EP4278032A1 - Fibres polymères à composants multiples biodégradables - Google Patents
Fibres polymères à composants multiples biodégradablesInfo
- Publication number
- EP4278032A1 EP4278032A1 EP22702168.0A EP22702168A EP4278032A1 EP 4278032 A1 EP4278032 A1 EP 4278032A1 EP 22702168 A EP22702168 A EP 22702168A EP 4278032 A1 EP4278032 A1 EP 4278032A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- fibre
- astm
- copolymer
- additive
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 152
- 239000000835 fiber Substances 0.000 claims abstract description 126
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 claims description 245
- 229920001169 thermoplastic Polymers 0.000 claims description 144
- 239000000654 additive Substances 0.000 claims description 139
- 230000000996 additive effect Effects 0.000 claims description 97
- 239000000463 material Substances 0.000 claims description 92
- 229920003023 plastic Polymers 0.000 claims description 84
- 239000004033 plastic Substances 0.000 claims description 84
- 229920001577 copolymer Polymers 0.000 claims description 77
- 238000002844 melting Methods 0.000 claims description 68
- 230000008018 melting Effects 0.000 claims description 68
- 238000006065 biodegradation reaction Methods 0.000 claims description 61
- 238000007655 standard test method Methods 0.000 claims description 52
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 49
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 49
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 48
- 229920000728 polyester Polymers 0.000 claims description 47
- 230000009477 glass transition Effects 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 40
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 39
- 229920001222 biopolymer Polymers 0.000 claims description 36
- 239000004743 Polypropylene Substances 0.000 claims description 34
- 229920003232 aliphatic polyester Polymers 0.000 claims description 34
- 239000004744 fabric Substances 0.000 claims description 34
- 229920001155 polypropylene Polymers 0.000 claims description 34
- 229920002678 cellulose Polymers 0.000 claims description 33
- 239000001913 cellulose Substances 0.000 claims description 33
- 239000004753 textile Substances 0.000 claims description 32
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 31
- 239000000194 fatty acid Substances 0.000 claims description 31
- 229930195729 fatty acid Natural products 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000004952 Polyamide Substances 0.000 claims description 25
- 229920002472 Starch Polymers 0.000 claims description 25
- 238000009264 composting Methods 0.000 claims description 25
- 229920002647 polyamide Polymers 0.000 claims description 25
- 235000019698 starch Nutrition 0.000 claims description 25
- 235000014655 lactic acid Nutrition 0.000 claims description 23
- 239000008107 starch Substances 0.000 claims description 23
- 125000001931 aliphatic group Chemical group 0.000 claims description 22
- 150000001720 carbohydrates Chemical class 0.000 claims description 22
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- 238000006731 degradation reaction Methods 0.000 claims description 22
- 150000002772 monosaccharides Chemical class 0.000 claims description 22
- 150000002482 oligosaccharides Chemical class 0.000 claims description 22
- 229920001610 polycaprolactone Polymers 0.000 claims description 22
- 229920005862 polyol Polymers 0.000 claims description 22
- 150000003077 polyols Chemical class 0.000 claims description 22
- 235000000346 sugar Nutrition 0.000 claims description 22
- 150000008163 sugars Chemical class 0.000 claims description 22
- 230000015556 catabolic process Effects 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 20
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 20
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 claims description 20
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000004310 lactic acid Substances 0.000 claims description 19
- 238000004806 packaging method and process Methods 0.000 claims description 19
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 19
- 229920000573 polyethylene Polymers 0.000 claims description 19
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 19
- 239000002689 soil Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 16
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000005809 transesterification reaction Methods 0.000 claims description 15
- 229920002292 Nylon 6 Polymers 0.000 claims description 14
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- 239000004631 polybutylene succinate Substances 0.000 claims description 13
- 229920002961 polybutylene succinate Polymers 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- 238000011156 evaluation Methods 0.000 claims description 12
- 239000002054 inoculum Substances 0.000 claims description 12
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- 239000013535 sea water Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 150000003623 transition metal compounds Chemical class 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 10
- 239000004632 polycaprolactone Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 229920001634 Copolyester Polymers 0.000 claims description 9
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 8
- 229920001542 oligosaccharide Polymers 0.000 claims description 8
- 239000004630 polybutylene succinate adipate Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- 150000002016 disaccharides Chemical class 0.000 claims description 7
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 229920003051 synthetic elastomer Polymers 0.000 claims description 7
- 239000005061 synthetic rubber Substances 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- 229920000704 biodegradable plastic Polymers 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 238000002372 labelling Methods 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229920001748 polybutylene Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000010801 sewage sludge Substances 0.000 claims description 6
- 125000001174 sulfone group Chemical group 0.000 claims description 6
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 5
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 4
- 229920000090 poly(aryl ether) Polymers 0.000 claims description 4
- 229920006260 polyaryletherketone Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- AFENDNXGAFYKQO-UHFFFAOYSA-N 2-hydroxybutyric acid Chemical compound CCC(O)C(O)=O AFENDNXGAFYKQO-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229920002347 Polypropylene succinate Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 2
- 229920001780 ECTFE Polymers 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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- D—TEXTILES; PAPER
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/12—Physical properties biodegradable
Definitions
- the invention relates to a biologically degradable polymer fibre with advantageous physical properties, to a process for its production, as well as to its use.
- Polymer fibres i.e. fibres based on synthetic polymers
- the basic synthetic polymer is processed using a melt spinning process.
- the thermoplastic polymeric material is melted and fed in the liquid state into a spinning beam by means of an extruder. From this spinning beam, the molten material is fed to what are known as spinnerets.
- the spinneret usually comprises a spinneret plate provided with a plurality of holes out of which the individual capillaries (filaments) of the fibre are extruded.
- wet spinning or solvent spinning processes are also used for the production of spun fibres.
- the polymer fibres produced in this manner are used for textile and/or technical applications.
- Modifying or equipping polymer fibres for the respective end use or for the necessary intermediate treatment steps, for example drawing and/or crimping, is usually carried out by applying suitable softening agents or dressings which are applied to the surface of the prepared polymer fibres or the polymer fibres to be treated.
- a further possibility for modification is the chemical modification of the polymer skeleton itself, for example by incorporating flame-retardant co-monomers into the polymeric main and/or side chain.
- additives for example antistatic agents or coloured pigments
- the present invention allows the degradation behaviour of the fibre to be controlled by using two components which behave differently with respect to each other as regards degradation.
- the component A comprises a thermoplastic polymer A
- the component B comprises a thermoplastic polymer B, characterized in that
- the component A additionally has at least one additive A which increases the biological degradability of the multi-component fibre and the component B does not have an additive B which increases the biological degradability of the multicomponent fibre, or
- the component B additionally has at least one additive B which increases the biological degradability of the multi-component fibre and the component A does not have an additive A which increases the biological degradability of the multicomponent fibre, or
- the component A additionally has at least one additive A and the component B additionally has at least one additive B which together increase the biological degradability of the multi-component fibre, with the proviso that when (i) the thermoplastic polymer A and the thermoplastic polymer B are identical, the additives A and B are different, or (ii) when the additives A and B are identical, thermoplastic polymer A and thermoplastic polymer B are different.
- an increased biological degradability of the multi-component fibre means that this multi-component fibre, compared with a multi-component fibre without additives A and/or B, is degraded more rapidly, wherein the determination is carried out in accordance with at least one method selected from the group (i) ASTM D5338-15 (2021 ) (Standard Test Method for
- ASTM D5511 ASTM D5511-11 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solids Anaerobic Digestion Conditions (DOI: 10.1520/D5511-11 ) and ASTM D5511 -18 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solids Anaerobic-Digestion Conditions; (DOI: 10.1520/D5511-18)
- ASTM D6691 ASTM D6691-09 Standard Test Method for Determining Aerobic
- the multi-component polymer fibre in accordance with the invention is usually deposited as a tow and subsequently drawn on a rolling mill using the usual methods and then posttreated.
- the tow can also be processed further directly and so deposition of the tow in what are known as cans can be entirely or partially dispensed with.
- the multi-component polymer fibre in accordance with the invention can be cooled directly following exit from the spinneret and drawn and deposited on a collecting belt or wound onto bobbins.
- the filaments may be drawn further for further processing in order to increase the orientation of the molecular chains, in particular with a draw ratio between 0.5 and 3. Furthermore, it is possible to texturize the filaments.
- the combination of different biological degradabilities for the components A and B means that the biological degradability of the products resulting from these multi-component polymer fibres can be designed and customized.
- Textile fabrics for example nonwovens, can be produced from the multicomponent polymer fibres in accordance with the invention.
- the textile fabrics, in particular nonwovens are consolidated using thermobonding, it is advantageous for the melting point of the thermoplastic polymer in component A to be at least 5°C higher than the melting point of the thermoplastic polymer in component B.
- the multi-component polymer fibres are preferably bi-component fibres in which component A forms the core and component B forms the shell.
- the melting point of the thermoplastic polymer in component A is at least 10°C higher than the melting point of the thermoplastic polymer in component B.
- the fibres are bonded together at the contact or crossover points.
- component B formed from thermoplastic polymer B with additive B has a higher biological degradability than component A formed from thermoplastic polymer A with additive A
- the contact or crossover points of the fibres are degraded together first and the textile fabric, for example a nonwoven, disintegrates faster, whereupon the overall degradability is increased.
- a multi-component fibre which comprises a very rapidly biologically degradable component A with at least one further component B, wherein component B has a lower biological degradation rate than component A.
- component B has a lower biological degradation rate than component A.
- the components in the multi-component fibre in addition to the core/shell structure, wherein the core may be concentric with and also may be eccentric with respect to the shell are a side-by-side structure, a matrix-fibril structure as well as slice-of-cake structures or orange-slice structures.
- multi-component polymer fibres in particular bi-component polymer fibres, which combine a very rapidly biologically degradable core (component A) produced from thermoplastic polymer A and optionally an additive A, with an equally biologically degradable shell (component B) produced from thermoplastic polymer B with additive B, so that the component A is only biologically degraded when component B has already been biologically degraded.
- component A very rapidly biologically degradable core
- component B equally biologically degradable shell
- the present invention provides a bi-component fibre with a core/shell structure wherein,
- the component A in the core comprises thermoplastic polymer A
- the component B comprises a thermoplastic polymer B
- the melting point of the thermoplastic polymer in the component A in the core is at least 5°C higher than the melting point of the thermoplastic polymer in the component B in the shell; preferably, the melting point is at least 10°C higher, characterized in that
- the component A has a higher biological degradability than the component B; preferably, the component A has at least one additive A, or
- the component B has a higher biological degradability than the component A; preferably, the component B has at least one additive B.
- the higher biological degradability is determined in accordance with at least one method selected from the group formed by:
- ASTM D5511 ASTM D5511-11 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solids Anaerobic- Digestion Conditions (DOI: 10.1520/D5511-11 ) and ASTM D5511 -18 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solids Anaerobic-Digestion Conditions; (DOI: 10.1520/D5511-18)
- ASTM D6691 ASTM D6691 (ASTM D6691-09 Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in the Marine Environment by a Defined Microbial Consortium or Natural Sea Water Inoculum) (DOI: 10.1520/D6691-09) and ASTM D6691-17, Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in the Marine Environment by a Defined Microbial Consortium or Natural Sea Water Inoculum (DOI: 10.1520/D6691- 17)),
- PAS 9017:2020 Puls - Biodegradation of polyolefins in an open-air terrestrial environment - Specification
- ISBN 978 0 539 17478 6; 2021-10-31 ISBN 978 0 539 17478 6; 2021-10-31 .
- ASTM D5988 ASTM D5988-12 Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in Soil
- ASTM D5988-18 Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in Soil
- ASTM D5988-03 Standard Test Method for Determining Aerobic Biodegradation in Soil of Plastic Materials or Residual Plastic Materials After Composting (DOI: 10.1520/D5988-03)
- the bi-component fibre in accordance with the invention can therefore be tailored for any intended purpose and any environment.
- the shell component B - which protects against biological degradability - is biologically degraded and after it has degraded, component A is degraded.
- materials may be used as component A which have a biological degradability which is so high that they usually cannot be engineered, because their high biological degradability means that they are is assumed to be unstable or unsuitable.
- the protective shell can also have a retarding action, i.e. the shell initially at least slows down the biological degradability and after a specific time or period of use, a rapid biological degradation occurs.
- textile fabrics which have the one bi-component fibre in accordance with the invention may be used in agriculture, in which the component A has a high biological degradability in accordance with ASTM D5338-15 or ASTM D6400 or ASTM D5988, but is initially protected by the shell. Textile fabrics of this type can be disposed of after the intended use by means of controlled composting.
- a further advantage of the present invention is that textile fabrics which have a bi- component fibre in accordance with the invention can be provided which on the one hand, for example in agriculture, can be used as intended, but which can reach the ocean via rivers in the event of incorrect disposal.
- a component A which has a high biological degradability in accordance with ASTM D6691 . Because incorrect disposal usually breaks or damages the protective shell, a controlled biological degradability, for example in a maritime environment, is ensured.
- component B has a higher biological degradability than component A, initially the shell component B is degraded, which leads to a faster disintegration of textile fabrics which have the bi-component fibres in accordance with the invention.
- hygiene articles can be composted in a controlled manner in household waste or a sewage plant.
- a step-wise biological degradation may be obtained, bringing with it technical advantages, for example signalling mechanical failure, a comparatively high residual stability of the fibres in the case of advanced biological degradation, etc.
- the bi-component fibre in accordance with the invention may be a finite-length fibre, for example what is known as a staple fibre, or a continuous fibre (filament).
- a finite-length fibre for example what is known as a staple fibre, or a continuous fibre (filament).
- the individual linear density of the bi-component fibre in accordance with the invention is preferably between 0.5 and 30 dtex, in particular 0.7 to 13 dtex.
- linear densities of between 0.5 and 3 dtex and fibre lengths of ⁇ 10 mm, in particular ⁇ 8 mm, particularly preferably ⁇ 6 mm, particularly preferably ⁇ 5 mm, are particularly suitable.
- the cross-sectional proportion of the core with respect to the total cross sectional area of the fibres is between 20% and 90% and the cross-sectional proportion of the shell with respect to the total cross sectional area of the fibres is between 80% and 10%.
- the ratio of the cross sectional area of component A and component B may also contribute to fine tuning the biological degradability behaviour of the fibre.
- Particularly preferred bi-component polymer fibres are those in which the additive A and/or additive B are selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii) aliphatic polyesters, (iii) sugars, in particular monosaccharides, di-saccharides and oligo-saccharides, (iv) catalysts for transesterifications, in particular under basic conditions, (v) carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof.
- the additive A and/or additive B are selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii) aliphatic polyester
- thermoplastic polymer A and/or the thermoplastic polymer B comprises at least one polyester and the additive A and/or additive B is selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii) aliphatic polyesters, (iii) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, (iv) catalysts for transesterifications, in particular under basic conditions, (v) carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof.
- the additive A and/or additive B is selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii
- the aforementioned aliphatic polyesters are distinguished from the polyesters of the thermoplastic polymer A and polymer B in respect of their chemical nature, i.e. the polyester of the thermoplastic polymer A and polymer B is an araliphatic polyester or copolyester, which has been produced from polyols and aliphatic and/or aromatic dicarboxylic acids or their derivatives (anhydrides, esters) by means of polycondensation.
- Particularly preferred additives A and/or additives B contain at least two substances, wherein preferred combinations are:
- A) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO in combination with catalysts for transesterifications, in particular under basic conditions;
- sugars in particular mono-saccharides, di-saccharides and oligo-saccharides, in combination with carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof;
- C) aliphatic polyesters optionally in combination with sugars, in particular monosaccharides, di-saccharides and oligo-saccharides, or carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof.
- thermoplastic polymer A are containing at least basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, preferably in combination with catalysts for transesterifications, in particular under basic conditions; and aliphatic polyesters, especially aliphatic polyester having no side chain carbon atoms, optionally in combination with (i) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, (ii) carbohydrates, in particular starch and/or (iii) cellulose, as well as mixtures thereof.
- basic alkali and/or alkaline earth compounds pH>7 dissolved in water
- carbonates hydrogen carbonates
- sulphates particularly preferably CaCOs
- alkaline additives particularly preferably CaO
- thermoplastic polymer A is polyester and the thermoplastic polymer B is a polyester being different from the polyester in polymer A, and preferably is a co-polyester, and - each - the additive A and the additive B is independently selected from the combination of basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, preferably in combination with catalysts for transesterifications, in particular under basic conditions; and aliphatic polyesters, especially aliphatic polyester having no side chain carbon atoms, optionally in combination with (i) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, (ii) carbohydrates, in particular starch and/or (iii) cellulose, as well as mixtures thereof.
- basic alkali and/or alkaline earth compounds pH>7 dissolved in water
- thermoplastic polymer B is a polyolefin, in particular a polypropylene polymer, which includes as additive B at least (i) metal compounds, in particular transition metal compounds, as well as their salts, preferably at least two chemically different transition metal compounds and (ii) unsaturated carboxylic acids or their anhydrides/esters/amides, preferably in combination with synthetic rubber and/or natural rubber, and - optionally - further comprising (iii) sugars, in particular monosaccharides, disaccharides and oligosaccharides, (iv) carbohydrates, in particular starch and/or (v) cellulose, as well as mixtures thereof.
- phenolic antioxidant stabilizer and CaO can be present.
- the biological degradability can be fine tuned by means of the quantity of additive A in component A or additive B in component B.
- the quantity of additive is usually between 0.005% by weight and 20% by weight, particularly preferably between 0.01 % by weight and 5% by weight, with respect to the total quantity of component A or component B.
- additives described above the following in particular are suitable: (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, (ii) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, as well as (iii) carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof, as well as the aforementioned combinations A), B) or C), because their degradability in accordance with ASTM D6691 or in accordance with ASTM D5338- 15, ASTM D6400 or ASTM D5988 can specifically be adjusted.
- basic alkali and/or alkaline earth compounds pH>7 dissolved in water
- carbonates hydrogen carbonates
- sulphates particularly preferably CaCOs
- sugars in particular mono-saccharides, di-saccharides and oligo-saccharides
- carbohydrates in particular starch and/or cellulose,
- the polymers used in accordance with the invention are thermoplastic polymers.
- thermoplastic polymer as used in the present invention means a synthetic material which can be deformed in a specific range of temperatures, preferably in the range 25°C to 350°C, (thermoplastic). This procedure is reversible, i.e. it can be put into its viscous state any number of times by cooling and heating again, as long as the material is not damaged too much by overheating, which causes what is known as thermal decomposition, or by shaping the material under mechanical load. This is the difference between thermoplastic polymers and thermosets and elastomers.
- thermoplastic polymers used in accordance with the invention are preferably polymers selected from the group formed by acrylonitrile-ethylene-propylene-(diene)- styrene copolymer, acrylonitrile-methacrylate copolymer, acrylonitrilemethylmethacrylate copolymer, chlorinated acrylonitrile, polyethylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-ethylene- propylene-styrene copolymer, cellulose acetobutyrate, cellulose acetopropionate, hydrated cellulose, carboxymethylcellulose, cellulose nitrate, cellulose propionate, cellulose triacetate, polyvinyl chloride, ethylene-acrylic acid copolymer, ethylenebutylacrylate copolymer, ethylene-chlorotrifluoroethylene copolymer, ethylene- ethlyacrylate copolymer, ethylene
- polyamide 612, polyamide 6I, polyamide MXD 6, polyamide PDA-T polyamide, polyarylether, polyaryletherketone, polyamideimide, polyarylamide, polyamino-bis-maleimide, polyarylate, polybutene-1 , polybutylacrylate, polybenzimidazole, poly-bis-maleimide, polyoxadiazobenzimidazole, polybutylterephthalate, polycarbonate, polychlorotrifluoroethylene, polyethylene, polyestercarbonate, polyaryletherketone, polyetheretherketone, polyetherimide, polyetherketone, polyethylene oxide, polyarylether sulphone, polyethylene terephthalate, polyimide, polyisobutylene, polyisocyanurate, polyimide sulphone, polymethacrylimide, polymethacrylate, poly-4- methylpentene, polyacetal, polypropylene, polyphenyl oxide, polypropylene oxide, polyphenylene sulphide
- melt spinnable synthetic biopolymers are preferred, particularly preferably polycondensates and polymerisates produced from bio-based starting materials.
- synthetic biopolymer designates a substance which primarily consists of biogenic raw materials (sustainable raw materials). This differentiates them from conventional mineral oil-based substances or plastics such as, for example, polyethylene (PE), polypropylene (PP) and polyvinyl chloride (PVC), as long as their feedstock ist not renewable (e.g. bio-PE/green PE).
- PE polyethylene
- PP polypropylene
- PVC polyvinyl chloride
- the multi-component fibres in accordance with the invention are produced from biologically degradable synthetic biopolymers, wherein the term “biologically degradable” may, for example, be specified, tested and/or determined in accordance with at least one method selected from the group formed by (i) ASTM D5338-15 (2021 ) (Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials Under Controlled Composting Conditions, Incorporating Thermophilic Temperatures (DOI:10.1520/D5338-15R21 ) ASTM International, West Conshohocken, PA, 2015, www.astm.org), (ii) ASTM D6400-12 (Standard Specification for Labelling of Plastics Designed to be Aerobically Composted in Municipal or Industrial Facilities) (DOI: 10.1520/D6400-12), (iii) ASTM D5511 (ASTM D5511-11 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solid
- Preferred synthetic biopolymers in the context of the present invention are aliphatic, araliphatic polyesters or copolyesters which are produced from polyols, and aliphatic and/or aromatic dicarboxylic acids or their derivatives (anhydrides, esters) by polycondensation, wherein the polyols may be substituted or unsubstituted, and the polyols may be linear or branched polyols.
- Preferred polyols are polyols containing 2 to 8 carbon atoms, polyalkylene etherglycols containing 2 to 8 carbon atoms and cycloaliphatic diols containing 4 to 12 carbon atoms.
- Non-limiting examples of polyols which may be used include ethylene glycol, diethylene glycol, propylene glycol, 1 ,3-propanediol, 2,2-dimethyl- 1 ,3-propanediol, 2-methyl-1 ,3-propanediol, 1 ,3-butanediol, 1 , 4-butanediol, 1 ,5- pentanediol, 1 ,6-hexanediol, polyethylene glycol, diethylene glycol, 2,2,4-trimethyl- 1 ,6-hexanediol, thiodiethanol, 1 ,3-cyclohexanedimethanol, 1 ,4- cyclo
- Preferred polyols include 1 , 4-butanediol, 1 ,3-propanediol, ethylene glycol, 1 ,6-hexanediol, diethylene glycol, isosorbitol and 1 ,4- cyclohexanedimethanol.
- Preferred aliphatic dicarboxylic acids include substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from the group formed by aliphatic dicarboxylic acids containing 2 to 12 carbon atoms and cycloaliphatic dicarboxylic acids containing 5 to 10 carbon atoms, wherein the cycloaliphatic dicarboxylic acids may also contain heteroatoms in the ring.
- the substituted non-aromatic dicarboxylic acids typically contain 1 to 4 substituents selected from halogens, C6-C10 aryl and C1-C4 alkoxy.
- Non-limiting examples of aliphatic and cycloaliphatic dicarboxylic acids include maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2- dimethylglutaric acid, suberic acid, 1 ,3-cyclopentane dicarboxylic acid, 1 ,4- cyclohexane dicarboxylic acid, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, 2,5-norbornane dicarboxylic acid.
- Preferred aromatic dicarboxylic acids include substituted or unsubstituted aromatic dicarboxylic acids selected from the group formed by aromatic dicarboxylic acids containing 6 to 12 carbon atoms, wherein these carboxylic acids may also comprise heteroatoms in the aromatic ring and/or in the substituents.
- the substituted aromatic dicarboxylic acids may typically contain 1 to 4 substituents selected from halogens, C6-C10 aryl and C1-C4 alkoxy.
- aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid , naphthalene dicarboxylic acid and furan dicarboxylic acid.
- the aforementioned aliphatic dicarboxylic acids may also be together with the aforementioned aromatic dicarboxylic acids in the form of copolymers or terpolymers; non-limiting examples are polybutylene-adipate-terephthalate and biobased PTA.
- Particularly preferred synthetic biopolymers in the context of the present invention are aliphatic polyesters with repeat units of at least 4 carbon atoms, for example polyhydroxyalkanoates such as polyhydroxyvalerate and polyhydroxybutyrate- hydroxyvalerate copolymer, polycaprolactone, furan dicarboxylic acid, and succinate- based aliphatic polymers (for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate).
- polyhydroxyalkanoates such as polyhydroxyvalerate and polyhydroxybutyrate- hydroxyvalerate copolymer
- polycaprolactone furan dicarboxylic acid
- succinate- based aliphatic polymers for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- Special examples may be selected from polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate and blends and copolymers of these compounds.
- the preferred synthetic biopolymers are aliphatic polyesters comprising repeat units of lactic acid (PLA), hydroxy fatty acid (PHF) (also designated as polyhydroxyalkanoate, PHA), in particular hydroxybutanoic acid (PHB) and succinate-based aliphatic polymers, for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- PHA lactic acid
- PHF hydroxy fatty acid
- PHB hydroxybutanoic acid
- succinate-based aliphatic polymers for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- aliphatic polyesters should be understood to mean those polyesters which typically have at least approximately 50% molar, preferably at least approximately 60% molar, particularly preferably at least approximately 70% molar, particularly preferably at least 95% molar aliphatic monomers.
- thermoplastic polymers with a glass transition temperature of more than -125°C, advantageously more than -30°C, preferably more than 30°C, particularly preferably more than 50°C, in particular more than 70°C, are extremely advantageous.
- the glass transition temperature of the polymer is in the range -125°C to 200°C, in particular in the range -125°C to 100°C.
- the glass transition temperature is preferably more than 20°C, advantageously more than 25°C, preferably more than 30°C, particularly preferably more than 35°C, in particular more than 40°C.
- the glass transition temperature of the polymer is in the range 35°C to 55°C, in particular in the range 40°C to 50°C.
- polyesters are PET with a glass transition temperature of at least 70°C, PLA with a glass transition temperature in the range 40°C to 70°C, PHA and PHB with a glass transition temperature in the range -40°C to 62°C, PBS, as well as PBS copolymers such as PBSA with a glass transition temperature in the range - 45°C to 45°C and polycaprolactone with a glass transition temperature in the range - 75°C to 45°C.
- PLA glass transition temperature in the range 40°C to 70°C
- PHA and PHB with a glass transition temperature in the range -40°C to 62°C
- PBS as well as PBS copolymers
- PBSA with a glass transition temperature in the range - 45°C to 45°C
- polycaprolactone with a glass transition temperature in the range - 75°C to 45°C.
- Polyesters in particular polyethylene terephthalate, usually have a molecular weight corresponding to an intrinsic viscosity (IV) of 0.4 to 1 .4 (dl/g), measured for solutions in dichloroacetic acid at 25°C.
- IV intrinsic viscosity
- polyesters are those such as PET, PEN, PLA, PBS, PEIT with a number average molecular weight (Mn), preferably determined by gel permeation chromatography against polystyrene standards with a narrow distribution or by end group titration, of at least 20000 g/mol. Better still, the polydispersibility of these polymers is at least 1 .7.
- Mn number average molecular weight
- Polyesters of particular interest are those such as PET with a melting point between 250°C and 260°C.
- polyesters are those such as PET with a melting enthalpy of (80%: 43 J/g; 100% crystal/theoretical): 115 J/g.
- Polyesters of particular interest are those such as PET with a crystallization temperature of at least 125°C and a crystallization enthalpy (125°C) of at least 31 J/g.
- Polyesters of particular interest are those which are commercially available from Trevira GmbH, for example such as Trevira® T298.
- Particularly preferred polyamides have a glass transition temperature in the range 30°C to 80°C, in particular in the range 35°C to 65°C, particularly preferably in the range 50°C to 60°C, wherein these values are intended for PA 6.6 and PA 6 in particular.
- Polyamides of particular interest are those such as PA 6.6 and PA 6 with a number average molecular weight (Mn), preferably determined by gel permeation chromatography against polystyrene standards with a narrow distribution or by end group titration, of at least 10000 g/mol.
- Mn number average molecular weight
- Polyamides of particular interest are those such as PA 6.6 and PA 6, with a melting point between 170°C and 280°C, more preferably between 200°C and 260°C.
- Polyamides of particular interest are those such as PA 6.6 and PA 6 with a Crystal melting enthalpy (100% crystal) of 190°C.
- Particularly interesting polyamides are those such as PA 6.6 and PA 6 with a softening temperature of 204°C.
- polyamides such as Nylon, Perlon or Grilon are of particular interest.
- Polyolefins of particular interest are those such as polyethylene (PE) or polypropylene (PP) hompolymers, as well as copolymers or terpolymers which comprise at least 50 mol % of ethylene and/or propylene repeat units.
- PE polyethylene
- PP polypropylene
- Polyethylenes of particular interest are low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (LILDPE), medium density polyethylene (MDPE), polymethylpentene ( PMP), polybutene-1 (PB-1 ); ethylene-octene copolymers, stereoblock PP, olefin block copolymers, propylene-butane copolymers.
- Particularly preferred polyolefins are PE with a glass transition temperature in the range -100°C to -35°C and PP with a glass transition temperature in the range -10°C to -5°C.
- Polyethylenes of particular interest are those with a melting point between 120°C and 135°C and polypropylene with a melting point between 158°C and 170°C.
- Polyethylenes of particular interest are those with a crystal melting enthalpy (100% crystal) of 290 J/g and polypropylene with a crystal melting enthalpy of 190 J/g.
- LDPE PE Aspun 6834, Dow
- HDPE SKGC MK 910
- PP Braskem
- suitable polymers are those which have a melting temperature of more than 50°C, advantageously at least 75°C, preferably more than 150°C.
- the melting temperature is in the range 120°C to 285°C, in particular in the range 150°C to 270°C, particularly preferably in the range 175°C to 270°C.
- the glass transition temperature and the melting temperature of the polymer are preferably determined by means of Differential Scanning Calorimetry (DSC).
- thermoplastic polycondensates based on what are known as biopolymers, which contain the repeat units of lactic acid, hydroxybutyric acid, succinic acid, glycolic acid and/or furan dicarboxylic acid, preferably lactic acid and/or glycolic acid, in particular lactic acid.
- Polylactic acids are particularly preferred in this regard.
- a variety of high melting point synthetic biopolymers (melting point between 110°C and 270°C, preferably between 140°C and 270°C, more preferably between 180°C and 270°C), such as polyesters, may be used in the present invention, such as polyesteramides, modified polyethylene terephthalate, polylactic acid (PLA), terpolymers based on polylactic acid, polybutylene succinate, polyalkylene furanoate such as PEF, polyglycolic acid, polyalkylene carbonates (such as polyethylene carbonate), polyhydroxyalkanoates (PHA) such as polyhydroxybutyrates (PHB), polyhydroxyvalerates (PHV) or polyhydroxybutyrate-hydroxyvalerate copolymers (PHBV).
- PFA polyhydroxyalkanoates
- PVB polyhydroxybutyrates
- PV polyhydroxyvalerates
- PHBV polyhydroxybutyrate-hydroxyvalerate copolymers
- polylactic acid should be understood here to mean polymers which are constructed from lactic acid units. Such polylactic acids are usually produced by condensation of lactic acids, but are also obtained by ring-opening polymerization of lactides under suitable conditions.
- Particularly suitable polylactic acids in accordance with the invention include poly(glycolide-co-L-lactide), poly(L-lactide), poly(L-lactide-co-s-caprolactone), poly(L- lactide-co-glycolide), poly(L-lactide -co-D,L-lactide), poly(D,L-lactide-co-glycolide) as well as poly(dioxanone).
- polymers of this type are commercially available from Boehringer Ingelheim Pharma KG (Germany) under the trade names Resomer® GL 903, Resomer® L 206 S, Resomer® L 207 S, Resomer® L 209 S, Resomer® L 210, Resomer® L 210 S, Resomer® LC 703 S, Resomer® LG 824 S, Resomer® LG 855 S, Resomer® LG 857 S, Resomer® LR 704 S, Resomer® LR 706 S, Resomer® LR 708, Resomer® LR 927 S, Resomer® RG 509 S and Resomer® X 206 S from Biomer, Inc. (Germany) with the name Biomer(TM) L9000.
- Other suitable polylactic acid polymers are commercially available from Natureworks, LLC, Minneapolis, Minnesota, USA.
- polylactic acids for the purposes of the present invention are poly-D-, poly-L- or poly-D,L-lactic acids in particular.
- polylactic acid generally refers to homopolymers of lactic acid such as poly (L-lactic acid), poly (D-lactic acid), poly (DL-lactic acid), mixtures thereof and copolymers, which contain lactic acid as the primary component and a small proportion, preferably less than 10% molar, of a co-polymerizable co-monomer.
- polyalkylene carbonates such as polyethylene carbonate
- PHA polyhydroxyalkanoates
- PB polyhydroxybutyrates
- PV polyhydroxyvalerates
- PHBV polyhydroxybutyrate-hydroxyvalerate copolymers
- the biopolymer is exclusively a thermoplastic polycondensate based on lactic acids.
- the polylactic acids used in accordance with the invention preferably have a number average molecular weight (Mn) which is a minimum of 500 g/mol, preferably a minimum of 1000 g/mol, particularly preferably a minimum of 5000 g/mol, appropriately a minimum of 10000 g/mol, in particular a minimum of 25000 g/mol.
- Mn number average molecular weight
- the number average is preferably a maximum of 1000000 g/mol, appropriately a maximum of 500000 g/mol, advantageously a maximum of 100000 g/mol, in particular a maximum of 50000 g/mol.
- a number average molecular weight in the range from a minimum of 10000 g/mol to 500000 g/mol has proved to be particularly advantageous in the context of the present invention.
- the mass average molecular weight (Mw) of preferred lactic acid polymers is preferably in the range 750 g/mol to 5000000 g/mol, preferably in the range 5000 g/mol to 1000000 g/mol, particularly preferably in the range 10000 g/mol to 500000 g/mol, in particular in the range 30000 g/mol to 500000 g/mol, and the polydispersity of these polymers is advantageously in the range 1 .5 to 5.
- the inherent viscosity of particularly suitable lactic acid polymers, poly-D-, poly-L- or poly-D, L-lactic acids in particular, measured in chloroform at 25°C, 0.1 % polymer concentration, is in the range 0.5 dl/g to 8.0 dl/g, preferably in the range 0.8 dl/g to 7.0 dl/g, in particular in the range 1 .5 dl/g to 3.2 dl/g.
- the inherent viscosity of particularly suitable lactic acid polymers is in the range from 1.0 dl/g to 2.6 dl/g, in particular in the range from 1 .3 dl/g to 2.3 dl/g.
- polylactic acids with a glass transition temperature between 50°C and 65°C.
- polylactic acids with a melting point between 155°C and 180°C.
- polyhydroxy fatty acid esters should preferably be understood to mean the following polymers: poly(3- hydroxypropionate) (PHP), poly(3-hydroxybutyrate) (PHB, P3HB), polyphydroxy vale rate) (PHV), poly(3-hydroxyhexanoate) (PHHx), poly(3- hydroxyheptanoate) (PHH), poly(3-hydroxyoctanoate (PHO), poly(3- hydroxynonanoate) (PHN), poly(3-hydroxydecanoate) (PHD), poly(3- hydroxyundecanoate) (PHUD), poly(3-hydroxydodecanoate) (PHDD), poly(3- hydroxytetradecanoate) (PHTD), poly(3-hydroxypentadecanoate) (PHPD), poly(3- hydroxyhexadecanoate) (PHHxD) as well as blends of the aforementioned polymers.
- polyhydroxy fatty acid ester copolymers such as poly(3-hydroxypropionate-co-3-hydroxybutyrate) (P3HP-3HB), poly(3-hydroxypropionate-co-4-hydroxybutyrate) (P3HP-4HB), poly(3- hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-4HB)), poly(3-hydroxybutyrate-co-3- hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3- hydroxyhexanoate) (PHBV-HHx) as well as blends of the aforementioned copolymers, may be used together or with the aforementioned homopolymers.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention are commercially available; examples are Mirel, Biomer P 209, Biopol, Aonilex X, Proganic.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a glass transition temperature in the range -2°C to 62°C.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a melting temperature in the range 100°C to 177°C.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a melt flow index (MFI) of 5-10 g/10 min (190°C, 2.16 kg) determined in accordance with ISO 1133-1 :2011 .
- MFI melt flow index
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a number average molecular weight (Mn) of at least 200000 Dalton, in particular at least 220000 Dalton, particularly preferably at least 250000 Dalton, and a maximum of up to 3000000 Dalton, in particular up to 2500000 Dalton, particularly preferably up to 2000000 Dalton.
- Mn number average molecular weight
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention usually have a mass average molecular weight (Mw) which is about a factor of 2, preferably a factor of 3, times the number average molecular weight (Mn).
- uccinate-based aliphatic polymers should be understood to mean polymers with the following general formula: wherein Ri , R2 ,Rs ,R4 represent linear or branched aliphatic hydrocarbon residues consisting of 2 to 20 carbon atoms.
- Examples in this regard are polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- thermoplastic succinate-based aliphatic polymers used in accordance with the invention are commercially available; examples are Bionolle 1000, BioPBS.
- thermoplastic succinate polymers used in accordance with the invention preferably have a glass transition temperature in the range -45°C to 45°C.
- thermoplastic succinate polymers used in accordance with the invention preferably have a crystallization temperature in the range 70°C to 90°C.
- thermoplastic succinate polymers used in accordance with the invention preferably have a melting temperature in the range 60°C to 180°C.
- thermoplastic succinate polymers used in accordance with the invention preferably have a melt flow index (MFI) of 5-10 g/10 min (190°C, 2.16 kg), determined in accordance with ISO 1133-1 :2011 .
- MFI melt flow index
- thermoplastic succinate polymers used in accordance with the invention preferably have a number average molecular weight (Mn) of at least 20000 Dalton, in particular at least 30000 Dalton, particularly preferably at least 35000 Dalton, and a maximum of up to 140000 Dalton, in particular up to 120000 Dalton, particularly preferably up to 110000 Dalton.
- Mn number average molecular weight
- thermoplastic succinate polymers used in accordance with the invention preferably have a mass average molecular weight (Mw) which is about a factor of 2, preferably a factor of 3, times the number average molecular weight (Mn).
- PCL Polycaprolactone
- polycaprolactones with a glass transition temperature between -45°C and 45°C.
- polycaprolactones with a crystallization temperature between 70°C and 90°C.
- polycaprolactones with a melting point between 60°C and 180°C.
- polycaprolactones with a melting enthalpy of 70-145 J/g.
- polycaprolactones with a number average molecular weight (Mn), preferably determined by gel permeation chromatography against polystyrene standards with a narrow distribution or by end group titration, of at least 20000 Dalton to 140000 Dalton.
- Mn number average molecular weight
- thermoplastic polymer A is selected from the aforementioned group of thermoplastic polymers.
- melt spinnable synthetic biopolymers are preferred, particularly preferably polycondensates and polymerisates produced from bio-based starting materials.
- the synthetic biopolymer is selected from the aforementioned group of synthetic biopolymers.
- Preferred synthetic biopolymers are aliphatic, araliphatic polyesters or copolyesters which are produced from polyols, and aliphatic and/or aromatic dicarboxylic acids or their derivatives (anhydrides, esters) by polycondensation, wherein the polyols may be substituted or unsubstituted, linear or branched polyols.
- Preferred polyols are polyols containing 2 to 8 carbon atoms, polyalkylene etherglycols containing 2 to 8 carbon atoms and cycloaliphatic diols containing 4 to 12 carbon atoms.
- Non-limiting examples of polyols which may be used are ethylene glycol, diethylene glycol, propylene glycol, 1 ,3-propanediol, 2,2-dimethyl-1 ,3- propanediol, 2-methyl-1 ,3-propanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,5- pentanediol, 1 ,6-hexanediol, polyethylene glycol, diethylene glycol, 2,2,4-trimethyl- 1 ,6-hexanediol, thiodiethanol, 1 ,3-cyclohexanedimethanol, 1 ,4- cyclohex
- Preferred polyols include 1 ,4-butanediol, 1 ,3-propanediol, ethylene glycol, 1 ,6-hexanediol, diethylene glycol, isosorbitol and 1 ,4- cyclohexanedimethanol.
- Preferred aliphatic dicarboxylic acids include substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from the group formed by aliphatic dicarboxylic acids containing 2 to 12 carbon atoms and cycloaliphatic dicarboxylic acids containing 5 to 10 carbon atoms, wherein the cycloaliphatic dicarboxylic acids may also contain heteroatoms in the ring.
- the substituted non-aromatic dicarboxylic acids typically contain 1 to 4 substituents selected from halogens, C6-C10 aryl and C1-C4 alkoxy.
- Non-limiting examples of aliphatic and cycloaliphatic dicarboxylic acids include maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2- dimethylglutaric acid, suberic acid, 1 ,3-cyclopentane dicarboxylic acid, 1 ,4- cyclohexanedicarboxylic acid, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, 2,5-norbornane dicarboxylic acid.
- Preferred aromatic dicarboxylic acids include substituted or unsubstituted, aromatic dicarboxylic acids selected from the group formed by aromatic dicarboxylic acids containing 6 to 12 carbon atoms, wherein these carboxylic acids may also comprise heteroatoms in the aromatic ring and/or in the substituents.
- the substituted aromatic dicarboxylic acids may typically have 1 to 4 substituents selected from halogens, C6-C10 aryl and C1-C4 alkoxy.
- aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid and furan dicarboxylic acid.
- the aforementioned aliphatic dicarboxylic acids may also be present in the form of copolymers or terpolymers; non-limiting examples are polybutylene-adipate terephthalate and biobased PTA, for example.
- thermoplastic polymers A preferred melt spinnable synthetic biopolymers are aliphatic polyesters with repeat units of at least 4 carbon atoms, for example polyhydroxyalkanoates such as polyhydroxyvalerate and polyhydroxybutyrate- hydroxyvalerate copolymer, polycaprolactone, furan dicarboxylic acid, and succinate- based aliphatic polymers (for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate).
- polyhydroxyalkanoates such as polyhydroxyvalerate and polyhydroxybutyrate- hydroxyvalerate copolymer
- polycaprolactone furan dicarboxylic acid
- succinate- based aliphatic polymers for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- Special examples may be selected from polyethylene oxalate, polyethylene malonate, polyethylene succinate, polypropylene oxalate, polypropylene malonate, polypropylene succinate, polybutylene oxalate, polybutylene malonate, polybutylene succinate and blends and copolymers of these compounds.
- Particularly preferred synthetic biopolymers are aliphatic polyesters comprising repeat units of lactic acid (PLA), hydroxy fatty acid (PHF) (also known as polyhydroxyalkanoate, PHA), in particular hydroxybutanoic acid (PHB) and succinate-based aliphatic polymers, for example polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- “Aliphatic polyesters” should be understood to mean those polyesters which typically have at least approximately 50% molar, preferably at least approximately 60% molar, particularly preferably at least approximately 70% molar, particularly preferably at least 95% molar aliphatic monomers.
- thermoplastic polymers A thermoplastic polymers with a glass transition temperature of more than -125°C, advantageously more than -30°C, preferably more than 30°C, particularly preferably more than 50°C, in particular more than 70°C, are preferred.
- the glass transition temperature of the polymer is in the range -125°C to 200°C, in particular in the range -125°C to 100°C.
- thermoplastic synthetic biopolymers which are preferred are those with a glass transition temperature which is preferably more than 20°C, advantageously more than 25°C, preferably more than 30°C, particularly preferably more than 35°C, in particular more than 40°C.
- the glass transition temperature of the polymer is in the range 35°C to 55°C, in particular in the range 40°C to 50°C.
- polyesters are PET with a glass transition temperature of at least 70°C, PLA with a glass transition temperature in the range 40°C to 70°C, PHA and PHB with a glass transition temperature in the range -40°C to 62°C, PBS as well as PBS copolymers such as PBSA with a glass transition temperature in the range - 45°C to 45°C and polycaprolactone with a glass transition temperature in the range - 75°C to 45°C.
- PLA glass transition temperature in the range 40°C to 70°C
- PHA and PHB with a glass transition temperature in the range -40°C to 62°C
- PBS as well as PBS copolymers
- PBSA with a glass transition temperature in the range - 45°C to 45°C
- polycaprolactone with a glass transition temperature in the range - 75°C to 45°C.
- Polyesters in particular polyethylene terephthalate, usually have a molecular weight corresponding to an intrinsic viscosity (IV) of 0.4 to 1 .4 (dl/g), measured for solutions in dichloroacetic acid at 25°C.
- IV intrinsic viscosity
- Polyesters of particular interest are those such as PET, PEN, PLA, PBS, PEIT with a number average molecular weight (Mn), preferably determined by gel permeation chromatography against polystyrene standards with a narrow distribution or by end group titration, of at least 20000 g/mol. Better still, the polydispersibility of these polymers is at least 1 .7.
- Polyesters of particular interest are those such as PET with a melting point between 250°C and 260°C.
- polyesters are those such as PET with a melting enthalpy of (80%: 43 J/g; 100% crystal/theoretical): 115 J/g.
- Polyesters of particular interest are those such as PET with a crystallization temperature of at least 125°C and a crystallization enthalpy (125°C) of at least 31 J/g.
- Polyesters of particular interest are those which are commercially available from Trevira GmbH , for example such as Trevira® T298.
- Particularly preferred polyamides have a glass transition temperature in the range 30°C to 80°C, in particular in the range 35°C to 65°C, particularly preferably in the range 50°C to 60°C, wherein these values are intended for PA 6.6 and PA 6 in particular.
- Polyamides of particular interest are those such as PA 6.6 and PA 6 with a number average molecular weight (Mn), preferably determined by gel permeation chromatography against polystyrene standards with a narrow distribution or by end group titration, of at least 10000 g/mol.
- Mn number average molecular weight
- Polyamides of particular interest are those such as PA 6.6 and PA 6, with a melting point between 170°C and 280°C, more preferably between 200°C and 260°C.
- Polyamides of particular interest are those such as PA 6.6 and PA 6 with a crystallization melting enthalpy (100% crystal) of 190°C.
- Particularly interesting polyamides are those such as PA 6.6 and PA 6 with a softening temperature of 204°C.
- polyamides such as Nylon, Perlon or Grilon are of particular interest.
- Polyolefins of particular interest are those such as polyethylene (PE) or polypropylene (PP) hompolymers, as well as copolymers or terpolymers which comprise at least 50 mol % of ethylene and/or propylene repeat units.
- Polyethylenes of particular interest are low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultra low density polyethylene (LILDPE), medium density polyethylene (MDPE), polymethylpentene ( PMP), polybutene-1 (PB-1 ); ethylene-octene copolymers, stereoblock PP, olefin block copolymers, propylene-butane copolymers.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- VLDPE very low density polyethylene
- LILDPE ultra low density polyethylene
- MDPE medium density polyethylene
- PMP polymethylpentene
- PB-1 polybutene-1
- Particularly preferred polyolefins are PE with a glass transition temperature in the range -100°C to -35°C and PP with a glass transition temperature in the range -10°C to -5°C.
- Polyethylenes of particular interest are those with a melting point between 120°C and 135°C and polypropylene with a melting point between 158°C and 170°C.
- Polyethylenes of particular interest are those with a crystallization melting enthalpy (100% crystal) of 290 J/g and polypropylene with a crystallization melting enthalpy of 190 J/g.
- polystyrene resin polystyrene resin
- LDPE PE Aspun 6834, Dow
- HDPE SKGC MK 910
- PP Braskem
- suitable polymers are those which have a melting temperature of more than 50°C, advantageously at least 75°C, preferably of more than 150°C.
- the melting temperature is in the range from 120°C to 285°C, in particular in the range from 150°C to 270°C, particularly preferably in the range from 175°C to 270°C.
- the glass transition temperature and the melting temperature of the polymer are preferably determined by means of Differential Scanning Calorimetry (DSC).
- thermoplastic polycondensates based on what are known as biopolymers, which contain the repeat units of lactic acid, hydroxybutyric acid, succinic acid, glycolic acid and/or furan dicarboxylic acid, preferably lactic acid and/or glycolic acid, in particular lactic acid.
- Polylactic acids are particularly preferred in this regard.
- a variety of high melting point synthetic biopolymers (melting point between 110°C and 270°C, preferably between 140°C and 270°C, more preferably between 180°C and 270°C), such as polyesters, may be used in the present invention, such as polyesteramides, modified polyethylene terephthalate, polylactic acid (PLA), terpolymers based on polylactic acid, polybutylene succinate, polyalkylene furanoate such as PEF, polyglycolic acid, polyalkylene carbonates (such as polyethylene carbonate), polyhydroxyalkanoates (PHA) such as polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV) or polyhydroxybutyrate-hydroxyvalerate copolymers (PHBV).
- PFA polyhydroxyalkanoates
- PHB polyhydroxybutyrate
- PV polyhydroxyvalerate
- PHBV polyhydroxybutyrate-hydroxyvalerate copolymers
- polylactic acid should be understood to mean polymers which are constructed from lactic acid units. Such polylactic acids are usually produced by condensation of lactic acids, but are also obtained by ring-opening polymerization of lactides under suitable conditions.
- Particularly suitable polylactic acids in accordance with the invention include poly(glycolide-co-L-lactide), poly(L-lactide), poly(L-lactide-co-s-caprolactone), poly(L- lactide-co-glycolide), poly(L-lactide -co-D,L-lactide), poly(D,L-lactide-co-glycolide) as well as poly(dioxanone).
- polymers of this type are commercially available from Boehringer Ingelheim Pharma KG (Germany) under the trade names Resomer® GL 903, Resomer® L 206 S, Resomer® L 207 S, Resomer® L 209 S, Resomer® L 210, Resomer® L 210 S, Resomer® LC 703 S, Resomer® LG 824 S, Resomer® LG 855 S, Resomer® LG 857 S, Resomer® LR 704 S, Resomer® LR 706 S, Resomer® LR 708, Resomer® LR 927 S, Resomer® RG 509 S and Resomer® X 206 S, from Biomer, Inc. (Germany) with the name Biomer(TM) L9000.
- Other suitable polylactic acid polymers are commercially available from Natureworks, LLC, Minneapolis, Minnesota, USA.
- polylactic acids for the purposes of the present invention are poly-D-, poly-L- or poly-D,L-lactic acids in particular.
- polylactic acid generally refers to homopolymers of lactic acid such as z. y (L-lactic acid), poly (D-lactic acid), poly (DL-lactic acid), mixtures thereof and copolymers which contain lactic acid as the primary component and a small proportion, preferably less than 10% molar, of a co-polymerizable co-monomer.
- polyalkylene carbonates such as polyethylene carbonate
- PHA polyhydroxyalkanoates
- PB polyhydroxybutyrates
- PV polyhydroxyvalerates
- PHBV polyhydroxybutyrate-hydroxyvalerate copolymers
- the biopolymer is exclusively a thermoplastic polycondensate based on lactic acids.
- the polylactic acids used in accordance with the invention preferably have a number average molecular weight (Mn) which is a minimum of 500 g/mol, preferably a minimum of 1000 g/mol, particularly preferably a minimum of 5000 g/mol, appropriately a minimum of 10000 g/mol, in particular a minimum of 25000 g/mol.
- Mn number average molecular weight
- the number average is preferably a maximum of 1000000 g/mol, appropriately a maximum of 500000 g/mol, advantageously a maximum of 100000 g/mol, in particular a maximum of 50000 g/mol.
- a number average molecular weight in the range from a minimum of 10000 g/mol to 500000 g/mol has proved to be particularly advantageous in the context of the present invention.
- the mass average molecular weight (Mw) of preferred lactic acid polymers is preferably in the range 750 g/mol to 5000000 g/mol, preferably in the range 5000 g/mol to 1000000 g/mol, particularly preferably in the range 10000 g/mol to 500000 g/mol, in particular in the range 30000 g/mol to 500000 g/mol, and the polydispersity of these polymers is advantageously in the range 1 .5 to 5.
- the inherent viscosity of particularly suitable lactic acid polymers, poly-D-, poly-L- or poly-D, L-lactic acids in particular, measured in chloroform at 25°C, 0.1 % polymer concentration, is in the range 0.5 dl/g to 8.0 dl/g, preferably in the range 0.8 dl/g to 7.0 dl/g, in particular in the range 1 .5 dl/g to 3.2 dl/g.
- the inherent viscosity of particularly suitable lactic acid polymers is in the range from 1.0 dl/g to 2.6 dl/g, in particular in the range from 1 .3 dl/g to 2.3 dl/g.
- polylactic acids with a glass transition temperature between 50°C and 65°C.
- polylactic acids with a melting point between 155°C and 180°C.
- polyhydroxy fatty acid esters should be understood to mean the following polymers: poly(3-hydroxypropionate) (PHP), poly(3-hydroxybutyrate) (PHB, P3HB), poly(3-hydroxyvalerate) (PHV), poly(3- hydroxyhexanoate) (PHHx), poly(3-hydroxyheptanoate) (PHH), poly(3- hydroxyoctanoate (PHO), poly(3-hydroxynonanoate) (PHN), poly(3- hydroxydecanoate) (PHD), poly(3-hydroxyundecanoate) (PHLID), poly(3- hydroxydodecanoate) (PHDD), poly(3-hydroxytetradecanoate) (PHTD), poly(3- hydroxypentadecanoate) (PHPD), poly(3-hydroxyhexadecanoate) (PHHxD) as well as blends of the aforementioned polymers.
- polyhydroxy fatty acid ester copolymers such as poly(3- hydroxypropionate-co-3-hydroxybutyrate) (P3HP-3HB), poly(3-hydroxypropionate-co- 4-hydroxybutyrate) (P3HP-4HB), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-4HB)), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3- hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (PHBV-HHx) as well as blends of the aforementioned copolymers, may be used together or with the aforementioned homopolymers.
- P3HP-3HB poly(3-hydroxypropionate-co-3-hydroxybutyrate)
- P3HP-4HB poly(3-hydroxypropionate-co- 4-hydroxybutyrate)
- P(3HB-4HB) poly(3-hydroxybutyrate-co-4-hydroxybutyrate)
- PHBV poly
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention are commercially available; examples are Mirel, Biomer P 209, Biopol, Aonilex X, Proganic.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a glass transition temperature in the range -2°C to 62°C.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a melting temperature in the range 100°C to 177°C.
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a melt flow index (MFI) of 5-10 g/10 min (190°C, 2.16 kg) determined in accordance with ISO 1133-1 :2011 .
- MFI melt flow index
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention preferably have a number average molecular weight (Mn) of at least 200000 Dalton, in particular at least 220000 Dalton, particularly preferably at least 250000 Dalton, and a maximum of up to 3000000 Dalton, in particular up to 2500000 Dalton, particularly preferably up to 2000000 Dalton.
- Mn number average molecular weight
- thermoplastic polyhydroxy fatty acid ester polymers used in accordance with the invention usually have a mass average molecular weight (Mw) which is about a factor of 2, preferably a factor of 3, times the number average molecular weight (Mn).
- uccinate-based aliphatic polymers should be understood to mean polymers with the following general formula: wherein Ri , R2 ,Rs ,R4 represent linear or branched aliphatic hydrocarbon residues consisting of 2 to 20 carbon atoms.
- Examples in this regard are polybutylene succinate, polybutylene succinate adipate and polyethylene succinate.
- thermoplastic succinate-based aliphatic polymers used in accordance with the invention are commercially available; examples are Bionolle 1000, BioPBS.
- thermoplastic succinate polymers used in accordance with the invention preferably have a glass transition temperature in the range -45°C to 45°C.
- thermoplastic succinate polymers used in accordance with the invention preferably have a crystallization temperature in the range 70°C to 90°C.
- thermoplastic succinate polymers used in accordance with the invention preferably have a melting temperature in the range 60°C to 180°C.
- thermoplastic succinate polymers used in accordance with the invention preferably have a melt flow index (MFI) of 5-10 g/10 min (190°C, 2.16 kg), determined in accordance with ISO 1133-1 :2011 .
- MFI melt flow index
- thermoplastic succinate polymers used in accordance with the invention preferably have a number average molecular weight (Mn) of at least 20000 Dalton, in particular at least 30000 Dalton, particularly preferably at least 35000 Dalton, and a maximum of up to 140000 Dalton, in particular up to 120000 Dalton, particularly preferably up to 110000 Dalton.
- Mn number average molecular weight
- thermoplastic succinate polymers used in accordance with the invention usually have a mass average molecular weight (Mw) which is about a factor of 2, preferably a factor of 3, times the number average molecular weight (Mn).
- Polycaprolactone is a synthetic biopolymer within the meaning of the present invention. Of particular interest are polycaprolactones with a glass transition temperature between -45°C and 45°C.
- polycaprolactones with a crystallization temperature between 70°C and 90°C.
- polycaprolactones with a melting point between 60°C and 180°C.
- polycaprolactones with a melting enthalpy of 70-145 J/g.
- polycaprolactones with a number average molecular weight (Mn), preferably determined by gel permeation chromatography against polystyrene standards with a narrow distribution or by end group titration, of at least 20000 Dalton to 140000 Dalton.
- Mn number average molecular weight
- thermoplastic polymer B is selected from the aforementioned group of thermoplastic polymers and preferred embodiments of thermoplastic polymer B correspond to the preferred embodiments of thermoplastic polymer A, as described above.
- thermoplastic polymer A and/or the thermoplastic polymer B is/are selected from the group formed by the melt spinnable synthetic biopolymer, wherein polycondensates and polymerisates from bio-based starting materials are particularly preferred.
- both thermoplastic polymers A and B are selected from the group formed by melt spinnable synthetic biopolymers, it is preferable to select biopolymers which differ as regards their chemical nature and/or as regards their melting points.
- the multi-component polymer fibres are preferably bi-component fibres in which the component A forms the core and the component B forms the shell.
- the melting point of the thermoplastic polymer in the component A is at least 5°C, preferably at least 10°C, higher than the melting point of the thermoplastic polymer in the component B.
- the additives A and B increase the biological degradability of the multi-component polymer fibres in accordance with the invention, in particular of the bi-component fibres in accordance with the invention, in that these additives increase the biological degradability of the thermoplastic polymer A and/or of the thermoplastic polymer B.
- the multi-component polymer fibre in accordance with the invention contains (i) at least one additive A in the component A, or (ii) at least one additive B in the component B, or (iii) at least one additive A in the component A and at least one additive B in the component B.
- the additive A and the additive B are different, or when at least one additive A is present in the component A and at least one additive B is present in the component B, the additive A and the additive B may also be identical, if the thermoplastic polymer A and thermoplastic polymer B are different.
- the term “different” in the context of this paragraph means that the substances differ at least as regards their chemical natures or as regards their physical natures or as regards their concentrations.
- additives A and B are:
- aliphatic polyesters preferably aliphatic polyesters having no side chain carbon atoms, preferably polycaprolactone
- fatty acid ester preferably C1-C40-alkyl stearate, more preferred C2-C20-alkyl stearate, most preferred ethyl stearate
- sugars in particular monosaccharides, disaccharides and oligosaccharides
- metal compounds in particular transition metal compounds, preferably at least two transition metal compounds, as well as their salts
- carbohydrates in particular starch and/or cellulose as well as mixtures of the aforementioned substances.
- Multi-component polymer fibres in particular bi-component polymer fibres, in which the thermoplastic polymer A and/or the thermoplastic polymer B comprise(s) at least one polyester and the additive A and/or additive B is/are selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii) aliphatic polyester, (iii) fatty acid ester, preferably C1-C40-alkyl stearate, more preferred C2-C20-alkyl stearate, most preferred ethyl stearate, (iv) sugars, in particular monosaccharides, disaccharides and oligosaccharides, (v) catalysts for transesterifications, in particular under basic conditions, (vi) carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof, are preferred.
- thermoplastic polymer A and/or the thermoplastic polymer B comprises at least one polyester and the additive A and/or additive B is selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii) aliphatic polyesters, (iii) fatty acid ester, preferably C1-C40-alkyl stearate, more preferred C2-C20-alkyl stearate, most preferred ethyl stearate, (iv) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, (v) catalysts for transesterifications, in particular under basic conditions, (vi) carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof.
- basic alkali and/or alkaline earth compounds pH>7 dissolved in water
- carbonates
- the aforementioned aliphatic polyesters are distinguished from the polyesters of the thermoplastic polymer A and polymer B in respect of their chemical nature, i.e. the polyester of the thermoplastic polymer A and polymer B is an araliphatic polyester or copolyester, which has been produced from polyols and aliphatic and/or aromatic dicarboxylic acids or their derivatives (anhydrides, esters) by means of polycondensation.
- Particularly preferred additives A and/or additives B contain at least two substances, wherein preferred combinations are:
- A) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO in combination with catalysts for transesterifications, in particular under basic conditions;
- sugars in particular mono-saccharides, di-saccharides and oligo-saccharides, in combination with carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof;
- C) aliphatic polyesters optionally in combination with sugars, in particular monosaccharides, di-saccharides and oligo-saccharides, or carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof;
- D) fatty acid ester preferably C1-C40-alkyl stearate, more preferred C2-C20-alkyl stearate, most preferred ethyl stearate.
- Most preferred additives A for partially aromatic “araliphatic” polyester or copolyester as thermoplastic polymer A are containing at least basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO in combination with catalysts for transesterifications, in particular under basic conditions; and aliphatic polyesters, especially aliphatic polyester having no side chain carbon atoms, optionally in combination with (i) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, (ii) carbohydrates, in particular starch and/or (iii) cellulose, (iv) fatty acid ester, preferably C1-C40
- thermoplastic polymer A is polyester and the thermoplastic polymer B is a polyester being different from the polyester in polymer A, and preferably is a co-polyester, and - each - the additive A and the additive B is independently selected from the combination of basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO in combination with catalysts for transesterifications, in particular under basic conditions; and aliphatic polyesters, especially aliphatic polyester having no side chain carbon atoms, optionally in combination with (i) sugars, in particular mono-saccharides, di-saccharides and oligo-saccharides, (ii) carbohydrates, in particular starch and/or (iii) cellulose, (iv) fatty acid ester, preferably C1-C40-alky
- the aforementioned fatty acid esters are present and not optionally.
- Multi-component polymer fibres in particular bi-component polymer fibres, in which the thermoplastic polymer A and/or the thermoplastic polymer B comprise(s) at least one polyolefin and the additive A and/or additive B is/are selected from the group (i) sugars, in particular monosaccharides, disaccharides and oligosaccharides, (ii) metal compounds, in particular transition metal compounds, as well as their salts, (iii) unsaturated carboxylic acids or their anhydrides/esters/amides, (iv) synthetic rubber and/or natural rubber, (v) carbohydrates, in particular starch and/or cellulose, as well as mixtures thereof, are preferred.
- additive A and/or additive B comprising (a) transition metal compounds and (b) unsaturated carboxylic acids or their anhydrides, which are in particular preferred combined with (c) synthetic rubber and/or natural rubber and (d) starch.
- thermoplastic polymer B is a polyolefin, in particular a polypropylene polymer, which includes as additive B at least (i) metal compounds, in particular transition metal compounds, as well as their salts, preferably at least two chemically different transition metal compounds and (ii) unsaturated carboxylic acids or their anhydrides/esters/amides, preferably in combination with synthetic rubber and/or natural rubber, and - optionally - further comprising (iii) sugars, in particular monosaccharides, disaccharides and oligosaccharides, (iv) carbohydrates, in particular starch and/or (v) cellulose, as well as mixtures thereof.
- phenolic antioxidant stabilizer and CaO can be present.
- Multi-component polymer fibres in particular bi-component polymer fibres, in which the thermoplastic polymer A and/or the thermoplastic polymer B comprise(s) at least one polyamide and the additive A and/or additive B is/are selected from the group (i) basic alkali and/or alkaline earth compounds (pH>7 dissolved in water), in particular carbonates, hydrogen carbonates, sulphates, particularly preferably CaCOs, and alkaline additives, particularly preferably CaO, (ii) aliphatic polyester, (iii) fatty acid ester, preferably C1-C40-alkyl stearate, more preferred C2-C20-alkyl stearate, most preferred ethyl stearate, (iv) sugars, in particular monosaccharides, disaccharides and oligosaccharides, (v) catalysts for transesterifications, in particular under basic conditions, (vi) metal compounds, in particular transition metal compounds, as well as their salts, (vii) unsatur
- the additive A is in a proportion with respect to the component A which is preferably between 0.005% by weight and 20% by weight, particularly preferably between 0.01 % by weight and 5% by weight, with respect to the total weight of the component
- the additive B is in a proportion with respect to the component B which is preferably between 0.005% by weight and 20% by weight, particularly preferably between 0.01 % by weight and 5% by weight, with respect to the total weight of the component
- the additives are preferably added to the polymer material in the extruder in the form of what is known as a masterbatch.
- masterbatch should be understood to mean a granulate which is added to the polymer melt during the spinning process.
- the granulate has a polymeric support material as well as at least one additive.
- the concentration of the additive/additives in the masterbatch is preferably tailored.
- the dosage of masterbatch in the spinning process is between 0.1 % by weight and 30% by weight, particularly preferably between 0.5% by weight and 15% by weight.
- thermoplastic polymers for thermobonding, suitable thermoplastic polymers, copolymers and blends in particular, in particular thermoplastic biopolymers are those which have a high degree of enthalpies of fusion and crystallization.
- the polymers B are selected in a manner such that they have a degree of crystallinity or a latent heat of fusion (delta Hf) of more than approximately 25 joules per gram (“J/g”), particularly preferably more than 35 J/g, in particular more than 50 J/g.
- the determination of the latent heat of melting (AHf), the latent heat of crystallization (AHC) and the crystallization temperature is carried out by means of Differential Scanning Calorimetry ("DSC") in particular in accordance with ASTM D-3418 (ASTM D3418- 15, Standard Test Method for Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers by Differential Scanning Calorimetry, ASTM International, West Conshohocken, PA, 2015, www.astm.org).
- thermoplastics A and B Further additives to thermoplastics A and B
- thermoplastic polymers, copolymers and blends described above, in particular the biopolymers described above, have the usual additives such as antioxidants, inter alia.
- additives are pigments, stabilizers, surfactants, waxes, flow promoters, solid solvents, plasticizers and other materials, for example nucleating agents, which are added in order to improve the processability of the thermoplastic composition.
- the multi-component fibres in accordance with the invention are constituted by at least 90% by weight of thermoplastic polymers, copolymers, blends described above, in particular of thermoplastic biopolymers, and typically have less than approximately 10% by weight, preferably less than approximately 8% by weight, particularly preferably less than approximately 5% by weight of additives, in particular in the shell.
- the multi-component fibres in accordance with the invention may be continuous fibres, for example what are known as staple fibres, or continuous fibres (filaments).
- the multi-component fibres in particular the bi-component fibre in accordance with the invention, are combined together and post-treated in a rolling mill using methods which are known in principle, in particular drawn and optionally also crimped or texturized.
- the multi-component polymer fibres in accordance with the invention are cooled immediately after exiting the spinneret and drawn and deposited on a collecting belt or preferably wound onto bobbins. Further steps in particular include drawing, texturizing and heat bonding of the filaments.
- spunbonds A number of production methods are available for the production of nonwovens.
- the intermediate step of staple fibre production is not carried out.
- the multi-component fibres are swirled directly after exiting the spinnerets, preferably by means of a stream of air, so that they are deposited as a nonwoven.
- the production of spunbonds is known to the person skilled in the art and has been described in the literature, for example in Fourne (Synthetician Fasern [Synthetic Fibres]; 1995, Chapter 5.5).
- the fibre is preferably in the form of a staple fibre.
- the length of said staple fibres is not limited in principle, but in general is 2 to 200 mm, preferably 3 to 120 mm, particularly preferably 4 to 60 mm.
- the individual linear density of the multi-component fibres in accordance with the invention, in particular of the bi-component fibres in accordance with the invention, preferably staple fibres, is between 0.5 and 30 dtex, preferably 0.7 to 13 dtex.
- linear densities between 0.5 and 3 dtex and fibre lengths of ⁇ 10mm, in particular ⁇ 8mm, particularly preferably ⁇ 6mm, particularly preferably ⁇ 5mm, are particularly suitable.
- the multi-component fibres in accordance with the invention in particular the bicomponent fibres in accordance with the invention, preferably have a low hot air heat shrinkage in the range 0% to 10%, preferably > 0% to 8%, respectively measured at 110°C.
- the production of the polymer fibres in accordance with the invention is in principle carried out using the usual processes. Firstly, the polymer, if necessary, is dried and supplied to an extruder. Next, the molten material is spun using the regular equipment with appropriate spinnerets. The mass throughput and the draw-off speed of the capillaries from the spinneret outlet plates are set so that a fibre with the desired linear density is produced.
- the fibres formed may have different shapes, for example round, oval, star-shaped, dog-bone shaped, barbell-shaped, kidney-shaped, triangular or polygonal, cloverleafshaped, horseshoe-shaped, lens-shaped, rod-shaped, gearwheel-shaped, cloudshaped, x-shaped, y-shaped, o-shaped, u-shaped; this list is not limiting and other suitable cross sections are also possible.
- the fibre filaments produced in accordance with the invention are collected into yarns and then in turn into tows.
- the tows are initially deposited into cans for further processing.
- the tows which are temporarily stored in the cans are picked up and a large cable tow is produced.
- the present invention also concerns the post-treatment of the cable tow produced by means of the known process; usually, it is 10-600 ktex using conventional rolling mills, and special drawing.
- An infeed speed for the cable tow into the drawing or drawing equipment is preferably 10 to 110 m/min (infeed speed).
- other preparations may also be applied which aid drawing but which do not have a deleterious effect on the subsequent properties.
- Drawing may be carried out in a single step or optionally using a two-stage drawing process (see in this regard US 3 816 486, for example). Prior to and during drawing, one or more finishing agents may be applied using conventional methods.
- the drawing in accordance with the invention is carried out with a draw ratio, in particular when biopolymers are used, of between 1 .2 and 6.0, preferably between 2.0 and 4.0, wherein the temperature when drawing the tow is preferably between 30°C and 100°C. Drawing is thus carried out in the glass transition temperature range for the tow to be drawn.
- Drawing in accordance with the invention is carried out in the presence of steam, i.e. in what are known as steam boxes, so that the fibres are drawn in the steam boxes.
- the steam boxes are normally operated under a pressure of 3 bar.
- thermal shrinkage of the fibres can be reduced and controlled in a specific manner.
- the tow is preferably 24-360 ktex prior to drawing.
- Drawing is preferably in one stage or in multiple stages, wherein the godets of the drawing unit may be at different temperatures and also the draw ratios between the drawing unit may be different.
- a steam box is positioned between at least two of the drawing units, i.e. the drawing point for the fibres is in the steam box or close to the steam box. All of the godets (usually 7 per drawing unit) are at a temperature of 30 - 250°C. All of the drawing is preferably carried out at least partially or entirely in the steam box.
- the steam box is operated at a pressure of 3 bar of steam.
- Drawing may also be carried out cold, wherein “cold” means room temperature (approximately 20 - 35°C).
- crimping/texturizing of the drawn fibres conventional methods of mechanical crimping with crimping machines which are known per se may be used.
- a mechanical device for fibre crimping with steam support is used, such as a stuffer box.
- crimped fibres may be obtained using other processes, including three-dimensionally crimped fibres, for example.
- the tow is initially and usually brought to a constant temperature in the range 50°C to 100°C, preferably 70°C to 85°C, particularly preferably to approximately 78°C and treated at a pressure for the tow infeed rolls of 1 .0 to 6.0 bar, particularly preferably at approximately 2.0 bar, a pressure in the crimping box of 0.5 to 6.0 bar, particularly preferably 1 .5-3.0 bar, with steam at a rate of between 1.0 and 2.0 kg/min, particularly preferably 1 .5 kg/min.
- the smooth or optionally crimped fibres are picked up, followed by cutting and depositing into compressed bales as flock.
- the staple fibres of the present invention are preferably cut on a mechanical cutting device which is downstream of relaxation.
- cutting may be dispensed with. These types of tow are deposited and compressed in the uncut form in bales.
- the degree of crimping is preferably at least 2 crimps (arched crimps) per cm, preferably at least 3 crimps per cm, preferably 3 crimps per cm to 9.8 crimps per cm and particularly preferably 3.9 crimps per cm to 8.9 crimps per cm.
- values for the degree of crimping of approximately 5 to 5.5 crimps per cm are particularly preferred.
- the degree of crimping has to be set individually.
- the PET raw material is dried, typically up to 4-6 h @ temp up to 180°C; Typically, polypropylene (PP) does not require drying;
- the melt extrusion is typically done extruders having one or more screws;
- the bicomponent spinneret configuration is concentric or eccentric with PP as shell (sheath) material and PET as core component;
- extruder melt temperatures for core is typically in the range 250-300°C for PET and for sheath material typically in the range 220-270°C for PP;
- Fibre Quench is typically crossflow and the air temperature is typically in the range 18-24°C;
- typical fibre drawdown speeds are in the range 800-1300m/m in; fibre drawing can be single or duo-stage drawing with draw ratio up to 4 and heat setting at 110-130°C.
- the PET raw materials are dried, typically up to 4-6 h @ temp up to 180°C;
- the melt extrusion is typically done extruders having one or more screws, one extruder for shell (sheath) material (coPET) and one for core material (PET);
- the bicomponent spinneret configuration is concentric or eccentric with coPET as shell (sheath) material and PET as core component;
- the extruder melt temperatures are typically in the range 250-300°C;
- Fibre quench is typically crossflow or in-flow or radial out-flow and the air temperature is typically in the range 18-50°C; typical fibre drawdown speeds are in the range 400-1800m/m in, preferably 1400m/min; fibre drawing can be single or duo-stage drawing with draw ratio up to 4.5, specifically 2.5 - 3.5, finish bath temperature up to 80°C, godet temperatures up to 70°C, specifically 30°C before steam-bath if present, and temperature after stretch point up to 80°C, heat setting, typically in a hot air oven, at temperatures up to 190°C.
- Textile fabrics can be produced from the fibres in accordance with the invention; these also constitute the subject matter of the invention.
- textile fabric as used in the context of this description should be construed in its broadest sense. Thus, they may be any structure containing the fibres in accordance with the invention which have been produced using a technique for producing a fabric. Examples of such textile fabrics are nonwovens, in particular wet laid nonwovens or dry laid nonwovens, preferably based on staple fibres which are produced by means of thermobonding. Other examples of nonwovens are carded or airlaid nonwovens, preferably based on staple fibres or nonwovens, produced using a melt blowing and/or spunbond filament process.
- meltblown processes for example as described in "Complete Textile Glossary", Celanese Acetate LLC, from 2000 or in “Chemiefaser-Lexikon, Robert Bauer, 10th edition, 1993
- electrospinning processes are the most suitable.
- the freshly spun fibres preferably freshly spun bi-component fibres
- the spunbond nonwoven can be consolidated further, for example using the hot embossing process with the use of an embossing roller or using known needling/water jet processes, to further entangle the nonwoven.
- bi-component fibres wherein the bi-component fibres have a higher and a lower melting point component
- the nonwoven is consolidated by means of thermobonding using the lower melting point component.
- the textile fabric which contains the bi- component/multi-component fibres is fed into an oven, for example a ventilated dryer which contains one or more heating zones which are used to heat the air to a temperature which is higher than the melting temperature of the lower melting point component (for example the shell) of the multi-component fibres, but lower than the melting temperature of the higher melting point component (for example the core).
- an oven for example a ventilated dryer which contains one or more heating zones which are used to heat the air to a temperature which is higher than the melting temperature of the lower melting point component (for example the shell) of the multi-component fibres, but lower than the melting temperature of the higher melting point component (for example the core).
- This heated air flows through the textile fabric, typically a nonwoven, whereupon the lower melting point component melts and forms bonds between the fibres in order to stabilize the fabric thermally.
- the air flowing through the thermobonding oven is at a temperature in the range from 100°C to approximately 180°C.
- the residence time in the oven is approximately 180 seconds or less. It should be understood, however, that the parameters of the thermobonding oven are a function of the type of polymers used and the thickness of the material.
- Ultrasound consolidation techniques may also be used, which employ a stationary or rotating horn and a rotating patterned embossing roller. Examples of such techniques are described in US patent 3 939 033; US patent 3 844 869; US patent 4 259 399;
- the nonwoven may be thermally spot welded in order to provide a fabric with a great many small, discrete binding points.
- This process in general involves guiding the fabric between two heated rollers such as, for example, a roller with an engraved pattern and a second binding roller.
- the engraved roller is patterned in a manner such that the web is not bonded over its entire surface, and the second roller may be smooth or patterned.
- binding patterns include but are not limited to those described in in US patent 3 855 046; US patent 5 620 779; US patent 5 962 112; US patent 6 093 665; US patent of design, number 428267 and US patent of design, number 390 708, which are incorporated herein by reference in their entirety for all purposes.
- the basis weight of the textile fabric in particular the basis weight of the nonwoven, is between 10 and 500 g/m 2 , preferably 25 to 450 g/m 2 , in particular 30 to 300 g/m 2
- the textile fabric which is produced from the multi-component fibres in accordance with the invention, in particular from the bi-component fibres in accordance with the invention, in particular nonwovens, can be produced in a known manner using a calendar roller or can be thermally consolidated in an oven.
- the textile fabric which is produced from the multi-component fibres in accordance with the invention are usually produced by means of thermobonding because of the different melting points of the components. This bonds the fibres together at the contact or crossover points.
- the component B produced from thermoplastic polymer B with additive B has a higher biological degradability than the component A produced from thermoplastic polymer A with additive A
- the contact or crossover points of the fibres with each other are degraded first and the textile fabric, for example a nonwoven, disintegrates faster, whereupon the overall degradability is increased.
- the textile fabrics in particular the nonwovens, can- in addition to the multi-component fibres - comprise still other fibres, depending on the intended purpose.
- the “filler fibres” described in WO 2007/107906 should in particular be highlighted.
- the “filler fibres” described in WO 2007/107906 also form part of the subject matter of the invention and are incorporated into the present invention.
- the textile fabrics include the aforementioned biologically degradable polymer material fibres which may be mixed with other fibrous materials, chemical fibres, preferably natural fibres such as cotton or cellulose fibres, fibres of animal origin such as wool or other biologically degradable fibres.
- cellulose fibres include softwood kraft pulp fibres.
- Softwood kraft pulp fibres are obtained from conifers and include cellulose fibres such as, but not restricted to, northern, western and southern softwood species such as redwood, red cedar, hemlock spruce, Douglas fir, true spruces, pine trees (for example southern pine), spruce (for example black spruce), combinations thereof etc.
- northern softwood kraft pulp fibres may be used.
- Another suitable cellulose material for use in the present invention is a bleached sulphate wood cellulose material which primarily contains softwood fibres. Fibres with smaller average lengths may also be used in the present invention.
- An example of suitable cellulose material fibre with a low average length are hardwood kraft pulp fibres.
- Hardwood kraft pulp fibres are derived from deciduous trees and include cellulose material fibres such as, but not restricted to eucalyptus, maple, beech, aspen etc.
- Eucalyptus kraft pulp fibres may be particularly favoured in order to increase softness, increase sheen, increase opacity and change the pore structure of the sheet in order to increase its absorbency.
- cellulose material fibres make up approximately 30% by weight to approximately 95% by weight, in some embodiments approximately 40% by weight to approximately 90% by weight and in some embodiments approximately 50% by weight to approximately 85% by weight of the nonwoven.
- superabsorbent materials may also be contained in the nonwoven.
- Superabsorbent materials are materials which swell in water which can absorb 20 times their weight and in some case at least 30 times their weight in an aqueous solution containing 0.9% by weight of sodium chloride.
- the superabsorbent materials may be natural, synthetic and modified natural polymers and materials.
- Examples of synthetic superabsorbent polymers include alkali metal and ammonium salts of poly(acrylic acid) and poly(methacrylic acid), poly(acrylamides), polyvinylethers), maleic acid anhydride copolymers with vinyl ethers and alpha olefins, polyvinylpyrrolidone), poly(vinylmorpholinone), polyvinylalcohol) and mixtures and copolymers thereof.
- superabsorbent materials include natural and modified natural polymers such as hydrolysed acrylonitrile-grafted starches, acrylic acid- grafted starches, methylcelluloses, chitosan, carboxymethylcelluloses, hydroxypropylcelluloses and natural gums such as alginates, xanthan gums, carob bean gum etc. Mixtures of natural and completely or partially synthetic superabsorbent polymers may also be useful in the present invention. When the superabsorbent material is used, it may make up approximately 30% by weight to approximately 95% by weight, in some embodiments approximately 40% by weight to approximately 90% by weight and in some embodiments approximately 50% by weight to approximately 85% by weight of the nonwoven.
- the present textile fabrics may be used in an absorbent article such as, for example, absorbent articles for body care such as, for example, nappies, training pants, absorbent underwear, incontinence articles, sanitary wear for women, but not restricted thereto (for example sanitary towels), swimwear, baby wipes etc; medical absorbent articles such as clothing, window materials, underlays, bed protectors, bandages, absorbent cloths and medical wipes; wipes for the food industry; items of clothing, etc. Materials and processes which are suitable for the production of absorbent articles of this type are known to the person skilled in the art.
- absorbent articles comprise a substantially liquid- impermeable layer (for example the outer shell), a liquid-permeable layer (for example the layer facing the body), barrier layer etc) and an absorbent core.
- the nonwoven in the present invention may be used as one or more of the liquid- impermeable, liquid-permeable and/or absorbent layers.
- the present textile fabrics are not limited to the aforementioned applications and may be used in any application such as, for example, in hygiene, medicine, personal protection, in the household (fibre fill etc), clothing, mobility/transport (car, train, aircraft, shipping), engineering (insulation), agriculture, packaging, filtration and any disposable applications.
- ASTM D5511 ASTM D5511-11 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solids Anaerobic digestion Conditions (DOI: 10.1520/D5511-11 ) and ASTM D5511-18 Standard Test Method for Determining Anaerobic Biodegradation of Plastic Materials Under High-Solids Anaerobic-digestion Conditions; (DOI: 10.1520/D5511-18)
- ASTM D6691 ASTM D6691-09 Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in the Marine Environment by a Defined Microbial Consortium or Natural Sea Water Inoculum) (DOI: 10.1520/D6691-09) and ASTM D6691-17, Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in the Marine Environment by a Defined Microbial Consortium or Natural Sea Water Inoculum (DOI: 10.1520/D6691-17), Standard Test Method for Determining Aerobic Biodegradation of Plastic Materials in the Marine Environment by
- Mn/Mw Number and mass average molecular weight
- Glass transition temperature and melting temperature In particular, determination of the glass transition temperature in accordance with DIN EN ISO 11357-2:2020-08 (Plastics - Differential Scanning Calorimetry (DSC) - Part 2: Determination of glass transition temperature and the step height related to glass transition).
- the final temperature was always approximately 50°C above the highest expected melting point.
- the melt viscosity was determined using a Gdttfert Rheo Tester 1000 at a temperature suitable for the polymer, between approximately 190°C and 280°C.
- a Gdttfert Rheo Tester 1000 at a temperature suitable for the polymer, between approximately 190°C and 280°C.
- ASTM D2196 - 20 Standard Test Methods for Rheological Properties of Non-Newtonian Materials by Rotational Viscometer.
- the melt flow index is the weight of a polymer (in grams) that can be pressed through an extrusion rheometer opening (for example 0.0825 inch diameter) when a force of 2160 grams, for example, is applied over a period of 10 minutes, for example, at 190°C, for example.
- the terminal block with the test specimens was fastened into a support stand so that the test specimens were freely suspended in the support stand under pre-tension.
- the selected starting length in normal cases 150 mm
- the selected starting length was marked here on each fibre. This was carried out with the aid of marking lines in the support stand and marking points applied to the test specimens.
- the filled terminal block was picked up and replaced on the plate.
- the decrimping weights were removed and the free fibre ends were clamped into a second terminal block.
- the test specimens spanning the two terminal blocks were suspended in a wire frame, not under tension. This wire frame was introduced into the centre of the shrinkage oven preheated to the correct treatment temperature (usual temperatures are 200°C, 110°C, 80°C).
- the wire frame was removed from the oven. After a cooling period for the terminal blocks of at least 30 min, the terminal blocks with the test specimens were removed from the frame and the fibres replaced on the plate. The back measurement could then be carried out. To this end, the test specimens were once again loaded with the decrimping weights and suspended in the support stand. For the back measurement, the adjustable marking line of the support stand was positioned such that the respective upper edge of the marking point could cover the marking line. Then, for each individual fibre, the length between the marks could be read off from the counters on the support stand to an accuracy of 1/10 mm.
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- the melt extrusion is done by an extruder having one or more screws at a temperature of 280-290 °C for PET
- Additive A is added at the extruder feed-throat at a level of 2 wt.-% masterbatch dosage.
- This masterbatch consists of a PET polyester as carrier and the additive, which comprises an aliphatic polyester and CaCO3.
- the fibre quench occurs by crossflow and air temperature of 40°C; fibre drawdown speed is 1400 m/min. Spun fiber fineness is 5.4 dtex.
- the fibre drawing is done by single or duo-stage drawing with draw ratio up to 4 and the final dtex is 2.5 dtex.
- Heat setting is done at 110-130°C.
- the fibre produced is cut into staple fibre having a length of 38 mm.
- the fibre produced is tested in accordance with ASTM D5511 and results are obtained after 208 days:
- the biodegradation is shown in Figure 1 versus the control.
- thermoplastic polymer A polyethylene terephthalate (PET) as core (thermoplastic polymer A) and polypropylene (PP) as shell (sheath) (thermoplastic polymer B) is spun from a polyethylene terephthalate (PET) resin and a polypropylene (PP) resin having the following properties:
- the melt extrusion is done by an extruder having one or more screws at a temperature of 270 °C for PET and by another extruder having one or more screws at a temperature at a temperature of 250 °C for PP.
- Additive A is added to the PET at the extruder feed-throat at a level of 2 wt.-% masterbatch dosage.
- This masterbatch consists of a PET polyester as carrier and the additive, which comprises an aliphatic polyester and CaCO3.
- Additive B is added to the PP at the extruder feed-throat at a level of 2 wt.-% masterbatch dosage.
- This masterbatch consists of PP as carrier and the additive, which comprises transition metal compounds and unsaturated carboxylic acids.
- the fibre quench occurs by crossflow and air temperature of 20 °C; fibre drawdown speed is 1000 m/min. Spun fiber fineness is 5.4 dtex.
- the fibre drawing is done by can be single or duo-stage drawing with draw ratio up to 4 and the final dtex is 2.5dtex. Heat setting is done at 110-130°C.
- the fibre produced is cut into staple fibre having a length of 38 mm and a nonwoven is produced by thermo-bonding.
- a nonwoven thus produced is kept as control in a sealed, evacuated bag and another nonwoven thus produced is tested over a one year period (365 days) at 60°C and 60% relative humidity.
- FIG. 2 a-e The degradation is shown in Figure 2 a-e versus the control.
- the degradation of the PP sheath becomes clearly visible.
- Figure 2e illustrates the degradation of the PET core as the shape of the fraction changes clearly from the mushroom-shape, which is typical for PET, to a shape indicating that the material has become brittle. In this test the fibers have been axially stressed in a reproducible way (defined speed) by a mechanical testing machine.
- the core of this bico fiber has the same material composition (polymer and additive) as the fiber described in Example 1 , where degradation has been proven according to ASTM D5511 .
- thermoplastic polymer A polyethylene terephthalate
- coPET co-polyethlyene terephthalate
- thermoplastic polymer B is spun from a polyethylene terephthalate (PET) resin and a co-polyethlyene terephthalate (coPET) resin having the following properties:
- the melt extrusion is done by an extruder having one or more screws at a temperature of 290 °C for PET and by another extruder having one or more screws at a temperature at a temperature of 280 °C for coPET.
- Additive A is added to the PET at the extruder feed-throat at a level of 2 wt.-% masterbatch dosage.
- This masterbatch consists of a PET polyester as carrier and the additive, which comprises an aliphatic polyester and CaCO3.
- Additive B is added to the coPET at the extruder feed-throat at a level of 2 wt.-% masterbatch dosage. This additive B is identical to additive A.
- the fibre quench occurs by crossflow and air temperature of 35 °C; fibre drawdown speed is 1200 m/min. Spun fiber fineness is 5.4 dtex.
- the fibre drawing is done by single or duo-stage drawing with draw ratio up to 4.5 and the final dtex is 2.5dtex. Heat setting is done at 80°C.
- the fibre produced is cut into staple fibre having a length of 38 mm and a nonwoven is produced by thermo-bonding.
- the resulting fiber meets all requirements imposed.
- the core of this bico fiber has the same material composition (polymer and additive) as the fiber described in Example 1 , where degradation has been proven according to ASTM D5511.
- the sheath differs in that the melting point of the copolyester is lower than the polyester of the core, which renders possible to use the fiber for thermobonded nonwovens.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Multicomponent Fibers (AREA)
- Nonwoven Fabrics (AREA)
- Woven Fabrics (AREA)
Abstract
L'invention concerne une fibre polymère à composants multiples biodégradable, en particulier des fibres à deux composants, présentant des propriétés physiques avantageuses, un procédé pour sa production, ainsi que son utilisation.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US202163137901P | 2021-01-15 | 2021-01-15 | |
US202163143247P | 2021-01-29 | 2021-01-29 | |
PCT/EP2022/050774 WO2022152867A1 (fr) | 2021-01-15 | 2022-01-14 | Fibres polymères à composants multiples biodégradables |
Publications (1)
Publication Number | Publication Date |
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EP4278032A1 true EP4278032A1 (fr) | 2023-11-22 |
Family
ID=80168058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP22702168.0A Pending EP4278032A1 (fr) | 2021-01-15 | 2022-01-14 | Fibres polymères à composants multiples biodégradables |
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EP (1) | EP4278032A1 (fr) |
JP (1) | JP2024507060A (fr) |
KR (1) | KR20230130670A (fr) |
IL (1) | IL304461A (fr) |
MX (1) | MX2023008352A (fr) |
TW (1) | TW202240038A (fr) |
WO (1) | WO2022152867A1 (fr) |
Families Citing this family (1)
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CN115821426B (zh) * | 2022-12-16 | 2024-04-26 | 扬州富威尔复合材料有限公司 | 一种具有抗菌功能的结晶型生物基低熔点聚酯复合纤维及其制备方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816486A (en) | 1969-11-26 | 1974-06-11 | Du Pont | Two stage drawn and relaxed staple fiber |
CA948388A (en) | 1970-02-27 | 1974-06-04 | Paul B. Hansen | Pattern bonded continuous filament web |
US3844869A (en) | 1972-12-20 | 1974-10-29 | Crompton & Knowles Corp | Apparatus for ultrasonic welding of sheet materials |
US3939033A (en) | 1974-12-16 | 1976-02-17 | Branson Ultrasonics Corporation | Ultrasonic welding and cutting apparatus |
US4259399A (en) | 1978-08-31 | 1981-03-31 | Burlington Industries, Inc. | Ultrasonic nonwoven bonding |
US5096532A (en) | 1990-01-10 | 1992-03-17 | Kimberly-Clark Corporation | Ultrasonic rotary horn |
US5110403A (en) | 1990-05-18 | 1992-05-05 | Kimberly-Clark Corporation | High efficiency ultrasonic rotary horn |
US6093665A (en) | 1993-09-30 | 2000-07-25 | Kimberly-Clark Worldwide, Inc. | Pattern bonded nonwoven fabrics |
CA2123330C (fr) | 1993-12-23 | 2004-08-31 | Ruth Lisa Levy | Non-tisse cotele ressemblant a une etoffe et procede pour sa fabrication |
US5962112A (en) | 1996-12-19 | 1999-10-05 | Kimberly-Clark Worldwide, Inc. | Wipers comprising point unbonded webs |
US5817199A (en) | 1996-12-20 | 1998-10-06 | Kimberly-Clark Worldwide, Inc. | Methods and apparatus for a full width ultrasonic bonding device |
US6509092B1 (en) * | 1999-04-05 | 2003-01-21 | Fiber Innovation Technology | Heat bondable biodegradable fibers with enhanced adhesion |
US7056580B2 (en) * | 2003-04-09 | 2006-06-06 | Fiber Innovation Technology, Inc. | Fibers formed of a biodegradable polymer and having a low friction surface |
US20070122614A1 (en) * | 2005-11-30 | 2007-05-31 | The Dow Chemical Company | Surface modified bi-component polymeric fiber |
DE602005023671D1 (de) | 2005-12-15 | 2010-10-28 | Kimberly Clark Co | Biologisch abbaubare mehrkomponentenfasern |
US7790640B2 (en) | 2006-03-23 | 2010-09-07 | Kimberly-Clark Worldwide, Inc. | Absorbent articles having biodegradable nonwoven webs |
-
2022
- 2022-01-14 EP EP22702168.0A patent/EP4278032A1/fr active Pending
- 2022-01-14 MX MX2023008352A patent/MX2023008352A/es unknown
- 2022-01-14 JP JP2023542896A patent/JP2024507060A/ja active Pending
- 2022-01-14 TW TW111101733A patent/TW202240038A/zh unknown
- 2022-01-14 WO PCT/EP2022/050774 patent/WO2022152867A1/fr active Application Filing
- 2022-01-14 KR KR1020237025841A patent/KR20230130670A/ko unknown
-
2023
- 2023-07-13 IL IL304461A patent/IL304461A/en unknown
Also Published As
Publication number | Publication date |
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MX2023008352A (es) | 2023-08-21 |
JP2024507060A (ja) | 2024-02-16 |
WO2022152867A1 (fr) | 2022-07-21 |
KR20230130670A (ko) | 2023-09-12 |
IL304461A (en) | 2023-09-01 |
TW202240038A (zh) | 2022-10-16 |
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