EP1452631A1 - Chlorine-resistant elasthane fibers - Google Patents
Chlorine-resistant elasthane fibers Download PDFInfo
- Publication number
- EP1452631A1 EP1452631A1 EP04000698A EP04000698A EP1452631A1 EP 1452631 A1 EP1452631 A1 EP 1452631A1 EP 04000698 A EP04000698 A EP 04000698A EP 04000698 A EP04000698 A EP 04000698A EP 1452631 A1 EP1452631 A1 EP 1452631A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- polyurethane urea
- fibers
- fatty acid
- hydrotalcite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 106
- 239000000460 chlorine Substances 0.000 title claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 32
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 90
- 238000009987 spinning Methods 0.000 claims abstract description 47
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 44
- 239000000194 fatty acid Substances 0.000 claims abstract description 44
- 229930195729 fatty acid Natural products 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- -1 fatty acid salt Chemical class 0.000 claims abstract description 40
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 29
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 29
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000000578 dry spinning Methods 0.000 claims abstract description 13
- 238000002166 wet spinning Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002635 polyurethane Polymers 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 239000004753 textile Substances 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001059 synthetic polymer Polymers 0.000 claims abstract description 4
- 229920000742 Cotton Polymers 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 210000002268 wool Anatomy 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 30
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 13
- 235000019359 magnesium stearate Nutrition 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical class CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 2
- 229940063655 aluminum stearate Drugs 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Chemical class CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000008117 stearic acid Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 150000002888 oleic acid derivatives Chemical class 0.000 claims 1
- 150000004671 saturated fatty acids Chemical class 0.000 claims 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 16
- 239000003381 stabilizer Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 150000002009 diols Chemical class 0.000 description 11
- 229920002334 Spandex Polymers 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000009182 swimming Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- RHUISYVRPZCGKL-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,5-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound OC1=C(C(C)(C)C)C(C)=CC(CN2C(N(CC=3C(=C(O)C(=C(C)C=3)C(C)(C)C)C)C(=O)N(CC=3C(=C(O)C(=C(C)C=3)C(C)(C)C)C)C2=O)=O)=C1C RHUISYVRPZCGKL-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 206010010774 Constipation Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- KMGARVOVYXNAOF-UHFFFAOYSA-N benzpiperylone Chemical compound C1CN(C)CCC1N1C(=O)C(CC=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 KMGARVOVYXNAOF-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- 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
- 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
Definitions
- the invention relates to elastic polyurethane urea fibers which, in aqueous, chlorine-containing environments, such as can be used in swimming pools for swimwear.
- the invention relates to elastic polyurethane urea fibers which contain coated hydrotalcites.
- fiber used in the context of the present invention includes staple fibers and / or continuous filaments made by spinning processes known in principle, e.g. the Dry spinning or wet spinning, as well as melt spinning can.
- Elastic polyurethane urea fibers made of long-chain synthetic polymers, at least 85% from segmented polyurethane ureas based on e.g. Polyethers, polyesters and / or Polycarbonates are well known. Yarns made from such fibers are used in manufacturing of knitted fabrics or fabrics, which in turn for corsetry, stockings and Sportswear e.g. Swimsuits or swimming trunks are suitable. In swimming pools it will However, water is often so chlorinated for hygienic reasons that the active chlorine content usually between 0.5 and 3 ppm (parts per million) or even higher. If polyurethane urea fibers exposed to such an environment can cause degradation or degradation Impairment of physical properties, e.g. the strength of the fibers and thereby lead to premature textile wear.
- polyurethane ureas were often based on polyesters as swimwear low molecular weight mono-, di- or polyhydroxy-functional polymer. Aliphatic polyester however, show high biological activity. That's why they got out of this Polymer-made polyurethane ureas have the disadvantage that they easily pass through microbes and fungi be dismantled. It has also been shown that the resistance to chlorinated water of polyurethane ureas based on polyesters is not satisfactory.
- EP-A-558 758 describes a polyurethane urea composition which contains a hydrotalcite with attached fatty acid containing water of crystallization.
- disadvantage this composition is that the chlorinated water resistance of the polyurethane urea fibers described is not sufficient, the dyeability of the polyurethane urea fibers described processing with polyamide hard fibers by acid dyes such as Telon dyes is not sufficient and a tone-on-tone dyeing between blended fabrics from e.g. Polyurethane urea fibers and polyamide hard fibers fail.
- the adhering fatty acid sublimes during the dry spinning process together with the solvent out of the fiber and has contamination of the working environment and blockage of e.g. Heat exchangers for cooling of the solvent.
- the published patent application JP 9 217 227 describes the production of polyurethane urea fibers Incorporation of hydrotalcite, metal fatty acid salts and modified silicones into filaments described.
- a disadvantage of this composition is that the uncoated hydrotalcite in polar solvents such as dimethylacetamide or dimethylformamide and even in spinning solutions for polyurethane urea fibers agglomerated as described above. Agglomerates in spinning solutions For polyurethane urea fibers, constipation can quickly occur during the spinning process of the spinnerets cause the spinning process due to frequently breaking fibers and / or increasing Pressure at the spinnerets often has to be interrupted. A spinning of such PU compositions over a longer period of time is therefore also not according to this procedure possible.
- Patent application EP-A-843 029 describes a polyurethane urea composition and The resulting elastic polyurethane urea fibers are described in particular with polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane coated Contain hydrotalcites and / or other basic metal-aluminum-hydroxy compounds.
- disadvantage this composition is that the chlorinated water resistance of the polyurethane urea fibers described is not yet sufficient.
- there is a continuous one Neither does the spinning process of such polyurethane urea fibers over a longer period of time possible because after a few days of spinning the thread will tear off when winding onto the bobbin starts.
- the invention has for its object a polyurethane urea composition in particular for polyurethane urea fibers (also called elastane fibers), the one improved or at least equivalent resistance to chlorine water compared to the prior art possesses, the chlorine water stability preferably not by the addition of heavy metals Additives is achieved and their stabilizer both the spinning process as such and the physical properties of the polyurethane fiber are not negatively affected.
- the object is achieved in that the polyurethane urea fibers effective amount of finely divided hydrotalcites coated with metal fatty acid salt can be added.
- the amount of hydrotalcite coated with metal fatty acid salt contained in the polyurethane urea fibers is finely divided, is 0.05 wt .-% to 10 wt .-%, preferably from 0.5% by weight to 8% by weight, particularly preferably from 1.5% by weight to 7% by weight and very particularly preferably from 2% by weight to 5% by weight, based on the weight of the polyurethane urea fiber. at The amount of hydrotalcite within the elastane fibers and / or on the Fiber surface to be distributed.
- the hydrotalcites are particularly preferably those such as those shown in formulas (3) and (4): Mg 6 Al 2 (OH) 16 (A 2- ) . wH 2 O Mg 4 Al 2 (OH) 12 (A 2- ) . wH 2 O in which A 2- and w have the meaning given above for formula (2).
- hydrotalcites are those with the formulas (5) and (6): Mg 6 Al 2 (OH) 16 CO 3 . 5H 2 O Mg 4 Al 2 (OH) 12 CO 3 . 4H 2 O
- the metal salts of fatty acids described are used to coat the hydrotalcites with a Content of preferably 0.2 to 15 wt .-% based on the weight of the hydrotalcite used. It is particularly preferred to use hydrotalcites containing from 0.3 to 12% by weight of metal fatty acid salt are coated. In particular, hydrotalcites are preferably used, which with 0.5 up to 8% by weight of fatty acid metal salt are coated.
- the metal salts of fatty acids used are those whose metal is a metal selected from the first to third main groups of the periodic table or zinc.
- the fatty acids can be saturated or unsaturated, from at least six to at most 30 carbon atoms be constructed and be mono- or bifunctional.
- the metal salts of fatty acids are particularly preferably lithium, magnesium, calcium, aluminum and zinc salts of the oil, Palmitic or stearic acid, particularly preferably around magnesium stearate, calcium stearate or Aluminum stearate and very particularly preferably magnesium stearate.
- the hydrotalcites can be coated by spraying and / or mixing in the metal fatty acid salt together or separately in any order, preferably before and / or during a final grinding of the hydrotalcite. It is irrelevant whether the metal fatty acid salt in the production of hydrotalcites in wet filter cakes, pastes or Slurries are added before drying or whether it is immediately dry before the final grinding in a suitable manner, for example by spraying or, in the case of steam jet drying, the steam immediately as it is fed into the jet mill is added.
- the metal fatty acid salt may optionally be added to an emulsion prior to addition be transferred.
- hydrotalcites as such are prepared, for example, according to known principles Method. Such methods are e.g. described in published patent applications EP 129 805-A1 or EP 117 289-A1.
- the hydrotalcites coated with metal fatty acid salt are preferably prepared from their starting compounds, for example from MgCO 3 , Al 2 O 3 and water in the presence of metal fatty acid salt and a solvent such as. B. water, a C 1 -C 8 alcohol or chlorinated hydrocarbons with subsequent drying, for example spray drying and optionally subsequent grinding, for example by a bead mill.
- a solvent such as. B. water, a C 1 -C 8 alcohol or chlorinated hydrocarbons with subsequent drying, for example spray drying and optionally subsequent grinding, for example by a bead mill.
- preferably coated hydrotalcites with an average diameter (number average) of at most 5 ⁇ m are used, particularly preferably those with at most 3 ⁇ m, very particularly preferably those with at most 2 ⁇ m and particularly particularly preferably those with at most 1 ⁇ m medium diameter.
- the hydrotalcites coated with metal fatty acid salt can be of the polyurethane urea composition can be added at any point in the production of polyurethane urea fibers.
- the hydrotalcites coated with metal fatty acid salt can be in the form of a solution or slurry added to a solution or dispersion of other fiber additives and then mixed with or into the polymer solution upstream of the fiber spinnerets be injected.
- the hydrotalcites coated with metal fatty acid salt can also separated from the polymer dope as a dry powder or as a slurry in one suitable medium can be added.
- the hydrotalcites coated with metal fatty acid salt can in principle optionally also as a mixture with uncoated or with known Coating agents (e.g.
- fatty acids or polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane) coated hydrotalcites for the production of polyurethane urea fibers are used in accordance with the procedure described above, if the disadvantages of the known coated hydrotalcites in the mixture described above are tolerable.
- the polyurethane urea fibers of the invention can be a variety of different ones contain further additives for various purposes, for example matting agents, fillers, Antioxidants, dyes, stains, stabilizers against heat, light, UV radiation and Fumes.
- antioxidants examples include stabilizers from the group of sterically hindered phenols, HALS stabilizers (h indered a mine l ight s tabilizer), triazines, benzophenones and benzotriazoles.
- pigments and matting agents are titanium dioxide, zinc oxide and barium sulfate.
- dyes examples include acid dyes, disperse and pigment dyes and optical brighteners.
- the stabilizers mentioned can also be used in mixtures and contain an organic or inorganic coating agent.
- the additives mentioned should preferably be dosed in amounts such that they do not show any effects contrary to the hydrotalcites coated with metal fatty acid salts.
- hydrotalcites agglomerate in polar solvents such as. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, which are in the dry or wet spinning process are usually used for the production of fibers from polyurethane urea. For this reason, spinning solutions with incorporated hydrotalcites during the spinning process Difficulties due to clogging of the spinnerets occur, resulting in a steep increase Nozzle pressure results and / or it tears off the freshly formed fibers before or comes up on a bobbin.
- Example 1 the durability is also more obtained Filaments against degradation induced by chlorine-containing water improved compared to Fibers that are obtained from agglomerate-containing spinning solutions or polymer melts.
- the invention also relates to a process for producing polyurethane urea fibers, where a long chain synthetic polymer with at least 85% segmented polyurethane in an organic solvent, e.g. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, with a proportion of 20 to 50% by weight in relation to the polyurethane urea composition, preferably in a proportion of 25 to 45% by weight with respect to the polyurethane urea composition solved, and then this solution through spinnerets after the drying or Wet spinning process is spun into filaments, characterized in that with a metal fatty acid salt jacketed hydrotalcite in an amount of 0.05 wt% to 10 wt%, preferably an amount of 0.5 wt .-% to 8 wt .-%, particularly preferably an amount of 1.5% by weight to 7% by weight, and very particularly preferably an amount of 2% by weight to 5% by weight, based on the weight of the polyurethane urea fiber, added
- the hydrotalcites coated with metal fatty acid salt are contained within of the filament or distributed on the filament surface, the effectiveness against the degradation of the Polymers may be less satisfactory due to chlorine.
- the dispersion of essential more than 10% by weight of the hydrotalcites coated with metal fatty acid salt within the filament or on the filament surface can cause adverse physical properties of the Lead fibers and is therefore less recommended.
- the improved polyurethane urea fibers according to the invention consist of segmented polyurethanes, for example those based on polyethers, polyesters, polyether esters, polycarbonates, and the like are based. Fibers of this type can be produced by processes which are known in principle such as those described in the documents: US-A-2 929 804, US-A-3 097 192, US-A-3 428 711, US-A-3 553 290 or US-A-3 555 115. Furthermore, the polyurethane urea fibers made of thermoplastic polyurethanes, their production described for example in EP 679 738.
- the segmented polyurethanes are basically made in particular from a linear homo- or Copolymer with one hydroxy group at the end of the molecule and a molecular weight of 600 up to 4000, e.g. from the group of polyester diols, polyether diols, polyester amido diols, polycarbonate diols, Polyacrylic diols, polythioester diols, polythioether diols, polyhydrocarbondiols or one Mixture or copolymers of compounds of this group. Furthermore, that is based segmented polyurethane especially on organic diisocyanates and chain extenders several active hydrogen atoms, such as. B. di- and polyols, di- and polyamines, hydroxylamines, Hydrazines, polyhydrazides, polysemicarbazides, water or a mixture of these Components.
- polyurethane urea fibers are made from a polyether Polyurethane urea much more sensitive than polyurethane urea fibers from one Polyester based polyurethane urea. For this reason, polyurethane urea fibers are special preferred which comprise polyether-based polyurethaneureas.
- the hydrotalcites coated with metal fatty acid salt are additives that do not Contain heavy metal and are harmless from a toxicological point of view and are therefore preferred become. This can ensure that during the further processing of the polyurethane urea fibers such as. the dyeing does not give rise to any wastewater that functions as a biological reduce or destroy working sewage treatment plant.
- the service life of spinnerets and the duration of the continuous spinning process is crucial Aspect related to operational safety and economy in dry and wet spinning processes.
- the Service life of the spinnerets and the associated operational reliability and economy in the Dry or wet spinning process can be improved.
- Example 3 the addition of anti-adhesive, e.g. Magnesium stearate, to set the liability value as a measure of the liability of the filaments on the Reduced bobbin when using hydrotalcites coated with metal fatty acid salts become.
- anti-adhesive e.g. Magnesium stearate
- the invention further relates to textile goods, in particular knitted, knitted or woven goods, produced using the polyurethane urea fibers according to the invention, preferably in Mix with synthetic hard fibers such as polyamide, polyester or polyacrylic fibers and / or Natural fibers such as wool, silk or cotton.
- synthetic hard fibers such as polyamide, polyester or polyacrylic fibers
- Natural fibers such as wool, silk or cotton.
- test procedures described below are used to measure the various parameters used, which are needed for evaluating the advantages of the invention.
- a simple tensile test is used to determine the maximum tensile strength elongation and the tenacity performed on the elastane filament yarn in an air-conditioned condition.
- the test method is in Based on DIN 53834 part 1.
- the prepared test object is looped around the hook of the measuring head and around a 10 mm loop clamp with a pretensioning force of 0.001 cN / dtex.
- the clamping length is 200 mm.
- a flag made of aluminum foil is hung exactly at the height of the light barrier.
- the sled travels at a rate of deformation from 400% / minute (800 mm take-off) until the thread breaks and after the Measurement back to its original position. 20 measurements are made per test object.
- the sample is then at room temperature 5 and 10 times each for one hour in the dark in the test solution consisting of one Buffer solution (51.0 ml of 1.0 N NaOH, 18.6g KCl and 15.5g boric acid are dissolved in distilled water dissolved and made up to 1000 ml) and chlorine solution, with a chlorine content of 20 mg / l at pH 8.5 treated. After each treatment, the sample is washed with distilled water and on the Air dried. After completing the 5 or 10 treatments, the physical Properties of the sample measured as described in the previous paragraphs. The Behavior of the yarns in this "chlorine bath water test" corresponds to the behavior of the corresponding ones Yarns in swimwear fabrics that are exposed to the chlorine present in swimming pools become.
- the chlorine concentration in the "chlorinated" water is defined here as the chlorine concentration which is able to oxidize iodide ions to iodine. This concentration is measured with a potassium iodide, sodium thiosulfate titration and stated as ppm "active chlorine" (Cl 2 ) per liter of test solution.
- the titration procedure is carried out by adding 1 g of potassium iodide, 2 ml of phosphoric acid (85%) and 1 ml of a 10% starch solution to 100 ml of chlorinated water to be analyzed and the mixture to a starch / iodine solution. End point titrated with 0.1 N sodium thiosulfate solution.
- the determination of the adhesion of the thread on a bobbin is made by first the thread from cut the coil with a weight of 500 g to 3 mm above the coil sleeve becomes. Then hang a weight on the thread and determine the weight with which the thread unwinds from the bobbin.
- the liability determined in this way is a measure of the processability of the coils. If the adhesion is too high, the processability may increase due to thread breaks textile fabrics are made more difficult. If the adhesion is too low, the thread can be wound up on the dry spinning shaft or during further processing into textile fabrics from fall off the spool, tear off and are no longer processed.
- polyurethane urea fibers consisting of a polyether diol were Polytetrahydrofuran (PTHF) with an average number average molecular weight of 2000 g / mol produced.
- PTHF Polytetrahydrofuran
- MDI methylene bis (4-phenyl diisocyanate)
- EDA ethylenediamine
- DEA diethylamine
- a basic batch of additives was then added to the polymers.
- This basic approach consisted of 55.3% by weight dimethylacetamide (DMAC), 11.1% by weight Cyanox 1790 ((1,3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Cytec), 7.6% by weight of Aerosol OT 100 (Cytec), 26.0% by weight of 30% spinning solution and 0.001% by weight of the Macrolex violet dye (Bayer AG).
- This master batch was added to the spinning solution in such a way that in the finished fiber the content of Cyanox 1790 1% by weight based on the solid of the fiber polymer scam.
- a second master batch consisting of 30.9% by weight of titanium dioxide was mixed into this spinning solution Type RKB 3 (Kerr-McGee Pigments GmbH & Co. KG), 44.5% by weight DMAC and 24.6% by weight 22% spinning solution, in such a way that the finished fiber has a titanium dioxide content of 0.05% by weight based on the polyurethane-urea polymer resulted.
- Type RKB 3 Kerr-McGee Pigments GmbH & Co. KG
- a polyurethane urea solution based on a polyester diol was prepared according to following procedure:
- MDI methylene bis (4-phenyl diisocyanate
- EDA ethylenediamine
- DEA Diethylamine
- polyester diol 50% by weight were used a number average molecular weight of 2000 g / mol with 1% by weight of 4-methyl-4-azaheptanediol-2,6 and 36.2 wt% dimethylacetamide (DMAc) and 12.8 wt% MDI mixed at 25 ° C Heated 50 ° C and held at this temperature for 110 minutes to form an isocyanate capped To win polymer with an NCO content of 2.65% NCO.
- DMAc dimethylacetamide
- This master batch consisted of 65.6% by weight of DMAC, 11.5% by weight of Cyanox 1790 ((1,3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6 - (1H, 3H, 5H) -trione, Cytec), 5.7% by weight Tinuvin 622 (polymer with a molecular weight of approx.
- This spinning solution was a second stock, consisting of 31 wt .-% titanium dioxide (Tronox TiO 2 R-KB-3, Kerr-McGee Pigments GmbH & Co. KG), 44.5 wt .-% dimethylacetamide and 24.5 % By weight 22% spinning solution, mixed in such a way that a titanium dioxide content of 0.05% by weight, based on the finished polyurethane urea fiber, resulted in the finished thread.
- the finished spinning solutions were fed through spinnerets in a typical spinning apparatus Filaments with a titer of 15 dtex dry spun, with three individual filaments each coalescing filament yarns with a total titre of 44 dtex were combined.
- the Fiber preparation consisting of polydimethylsiloxane with a viscosity of 3 cSt / 25 ° C and was applied over a preparation roller, with about 4.0 wt .-% based on the weight of the fiber were applied. The fiber was then spun at a speed of 900 m / min wound.
- polyurethane urea compositions based on polyether were mixed with the coated hydrotalcites mentioned in Table 3 and spun out as 44dtex f3.
- the thread data were determined in accordance with the test instructions described above.
- the adhesion is highly dependent on the substance used to coat the hydrotalcite.
- an adhesion of 0.20 to 0.25 cN is required.
- the elastane fiber, which contains a hydrotalcite coated with polyorganosiloxane must be given an additional amount of non-stick agent, for example magnesium stearate.
Abstract
Description
Die Erfindung betrifft elastische Polyurethanharnstofffasern, die in wässrigen, chlorhaltigen Umgebungen, wie beispielsweise in Schwimmbädern für Badebekleidung eingesetzt werden können. Die Erfindung betrifft elastische Polyurethanharnstofffasern, die beschichtete Hydrotalcite enthalten.The invention relates to elastic polyurethane urea fibers which, in aqueous, chlorine-containing environments, such as can be used in swimming pools for swimwear. The The invention relates to elastic polyurethane urea fibers which contain coated hydrotalcites.
Der im Rahmen der vorliegenden Erfindung verwendete Ausdruck "Faser" umfasst dabei Stapelfasern und/oder kontinuierliche Filamente, die durch im Prinzip bekannte Spinnprozesse, z.B. das Trockenspinnverfahren oder das Nassspinnverfahren, sowie das Schmelzspinnen hergestellt werden können.The term “fiber” used in the context of the present invention includes staple fibers and / or continuous filaments made by spinning processes known in principle, e.g. the Dry spinning or wet spinning, as well as melt spinning can.
Elastische Polyurethanharnstofffasern aus langkettigen synthetischen Polymeren, die zu wenigstens 85 % aus segmentierten Polyurethanharnstoffen auf Basis von z.B. Polyethern, Polyestern und/oder Polycarbonaten aufgebaut sind, sind gut bekannt. Garne aus solchen Fasern werden zur Herstellung von Gewirken bzw. Stoffen verwendet, die ihrerseits unter anderem für Miederwaren, Strümpfe und Sportbekleidung z.B. Badeanzüge bzw. Badehosen, geeignet sind. In Schwimmbädern wird das Wasser jedoch häufig aus hygienischen Gründen so stark chloriert, dass der aktive Chlorgehalt gewöhnlich zwischen 0,5 und 3 ppm (parts per million) oder sogar höher liegt. Wenn Polyurethanharnstofffasern einer solchen Umgebung ausgesetzt werden, kann dies zu einem Abbau bzw. einer Beeinträchtigung der physikalischen Eigenschaften, z.B. der Festigkeit der Fasern und dadurch bedingt zu einem vorzeitigen Textilverschleiß führen.Elastic polyurethane urea fibers made of long-chain synthetic polymers, at least 85% from segmented polyurethane ureas based on e.g. Polyethers, polyesters and / or Polycarbonates are well known. Yarns made from such fibers are used in manufacturing of knitted fabrics or fabrics, which in turn for corsetry, stockings and Sportswear e.g. Swimsuits or swimming trunks are suitable. In swimming pools it will However, water is often so chlorinated for hygienic reasons that the active chlorine content usually between 0.5 and 3 ppm (parts per million) or even higher. If polyurethane urea fibers exposed to such an environment can cause degradation or degradation Impairment of physical properties, e.g. the strength of the fibers and thereby lead to premature textile wear.
In praktischer Hinsicht kann bei grobtitrigen Fasern ein gewisser Abbau der Faser toleriert werden, ohne dass seine Auswirkungen von dem Benutzer der aus diesen Fasern hergestellten Geweben bemerkt werden. Dennoch ist eine Verbesserung der Beständigkeit des Fasermaterials gegenüber einem durch Chlor induzierten Abbau notwendig, insbesondere für Garne mit einer hohen Feinheit (beispielsweise Fasern mit einem Titer von weniger als 220 Denier).In practical terms, a certain degradation of the fiber can be tolerated with coarse-titer fibers, without its effects from the user of the fabrics made from these fibers be noticed. Nevertheless, there is an improvement in the resistance of the fiber material to chlorine-induced degradation is necessary, especially for yarns with a high degree of fineness (for example fibers with a titer of less than 220 denier).
Zur Verbesserung der Chlorwasserbeständigkeit von elastischen Polyurethanharnstoff-Garnen für das Einsatzgebiet Badebekleidung wurden die Polyurethanharnstoffe häufig auf Basis von Polyestern als niedermolekulares mono-, di- oder polyhydroxy-funktionelles Polymer hergestellt. Aliphatische Polyester zeigen jedoch eine hohe biologische Aktivität. Aus diesem Grunde haben die aus diesem Polymer hergestellten Polyurethanharnstoffe den Nachteil, dass sie leicht durch Mikroben und Pilze abgebaut werden. Weiterhin hat sich gezeigt, dass die Chlorwasserbeständigkeit von Polyurethanharnstoffen auf Basis von Polyestern nicht zufriedenstellend ist.To improve the chlorine water resistance of elastic polyurethane urea yarns for the Field of application The polyurethane ureas were often based on polyesters as swimwear low molecular weight mono-, di- or polyhydroxy-functional polymer. Aliphatic polyester however, show high biological activity. That's why they got out of this Polymer-made polyurethane ureas have the disadvantage that they easily pass through microbes and fungi be dismantled. It has also been shown that the resistance to chlorinated water of polyurethane ureas based on polyesters is not satisfactory.
Eine Vielzahl von Additiven in Elastan-Fasern wurde beschrieben, um die Chlorwasserbeständigkeit von elastischen Polyurethanfilamenten zu verbessern. A variety of additives in elastane fibers have been described to make them resistant to chlorine of elastic polyurethane filaments to improve.
In den Schriften US 5 028 642 und US 6 406 788 ist die Einarbeitung von Zinkoxid in Filamente aus segmentierten Polyurethanharnstoffen zur Chlorstabilisierung beschrieben. Zinkoxid hat jedoch den gravierenden Nachteil, dass es während des Färbeprozesses der Gewebe, insbesondere unter sauren Bedingungen (pH 3 bis 4), aus dem Filament herausgewaschen wird. Dadurch wird die Chlorwasserbeständigkeit der Faser stark gemindert. Weiterhin werden durch die zinkhaltigen Färbeabwässer Bakterienkulturen in biologisch arbeitenden Kläranlagen zur Verarbeitung der Abwässer abgetötet. In der Folge kann die Wirkungsweise solcher Kläranlagen erheblich beeinträchtigt werden.In the documents US 5 028 642 and US 6 406 788 the incorporation of zinc oxide in filaments is over segmented polyurethane ureas for chlorine stabilization. However, zinc oxide has that serious disadvantage that it is during the dyeing process of the tissues, especially under acid Conditions (pH 3 to 4) from which the filament is washed out. This makes the water resistant to chlorine the fiber greatly reduced. Furthermore, the zinc-containing dyeing waste water Bacterial cultures in biological sewage treatment plants for processing the waste water are killed. In As a result, the operation of such sewage treatment plants can be significantly impaired.
In der Offenlegungsschrift JP 59-133 248 ist zur Verbesserung der Chlorwasserbeständigkeit die Einarbeitung von Hydrotalcit in Filamente aus segmentierten Polyurethanharnstoffen beschrieben. Neben der schwermetallfreien Stabilisierung wird beschrieben, dass nur geringe Mengen von dispergiertem Hydrotalcit bei Färbebedingungen im sauren Bereich (pH 3 bis 4) ausgewaschen werden und somit eine gute Chlorwasserbeständigkeit erhalten bleibt. Als Nachteil zeigt sich jedoch, dass Hydrotalcit in polaren Lösungsmitteln wie Dimethylacetamid oder Dimethylformamid und sogar in Spinnlösungen für Polyurethanharnstofffasern stark agglomeriert. Agglomerate in Spinnlösungen für Polyurethanharnstofffasern führen während des Spinnprozesses rasch zu Verstopfung der Spinndüsen, wodurch der Spinnprozess wegen häufig brechender Fasern und/oder steigendem Druck an den Spinndüsen häufig unterbrochen werden muss. Ein Spinnen solcher PU-Zusammensetzungen über einen längeren Zeitraum mit hinreichender Betriebsicherheit ist somit gemäß diesem Verfahren nicht möglich. Zudem weisen solche Filamente keine ausreichende Beständigkeit gegen chlorhaltiges Wasser auf.In the published patent application JP 59-133 248 the is to improve the resistance to chlorine water Incorporation of hydrotalcite in filaments from segmented polyurethane ureas is described. In addition to the heavy metal-free stabilization, it is described that only small amounts of dispersed Hydrotalcite can be washed out under dyeing conditions in the acidic range (pH 3 to 4) and thus good chlorine water resistance is maintained. A disadvantage, however, is that hydrotalcite in polar solvents such as dimethylacetamide or dimethylformamide and even in spinning solutions strongly agglomerated for polyurethane urea fibers. Agglomerates in spinning solutions for polyurethane urea fibers quickly clog the spinnerets during the spinning process, whereby the spinning process due to frequently breaking fibers and / or increasing pressure on the Spinnerets must be interrupted frequently. Spinning over such PU compositions a longer period with sufficient operational safety is therefore not in accordance with this method possible. In addition, such filaments do not have sufficient resistance to chlorine Water on.
In der Offenlegungsschrift EP -A- 558 758 wird eine Polyurethanharnstoffzusammensetzung beschrieben, die ein Kristallwasser enthaltendes Hydrotalcit mit anhaftender Fettsäure enthält. Nachteil dieser Zusammensetzung ist, dass die Chlorwasserbeständigkeit der beschriebenen Polyurethanharnstofffasern nicht ausreichend ist, die Anfärbbarkeit der beschriebenen Polyurethanharnstofffasern bei der Verarbeitung mit Polyamid-Hartfasern durch Säurefarbstoffe wie Telon-Farbstoffe nicht ausreichend ist und eine Ton-in-Ton-Färbung zwischen Mischgeweben aus z.B. Polyurethanharnstofffasern und Polyamid-Hartfasern nicht gelingt. Des weiteren sublimiert die anhaftende Fettsäure während des Trockenspinnprozesses zusammen mit dem Lösungsmittel aus der Faser heraus und hat die Kontamination der Arbeitsumgebung und die Verstopfung von z.B. Wärmetauschern zur Abkühlung des Lösungsmittels zur Folge.The published patent application EP-A-558 758 describes a polyurethane urea composition which contains a hydrotalcite with attached fatty acid containing water of crystallization. disadvantage this composition is that the chlorinated water resistance of the polyurethane urea fibers described is not sufficient, the dyeability of the polyurethane urea fibers described processing with polyamide hard fibers by acid dyes such as Telon dyes is not sufficient and a tone-on-tone dyeing between blended fabrics from e.g. Polyurethane urea fibers and polyamide hard fibers fail. Furthermore, the adhering fatty acid sublimes during the dry spinning process together with the solvent out of the fiber and has contamination of the working environment and blockage of e.g. Heat exchangers for cooling of the solvent.
In der Offenlegungsschrift JP 9 217 227 wird zur Herstellung von Polyurethanharnstofffasern die Einarbeitung von Hydrotalcit, Metallfettsäuresalzen und modifizierten Silikonen in Filamente beschrieben. Als Nachteil dieser Zusammensetzung zeigt sich jedoch, dass das unbeschichtete Hydrotalcit in polaren Lösungsmitteln wie Dimethylacetamid oder Dimethylformamid und sogar in Spinnlösungen für Polyurethanharnstofffasern wie oben beschrieben agglomeriert. Agglomerate in Spinnlösungen für Polyurethanharnstofffasern können während des Spinnprozesses rasch zu Verstopfung der Spinndüsen führen, wodurch der Spinnprozess wegen häufig brechender Fasern und/oder steigendem Druck an den Spinndüsen häufig unterbrochen werden muss. Ein Spinnen solcher PU-Zusammensetzungen über einen längeren Zeitraum ist somit gemäß diesem Verfahren auch nicht möglich.The published patent application JP 9 217 227 describes the production of polyurethane urea fibers Incorporation of hydrotalcite, metal fatty acid salts and modified silicones into filaments described. A disadvantage of this composition, however, is that the uncoated hydrotalcite in polar solvents such as dimethylacetamide or dimethylformamide and even in spinning solutions for polyurethane urea fibers agglomerated as described above. Agglomerates in spinning solutions For polyurethane urea fibers, constipation can quickly occur during the spinning process of the spinnerets cause the spinning process due to frequently breaking fibers and / or increasing Pressure at the spinnerets often has to be interrupted. A spinning of such PU compositions over a longer period of time is therefore also not according to this procedure possible.
In der Patentanmeldung EP-A- 843 029 wird eine Polyurethanharnstoff-zusammensetzung und speziell daraus resultierende elastische Polyurethanharnstofffasern beschrieben, die mit Polyorganosiloxan oder einer Mischung von Polyorganosiloxan und Polyorganohydrogensiloxan beschichtete Hydrotalcite und/oder andere basische Metall-Aluminium-Hydroxy-Verbindungen enthalten. Nachteil dieser Zusammensetzung ist, dass die Chlorwasserbeständigkeit der beschriebenen Polyurethanharnstofffasern noch nicht ausreichend ist. Weiterhin ist gemäß diesem Verfahren ein kontinuierlicher Spinnprozess solcher Polyurethanharnstofffasern über einen längeren Zeitraum ebenfalls nicht möglich, da nach wenigen Tagen Spinndauer der Faden beim Aufwickeln auf den Spulkörper abzureißen beginnt.Patent application EP-A-843 029 describes a polyurethane urea composition and The resulting elastic polyurethane urea fibers are described in particular with polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane coated Contain hydrotalcites and / or other basic metal-aluminum-hydroxy compounds. disadvantage this composition is that the chlorinated water resistance of the polyurethane urea fibers described is not yet sufficient. Furthermore, according to this method, there is a continuous one Neither does the spinning process of such polyurethane urea fibers over a longer period of time possible because after a few days of spinning the thread will tear off when winding onto the bobbin starts.
Der Erfindung liegt die Aufgabe zugrunde, eine Polyurethanharnstoffzusammensetzung insbesondere für Polyurethanharnstofffasern (auch Elastanfasern genannt) zur Verfügung zu stellen, die eine gegenüber dem Stand der Technik verbesserte oder mindestens gleichwertige Chlorwasserbeständigkeit besitzt, deren Chlorwasserstabilität bevorzugt nicht durch Zusatz von schwermetallhaltigen Additiven erzielt wird und deren Stabilisator sowohl den Spinnprozess als solchen als auch die physikalische Eigenschaften der Polyurethan-Faser nicht negativ beeinflusst.The invention has for its object a polyurethane urea composition in particular for polyurethane urea fibers (also called elastane fibers), the one improved or at least equivalent resistance to chlorine water compared to the prior art possesses, the chlorine water stability preferably not by the addition of heavy metals Additives is achieved and their stabilizer both the spinning process as such and the physical properties of the polyurethane fiber are not negatively affected.
Die Aufgabe wird erfindungsgemäß dadurch gelöst, dass den Polyurethanharnstofffasern eine wirksame Menge fein zerteilter, mit Metallfettsäuresalz beschichteter Hydrotalcite zugesetzt werden.The object is achieved in that the polyurethane urea fibers effective amount of finely divided hydrotalcites coated with metal fatty acid salt can be added.
Gegenstand der Erfindung sind Polyurethanharnstofffasern (Elastanfasern) mit erhöhter Chlorbeständigkeit
aus mindestens 85 % segmentiertem Polyurethanharnstoff, wobei die Polyurethanharnstofffasern
0,05 bis 10 Gew.-% fein zerteiltes Hydrotalcit insbesondere solches der allgemeinen
Formel (1)
- M2+
- für Magnesium steht,
- A'n-
- ein Anion mit der Valenzzahl n aus der Reihe OH-, F-, Cl-, Br-, CO3 2-, SO4 2-,
0 < x ≤ 0,5 und
0 ≤ m < 1
oder Hydrotalcit der Formel (2)
enthalten,
dadurch gekennzeichnet, dass die Hydrotalcite mit 0,2 bis 15 Gew.-% eines Metallfettsäuresalzes beschichtet sind.The invention relates to polyurethane urea fibers (elastane fibers) with increased chlorine resistance made from at least 85% segmented polyurethane urea, the polyurethane urea fibers 0.05 to 10% by weight finely divided hydrotalcite, in particular those of the general formula (1)
- M 2+
- stands for magnesium,
- A ' n
- an anion with the valence number n from the series OH - , F - , Cl - , Br - , CO 3 2- , SO 4 2- ,
0 <x ≤ 0.5 and
0 ≤ m <1
or hydrotalcite of the formula (2)
contain,
characterized in that the hydrotalcites are coated with 0.2 to 15 wt .-% of a metal fatty acid salt.
Die Menge des mit Metallfettsäuresalz beschichteten Hydrotalcits, die in den Polyurethanharnstofffasern fein verteilt enthalten ist, beträgt 0,05 Gew.-% bis 10 Gew.-%, vorzugsweise von 0,5 Gew.-% bis 8 Gew.-%, besonders bevorzugt von 1,5 Gew.-% bis 7 Gew.-% und ganz besonders bevorzugt von 2 Gew.-% bis 5 Gew.-%, bezogen auf das Gewicht der Polyurethanharnstofffaser. Bei den Elastanfasern kann die Menge an Hydrotalcit innerhalb der Elastanfasern und/oder auf der Faseroberfläche verteilt sein.The amount of hydrotalcite coated with metal fatty acid salt contained in the polyurethane urea fibers is finely divided, is 0.05 wt .-% to 10 wt .-%, preferably from 0.5% by weight to 8% by weight, particularly preferably from 1.5% by weight to 7% by weight and very particularly preferably from 2% by weight to 5% by weight, based on the weight of the polyurethane urea fiber. at The amount of hydrotalcite within the elastane fibers and / or on the Fiber surface to be distributed.
Bei den Hydrotalciten handelt es sich insbesondere bevorzugt um solche, wie sie z.B. in den Formeln
(3) und (4) gezeigt sind:
Besonders bevorzugte Beispiele der Hydrotalcite sind solche mit den Formeln (5) und (6):
Die beschriebenen Metallsalze von Fettsäuren werden zur Beschichtung der Hydrotalcite mit einem Gehalt von bevorzugt 0,2 bis 15 Gew.-% bezogen auf das Gewicht des Hydrotalcits eingesetzt. Besonders bevorzugt werden Hydrotalcite eingesetzt, die mit von 0,3 bis 12 Gew.-% Metallfettsäuresalz beschichtet sind. Insbesondere werden bevorzugt Hydrotalcite eingesetzt, die mit von 0,5 bis 8 Gew.-% Fettsäuremetallsalz beschichtet sind.The metal salts of fatty acids described are used to coat the hydrotalcites with a Content of preferably 0.2 to 15 wt .-% based on the weight of the hydrotalcite used. It is particularly preferred to use hydrotalcites containing from 0.3 to 12% by weight of metal fatty acid salt are coated. In particular, hydrotalcites are preferably used, which with 0.5 up to 8% by weight of fatty acid metal salt are coated.
Bei den eingesetzten Metallsalzen von Fettsäuren handelt es sich um solche, deren Metall ein Metall ausgewählt aus der ersten bis dritten Hauptgruppe des Periodensystems oder Zink ist. Die Fettsäuren können gesättigt oder ungesättigt, aus mindestens sechs bis höchstens 30 Kohlenstoffatomen aufgebaut sein und mono- oder bifunktionell sein. Bei den Metallsalzen von Fettsäuren handelt es sich besonders bevorzugt um Lithium-, Magnesium-, Calcium-, Aluminium- und Zinksalze der Öl-, Palmitin- oder Stearinsäure, besonders bevorzugt um Magnesiumstearat, Calciumstearat oder Aluminiumstearat und ganz besonders bevorzugt um Magnesiumstearat.The metal salts of fatty acids used are those whose metal is a metal selected from the first to third main groups of the periodic table or zinc. The fatty acids can be saturated or unsaturated, from at least six to at most 30 carbon atoms be constructed and be mono- or bifunctional. The metal salts of fatty acids are are particularly preferably lithium, magnesium, calcium, aluminum and zinc salts of the oil, Palmitic or stearic acid, particularly preferably around magnesium stearate, calcium stearate or Aluminum stearate and very particularly preferably magnesium stearate.
Die Beschichtung der Hydrotalcite kann durch Aufsprühen und/oder Untermischen des Metallfettsäuresalzes gemeinsam oder getrennt in beliebiger Reihenfolge vorzugsweise vor und/oder während einer abschließenden Mahlung des Hydrotalcits erfolgen. Es ist dabei gleichgültig, ob das Metallfettsäuresalz bei der Herstellung der Hydrotalcite in anfallenden feuchten Filterkuchen, Pasten oder Aufschlämmungen vor der Trocknung zugemischt wird oder ob es dem trockenen Gut unmittelbar vor der abschließenden Mahlung in geeigneter Weise, beispielsweise durch Aufsprühen beigegeben oder, im Falle einer Dampfstrahltrocknung, dem Dampf unmittelbar bei der Einspeisung in die Strahlmühle zugesetzt wird. Das Metallfettsäuresalz kann gegebenenfalls vor der Zugabe in eine Emulsion überführt werden.The hydrotalcites can be coated by spraying and / or mixing in the metal fatty acid salt together or separately in any order, preferably before and / or during a final grinding of the hydrotalcite. It is irrelevant whether the metal fatty acid salt in the production of hydrotalcites in wet filter cakes, pastes or Slurries are added before drying or whether it is immediately dry before the final grinding in a suitable manner, for example by spraying or, in the case of steam jet drying, the steam immediately as it is fed into the jet mill is added. The metal fatty acid salt may optionally be added to an emulsion prior to addition be transferred.
Die Herstellung der Hydrotalcite als solche erfolgt beispielsweise nach grundsätzlich bekannten Verfahren. Solche Verfahren sind z.B. beschrieben in den Offenlegungsschriften EP 129 805-A1 oder EP 117 289-A1.The hydrotalcites as such are prepared, for example, according to known principles Method. Such methods are e.g. described in published patent applications EP 129 805-A1 or EP 117 289-A1.
Bevorzugt erfolgt die Herstellung der mit Metallfettsäuresalz beschichteten Hydrotalcite aus ihren Ausgangsverbindungen z.B. aus MgCO3, Al2O3 und Wasser in Anwesenheit von Metallfettsäuresalz und einem Lösungsmittel wie z. B. Wasser, einem C1-C8-Alkohol oder von chlorierten Kohlenwasserstoffen mit anschließender Trocknung durch z.B. Sprühtrocknung und gegebenenfalls anschließender Mahlung durch z.B. eine Perlmühle. Bei der Anwendung der mit Metallfettsäuresalz beschichteten Hydrotalcite als Faseradditiv werden bevorzugt beschichtete Hydrotalcite mit einem mittleren Durchmesser (Zahlenmittel) von höchstens 5µm eingesetzt, besonders bevorzugt solche mit höchstens 3µm, ganz besonders bevorzugt solche mit höchstens 2µm und insbesondere ganz besonders bevorzugt solche mit höchstens 1 µm mittlerem Durchmesser. The hydrotalcites coated with metal fatty acid salt are preferably prepared from their starting compounds, for example from MgCO 3 , Al 2 O 3 and water in the presence of metal fatty acid salt and a solvent such as. B. water, a C 1 -C 8 alcohol or chlorinated hydrocarbons with subsequent drying, for example spray drying and optionally subsequent grinding, for example by a bead mill. When the hydrotalcites coated with metal fatty acid salt are used as fiber additive, preferably coated hydrotalcites with an average diameter (number average) of at most 5 µm are used, particularly preferably those with at most 3 µm, very particularly preferably those with at most 2 µm and particularly particularly preferably those with at most 1 µm medium diameter.
Die mit Metallfettsäuresalz beschichteten Hydrotalcite können der Polyurethanharnstoffzusammensetzung bei der Herstellung von Polyurethanharnstofffasern an beliebiger Stelle zugesetzt werden. Beispielsweise können die mit Metallfettsäuresalz beschichteten Hydrotalcite in Form einer Lösung oder Aufschlämmung zu einer Lösung oder Dispersion von anderen Faser-Zusätzen hinzugefügt und dann in Bezug auf die Faserspinndüsen stromaufwärts mit der Polymerlösung vermischt oder in diese eingespritzt werden. Natürlich können die mit Metallfettsäuresalz beschichteten Hydrotalcite auch getrennt zu der Polymerspinnlösung als trockene Pulver oder als Aufschlämmung in einem geeigneten Medium hinzugefügt werden. Die mit Metallfettsäuresalz beschichteten Hydrotalciten können grundsätzlich gegebenenfalls auch als Mischung mit unbeschichteten oder mit mit bekannten Beschichtungsmitteln (z.B. Fettsäuren oder Polyorganosiloxan oder einer Mischung von Polyorganosiloxan und Polyorganohydrogensiloxan) beschichteten Hydrotalciten zur Herstellung von Polyurethanharnstofffasern entsprechend der oben beschriebenen Verfahrensweise eingesetzt werden, wenn die oben beschriebenen Nachteile der bekannten beschichteten Hydrotalcite in der Mischung tolerierbar sind.The hydrotalcites coated with metal fatty acid salt can be of the polyurethane urea composition can be added at any point in the production of polyurethane urea fibers. For example, the hydrotalcites coated with metal fatty acid salt can be in the form of a solution or slurry added to a solution or dispersion of other fiber additives and then mixed with or into the polymer solution upstream of the fiber spinnerets be injected. Of course, the hydrotalcites coated with metal fatty acid salt can also separated from the polymer dope as a dry powder or as a slurry in one suitable medium can be added. The hydrotalcites coated with metal fatty acid salt can in principle optionally also as a mixture with uncoated or with known Coating agents (e.g. fatty acids or polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane) coated hydrotalcites for the production of polyurethane urea fibers are used in accordance with the procedure described above, if the disadvantages of the known coated hydrotalcites in the mixture described above are tolerable.
Die erfindungsgemäßen Polyurethanharnstofffasern können eine Vielzahl von verschiedenen weiteren Zusätzen für verschiedene Zwecke enthalten, beispielsweise Mattierungsmittel, Füllstoffe, Antioxidantien, Farbstoffe, Anfärbemittel, Stabilisatoren gegen Wärme, Licht, UV-Strahlung und Dämpfe.The polyurethane urea fibers of the invention can be a variety of different ones contain further additives for various purposes, for example matting agents, fillers, Antioxidants, dyes, stains, stabilizers against heat, light, UV radiation and Fumes.
Beispiele für Antioxidantien, Stabilisatoren gegen Wärme, Licht oder UV-Strahlung sind Stabilisatoren aus der Gruppe der sterisch gehinderten Phenole, HALS-Stabilisatoren (hindered amine light stabilizer), Triazine, Benzophenone und der Benzotriazole. Beispiele für Pigmente und Mattierungsmittel sind Titandioxid, Zinkoxid und Bariumsulfat. Beispiele für Farbstoffe sind saure Farbstoffe, Dispersions- und Pigmentfarbstoffe und optische Aufheller. Die genannten Stabilisatoren können auch in Mischungen eingesetzt werden und ein organisches oder anorganisches Beschichtungsmittel enthalten. Die genannten Zusätze sollen bevorzugt in solchen Mengen dosiert werden, dass sie keine den mit Metallfettsäuresalzen beschichteten Hydrotalciten entgegengesetzte Wirkungen zeigen.Examples of antioxidants, stabilizers against heat, light or UV radiation are stabilizers from the group of sterically hindered phenols, HALS stabilizers (h indered a mine l ight s tabilizer), triazines, benzophenones and benzotriazoles. Examples of pigments and matting agents are titanium dioxide, zinc oxide and barium sulfate. Examples of dyes are acid dyes, disperse and pigment dyes and optical brighteners. The stabilizers mentioned can also be used in mixtures and contain an organic or inorganic coating agent. The additives mentioned should preferably be dosed in amounts such that they do not show any effects contrary to the hydrotalcites coated with metal fatty acid salts.
Hydrotalcite agglomerieren wie eingangs beschrieben unter Umständen in polaren Lösungsmitteln wie z.B. Dimethylacetamid, Dimethylformamid oder Dimethylsulfoxid, die im Trocken- oder Nassspinnprozess zur Herstellung von Fasern aus Polyurethanharnstoff üblicherweise eingesetzt werden. Aus diesem Grund können bei Spinnlösungen mit eingearbeiteten Hydrotalciten während des Spinnprozesses Schwierigkeiten durch Verstopfungen der Spinndüsen auftreten, woraus ein stark ansteigender Düsendruck resultiert und/oder es zum Abriss von den frisch gebildeten Fasern vor oder bei dem Aufwickeln auf einen Spulkörper kommt. Bei Einarbeitung der mit Metallfettsäuresalz beschichteten Hydrotalcite in Polyurethanharnstoffspinnlösungen entsprechend der Erfindung tritt keine Agglomeration in der Spinnlösung auf und die mittlere Korngröße der mit Metallfettsäuresalz beschichteten Hydrotalcite bleibt unverändert. Dieses verbessert die Standzeit der Spinndüsen und damit verbunden die Betriebssicherheit und die Wirtschaftlichkeit im Trocken- oder Nassspinnprozess der erfindungsgemäßen Polyurethanharnstofffasern.Under certain circumstances, hydrotalcites agglomerate in polar solvents such as. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, which are in the dry or wet spinning process are usually used for the production of fibers from polyurethane urea. For this reason, spinning solutions with incorporated hydrotalcites during the spinning process Difficulties due to clogging of the spinnerets occur, resulting in a steep increase Nozzle pressure results and / or it tears off the freshly formed fibers before or comes up on a bobbin. When incorporating the with metal fatty acid salt coated hydrotalcites in polyurethane urea spinning solutions according to the invention occurs no agglomeration in the spinning solution and the average grain size of that with metal fatty acid salt coated hydrotalcite remains unchanged. This improves the service life of the spinnerets and associated with this is operational safety and economy in the dry or wet spinning process the polyurethane urea fibers according to the invention.
Demzufolge ist auch, wie nachstehend in Beispiel 1 gezeigt wird, die Beständigkeit so erhaltener Filamente gegen einen durch chlorhaltiges Wasser induzierten Abbau verbessert im Vergleich zu Fasern, die aus agglomerathaltigen Spinnlösungen oder Polymerschmelzen erhalten werden.Accordingly, as shown in Example 1 below, the durability is also more obtained Filaments against degradation induced by chlorine-containing water improved compared to Fibers that are obtained from agglomerate-containing spinning solutions or polymer melts.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung von Polyurethanharnstofffasern, bei dem ein langkettiges synthetisches Polymer mit wenigstens 85 % segmentiertem Polyurethan in einem organischen Lösungsmittel, z.B. Dimethylacetamid, Dimethylformamid oder Dimethylsulfoxid, mit einem Anteil von 20 bis 50 Gew.-% in Bezug auf die Polyurethanharnstoffzusammensetzung, vorzugsweise mit einem Anteil von 25 bis 45 Gew.-% in Bezug auf die Polyurethanharnstoffzusammensetzung gelöst, und diese Lösung dann durch Spinndüsen nach dem Trocken- oder Nassspinnprozess zu Filamenten versponnen wird, dadurch gekennzeichnet, dass mit einem Metallfettsäuresalz ummanteltes Hydrotalcit in einer Menge von 0,05 Gew.-% bis 10 Gew.-%, vorzugsweise einer Menge von 0,5 Gew.-% bis 8 Gew.-%, besonders bevorzugt einer Menge von 1,5 Gew.-% bis 7 Gew.-%, und ganz besonders bevorzugt einer Menge von 2 Gew.-% bis 5 Gew.-%, bezogen auf das Gewicht des Polyurethanharnstofffaser, der Spinnlösung zugesetzt und innerhalb der Filamente und/oder auf der Filamentoberfläche verteilt wird.The invention also relates to a process for producing polyurethane urea fibers, where a long chain synthetic polymer with at least 85% segmented polyurethane in an organic solvent, e.g. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, with a proportion of 20 to 50% by weight in relation to the polyurethane urea composition, preferably in a proportion of 25 to 45% by weight with respect to the polyurethane urea composition solved, and then this solution through spinnerets after the drying or Wet spinning process is spun into filaments, characterized in that with a metal fatty acid salt jacketed hydrotalcite in an amount of 0.05 wt% to 10 wt%, preferably an amount of 0.5 wt .-% to 8 wt .-%, particularly preferably an amount of 1.5% by weight to 7% by weight, and very particularly preferably an amount of 2% by weight to 5% by weight, based on the weight of the polyurethane urea fiber, added to the spinning solution and within the filaments and / or is distributed on the filament surface.
Werden weniger als 0,05 Gew.-% der mit Metallfettsäuresalz ummantelten Hydrotalcite innerhalb des Filamentes oder auf der Filamentoberfläche verteilt, ist die Wirksamkeit gegen den Abbau des Polymeren durch Chlor unter Umständen weniger zufriedenstellend. Die Dispergierung von wesentlich mehr als 10 Gew.-% der mit Metallfettsäuresalz ummantelten Hydrotalcite innerhalb des Filamentes oder auf der Filamentoberfläche kann zu nachteiligen physikalischen Eigenschaften der Fasern führen und ist daher weniger empfehlenswert.Less than 0.05% by weight of the hydrotalcites coated with metal fatty acid salt are contained within of the filament or distributed on the filament surface, the effectiveness against the degradation of the Polymers may be less satisfactory due to chlorine. The dispersion of essential more than 10% by weight of the hydrotalcites coated with metal fatty acid salt within the filament or on the filament surface can cause adverse physical properties of the Lead fibers and is therefore less recommended.
Die verbesserten erfindungsgemäßen Polyurethanharnstofffasern bestehen aus segmentierten Polyurethanen, beispielsweise solchen, die auf Polyethern, Polyestern, Polyetherestern, Polycarbonaten, und dergleichen basieren. Derartige Fasern können nach grundsätzlich bekannten Verfahren hergestellt werden, wie beispielsweise nach denjenigen Verfahren, die in den Schriften: US-A- 2 929 804, US-A-3 097 192, US-A-3 428 711, US-A-3 553 290 oder US-A-3 555 115 beschrieben werden. Ferner können die Polyurethanharnstofffasern aus thermoplastischen Polyurethanen, deren Herstellung beispielsweise in EP 679 738 beschrieben ist, bestehen. The improved polyurethane urea fibers according to the invention consist of segmented polyurethanes, for example those based on polyethers, polyesters, polyether esters, polycarbonates, and the like are based. Fibers of this type can be produced by processes which are known in principle such as those described in the documents: US-A-2 929 804, US-A-3 097 192, US-A-3 428 711, US-A-3 553 290 or US-A-3 555 115. Furthermore, the polyurethane urea fibers made of thermoplastic polyurethanes, their production described for example in EP 679 738.
Die segmentierte Polyurethane werden grundsätzlich insbesondere aus einem linearen Homo- oder Copolymer mit je einer Hydroxygruppe am Ende des Moleküls und einem Molekulargewicht von 600 bis 4000, z.B. aus der Gruppe der Polyesterdiole, Polyetherdiole, Polyesteramidodiole, Polycarbonatdiole, Polyacryldiole, Polythioesterdiole, Polythioetherdiole, Polyhydrocarbondiole oder einer Mischung oder Copolymeren von Verbindungen dieser Gruppe, hergestellt. Weiterhin basiert das segmentierte Polyurethan insbesondere auf organischen Diisocyanaten und Kettenverlängerern mit mehreren aktiven Wasserstoffatomen, wie z. B. Di- und Polyolen, Di- und Polyaminen, Hydroxylaminen, Hydrazinen, Polyhydraziden, Polysemicarbaziden, Wasser oder eine Mischung aus diesen Komponenten.The segmented polyurethanes are basically made in particular from a linear homo- or Copolymer with one hydroxy group at the end of the molecule and a molecular weight of 600 up to 4000, e.g. from the group of polyester diols, polyether diols, polyester amido diols, polycarbonate diols, Polyacrylic diols, polythioester diols, polythioether diols, polyhydrocarbondiols or one Mixture or copolymers of compounds of this group. Furthermore, that is based segmented polyurethane especially on organic diisocyanates and chain extenders several active hydrogen atoms, such as. B. di- and polyols, di- and polyamines, hydroxylamines, Hydrazines, polyhydrazides, polysemicarbazides, water or a mixture of these Components.
Einige von diesen Polymeren sind gegenüber einem durch Chlor induzierten Abbau empfindlicher als andere. Dies ist beispielsweise durch einen Vergleich der Ergebnisse in dem nachstehenden Beispiel 1 ersichtlich. Demnach sind Polyurethanharnstofffasern aus einem auf Polyether basierenden Polyurethanharnstoff wesentlich empfindlicher als Polyurethanharnstofffasern aus einem auf Polyester basierenden Polyurethanharnstoff. Aus diesem Grunde sind Polyurethanharnstofffasern besonders bevorzugt, die auf Polyether basierende Polyurethanharnstoffe umfassen.Some of these polymers are more sensitive to chlorine-induced degradation than other. This is for example by comparing the results in the following Example 1 can be seen. Accordingly, polyurethane urea fibers are made from a polyether Polyurethane urea much more sensitive than polyurethane urea fibers from one Polyester based polyurethane urea. For this reason, polyurethane urea fibers are special preferred which comprise polyether-based polyurethaneureas.
Bei den mit Metällfettsäuresalz beschichteten Hydrotalciten handelt es sich um Additive, die kein Schwermetall enthalten und aus toxikologischer Sicht unbedenklich sind und daher bevorzugt werden. Dadurch kann gewährleistet werden, dass bei der Weiterverarbeitung der Polyurethanharnstofffasern wie z.B. der Färbung keine Abwasser entstehen, die die Funktionsweise einer biologisch arbeitenden Kläranlage mindern oder zerstören.The hydrotalcites coated with metal fatty acid salt are additives that do not Contain heavy metal and are harmless from a toxicological point of view and are therefore preferred become. This can ensure that during the further processing of the polyurethane urea fibers such as. the dyeing does not give rise to any wastewater that functions as a biological reduce or destroy working sewage treatment plant.
Die Standzeit von Spinndüsen und die Dauer des kontinuierlichen Spinnprozesses ist ein entscheidender Aspekt in Bezug auf die Betriebssicherheit und die Wirtschaftlichkeit in Trocken- und Nassspinnprozess. Bei Einarbeitung der mit Metallfettsäuresalz beschichteten Hydrotalcite in Polyurethanharnstoffspinnlösungen entsprechend der Erfindung kann, wie in Beispiel 2 gezeigt wird, die Standzeit der Spinndüsen und damit verbunden die Betriebssicherheit und die Wirtschaftlichkeit im Trocken- oder Nassspinnprozess verbessert werden.The service life of spinnerets and the duration of the continuous spinning process is crucial Aspect related to operational safety and economy in dry and wet spinning processes. When incorporating the hydrotalcites coated with metal fatty acid salt in polyurethane urea spinning solutions according to the invention, as shown in Example 2, the Service life of the spinnerets and the associated operational reliability and economy in the Dry or wet spinning process can be improved.
Des weiteren kann, wie in Beispiel 3 gezeigt wird, die Zudosierung von Antihaftmittel, z.B. Magnesium-Stearat, zur Einstellung des Haftungswertes als Maß für die Haftung der Filamente auf dem Spulkörper bei Verwendung von mit Metallfettsäuresalzen beschichteten Hydrotalciten reduziert werden. Durch eine Reduktion der Einspinnmenge Antihaftmittel kann die Verstopfung von Spinndüsen reduziert werden und der Trocken- und Nassspinnprozess in seiner Betriebssicherheit und die Wirtschaftlichkeit verbessert werden. Furthermore, as shown in Example 3, the addition of anti-adhesive, e.g. Magnesium stearate, to set the liability value as a measure of the liability of the filaments on the Reduced bobbin when using hydrotalcites coated with metal fatty acid salts become. By reducing the amount of non-sticking agents that can be spun in, the spinnerets can become blocked be reduced and the dry and wet spinning process in its operational safety and the Profitability can be improved.
Weiterer Gegenstand der Erfindung sind textile Waren, insbesondere Strick-, Wirk- oder Webwaren, hergestellt unter Verwendung der erfindungsgemäßen Polyurethanharnstofffasern, bevorzugt in Mischung mit synthetischen Hartfasern wie Polyamid-, Polyester- oder Polyacrylfasern und/oder Naturfasern wie Wolle, Seide oder Baumwolle.The invention further relates to textile goods, in particular knitted, knitted or woven goods, produced using the polyurethane urea fibers according to the invention, preferably in Mix with synthetic hard fibers such as polyamide, polyester or polyacrylic fibers and / or Natural fibers such as wool, silk or cotton.
Die nachfolgend beschriebenen Testverfahren werden zum Messen der verschiedenen Parameter verwendet, die für die Beurteilung der Vorteile der Erfindung benötigt werden.The test procedures described below are used to measure the various parameters used, which are needed for evaluating the advantages of the invention.
Zur Bestimmung der Höchstzugkraftdehnung und der Feinheitsfestigkeit wird ein einfacher Zugversuch am Elastan-Filamentgarn im klimatisierten Zustand durchgeführt. Die Prüfmethode wird in Anlehnung an DIN 53834 Teil 1 durchgeführt. Der vorbereitete Prüfling wird in einer Schlinge um den Haken des Messkopfes und um eine 10 mm Umschlingungsklemme mit einer Vorspannkraft von 0,001 cN/dtex gelegt. Die Einspannlänge beträgt 200 mm. Ein aus Alufolie bestehendes Fähnchen wird genau auf der Höhe der Lichtschranke eingehängt. Der Schlitten fährt mit einer Verformungsgeschwindigkeit von 400 %/Minute (800 mm Abzug) bis zum Bruch des Fadens und nach der Messung wieder in seine Ausgangsstellung zurück. Pro Prüfling werden 20 Messungen gemacht.A simple tensile test is used to determine the maximum tensile strength elongation and the tenacity performed on the elastane filament yarn in an air-conditioned condition. The test method is in Based on DIN 53834 part 1. The prepared test object is looped around the hook of the measuring head and around a 10 mm loop clamp with a pretensioning force of 0.001 cN / dtex. The clamping length is 200 mm. A flag made of aluminum foil is hung exactly at the height of the light barrier. The sled travels at a rate of deformation from 400% / minute (800 mm take-off) until the thread breaks and after the Measurement back to its original position. 20 measurements are made per test object.
Um die Beständigkeit der Elastan-Fasern gegenüber einem durch Chlor induzierten Abbau zu testen, wird eine 60 cm lange Garnprobe (beispielsweise 4-filamentig, Gesamttiter 40 Denier), die aus den Fasern hergestellt worden ist, einem "Chlorwasserechtheitstest" in Anlehnung an DIN 54019 unterzogen. Bei diesem Test wird das Garn spannungsfrei mit einer Länge von 60 cm auf speziellen Probenhaltern befestigt. Vor dem eigentlichen "Chlorwasserechtheitstest" wird eine Blindfärbung bei pH 4,5 (Acetatpuffer) bei 98°C über eine Stunde durchgeführt. Die Probe wird dann bei Raumtemperatur 5 und 10 mal jeweils für eine Stunde im Dunkeln in der Prüflösung, bestehend aus einer Pufferlösung (51,0 ml 1,0 N NaOH, 18,6g KCl und 15,5g Borsäure werden in destilliertem Wasser gelöst und auf 1000 ml aufgefüllt) und Chlorlauge, mit einem Chlorgehalt von 20 mg/l bei pH 8,5 behandelt. Nach jeder Behandlung wird die Probe mit destilliertem Wasser gewaschen und an der Luft getrocknet. Nach Abschluss der 5 bzw. 10 maligen Behandlung werden die physikalischen Eigenschaften der Probe so gemessen, wie dies in vorstehenden Absätzen beschrieben wurde. Das Verhalten der Garne bei diesem "Chlorbadewassertest" entspricht dem Verhalten von entsprechenden Garnen in Schwimmbekleidungsgeweben, die den in Schwimmbädern vorhandenen Chlor ausgesetzt werden.To test the resistance of the elastane fibers to chlorine-induced degradation, is a 60 cm long yarn sample (for example 4 filaments, total denier 40 denier), which from the Fibers has been produced, subjected to a "chlorine water fastness test" based on DIN 54019. In this test, the yarn is tension-free with a length of 60 cm on special Sample holders attached. Before the actual "chlorine water fastness test" a blind coloring is done pH 4.5 (acetate buffer) carried out at 98 ° C for one hour. The sample is then at room temperature 5 and 10 times each for one hour in the dark in the test solution consisting of one Buffer solution (51.0 ml of 1.0 N NaOH, 18.6g KCl and 15.5g boric acid are dissolved in distilled water dissolved and made up to 1000 ml) and chlorine solution, with a chlorine content of 20 mg / l at pH 8.5 treated. After each treatment, the sample is washed with distilled water and on the Air dried. After completing the 5 or 10 treatments, the physical Properties of the sample measured as described in the previous paragraphs. The Behavior of the yarns in this "chlorine bath water test" corresponds to the behavior of the corresponding ones Yarns in swimwear fabrics that are exposed to the chlorine present in swimming pools become.
Die Chlorkonzentration in dem "chlorierten" Wasser wird hier definiert als diejenige Chlorkonzentration, die in der Lage ist, Jodidionen zu Jod zu oxidieren. Diese Konzentration wird mit einer Kaliumjodid, Natriumthiosulfat-Titration gemessen und als ppm "aktives Chlor" (Cl2) pro Liter Prüflösung angegeben. Das Titrationsverfahren wird so durchgeführt, dass man 1 g Kaliumjodid, 2 ml Phosphorsäure (85 %ig) und 1 ml einer 10 %igen Stärkelösung zu 100 ml chloriertem Wasser, das analysiert werden soll, hinzufügt und die Mischung bis zu einem Stärke/Jod-Endpunkt mit 0,1 N Natriumthiosulfatlösung titriert.The chlorine concentration in the "chlorinated" water is defined here as the chlorine concentration which is able to oxidize iodide ions to iodine. This concentration is measured with a potassium iodide, sodium thiosulfate titration and stated as ppm "active chlorine" (Cl 2 ) per liter of test solution. The titration procedure is carried out by adding 1 g of potassium iodide, 2 ml of phosphoric acid (85%) and 1 ml of a 10% starch solution to 100 ml of chlorinated water to be analyzed and the mixture to a starch / iodine solution. End point titrated with 0.1 N sodium thiosulfate solution.
Die Bestimmung der Haftung des Fadens auf einer Spule erfolgt, indem zunächst der Faden von der Spule mit einem Gewicht von 500 g bis auf 3 mm oberhalb der Spulenhülse abgeschnitten wird. Anschließend wird ein Gewicht an den Faden gehängt und das Gewicht bestimmt, mit dem sich der Faden von der Spule abrollt. Die so bestimmte Haftung ist ein Maß für die Verarbeitbarkeit der Spulen. Ist die Haftung zu hoch, kann aufgrund von Fadenrissen die Verarbeitbarkeit zu textilen Flächenwaren erschwert werden. Ist die Haftung zu niedrig, kann der Faden im Aufwickelprozess am Trockenspinnschacht oder bei der Weiterverarbeitung zu textilen Geweben von der Spule herunterfallen, abreißen und damit verbunden nicht mehr weiterverarbeitet werden.The determination of the adhesion of the thread on a bobbin is made by first the thread from cut the coil with a weight of 500 g to 3 mm above the coil sleeve becomes. Then hang a weight on the thread and determine the weight with which the thread unwinds from the bobbin. The liability determined in this way is a measure of the processability of the coils. If the adhesion is too high, the processability may increase due to thread breaks textile fabrics are made more difficult. If the adhesion is too low, the thread can be wound up on the dry spinning shaft or during further processing into textile fabrics from fall off the spool, tear off and are no longer processed.
Die Erfindung wird nachfolgend durch Beispiele, die jedoch keine Beschränkung darstellen, weiter erläutert, wobei alle Prozentangaben sich auf das Gesamtgewicht der Faser beziehen, sofern nichts anderes angegeben wird. The invention is further illustrated below by means of examples which, however, do not represent any limitation explained, where all percentages refer to the total weight of the fiber, if nothing other is indicated.
In den Beispielen 1 bis 3 wurden Polyurethanharnstofffasern aus einem Polyetherdiol, bestehend aus Polytetrahydrofuran (PTHF) mit einem durchschnittlichen Molekulargewicht (Zahlenmittel) von 2000 g/mol hergestellt. Das Diol wurde mit Methylen-bis(4-phenyldiisocyanat) (MDI) mit einem molaren Verhältnis von 1 zu 1,65 gekappt und dann mit einem Gemisch aus Ethylendiamin (EDA) und Diethylamin (DEA) in Dimethylacetamid kettenverlängert.In Examples 1 to 3, polyurethane urea fibers consisting of a polyether diol were Polytetrahydrofuran (PTHF) with an average number average molecular weight of 2000 g / mol produced. The diol was treated with methylene bis (4-phenyl diisocyanate) (MDI) with a molar ratio of 1 to 1.65 and then capped with a mixture of ethylenediamine (EDA) and diethylamine (DEA) chain extended in dimethylacetamide.
Danach wurde den Polymeren ein Stammansatz von Additiven beigemischt. Dieser Stammansatz bestand aus 55,3 Gew.-% Dimethylacetamid (DMAC), 11,1 Gew.-% Cyanox 1790 ((1,3,5-Tris(4-tert.-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazin-2,4,6-(1H,3H,5H)-trion, Fa. Cytec), 7,6 Gew.-% Aerosol OT 100 (Fa. Cytec), 26,0 Gew.-% 30 %iger Spinnlösung und 0,001 Gew.-% des Farbstoffs Makrolexviolett (Fa. Bayer AG). Dieser Stammansatz wurde der Spinnlösung so zugefügt, dass in der fertigen Faser der Gehalt an Cyanox 1790 1 Gew.-% bezogen auf den Feststoff des Faserpolymeren betrug.A basic batch of additives was then added to the polymers. This basic approach consisted of 55.3% by weight dimethylacetamide (DMAC), 11.1% by weight Cyanox 1790 ((1,3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, Cytec), 7.6% by weight of Aerosol OT 100 (Cytec), 26.0% by weight of 30% spinning solution and 0.001% by weight of the Macrolex violet dye (Bayer AG). This master batch was added to the spinning solution in such a way that in the finished fiber the content of Cyanox 1790 1% by weight based on the solid of the fiber polymer scam.
Dieser Spinnlösung wurde ein zweiter Stammansatz zugemischt, bestehend aus 30,9 Gew.-% Titandioxid Typ RKB 3 (Fa. Kerr-McGee Pigments GmbH & Co. KG ), 44,5 Gew.-% DMAC und 24,6 Gew.-% 22 %iger Spinnlösung, in der Art, dass in der fertigen Faser ein Titandioxidgehalt von 0,05 Gew.-% bezogen auf das Polyurethan-Harnstoff-Polymere resultierte.A second master batch consisting of 30.9% by weight of titanium dioxide was mixed into this spinning solution Type RKB 3 (Kerr-McGee Pigments GmbH & Co. KG), 44.5% by weight DMAC and 24.6% by weight 22% spinning solution, in such a way that the finished fiber has a titanium dioxide content of 0.05% by weight based on the polyurethane-urea polymer resulted.
Dieser Spinnlösung wurde ein dritter Stammansatz zugemischt, bestehend aus 13,8 Gew.-% der in Tabelle 1 angegebenen Hydrotalcite, 55,2 Gew.-% Dimethylacetamid und 31,0 Gew.-% 30 %ige Spinnlösung, in der Art, dass in der fertigen Elastanfaser 3,0 Gew.-% der in Tabelle 1 angegebenen Hydrotalcite bezogen auf das Polyurethan-Harnstoff-Polymere resultierte.A third stock batch consisting of 13.8% by weight of the in. Was mixed into this spinning solution Table 1 hydrotalcites, 55.2 wt .-% dimethylacetamide and 31.0 wt .-% 30% Spinning solution, in such a way that in the finished elastane fiber 3.0% by weight of that specified in Table 1 Hydrotalcite based on the polyurethane-urea polymer resulted.
Dieser Spinnlösung wurde nun ein weiterer Stammansatz zugemischt. Er bestand aus 5,3 Gew.-% Magnesium-Stearat, und 5,3 Gew.-% Silwet L 7607 (Fa. Crompton Specialities GmbH 49,6 Gew.-% Dimethylacetamid und 39,8 Gew.-% 30 %iger Spinnlösung und wurde so zugesetzt, dass ein Magnesium-Stearat-Gehalt von 0,3 Gew.-% bezogen auf das Polyurethan-Harnstoff Polymere resultierte.A further batch was now mixed into this spinning solution. It consisted of 5.3% by weight Magnesium stearate, and 5.3% by weight Silwet L 7607 (from Crompton Specialties GmbH 49.6% by weight Dimethylacetamide and 39.8 wt .-% 30% spinning solution and was added so that a magnesium stearate content of 0.3% by weight based on the polyurethane-urea polymer resulted.
Die Herstellung einer Polyurethanharnstofflösung auf Basis eines Polyesterdiols erfolgte nach folgender Verfahrensweise:A polyurethane urea solution based on a polyester diol was prepared according to following procedure:
Ein Polyesterdiol mit einem Molekulargewicht (Zahlenmittel) von 2000 g/Mol, bestehend aus Adipinsäure, Hexandiol und Neopentylglykol, wurde mit Methylen-bis(4-phenyldiisocyanat) (MDI, Fa. Bayer AG) gekappt und dann mit einem Gemisch von Ethylendiamin (EDA) und Diethylamin (DEA) kettenverlängert. A polyester diol with a number average molecular weight of 2000 g / mol, consisting of Adipic acid, hexanediol and neopentyl glycol, was treated with methylene bis (4-phenyl diisocyanate) (MDI, Bayer AG) and then with a mixture of ethylenediamine (EDA) and Diethylamine (DEA) chain extended.
Zur Herstellung der Polyurethanharnstoffzusammensetzung wurden 50 Gew.-% Polyesterdiol mit einem Molekulargewicht (Zahlenmittel) von 2000 g/Mol mit 1 Gew.-% 4-Methyl-4-azaheptandiol-2,6 und 36,2 Gew.-% Dimethylacetamid (DMAc) und 12,8 Gew.-% MDI bei 25°C gemischt, auf 50°C erwärmt und 110 Minuten bei dieser Temperatur gehalten, um ein isocyanatgekapptes Polymeres mit einem NCO-Gehalt von 2,65 % NCO zu gewinnen.To produce the polyurethane urea composition, 50% by weight of polyester diol were used a number average molecular weight of 2000 g / mol with 1% by weight of 4-methyl-4-azaheptanediol-2,6 and 36.2 wt% dimethylacetamide (DMAc) and 12.8 wt% MDI mixed at 25 ° C Heated 50 ° C and held at this temperature for 110 minutes to form an isocyanate capped To win polymer with an NCO content of 2.65% NCO.
Nach dem Abkühlen auf eine Temperatur von 25°C wurden 100 Gewichtsteilen des gekappten Polymeren zu einer Lösung von 1,32 Gewichtsteilen EDA und 0,04 Gewichtsteilen DEA in 187 Teilen DMAc so schnell untergemischt, so dass eine Polyurethanharnstoffzusammensetzung in DMAc mit einem Feststoffgehalt von 22 % entstand. Durch Zugabe von Hexamethylendiisocyanat (HDI, Fa. Bayer AG) wurde das Molekulargewicht des Polymeren so eingestellt, dass eine Viskosität von 70 Pa*s (25°C) resultierte.After cooling to a temperature of 25 ° C, 100 parts by weight of the capped Polymers to a solution of 1.32 parts by weight of EDA and 0.04 parts by weight of DEA in 187 Parts of DMAc mixed in so quickly that a polyurethane urea composition in DMAc with a solids content of 22% was formed. By adding hexamethylene diisocyanate (HDI, Bayer AG), the molecular weight of the polymer was adjusted so that a Viscosity of 70 Pa * s (25 ° C) resulted.
Nach der im vorstehenden Abschnitt beschriebenen Herstellung der Polymeren wurde diesen ein Stammansatz von Additiven beigemischt. Dieser Stammansatz bestand aus 65,6 Gew.-% DMAC, 11,5 Gew.-% Cyanox 1790 ((1,3,5-Tris(4-tert.-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazin-2,4,6-(1H,3H,5H)-trion, Fa. Cytec), 5,7 Gew.-% Tinuvin 622 (Polymer mit einer Molmasse von ca. 3500 g/Mol, bestehend aus Bernsteinsäure und 4-Hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol, Fa. Ciba Geigy), und 17,2 Gew.-% 22 %iger Spinnlösung und 0,001 Gew.-% des Farbstoffs Makrolexviolett B (Fa. Bayer AG). Dieser Stammansatz wurde der Spinnlösung so zudosiert, dass der Gehalt an Cyanox 1790 1,0 Gew.-% bezogen auf den gesamten Feststoffgehalt in der Polyurethanharnstoffzusammensetzung, betrug.After the preparation of the polymers described in the previous section, these became a Master batch of additives added. This master batch consisted of 65.6% by weight of DMAC, 11.5% by weight of Cyanox 1790 ((1,3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6 - (1H, 3H, 5H) -trione, Cytec), 5.7% by weight Tinuvin 622 (polymer with a molecular weight of approx. 3500 g / mol, consisting of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, Ciba Geigy), and 17.2% by weight of 22% spinning solution and 0.001% by weight of the dye Macrolex violet B (Bayer AG). This stock batch was metered into the spinning solution in such a way that the content of Cyanox 1790 1.0 wt .-% based on the total solids content in the Polyurethane urea composition.
Dieser Spinnlösung wurde ein zweiter Stammansatz, bestehend aus 31 Gew.-% Titandioxid (Tronox TiO2 R-KB-3, Fa. Kerr-McGee Pigments GmbH & Co. KG), 44,5 Gew.-% Dimethylacetamid und 24,5 Gew.-% 22 %iger Spinnlösung, in der Art zugemischt, dass im fertigen Faden ein Titandioxidgehalt von 0,05 Gew.-%, bezogen auf die fertige Polyurethanharnstofffaser resultierte.This spinning solution was a second stock, consisting of 31 wt .-% titanium dioxide (Tronox TiO 2 R-KB-3, Kerr-McGee Pigments GmbH & Co. KG), 44.5 wt .-% dimethylacetamide and 24.5 % By weight 22% spinning solution, mixed in such a way that a titanium dioxide content of 0.05% by weight, based on the finished polyurethane urea fiber, resulted in the finished thread.
Dieser Spinnlösung wurde nun ein weiterer Stammansatz zugemischt. Er bestand aus 5,3 Gew.-% Magnesium-Stearat, und 5,3 Gew.-% Silwet L 7607 (Fa. Crompton Specialities GmbH 49,6 Gew.-% Dimethylacetamid und 39,8 Gew.-% 30 %iger Spinnlösung und wurde so zugesetzt, dass ein Magnesium-Stearat-Gehalt von 0,45 Gew.-% bezogen auf das Polyurethan-Harnstoff Polymere resultierte.A further batch was now mixed into this spinning solution. It consisted of 5.3% by weight Magnesium stearate, and 5.3% by weight Silwet L 7607 (from Crompton Specialties GmbH 49.6% by weight Dimethylacetamide and 39.8 wt .-% 30% spinning solution and was added so that a Magnesium stearate content of 0.45% by weight based on the polyurethane-urea polymer resulted.
Die fertigen Spinnlösungen wurden durch Spinndüsen in einer typischen Spinnapparatur zu Filamenten mit einem Titer von 15 dtex trocken versponnen, wobei jeweils drei Einzelfilamente zu koaleszierenden Filamentgamen mit einem Gesamttiter von 44 dtex zusammengefasst wurden. Die Faserpräparation, bestehend aus Polydimethylsiloxan mit einer Viskosität von 3 cSt/25°C und wurde über eine Präparationswalze aufgetragen, wobei ca. 4,0 Gew.-% bezogen auf das Gewicht der Faser appliziert wurden. Die Faser wurde anschließend mit einer Geschwindigkeit von 900 m/min aufgewickelt.The finished spinning solutions were fed through spinnerets in a typical spinning apparatus Filaments with a titer of 15 dtex dry spun, with three individual filaments each coalescing filament yarns with a total titre of 44 dtex were combined. The Fiber preparation consisting of polydimethylsiloxane with a viscosity of 3 cSt / 25 ° C and was applied over a preparation roller, with about 4.0 wt .-% based on the weight of the fiber were applied. The fiber was then spun at a speed of 900 m / min wound.
Die Testergebnisse der Messungen zur Beständigkeit von Elastanfasern gegenüber einem durch Chlorwasser induzierten Abbau sind in Tabelle 1 gezeigt. Dabei wurden Polyurethanharnstoffe auf Basis von Polyethern und Polyestern eingesetzt, ebenso unterschiedliche Stabilisatoren und Beschichtungsmittel. Es zeigt sich, dass insbesondere bei der erfindungsgemäßen Probe 1-7 der höchste Prozent-Anteil der ursprünglichen Höchstzugkraft erhalten bleibt. Somit ist bei diese Probe die Stabilität gegen einen durch Chlorwasser induzierten Abbau wie gewünscht sehr gut.The test results of the measurements on the resistance of elastane fibers to one through Chlorine-induced degradation is shown in Table 1. In doing so, polyurethane ureas were found Base of polyethers and polyesters used, as well as different stabilizers and Coating agents. It can be seen that in particular in the case of sample 1-7 according to the invention highest percentage of the original maximum tractive force is retained. So with this sample the stability against degradation induced by chlorine water, as desired, is very good.
Zur Beurteilung der Standzeit von Spinndüsen und die Dauer des kontinuierlichen Spinnprozesses wurden Polyurethanharnstoffzusammensetzungen auf Basis von Polyether mit den in Tabelle 2 aufgeführten unbeschichteten und beschichteten Hydrotalciten versetzt und durch einen wie zuvor beschriebenen Trockenspinnprozess zu einer Polyurethanharnstofffaser verarbeitet. Bei Einarbeitung der mit Metallfettsäuresalz beschichteten Hydrotalcite in Polyurethanharnstoffspinnlösungen kann, wie in Beispiel 2 gezeigt wird, die Standzeit der Spinndüsen und damit verbunden die Betriebssicherheit und die Wirtschaftlichkeit im Trocken- oder Nassspinnprozess verbessert werden.To assess the service life of spinnerets and the duration of the continuous spinning process Polyurethane urea compositions based on polyether with the in Table 2 listed uncoated and coated hydrotalcites and added as before described dry spinning process processed into a polyurethane urea fiber. During training the hydrotalcite coated with metal fatty acid salt in polyurethane urea spinning solutions, As shown in Example 2, the service life of the spinnerets and the associated operational reliability and the economy in the dry or wet spinning process can be improved.
Zur Beurteilung der Fadendaten und hier besonders der Haftung von Polyurethanharnstofffasern
wurden Polyurethanharnstoffzusammensetzungen auf der Basis von Polyether mit den in Tabelle 3
genannten beschichteten Hydrotalciten versetzt und als 44dtex f3 ausgesponnen. Die Fadendaten
wurden gemäß der zuvor beschriebener Prüfvorschriften bestimmt. Wie in Tabelle 3 gezeigt wird,
ist die Haftung stark abhängig von der Substanz zur Beschichtung des Hydrotalcits. Zur
erfolgreichen Verarbeitung von Elastanfasern in der Rundstrickerei wird z.B. eine Haftung von
0,20 bis 0,25 cN benötigt. Zur Einstellung dieses Wertes muss die Elastanfaser, welche ein mit
Polyorganosiloxan beschichtetes Hydrotalcit enthält eine zusätzliche Menge Antihaftmittel, z.B.
Magnesium-Stearat erhalten. Durch eine Erhöhung der Einspinnmenge Antihaftmittel kann eine
raschere Verstopfung von Spinndüsen einhergehen und den Trocken- und Nassspinnprozess in
seiner Betriebssicherheit und Wirtschaftlichkeit verschlechtern.
(Gew.-%)
(Tage)
(Gew.-%)
(cN)
(Wt .-%)
(Days)
(Wt .-%)
(CN)
Claims (10)
- M2+
- für Magnesium steht,
- A'n-
- ein Anion mit der Valenzzahl n aus der Reihe OH-, F-, Cl-, Br-, CO3 2-, SO4 2-, HPO4 2-, Silikat, Acetat oder Oxalat, insbesondere OH-, F-, Cl-, Br-, Silikat, Acetat oder Oxalat ist,
0 ≤ m<1
oder Hydrotalcit der Formel (2)
enthalten,
dadurch gekennzeichnet, dass die Hydrotalcite mit 0,2 bis 15 Gew.-% eines Metallfettsäuresalz beschichtet sind.Polyurethane urea fiber with increased chlorine resistance made of at least 85% segmented polyurethane urea, the polyurethane urea fiber 0.05 to 10% by weight finely divided hydrotalcite, in particular that of the general formula (1)
- M 2+
- stands for magnesium,
- A ' n
- an anion with the valence number n from the series OH - , F - , Cl - , Br - , CO 3 2- , SO 4 2- , HPO 4 2- , silicate, acetate or oxalate, in particular OH - , F - , Cl - , Br - , silicate, acetate or oxalate,
0 ≤ m <1
or hydrotalcite of the formula (2)
contain,
characterized in that the hydrotalcites are coated with 0.2 to 15 wt .-% of a metal fatty acid salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10302912 | 2003-01-24 | ||
| DE10302912A DE10302912A1 (en) | 2003-01-24 | 2003-01-24 | Polyurethane urea fiber, useful for the production of textiles having enhanced chlorine resistance, contains a finely divided hydrotalcite, coated with a metal fatty acid salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1452631A1 true EP1452631A1 (en) | 2004-09-01 |
Family
ID=32694961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04000698A Withdrawn EP1452631A1 (en) | 2003-01-24 | 2004-01-15 | Chlorine-resistant elasthane fibers |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20050038138A1 (en) |
| EP (1) | EP1452631A1 (en) |
| JP (1) | JP2004232185A (en) |
| KR (1) | KR20040068490A (en) |
| CN (1) | CN1523140A (en) |
| CA (1) | CA2455713A1 (en) |
| DE (1) | DE10302912A1 (en) |
| MX (1) | MXPA04000674A (en) |
| SG (1) | SG114655A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2005311588A1 (en) * | 2004-12-03 | 2006-06-08 | Dow Global Technologies Inc. | Elastic fibers having reduced coefficient of friction |
| KR20060076166A (en) * | 2004-12-28 | 2006-07-04 | 주식회사 효성 | Polyurethane elastic fiber having excellent friction property and additive |
| DE102005012797A1 (en) * | 2005-03-19 | 2006-09-21 | Dorlastan Fibers & Monofil Gmbh | Spun-dyed polyurethane urea fibers, a process for their preparation and their use for the production of fabrics |
| KR100780395B1 (en) * | 2006-09-04 | 2007-11-29 | 태광산업주식회사 | Chlorine resistant polyurethaneurea elastic fiber and preparation of thereof |
| KR101166807B1 (en) * | 2008-10-28 | 2012-07-26 | 태광산업주식회사 | High heat and chlorine resistant polyurethaneurea elastic fiber and preparation of thereof |
| US9328215B2 (en) * | 2014-08-20 | 2016-05-03 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Dyeable resin composition |
| CN105369606A (en) * | 2015-10-30 | 2016-03-02 | 无锡市长安曙光手套厂 | Anti-radiation odor-resistant fabric |
| JP2020056116A (en) * | 2017-02-13 | 2020-04-09 | 旭化成株式会社 | Polyurethane elastic fiber |
| US11186952B2 (en) | 2017-02-14 | 2021-11-30 | Nippon Paper Industries Co., Ltd. | Composition which contains composite fibers composed of inorganic particles and fibers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0558758A1 (en) * | 1991-09-24 | 1993-09-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyurethane composition |
| EP0843029A1 (en) * | 1996-11-18 | 1998-05-20 | Bayer Ag | Chlorine-resistant elasthane fibers |
| EP0843031A2 (en) * | 1996-11-18 | 1998-05-20 | Bayer Ag | Method for protecting elastane fibres |
| EP1262499A1 (en) * | 2001-05-30 | 2002-12-04 | FILLATTICE S.p.A. | Composition of an elastic fiber which can resist water containing chlorine |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028642A (en) * | 1988-11-30 | 1991-07-02 | E. I. Du Pont De Nemours And Company | Discoloration-resistant spandex |
| IL97266A0 (en) * | 1990-03-06 | 1992-05-25 | Warner Lambert Co | Azabicyclo and azacyclo oximes and amines,their preparation and pharmaceutical compositions containing them |
| JP2887402B2 (en) * | 1990-04-10 | 1999-04-26 | 旭化成工業株式会社 | Polyurethane composition |
| ATE189826T1 (en) * | 1994-12-22 | 2000-03-15 | Reheis Inc | HALOGEN CATCHER FOR POLYMERS AND COPOLYMERS |
| JP3857741B2 (en) * | 1996-02-08 | 2006-12-13 | 旭化成せんい株式会社 | Elastic yarn for splitting |
| DE19647657A1 (en) * | 1996-11-18 | 1998-05-20 | Bayer Ag | Polymer compositions containing hydrotalcite |
| KR100396230B1 (en) * | 1998-08-10 | 2003-09-02 | 아사히 가세이 가부시키가이샤 | Elastomeric polyurethane fiber |
| JP2000290836A (en) * | 1999-04-05 | 2000-10-17 | Asahi Chem Ind Co Ltd | Polyurethaneurea elastic fiber |
| US6780958B2 (en) * | 2001-07-24 | 2004-08-24 | Radicispandex Corporation | Spandex compositions |
| KR100437988B1 (en) * | 2002-04-29 | 2004-06-30 | 주식회사 두본 | High chlorine and heat resistant spandex fiber and manufacturing method thereof |
-
2003
- 2003-01-24 DE DE10302912A patent/DE10302912A1/en not_active Ceased
-
2004
- 2004-01-15 EP EP04000698A patent/EP1452631A1/en not_active Withdrawn
- 2004-01-20 SG SG200400596A patent/SG114655A1/en unknown
- 2004-01-20 KR KR1020040004277A patent/KR20040068490A/en not_active Application Discontinuation
- 2004-01-20 US US10/760,512 patent/US20050038138A1/en not_active Abandoned
- 2004-01-21 CN CNA2004100073225A patent/CN1523140A/en active Pending
- 2004-01-21 CA CA002455713A patent/CA2455713A1/en not_active Abandoned
- 2004-01-22 MX MXPA04000674A patent/MXPA04000674A/en not_active Application Discontinuation
- 2004-01-22 JP JP2004014269A patent/JP2004232185A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0558758A1 (en) * | 1991-09-24 | 1993-09-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyurethane composition |
| EP0843029A1 (en) * | 1996-11-18 | 1998-05-20 | Bayer Ag | Chlorine-resistant elasthane fibers |
| EP0843031A2 (en) * | 1996-11-18 | 1998-05-20 | Bayer Ag | Method for protecting elastane fibres |
| EP1262499A1 (en) * | 2001-05-30 | 2002-12-04 | FILLATTICE S.p.A. | Composition of an elastic fiber which can resist water containing chlorine |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050038138A1 (en) | 2005-02-17 |
| CA2455713A1 (en) | 2004-07-24 |
| DE10302912A1 (en) | 2004-08-12 |
| SG114655A1 (en) | 2005-09-28 |
| KR20040068490A (en) | 2004-07-31 |
| JP2004232185A (en) | 2004-08-19 |
| MXPA04000674A (en) | 2004-11-12 |
| CN1523140A (en) | 2004-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0843029B1 (en) | Chlorine-resistant elasthane fibers | |
| EP1607499A1 (en) | Chlorine resistant elastane fibres protected against color change | |
| DE69825972T2 (en) | ELASTIC POLYURETHANE FIBERS AND METHOD FOR THE PRODUCTION THEREOF | |
| DE102005012797A1 (en) | Spun-dyed polyurethane urea fibers, a process for their preparation and their use for the production of fabrics | |
| DE112017005050B4 (en) | Polyurethane elastic fiber and method of making polyurethane elastic fiber | |
| EP0843031B1 (en) | Method for protecting elastane fibres | |
| DE19805130A1 (en) | Antistatic polyurethane and elastane fibers | |
| EP1452631A1 (en) | Chlorine-resistant elasthane fibers | |
| DE3124197C2 (en) | Chlorine-resistant spandex fibers | |
| EP0935018A1 (en) | Biodegradable coating agent | |
| EP1200518B1 (en) | Polyurethane-urea fibres with improved resistance | |
| DE10258587A1 (en) | Process for the production of polyurethane urea fibers by spinning a combination of polydimethylsiloxane, alkoxylated polydimethylsiloxane and fatty acid salt | |
| DE2633301A1 (en) | FIBER FROM AN ELASTOMER POLYESTER-POLYURETHANE-UREA POLYMERISATE AND PROCESS FOR THEIR PRODUCTION | |
| EP0643159A1 (en) | Process for the production of spandex fibres containing a combination of polydimethylsiloxane and ethoxylated polydimethylsiloxane | |
| DE102005056448A1 (en) | Polyurethane-urea fibre with improved ductility for use in elastic textiles, technical articles and mixed-fibre products, contains a trialkyl or triaryl phosphate ester as additive, e.g. triphenyl phosphate | |
| DE19647657A1 (en) | Polymer compositions containing hydrotalcite | |
| DE112019007638T5 (en) | Polyester based monofilament for toothbrush | |
| EP1175522B1 (en) | Elastane package | |
| DE102004003997A1 (en) | Polyurethane-urea fibers containing spinel pigment, useful for making e.g. dark elastic fabrics, are stable against change in shade during processing and use | |
| DE102017010466A1 (en) | Process for producing a yarn, yarn and its use | |
| DE202017005872U1 (en) | Polymer yarn containing low levels of ZnO and organic antioxidants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DORLASTAN FIBERS & MONOFIL GMBH |
|
| 17P | Request for examination filed |
Effective date: 20050301 |
|
| AKX | Designation fees paid |
Designated state(s): DE GB IT NL |
|
| RBV | Designated contracting states (corrected) |
Designated state(s): DE GB IT NL |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 20060804 |