aliphatic dicarboxylic acid, such as adipic acid and / or sebacic acid.
10. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 9, enthaltend mindestens ein Polylactid sowie Polyhydroxybuttersäure und/oder Polyhydroxybuttersäure/Valeriansäure-Copolyester und/oder Derivate davon.10. polymer blend, in particular according to one of claims 1 to 9, containing at least one polylactide and polyhydroxybutyric acid and / or polyhydroxybutyric acid / valeric acid copolyester and / or derivatives thereof.
11. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 10, weiter enthaltend native Stärke, wie beispielsweise - 26 -11. polymer blend, in particular according to one of claims 1 to 10, further containing native starch, such as - 26 -
Mais- oder Kartoffelstärke in weitgehendst kristalliner Form.Corn or potato starch in a largely crystalline form.
12. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 10, weiter enthaltend destrukturierte bzw. thermoplas- tische Stärke.12. polymer blend, in particular according to one of claims 1 to 10, further containing destructurized or thermoplastic starch.
13. Polymerblend, insbesondere nach einem der Ansprüche 1 bis 10 oder 12, gekennzeichnet durch13. polymer blend, in particular according to one of claims 1 to 10 or 12, characterized by
1 - 20 % destrukturierte oder thermoplastische Stärke,1 - 20% destructured or thermoplastic starch,
10 - 20 % eines Polylactides,10 - 20% of a polylactide,
40 - 80 % eines aliphatisch/aromatischen Polyesters sowie40 - 80% of an aliphatic / aromatic polyester as well
0 - 1 % einer Fliesshilfe.0 - 1% of a flow aid.
14. Verfahren zur Herstellung eines Polymerblends nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass mindestens ein teilaromatischer Polyester und mindestens ein aliphatischer Polyester auf Basis unter anderem mindestens einer Hydroxycarbonsäure und/oder mindestens eines Lactons in einem Extruder, wie vorzugsweise einem Zweiwellen-Extruder, in der Schmelze in einem Temperaturbereich von 120 - 250 °C intensiv gemischt werden, um anschliessend extrudiert und konditioniert zu werden.14. A method for producing a polymer blend according to any one of claims 1 to 13, characterized in that at least one partially aromatic polyester and at least one aliphatic polyester based, inter alia, at least one hydroxycarboxylic acid and / or at least one lactone in an extruder, such as preferably a twin-screw Extruder in which the melt is mixed intensively in a temperature range of 120 - 250 ° C in order to be subsequently extruded and conditioned.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass 10 - 25 % native Stärke mit einem natürlichen Wassergehalt von ca. 15 - 20 % mit 10 - 25 % einer Polymilchsäu- re, 60 - 80 % eines aliphatisch/aromatischen Polyester, 0 - 1 % eines Fliesshilfsmittels sowie ggf. weiteren Komponenten und Additiven in einem Extruder gemischt und die Schmelze wenigstens nahezu vollständig entgast und extru- - 27 -15. The method according to claim 14, characterized in that 10-25% native starch with a natural water content of approximately 15-20% with 10-25% of a polylactic acid, 60-80% of an aliphatic / aromatic polyester, 0- 1% of a flow aid and possibly other components and additives are mixed in an extruder and the melt is at least almost completely degassed and extruded. - 27 -
diert wird, wobei die erhaltenen Granulate eine Restfeuchte von 0,1 - 1 % aufweisen.is dated, the granules obtained have a residual moisture content of 0.1-1%.
16. Verfahren nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass dem Extruder Gleitmittel, anorganische Füll- Stoffe, wie beispielsweise Talk oder Kaolin oder weitere Additive, wie beispielsweise Farbstoffe, Titandioxid und dgl . beigemischt werden.16. The method according to claim 14 or 15, characterized in that the extruder lubricant, inorganic fillers such as talc or kaolin or other additives such as dyes, titanium dioxide and the like. be added.
17. Verwendung des Polymerblends nach einem der Ansprüche 1 bis 13 zur Herstellung von Lebensmittelfolien, insbesondere für die Verpackung von Lebensmitteln bzw. Fastfoodproduk- ten.17. Use of the polymer blend according to one of claims 1 to 13 for the production of food films, in particular for the packaging of foods or fast food products.
18. Verwendung des Polymerblends nach einem der Ansprüche 1 bis 13 zur Herstellung von Verpackungen für die Aufnahme von flüssigen bzw. viskosen oder pastösen Füllgütern, wie insbesondere von flüssigen Lebensmitteln, wie Getränke, Speiseöl und dgl.18. Use of the polymer blend according to one of claims 1 to 13 for the production of packaging for the reception of liquid or viscous or pasty filling materials, such as in particular liquid foods, such as drinks, cooking oil and the like.
19. Verwendung des Polymerblends nach Anspruch 13 zur Herstellung von Verpackungsmaterialien oder Formungen im Zusammenhang mit elektrischen oder elektronischen Anwendun- gen.19. Use of the polymer blend according to claim 13 for the production of packaging materials or moldings in connection with electrical or electronic applications.
20. Verwendung des Polymerblends nach einem der Ansprüche 1 bis 13 zur Herstellung von Verpackungsfolien im Nonfood- bereich.20. Use of the polymer blend according to one of claims 1 to 13 for the production of packaging films in the non-food area.
21. Getränkeverpackung, aufweisend eine mehrlagige Behält- niswandung, bestehend mindestens aus einer Wandungslage aus verstärktem Papier, Karton oder dgl. und mindestens einer Schicht, wie vorzugsweise der Innenschicht, hergestellt aus einem Polymerblend nach einem der Ansprüche 1 bis 13. 21. Beverage packaging, comprising a multi-layer container wall, consisting of at least one wall layer made of reinforced paper, cardboard or the like and at least one layer, such as preferably the inner layer, made from a polymer blend according to one of claims 1 to 13.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH156800 | 2000-08-11 | ||
CH15682000 | 2000-08-11 | ||
CH17472000 | 2000-09-07 | ||
CH174700 | 2000-09-07 | ||
PCT/IB2001/001407 WO2002014430A2 (en) | 2000-08-11 | 2001-08-07 | Biodegradable polymeric blend |
Publications (1)
Publication Number | Publication Date |
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EP1309661A2 true EP1309661A2 (en) | 2003-05-14 |
Family
ID=25738986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01954255A Withdrawn EP1309661A2 (en) | 2000-08-11 | 2001-08-07 | Biodegradable polymeric blend |
Country Status (7)
Country | Link |
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US (1) | US20030187149A1 (en) |
EP (1) | EP1309661A2 (en) |
JP (1) | JP2004506773A (en) |
CN (1) | CN1446247A (en) |
AU (1) | AU2001276597A1 (en) |
CA (1) | CA2419146A1 (en) |
WO (1) | WO2002014430A2 (en) |
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CN1446247A (en) | 2003-10-01 |
JP2004506773A (en) | 2004-03-04 |
CA2419146A1 (en) | 2003-02-06 |
US20030187149A1 (en) | 2003-10-02 |
WO2002014430A2 (en) | 2002-02-21 |
AU2001276597A1 (en) | 2002-02-25 |
WO2002014430A3 (en) | 2002-08-15 |
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