WO2006100249A1 - Procede de stabilisation de fibres de cellulose, notamment d'une bande de tissu contenant des fibres de cellulose - Google Patents
Procede de stabilisation de fibres de cellulose, notamment d'une bande de tissu contenant des fibres de cellulose Download PDFInfo
- Publication number
- WO2006100249A1 WO2006100249A1 PCT/EP2006/060924 EP2006060924W WO2006100249A1 WO 2006100249 A1 WO2006100249 A1 WO 2006100249A1 EP 2006060924 W EP2006060924 W EP 2006060924W WO 2006100249 A1 WO2006100249 A1 WO 2006100249A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cellulose fibers
- treatment solution
- water
- binding component
- fibers
- Prior art date
Links
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000004753 textile Substances 0.000 title claims abstract description 22
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000008961 swelling Effects 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims description 26
- 206010042674 Swelling Diseases 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 230000006641 stabilisation Effects 0.000 claims description 8
- 238000011105 stabilization Methods 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004627 regenerated cellulose Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 150000003567 thiocyanates Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 235000014633 carbohydrates Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Chemical class 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 229940044613 1-propanol Drugs 0.000 claims 1
- 238000010924 continuous production Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 229960004756 ethanol Drugs 0.000 claims 1
- 150000004694 iodide salts Chemical class 0.000 claims 1
- 229960004592 isopropanol Drugs 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 35
- 229910021529 ammonia Inorganic materials 0.000 abstract description 13
- 229920002678 cellulose Polymers 0.000 description 8
- 235000010980 cellulose Nutrition 0.000 description 8
- 239000002421 finishing Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005517 mercerization Methods 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- -1 gluconic acids Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical class [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ZEYUSQVGRCPBPG-UHFFFAOYSA-N 4,5-dihydroxy-1,3-bis(hydroxymethyl)imidazolidin-2-one Chemical compound OCN1C(O)C(O)N(CO)C1=O ZEYUSQVGRCPBPG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000009988 textile finishing Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- ALWXETURCOIGIZ-UHFFFAOYSA-N 1-nitropropylbenzene Chemical compound CCC([N+]([O-])=O)C1=CC=CC=C1 ALWXETURCOIGIZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000009666 routine test Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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- D—TEXTILES; PAPER
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/60—Ammonia as a gas or in solution
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/67—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with cyanogen or compounds thereof, e.g. with cyanhydric acid, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid or their salts, or with cyanamides; with carbamic acid or its salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/45—Shrinking resistance, anti-felting properties
Definitions
- ammonia is present as an anhydrous liquid swelling agent which, while very concentrated, is a much weaker alkali than aqueous alkali solutions. Accordingly, there is a changed swelling of the cellulose structure and it forms a limited stable form of cellulose, which is summarized under the term cellulose III.
- the ammonia process therefore also has certain advantages in practice, the disadvantage of this process is the high design complexity of the treatment devices, which is necessary due to the ammonia to be liquefied, with respect to their tightness in connection with strictly controlled pressure and / or temperature conditions, and associated therewith , high cost of such a facility.
- DE 24 05 006 A1 discloses a variant of the hot-mercerization of cellulose textiles in which only small amounts of an alcohol are added as a wetting aid.
- a method for stabilizing cellulose fibers with the features of the independent method claim and the use of a water-binding component as an additive in a treatment solution for the stabilization of cellulose fibers.
- the process according to the invention for stabilizing cellulose fibers, in particular materials comprising essentially exclusively cellulose fibers is characterized in that the cellulose fibers are brought into contact with a treatment solution, the treatment solution comprising:
- the cellulosic fiber-containing material is substantially, preferably completely, free of regenerated cellulose based yarns and fibers
- the proportion of water binding component (a) in the processing solution is at least 10% by weight, preferably between 10% and 90% by weight, and the components (a), (b) and (c) and their proportions of treatment solution are selected so as to cause swelling of the cellulose fibers predominantly in amorphous regions.
- the cellulose fibers to be treated are particularly preferably present as a textile material web; but also the treatment of non-cellulosic cellulosic fibers, such as, for example, threads, yarns, etc., is possible within the scope of the invention.
- a water-binding component (a) the water content of the treatment solution can be varied and in particular set low, so that results are obtained which are comparable or superior to those of the anhydrous ammonia treatment.
- the water content (c) must be at least so high that results in a homogeneous solution in particular of the swelling agent (b). Despite this residual water content, however, properties of the treated fibers which surprisingly result in the properties of fibers which have undergone an ammonia treatment known from the prior art are surprisingly obtained.
- the water-binding component preferably binds part of the water of the treatment solution in a so-called hydrate layer or via hydrogen bridges, so that this water content is not attributable to the free water content.
- the free water content that is to say the proportion of the water (c) which is not bound by the water-binding component (a), can thus be set and, in particular, minimized via the selection and / or the amount of the water-binding component (a).
- the cellulosic fibers or materials comprising cellulose fibers are substantially, preferably completely, free from regenerated cellulose based yarns and fibers.
- Regenerated cellulose-based yarns and fibers are understood here to mean in particular: viscose (CV), lyocell fibers (CLY), modal (CMD), cellulose fibers (CU) produced by the copper ammonia spinning process, viscose chemisides, rayon, viscose spun silk, viscose rayon, copper chemisides, copper chemical spun fiber, modifier - or Modalfasern, (HWM) Polynosic (see M. Peter, Handbook for Textile Engineers and Textile Practitioners, Foundations of Textile Finishing, 10th Edition 1970, Dr. Spohr-Verlag, Stuttgart).
- the components (a), (b) and (c) and their proportions of the treatment solution are selected such that swelling of the cellulose fibers is effected predominantly in amorphous regions, ie in particular no significant swelling also occurs in crystalline regions which among others expressed in a stiffening of the tissue. It can be seen that the proposed method swells the cellulose fibers predominantly in amorphous areas (formation of cellulose III / IV), whereas in the mercerization in the liquid phase the swelling occurs predominantly in crystalline areas (formation of cellulose II); As a result, particularly advantageous fiber properties can be achieved according to the invention, which are comparable or even superior to those of the ammonia process.
- a water-binding component (a) used is an alcohol, in particular a polyhydric, preferably aliphatic, alcohol, more preferably selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1,3 Propanediol, 1,2-propanediol, 1, 2, 3-propanetriol, 1-butanol, 2-butanol, tert-butyl alcohol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol and mixtures thereof.
- Such a component (a) under standard treatment conditions in the liquid phase, as described in the introductory part, in turn additionally and particularly advantageously on solvent properties, in addition to the existing water.
- water-binding component in another preferred embodiment of the invention it is used as a water-binding component.
- a solid which is selected from the group consisting of carbohydrates such as glucose, sucrose, fructose, galactose, mannose and other monosaccharides, disaccharides, oligosaccharides, their corresponding carboxylic acid derivatives such as gluconic acids, glucuronic acids; Urea, inorganic salts (especially with cations such as sodium, potassium, ammonium, magnesium, calcium, and anions such as chloride, nitrate, sulfate, phosphate, polyphosphate, silicate, and mixtures thereof); Particularly preferred inorganic salts are NaCl, KCl, MgCl 2 , Na 2 SO 4 , K 2 SO 4 , MgSO 4 , Na 3 PO 4 , K 3 PO 4 , NaNO 3 , KNO 3 , Mg
- the water-binding component (a) used is either 1,2,3-propanetriol or NaCl or mixtures thereof; these water-binding components (a) have proved to be particularly advantageous in practice because of their ease of handling, as well as their common and cost-effective availability and good to outstanding resulting fiber properties.
- the proportion and / or the nature of the water-binding component (a) in the treatment solution is particularly advantageously selected such that essentially values of fiber rigidity (detectable by the handle), fiber swelling (detectable by cross section, X-ray diffraction), dye absorption (detectable by dyeing tests) , Crosslinkability in the refining (detectable by dry and wet wrinkle recovery angle (especially with good dimensional stability), abrasion values and strength), as obtained in the conventional treatment in liquid ammonia.
- the adjustment of said pH values can be additionally supported by suitable selection and proportion of the water-binding component (a).
- the inventive method for stabilization at a temperature between -1O 0 C and 18O 0 C, preferably carried out at a temperature between 15 0 C and 105 0 C.
- the residence time is advantageously between 1 h and 4 h, with continuous implementation, the residence time in the treatment bath is advantageously between 1 and 30 min. In any case, it is important to adjust the composition of the treatment solution according to the invention of the possible treatment time.
- a high-level refinement of the cellulose fibers or of the material which in particular essentially exclusively comprises cellulose fibers is carried out.
- Processes of high-grade finishing are here and below understood to mean processes which improve the serviceability of the finished product in one or more directions in a permanent manner, in particular by changing the appearance of the goods by mechanical action (eg, ruling, moire, guarding, pleating, producing gloss effects , etc.), by chemical action (eg creation of breakthrough effects, devorant, air tips, stiffening equipment, swelling processes, stiff-finishings, lapping, softening, matting, metallization) or by combination mechanical / chemical treatment (eg Cloques, Seersucker, Köselkrepp, Craquele, Klebcloques), but also methods for increasing the utility value to effect better fullness, resistance, swelling resistance, freedom from shrinkage, crease, etc.
- the fabric's feel can be stiffer, while with reduced caustic concentration, the fabric's feel softens.
- the water retention capacity increases with higher alkali concentration, which the Differences to results of conventional liquid ammonia treatment increased.
- the high-grade finishing can be carried out after treatment with the treatment solution according to the invention either with or without intermediate drying.
- a particularly advantageous feature of the method according to the invention is that the treatment can be carried out without bonded goods guide. Due to the total reduced in the context of the invention, fiber swelling also occur much lower shrinkage forces, so that the jump of the product is lower than Mercerisierphal in the liquid phase according to the prior art.
- the invention further relates to the use of a water-binding component as additive in a treatment solution for stabilizing cellulose fibers, or of materials substantially exclusively comprising cellulose fibers, to increase the resulting proportion of cellulose fibers swollen in amorphous regions and / or to reduce the resulting proportion of cellulose fibers crystalline areas of swollen cellulose fibers.
- STK shock drying condensation.
- 40 g / l Arkofix® NDF DMDHEU-based product, Clariant AG, Basel, Switzerland
- 10 g / l MgCl 2 were used as catalyst at a liquor pick-up of about 50-70%. After drying for 1 min at 13O 0 C, condensation was carried out at 17O 0 C (duration 45 sec).
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0609467-8A BRPI0609467A2 (pt) | 2005-03-24 | 2006-03-21 | método para estabilizar fibras de celulose, especialmente de uma trama têxtil compreendendo fibras de celulose |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05102374A EP1705285B1 (fr) | 2005-03-24 | 2005-03-24 | Procédé de stabilisation de fibres cellulosiques, notamment d'une bande textile comprenant des fibres cellulosiques |
EP05102374.5 | 2005-03-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006100249A1 true WO2006100249A1 (fr) | 2006-09-28 |
Family
ID=35530806
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2006/060924 WO2006100249A1 (fr) | 2005-03-24 | 2006-03-21 | Procede de stabilisation de fibres de cellulose, notamment d'une bande de tissu contenant des fibres de cellulose |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1705285B1 (fr) |
CN (1) | CN101146949A (fr) |
AT (1) | ATE490367T1 (fr) |
BR (1) | BRPI0609467A2 (fr) |
DE (1) | DE502005010612D1 (fr) |
RU (1) | RU2007139334A (fr) |
WO (1) | WO2006100249A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103549692A (zh) * | 2013-09-25 | 2014-02-05 | 桐乡市中龙纺业有限责任公司 | 蚕丝蛋白异性纤维面料的生产方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB516162A (en) * | 1937-07-27 | 1939-12-22 | Walter Rotta | Process for producing wash-resistant stiffening effects on textiles |
GB612745A (en) * | 1946-05-31 | 1948-11-17 | Calico Printers Ass Ltd | Improvements in the treatment of regenerated cellulose fabrics to reduce their tendency to shrink |
GB727882A (en) * | 1950-01-17 | 1955-04-13 | Tootal Broadhurst Lee Co Ltd | Improvements in and relating to textile materials |
DE2405006A1 (de) * | 1973-02-14 | 1974-08-29 | Heberlein & Co Ag | Verfahren und vorrichtung zur verbesserung der faserstruktur von cellulosefasern enthaltendem textilgut |
WO2003050346A1 (fr) * | 2001-12-11 | 2003-06-19 | Kimberly-Clark Worldwide, Inc. | Fibres de cellulose gondolees a forte tolerance a l'humidite |
-
2005
- 2005-03-24 EP EP05102374A patent/EP1705285B1/fr not_active Not-in-force
- 2005-03-24 DE DE502005010612T patent/DE502005010612D1/de active Active
- 2005-03-24 AT AT05102374T patent/ATE490367T1/de active
-
2006
- 2006-03-21 WO PCT/EP2006/060924 patent/WO2006100249A1/fr not_active Application Discontinuation
- 2006-03-21 BR BRPI0609467-8A patent/BRPI0609467A2/pt not_active Application Discontinuation
- 2006-03-21 RU RU2007139334/04A patent/RU2007139334A/ru not_active Application Discontinuation
- 2006-03-21 CN CNA2006800089038A patent/CN101146949A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB516162A (en) * | 1937-07-27 | 1939-12-22 | Walter Rotta | Process for producing wash-resistant stiffening effects on textiles |
GB612745A (en) * | 1946-05-31 | 1948-11-17 | Calico Printers Ass Ltd | Improvements in the treatment of regenerated cellulose fabrics to reduce their tendency to shrink |
GB727882A (en) * | 1950-01-17 | 1955-04-13 | Tootal Broadhurst Lee Co Ltd | Improvements in and relating to textile materials |
DE2405006A1 (de) * | 1973-02-14 | 1974-08-29 | Heberlein & Co Ag | Verfahren und vorrichtung zur verbesserung der faserstruktur von cellulosefasern enthaltendem textilgut |
WO2003050346A1 (fr) * | 2001-12-11 | 2003-06-19 | Kimberly-Clark Worldwide, Inc. | Fibres de cellulose gondolees a forte tolerance a l'humidite |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103549692A (zh) * | 2013-09-25 | 2014-02-05 | 桐乡市中龙纺业有限责任公司 | 蚕丝蛋白异性纤维面料的生产方法 |
CN103549692B (zh) * | 2013-09-25 | 2015-11-18 | 桐乡市中龙纺业有限责任公司 | 蚕丝蛋白异性纤维面料的生产方法 |
Also Published As
Publication number | Publication date |
---|---|
RU2007139334A (ru) | 2009-04-27 |
EP1705285B1 (fr) | 2010-12-01 |
BRPI0609467A2 (pt) | 2010-04-13 |
DE502005010612D1 (de) | 2011-01-13 |
EP1705285A1 (fr) | 2006-09-27 |
CN101146949A (zh) | 2008-03-19 |
ATE490367T1 (de) | 2010-12-15 |
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