WO2006100249A1 - Method for stabilizing cellulose fibers, especially of a textile web that comprises cellulose fibers - Google Patents
Method for stabilizing cellulose fibers, especially of a textile web that comprises cellulose fibers 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
- 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
- D06M11/32—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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- 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
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- 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
- 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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- 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
- D06M11/58—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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- 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
- D06M11/58—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).
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- 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
The invention relates to a method for stabilizing cellulose fibers and/or a cellulose fiber-containing material, especially of a textile web that comprises cellulose fibers. Said method is characterized by contacting the cellulose fibers with a treatment solution. Said treatment solution comprises: (a) a water-binding component, (b) a swelling agent, and (c) water. The inventive method produces cellulose fibers that can be compared with or are even superior in terms of their properties to results that are obtained by conventional ammonia treatment.
Description
Verfahren zur Stabilisierung von Cellulosefasern, insbesondere einer textilen Warenbahn enthaltend CellulosefasernProcess for the stabilization of cellulose fibers, in particular a textile web containing cellulose fibers
Die Erfindung betrifft ein Verfahren zur Stabilisierung von Cellulosefasern, insbesondere von im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien gemäss dem Oberbegriff des unabhängigen Verfahrensanspruchs. Die Erfindung betrifft weiter die Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern oder von insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien.The invention relates to a process for the stabilization of cellulose fibers, in particular of substantially exclusively cellulose fibers comprising materials according to the preamble of the independent method claim. The invention further relates to the use of a water-binding component as an additive in a treatment solution for stabilizing cellulose fibers or, in particular, substantially exclusively cellulose fibers comprising materials.
Die Behandlung von Cellulosefasern und Materialien, welche aus Cellulosefasern bestehen oder diese umfassen, wie beispielsweise Baumwollmaterialien, in alkalischem Milieu ist im Stand der Technik bekannt. Diese alkalische Behandlung wird häufig unter dem Begriff der Mercerisierung zusammengefasst, gelegentlich wird auch zwischen Mercerisierung (höhere Laugenkonzentration und Spannung der Ware) und Laugierung (niedrigere Laugenkonzentration, keine Warenspannung) unterschieden. Oftmals wird auch zwischen Mercerisierung einerseits und Ammoniakbehandlung andererseits differenziert (vergl . Bernard P. Corbman, Textiles : Fiber to Fabric, 6th Edition 1983, McGraw-Hill Book Company) .The treatment of cellulosic fibers and materials consisting of or including cellulosic fibers, such as cotton materials, in alkaline medium is known in the art. This alkaline treatment is often summarized under the term mercerization, occasionally a distinction is also made between mercerisation (higher alkali concentration and product tension) and leaching (lower alkali concentration, no product tension). Often a distinction is also made between mercerization on the one hand and ammonia treatment on the other hand (see Bernard P. Corbman, Textiles: Fiber to Fabric, 6 th Edition 1983, McGraw-Hill Book Company).
Bei tiefen Temperaturen oder hohem Druck liegt Ammoniak als wasserfreies flüssiges Quellmittel vor, welches zwar sehr konzentriert ist, jedoch eine wesentlich schwächere Lauge darstellt als wässrige Alkalilösungen. Dementsprechend erfolgt eine veränderte Quellung der Cellulosestruktur und es bildet sich eine begrenzt stabile Form der Cellulose, die unter dem Begriff Cellulose III zusammengefaßt wird. Der Effekt einer Flüssigammoniakbehandlung ist insbesondere bei Entfernung des Ammoniaks durch Abdampfen vorhanden und ist im Verhalten mit einer schwach alkalischen
„Fixierung" vergleichbar. Wird das Textil in den folgenden Behandlungsschritten alkalisch bearbeitet, so geht der Effekt einer vorhergehenden Ammoniakbehandlung zum größten Teil verloren. Die Behandlung von Textilien in flüssigem Ammoniak ist daher von geringer Permanenz, jedoch von großer Bedeutung wenn der Behandlungsschritt unmittelbar vor einer Hochveredlung angeordnet wird. Der Hochveredlungsprozess kann dabei als Trockenvernetzung oder als Feuchtvernetzung durchgeführt werden. Durch diese Fixierung entstehen textile Produkte mit besten Knittereigenschaften und weichem Griff. Diese Besonderheit erklärt, warum der sicherheitstechnisch aufwendige, prozesstechnisch anspruchsvolle und damit sehr teure Prozess, einer Behandlung von Baumwolltextilien in flüssigem Ammoniak, durchgeführt wird.At low temperatures or high pressure, 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 effect of a liquid ammonia treatment is particularly present on removal of the ammonia by evaporation and is in behavior with a weakly alkaline The treatment of textiles in liquid ammonia is therefore of little permanence, but of great importance if the treatment step is immediately before a treatment of alkaline in the following treatment steps This fixation produces textile products with excellent wrinkling properties and a soft feel, which explains why the technically complex, process-technically demanding and therefore very expensive process of treating cotton textiles in liquid ammonia.
Entsprechend der Bedeutung der Ammoniakbehandlung vorgängig zu einer Hochveredlung wurden verschiedenste Alternativen mit geringem Erfolg erprobt. Hierzu gehören Verwendung wässriger Ammoniaklösungen, Einsatz anderer Amine und Quellmittel (Cuoxamlö- sungen, Thiocyanate) . Generell haben diese Prozesse jedoch keine vorteilhaften Behandlungsresultate erreicht.According to the importance of ammonia treatment previously to a high-grade finishing various alternatives were tested with little success. These include the use of aqueous ammonia solutions, the use of other amines and swelling agents (cuoxam solutions, thiocyanates). Generally, however, these processes have not achieved beneficial treatment results.
Obschon das Ammoniakverfahren also in der Praxis durchaus auch gewisse Vorteile aufweist, ist nachteilig bei diesem Verfahren der aufgrund des zu verflüssigenden Ammoniaks notwendige, hohe konstruktive Aufwand der Behandlungsvorrichtungen bzgl. deren Dichtigkeit in Verbindung mit strikt kontrollierten Druck- und/oder Temperaturbedingungen, und damit verbundene, hohe Kosten einer solchen Anlage.Although 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.
Bekannt sind aus den Dokumenten GB 612 745 A und GB 727 882 A Behandlungsverfahren für Regeneratcellulosen. Regeneratcellulo- sen erfordern aufgrund eines anderen Quellverhaltens grundsätzlich andere Behandlungsbedingungen als native Cellulosefasern.
Aus dem Dokument GB 516 162 A ist ein Verfahren der sehr intensiven Quellung von Cellulosefasern bekannt, welches eine dauerhafte Versteifung des Materials bewirken soll, vermutlich durch Anlösung der Fasern. Eine Versteifung der Fasern ist bei dem o.g. Ammoniakverfahren jedenfalls unerwünscht.From the documents GB 612 745 A and GB 727 882 A treatment methods for regenerated celluloses are known. Regenerated celluloses generally require different treatment conditions than native cellulose fibers due to a different swelling behavior. From the document GB 516 162 A a method of very intensive swelling of cellulose fibers is known which is intended to bring about a permanent stiffening of the material, presumably by dissolving the fibers. A stiffening of the fibers is in any case undesirable in the abovementioned ammonia process.
Aus DE 24 05 006 Al ist eine Variante der Heissmercerisation von Cellulosetextilien bekannt, bei welchem nur geringe Mengen eines Alkohols als Benetzungshilfe zugegeben werden.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.
Es ist daher eine Aufgabe der Erfindung, die Nachteile des Stands der Technik, insbesondere des Ammoniakverfahrens, zu überwinden, also ein alternatives Verfahren zur Stabilisierung von insbesondere vollständig regeneratcellulose-freien Cellulosefasern und/oder eines solche Cellulosefasern enthaltenden Materials, insbesondere einer textilen Warenbahnen enthaltend solche Cellulosefasern, bereitzustellen, welches einfach, kostengünstig und vorzugsweise auf konventionellen Behandlungsvorrichtungen durchführbar ist, wobei sich Fasereigenschaften nach dem Stabilisierungsverfahren - bzw. ggf. nach einer anschliessenden Hochveredelung - ergeben, welche mit denen vergleichbar oder besser sind, als sie durch eine konventionelle Ammoniakbehandlung - bzw. ggf. nach einer anschliessenden Hochveredelung — im Stand der Technik erzielt werden.It is therefore an object of the invention to overcome the disadvantages of the prior art, in particular of the ammonia process, ie an alternative process for stabilizing in particular completely regenerated cellulose-free cellulose fibers and / or such a cellulose fiber-containing material, in particular a textile webs containing such Cellulose fibers to provide, which is simple, inexpensive and preferably feasible on conventional treatment devices, with fiber properties after stabilization - or possibly after a subsequent refining - result, which are comparable or better than those by a conventional ammonia treatment or ., Where appropriate, after a subsequent refining - be achieved in the art.
Diese Aufgabe wird gelöst durch ein Verfahren zur Stabilisierung von Cellulosefasern mit den Merkmalen des unabhängigen Verfahrensanspruchs sowie der Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern.
Das erfindungsgemässe Verfahren zur Stabilisierung von Cellulo- sefasern, insbesondere von im wesentlichen ausschliesslich CeI- lulosefasern umfassenden Materialien, ist dadurch gekennzeichnet, dass die Cellulosefasern mit einer Behandlungslösung in Kontakt gebracht werden, wobei die Behandlungslösung umfasst:This object is achieved by 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:
(a) eine wasserbindende Komponente,(a) a water-binding component,
(b) ein Quellmittel, sowie(b) a swelling agent, as well
(c) Wasser.(c) water.
Weiter ist das Cellulosefasern enthaltende Material, insbesondere die textile Warenbahn enthaltend Cellulosefasern, im wesentlichen, vorzugsweise vollständig, frei von auf regenerierter Cellulose basierenden Garnen und Fasern, und der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung beträgt mindestens 10 Gew.-%, vorzugsweise zwischen 10 Gew.-% und 90 Gew.-%, und die Komponenten (a) , (b) und (c) und ihre Anteile an der Behandlungslösung sind derart ausgewählt, dass eine Quellung der Cellulosefasern vorwiegend in amorphen Bereichen bewirkt wird.Further, the cellulosic fiber-containing material, especially the textile web containing cellulosic fibers, is substantially, preferably completely, free of regenerated cellulose based yarns and fibers, and 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.
Die zu behandelnden Cellulosefasern liegen besonders bevorzugt als textile Warenbahn vor; aber auch die Behandlung von nicht- bahnförmigen Cellulosefasern, wie bspw. Fäden, Garnen etc. ist im Rahmen der Erfindung möglich. Durch das Vorsehen einer wasserbindenden Komponente (a) kann der Wassergehalt der Behandlungslösung variiert und insbesondere niedrig eingestellt werden, so dass Resultate erhalten werden, welche mit denen der wasserfreien Ammoniakbehandlung vergleichbar bzw. überlegen sind. Jedoch muss der Wassergehalt (c) zumindest derart hoch gewählt sein, dass sich eine homogene Lösung insbesondere des Quellmittels (b) ergibt. Trotz dieses Restwassergehalts ergeben sich jedoch überraschend Eigenschaften der behandelten Fasern, welche den Eigenschaften von Fasern, welche einer aus dem Stand der Technik bekannten Ammoniakbehandlung unterzogen wurden, ver-
gleichbar sind bzw. diese sogar übertreffen. Die wasserbindende Komponente bindet einen Teil des Wassers der Behandlungslösung vorzugsweise in einer sog. Hydratschicht bzw. über Wasserstoffbrücken, so dass dieser Wasseranteil nicht dem freien Wasseranteil zuzurechnen ist. Der freie Wasseranteil, also der nicht von der wasserbindenden Komponente (a) gebundene Anteil des Wassers (c) , kann somit über die Auswahl und/oder die Menge der wasserbindenden Komponente (a) eingestellt und insbesondere minimiert werden.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. By providing 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. However, 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. are equal or even exceed. 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).
Die Cellulosefasern bzw. die Cellulosefasern umfassenden Materialien sind im wesentlichen, vorzugsweise vollständig frei von auf regenerierter Cellulose basierenden Garnen und Fasern. Unter auf regenerierter Cellulose basierenden Garnen und Fasern werden hierbei insbesondere verstanden: Viskose (CV), Lyocellfasern (CLY) , Modal (CMD) , nach dem Kupferammoniakspinnverfahren hergestellte Cellulosefasern (CU) , Viskosechemieseide, Reyon, Viskosespinnseide, Zellwolle, Kupferchemieseide, Kupferchemiespinnfaser, Modifier- oder Modalfasern, (HWM) Polynosic (vergl . M. Peter, Handbuch für Textilingenieure und Textilpraktiker, Grundlagen der Textilveredlung, 10. Auflage 1970, Dr. Spohr-Verlag, Stuttgart) .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).
Der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung beträgt mindestens 10 Gew.-%. Die vorzugsweise einzusetzende Menge an wasserbindender Komponente (a) kann vom Fachmann aufgrund von Routineversuchen und/oder Berechnung, insbesondere in Abhängigkeit von der Löslichkeit bzw. Mischbarkeit mit Wasser und der Verträglichkeit mit dem Quellmittel (b) , leicht ermittelt werden. Gegebenenfalls kann der Anteil an wasserbindender Komponente (a) bis zu 90 Gew.-% betragen. Besonders bevorzugt macht der Anteil der Komponente (a) an der Behand-
lungslösung den grössten Einzelanteil der gesamten Behandlungslösung aus .The proportion of the water-binding component (a) in the treatment solution is at least 10% by weight. The amount of water-binding component (a) preferably to be used can easily be determined by a person skilled in the art on the basis of routine experiments and / or calculation, in particular depending on the solubility or miscibility with water and the compatibility with the swelling agent (b). Optionally, the proportion of water-binding component (a) can be up to 90 wt .-%. The proportion of component (a) in the treatment solution is the largest single component of the entire treatment solution.
Die Komponenten (a) , (b) und (c) und ihre Anteile an der Behandlungslösung sind derart ausgewählt, dass eine Quellung der CeI- lulosefasern vorwiegend in amorphen Bereichen bewirkt wird, also insbesondere keine signifikante Quellung auch in kristallinen Breichen auftritt, die sich u.a. in einer Versteifung des Gewebes äussert. Es zeigt sich, dass durch das vorgeschlagene Verfahren eine Quellung der Cellulosefasern vorwiegend in amorphen Bereichen erfolgt (Bildung von Cellulose III/IV) , wohingegen bei der Mercerisierung in flüssiger Phase die Quellung vorwiegend in kristallinen Bereichen erfolgt (Bildung von Cellulose II); hierdurch können gemäss der Erfindung besonders vorteilhafte Fasereigenschaften erzielt werden, welche mit jenen des Ammoniakverfahrens vergleichbar oder diesen sogar überlegen sind.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.
Gemäss einer weiteren Ausführungsform der Erfindung wird als eine wasserbindende Komponente (a) ein Alkohol, insbesondere ein mehrwertiger, vorzugsweise aliphatischer Alkohol, verwendet, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus Methanol, Ethanol, 1-Propanol, 2-Propanol, 1, 3-Propandiol, 1,2- Propandiol, 1, 2, 3-Propantriol, 1-Butanol, 2-Butanol, tert.- Butylalkohol, 1, 2-Butandiol, 1, 3-Butandiol, 1, 4-Butandiol, 2 , 3-Butandiol und Mischungen hiervon. Eine derartige Komponente (a) weist unter gängigen Behandlungsbedingungen in flüssiger Phase, wie im einleitenden Teil beschrieben, ihrerseits zusätzlich und besonders vorteilhaft Lösungsmitteleigenschaften auf, zusätzlich zum vorhandenen Wasser.According to a further embodiment of the invention, 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.
Alternativ oder zusätzlich zu einer der vorstehend genannten, wasserbindenden Komponenten (a) wird in einer weiteren bevorzugten Ausführungsform der Erfindung als eine wasserbindende Kompo-
nente (a) ein Feststoff der Behandlungslösung beigegeben, welcher ausgewählt ist aus der Gruppe bestehend aus Kohlenhydraten wie z.B. Glucose, Saccharose, Fructose, Galaktose, Mannose, sowie andere Monosaccharide, Disaccharide, Oligosacharide, deren entsprechende Carbonsäurederivate wie Gluconsäuren, Glucuronsau- ren; Harnstoff, anorganischen Salzen (insbesondere mit Kationen wie z. B Natrium, Kalium, Ammonium, Magnesium, Calzium; und Anio- nen wie z.B. Chlorid, Nitrat, Sulfat, Phosphat, Polyphosphat, Silikat; und Mischungen hiervon) ; besonders bevorzugte anorganische Salze sind NaCl, KCl, MgCl2, Na2SO4, K2SO4, MgSO4, Na3PO4, K3PO4, NaNO3, KNO3, Mg (NO3) 2.Alternatively or in addition to one of the abovementioned water-binding components (a), in another preferred embodiment of the invention it is used as a water-binding component. (a) adding a solid to the treatment solution 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 (NO 3 ) 2 .
Diese Stoffe sind derart auszuwählen und/oder werden in ihrer Menge derart beigegeben, dass sie sich in der vorstehend genannten, flüssigen wasserbindenden Komponente (a) und/oder dem Wasser (c) löst, so dass sich eine homogene Behandlungslösung ergibt.These substances are to be selected and / or added in their amount in such a way that they dissolve in the aforementioned liquid water-binding component (a) and / or the water (c), so that a homogeneous treatment solution results.
In einer besonders bevorzugten Ausführungsform wird als wasserbindende Komponente (a) entweder 1, 2, 3-Propantriol oder NaCl, oder Mischungen hiervon verwendet; diese wasserbindenden Komponenten (a) haben sich in der Praxis als besonders vorteilhaft aufgrund einfacher Handhabbarkeit sowie gängiger und kostengünstiger Verfügbarkeit sowie guten bis hervorragenden resultierenden Fasereigenschaften erwiesen.In a particularly preferred embodiment, 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.
Gemäss einer besonders vorteilhaften Ausführungsform der Erfindung ist der Anteil und/oder die Art der wasserbindenden Komponente (a) an der Behandlungslösung derart ausgewählt, dass ein verfügbarer, freier Wasseranteil - als der nicht von der wasserbindenden Komponente (a) gebundene Wasseranteil - der Behandlungslösung von höchstens 35 mol/1, vorzugsweise von höchstens 25 mol/1, besonders bevorzugt von höchstens 15 mol/1 resultiert.
Besonders vorteilhaft ist der Anteil und/oder die Art der wasserbindenden Komponente (a) an der Behandlungslösung derart ausgewählt, dass im wesentlichen Werte der Fasersteifigkeit (feststellbar durch den Griff) , Faserquellung (feststellbar durch Querschnitt, Röntgenbeugung) , Farbstoffaufnahme (feststellbar durch Färbeversuche) , Vernetzbarkeit in der Hochveredlung (feststellbar durch Trocken- und Nassknittererholungswinkel (insbesondere bei guter Dimensionsstabilität) , Scheuerwerte und Festigkeit) erhalten werden, wie sie bei der konventionellen Behandlung in Flüssigammoniak erhalten werden.According to a particularly advantageous embodiment of the invention, the proportion and / or the nature of the water-binding component (a) in the treatment solution is selected such that an available, free water content - as the non-bound by the water-binding component (a) water content - the treatment solution of at most 35 mol / 1, preferably at most 25 mol / 1, particularly preferably at most 15 mol / 1 results. 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.
Als Quellmittel (b) wird besonders bevorzugt eine Chemikalie oder eine Mischung von Chemikalien verwendet, welche insbesondere bei einer Konzentration von bereits 1 mol/1 in der Behandlungslösung und bei einem Wasseranteil von etwa 85 Gew.-% in einem pH Wert von >= 9, vorzugsweise von >= 11, besonders bevorzugt von >= 13 resultiert. Selbstverständlich kann im Rahmen der Erfindung die Einstellung der genannten pH Werte zusätzlich auch durch geeignete Auswahl und Anteil der wasserbindenden Komponente (a) unterstützt werden.As swelling agent (b) it is particularly preferred to use a chemical or a mixture of chemicals which, in particular at a concentration of already 1 mol / l in the treatment solution and at a water content of about 85% by weight in a pH of> = 9 , preferably of> = 11, particularly preferably of> = 13 results. Of course, in the context of the invention, the adjustment of said pH values can be additionally supported by suitable selection and proportion of the water-binding component (a).
In weiteren, besonders vorteilhaften Ausführungsformen der Erfindung wird als Quellmittel (b) mindestens eine Chemikalie eingesetzt, welche ausgewählt ist aus der Gruppe bestehend aus Al- kalimetallhydroxiden, Erdalkalimetallhydroxiden, Aminen (insbesondere Ethanolamin, Diethanolamin, Triethanolamin, Ethylendia- min, Diethylendiamin, Triethylendiamin, Hexamethylendiamin, He- xamethylentetramin, Diethylamin, Triethylamin, Isopropylamin, t-Butylamin, Glycin, Serin) , Thiocyanaten (insbesondere Natrium- , Kalium-, Ammonium-, und/oder Calciumthiocyanat) , Kalium- und/oder Natriumiodid, Metallkomplexen (insbesondere Eisen- Weinsäure-Natronlauge, Lösungen der Cuen- bzw. Cuoxamkomplexe) , Ammoniak-Lösung, und Mischungen hiervon.
Typischerweise wird das erfindungsgemässe Verfahren zur Stabilisierung bei einer Temperatur zwischen -1O0C und 18O0C, bevorzugt bei einer Temperatur zwischen 150C und 1050C durchgeführt. Bei Durchführung als batch-Prozess beträgt die Verweilzeit vorteilhaft zwischen 1 h und 4 h, bei kontinuierlicher Durchführung beträgt die Verweilzeit im Behandlungsbad vorteilhaft zwischen 1 und 30 min. Wichtig ist hierbei jedenfalls, die Zusammensetzung der Behandlungslösung entsprechend der Erfindung der möglichen Behandlungszeit anzupassen.In further, particularly advantageous embodiments of the invention, at least one chemical selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, amines (in particular ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenediamine, triethylenediamine), is used as swelling agent (b). Hexamethylenediamine, hexamethylenetetramine, diethylamine, triethylamine, isopropylamine, t-butylamine, glycine, serine), thiocyanates (in particular sodium, potassium, ammonium and / or calcium thiocyanate), potassium and / or sodium iodide, metal complexes (in particular iron Tartaric acid sodium hydroxide solutions of the Cu or Cuoxam complexes), ammonia solution, and mixtures thereof. Typically, 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. When carried out as a batch process, 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.
Selbstverständlich können die im Rahmen der im Stand der Technik üblicherweise zu optimierenden Parameter wie Behandlungsdauer, Behandlungstemperatur und Warenspannung während der Behandlung auch im Rahmen des erfindungsgemässen Verfahrens, insbesondere auf den jeweiligen Anwendungsfall abgestimmt, eingestellt werden. Die Einstellung dieser Parameter kann vom Fachmann, ggf. auf der Basis von Routineversuchen, leicht vorgenommen werden.Of course, within the scope of the parameters which are usually to be optimized in the prior art, such as treatment duration, treatment temperature and product tension during the treatment, they can also be adjusted in the context of the method according to the invention, in particular to the respective application. The adjustment of these parameters can easily be carried out by a person skilled in the art, possibly on the basis of routine tests.
In besonders vorteilhaften Ausführungsformen des erfindungsgemässen Verfahrens wird nach der Quellbehandlung eine Hochveredelung der Cellulosefasern oder des insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materials durchgeführt. Unter Verfahren der Hochveredlung werden hier und im folgenden Verfahren verstanden, welche die Gebrauchstüchtigkeit des Fertigerzeugnisses nach einer oder mehreren Richtungen hin in einer dauerhaften Art verbessern, insbesondere durch Änderung des Warenbildes durch mechanische Einwirkung (z.B. Ratinieren, Moirieren, Gaufrieren, Plissieren, Erzeugen von Glanzeffekten, etc.), durch chemische Einwirkung (z.B. Erzeugen von Durchbruch- effekten, Devorant, Luftspitzen, Steifausrüstungen, Quellungsverfahren, Steif-Appreturen, Versehen mit Einbügelstoffen, Weichmachen, Mattieren, Metallisierung) oder durch kombinierte
mechanische/chemische Behandlung (z.B. Cloques, Seersucker, Kräuselkrepp, Craquele, Klebcloques) , aber auch Verfahren zur Erhöhung des Gebrauchswerts zur Bewirkung von besserer Fülle, Widerstandsfähigkeit, Quellfestigkeit, Schrumpffreiheit, Knitterfreiheit, etc. (siehe hierzu auch M. Peter, Handbuch für Textilingenieure und Textilpraktiker, Grundlagen der Textilveredlung, 10. Auflage 1970, Dr. Spohr-Verlag, Stuttgart). Es hat sich in der Praxis gezeigt, dass das erfindungsgemässe Verfahren zur Stabilisierung überraschenderweise oftmals insbesondere nach einem anschliessenden Hochveredlungsverfahren herausragend zum Tragen kommt .In particularly advantageous embodiments of the process according to the invention, after the swelling treatment, 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, Kräuselkrepp, Craquele, Klebcloques), but also methods for increasing the utility value to effect better fullness, resistance, swelling resistance, freedom from shrinkage, crease, etc. (see also M. Peter, manual for Textile Engineers and Textile Practitioners, Basics of Textile Finishing, 10th edition 1970, Dr. Spohr-Verlag, Stuttgart). It has been shown in practice that the stabilization process according to the invention surprisingly often has an outstanding effect, in particular after a subsequent high-grade finishing process.
Es ist daher im Rahmen der Erfindung besonders vorteilhaft, in Abhängigkeit von einer nach der Hochveredelung zu erzielenden Eigenschaft die Komponenten (a) , (b) und (c) der Behandlungslösung auszuwählen und/oder in ihren Anteilen an der Behandlungslösung aufeinander abzustimmen. Eine derartige Anpassung der individuellen Behandlungslösung in Abhängigkeit einer nach der Hochveredlung gewünschten Eigenschaft ist vom Fachmann in Routineversuchen leicht vorzunehmen. Insbesondere hohe Laugenkonzentration beeinflusst die Modifikation der Cellulosefaser in Richtung der konventionellen Mercerisation; geringere Laugenkonzentrationen und höherer Anteil an der wasserbindenden Komponente (a) verschieben das erzielbare Produktprofil näher zu Resultaten der konventionellen Flüssigammoniakbehandlung. Unterschiede in den Eigenschaften werden insbesondere durch die Auswahl der Komponenten (a) und (b) bzw. deren Mischungsverhältnisse in der Behandlungslösung gesteuert. Z.B. wurde gefunden, dass durch Erhöhung der Laugenkonzentration der Griff des Textils steifer erhalten werden kann, während bei verminderter Laugenkonzentration der Griff des Textils weicher wird. Ebenso erhöht sich das Wasserrückhaltevermögen mit höherer Laugenkonzentration, was die
Unterschiede zu Ergebnissen der konventionellen Flüssigammoniakbehandlung vergrössert.It is therefore particularly advantageous within the scope of the invention to select the components (a), (b) and (c) of the treatment solution and / or to coordinate them in their proportions to the treatment solution, depending on a property to be achieved after the high-grade refinement. Such an adaptation of the individual treatment solution as a function of a desired after the refining property is easily carried out by the expert in routine experiments. In particular, high alkali concentration influences the modification of the cellulose fiber in the direction of conventional mercerization; lower lye concentrations and higher proportion of the water-binding component (a) shift the achievable product profile closer to the results of the conventional liquid ammonia treatment. Differences in properties are controlled in particular by the selection of components (a) and (b) or their mixing ratios in the treatment solution. For example, it has been found that by increasing the caustic concentration, the fabric's feel can be stiffer, while with reduced caustic concentration, the fabric's feel softens. Similarly, the water retention capacity increases with higher alkali concentration, which the Differences to results of conventional liquid ammonia treatment increased.
Die Hochveredlung kann hierbei nach der Behandlung mit der er- findungsgemässen Behandlungslösung entweder mit oder ohne Zwischentrocknung durchgeführt werden.The high-grade finishing can be carried out after treatment with the treatment solution according to the invention either with or without intermediate drying.
Eine besonders vorteilhafte Eigenschaft des erfindungsgemässen Verfahrens ist, dass die Behandlung ohne gebundene Warenführung erfolgen kann. Durch die insgesamt im Rahmen der Erfindung verringerte Faserquellung treten auch wesentlich geringere Schrumpfkräfte auf, so dass auch der Einsprung der Ware geringer ist als bei Mercerisierverfahren in flüssiger Phase gemäss Stand der Technik.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 Mercerisierverfahren in the liquid phase according to the prior art.
Die Erfindung betrifft weiter die Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern, oder von insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien, zur Erhöhung des resultierenden Anteils der in amorphen Bereichen gequollenen Cellulosefasern und/oder zur Verringerung des resultierenden Anteils der in kristallinen Bereichen gequollenen Cellulosefasern.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.
Die Erfindung wird nachfolgend anhand eines konkreten Ausführungsbeispiels näher erläutert, ohne dass der Gegenstand der Erfindung jedoch hierauf zu beschränken wäre.The invention will be explained in more detail with reference to a concrete embodiment, without, however, the subject matter of the invention would be limited thereto.
Ein Textil aus 100% Baumwolle wurde bei Raumtemperatur mit den in Tabelle 1 genannten Behandlungslösungen auf einem Foulard mit 1 m/min Warengeschwindigkeit mit einer Flottenaufnahme von 50 - 66% imprägniert und 4 h bei RT in der Lösung verweilt. An- schliessend wurde mit kaltem Weichwasser ausgewaschen, mit 1
ml/1 Essigsäure neutralisiert, bei 4O0C getrocknet und nach dem üblichen STK-Verfahren (STK = Schock Trocknung Kondensation) hochveredelt. Für die Hochveredlung wurden bei einer Flottenaufnahme von rund 50-70% 40 g/l Arkofix® NDF (DMDHEU-basiertes Produkt, Clariant AG, Basel, Schweiz) und 10 g/l MgCl2 als Katalysator eingesetzt. Nach 1 min Trocknung bei 13O0C erfolgte Kondensation bei 17O0C (Dauer 45 sec) .A textile made of 100% cotton was impregnated at room temperature with the treatment solutions listed in Table 1 on a pad at a speed of 1 m / min with a liquor pickup of 50-66% and left in the solution for 4 h at RT. Subsequently, it was washed out with cold soft water, with 1 ml / 1 acetic acid neutralized, dried at 4O 0 C and highly refined by the usual STK process (STK = shock drying condensation). For refining, 40 g / l Arkofix® NDF (DMDHEU-based product, Clariant AG, Basel, Switzerland) and 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).
Eine Bewertung des erreichten Effekts erfolgt durch Bestimmung des Wasserrückhaltevermögens (WRV) und des Trockenknitterwinkels (TKW K+S) nach DIN 53890 mit 5 Minuten Erholungszeit, der Steifigkeit (%) und der Schrumpfung (%) des ausgerüsteten Produkts. Zum Vergleich sind Resultate jeweils nach einer Behandlung mit 125 bzw. 200 g/l NaOH bzw. KOH in Wasser und nach einer Flüssigammoniakbehandlung, und anschließender, identischer Hochveredlung aufgeführt. Es zeigt sich, dass die resultierenden Eigenschaften des Textils unter Verwendung des erfindungsgemässen Verfahrens nach der Hochveredlung mit den Eigenschaften eines Textils nach einer Ammoniakbehandlung mit nachfolgender, identischer Hochveredlung vergleichbar, bzw. überlegen ist. Hohe TKW bestätigen gutes Knitterverhalten der erfindungsgemäss behandelten Proben, insbesondere im Vergleich zu den konventionell NH3 behandelten Proben. Die konventionelle Mercerisation fällt bei den Ergebnissen deutlich ab. Vergleichbare Werte bei Wasserrückhaltevermögen, Steifigkeit und Schrumpfung bestätigen die Möglichkeit durch systematische Anpassung der Zusammensetzung der Behandlungslösung Eigenschaften der textilen Materialien gezielt verändern zu können.
Tabelle 1: VergleichsmessungenAn evaluation of the achieved effect is carried out by determining the water retention capacity (WRV) and the dry crease angle (TKW K + S) according to DIN 53890 with 5 minutes recovery time, the stiffness (%) and the shrinkage (%) of the finished product. For comparison, results are given in each case after treatment with 125 g or 200 g / l NaOH or KOH in water and after liquid ammonia treatment, followed by identical high-grade finishing. It can be seen that the resulting properties of the textile using the process according to the invention after finishing are comparable or superior to the properties of a textile after ammonia treatment followed by identical high-grade finishing. High TKWs confirm good crease behavior of the samples treated according to the invention, in particular in comparison with the conventional NH 3- treated samples. Conventional mercerization falls significantly in the results. Comparable values for water retention, rigidity and shrinkage confirm the possibility of systematically adjusting the composition of the treatment solution to be able to change the properties of the textile materials in a targeted manner. Table 1: Comparison measurements
Claims
1. Verfahren zur Stabilisierung von Cellulosefasern und/oder eines Cellulosfasern enthaltenden Materials, insbesondere einer textilen Warenbahn enthaltend Cellulosefasern, dadurch gekennzeichnet, dass die Cellulosefasern mit einer Behandlungslösung in Kontakt gebracht werden, wobei die Behandlungslösung umfasst:1. A process for stabilizing cellulose fibers and / or a cellulose fiber-containing material, in particular a textile web containing cellulose fibers, characterized in that the cellulose fibers are brought into contact with a treatment solution, wherein the treatment solution comprises:
(a) eine wasserbindende Komponente,(a) a water-binding component,
(b) ein Quellmittel, sowie(b) a swelling agent, as well
(c) Wasser, wobei das Cellulosefasern enthaltende Material, insbesondere die textile Warenbahn enthaltend Cellulosefasern, im wesentlichen, vorzugsweise vollständig, frei ist von auf regenerierter Cellulose basierenden Garnen und Fasern, wobei der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung mindestens 10 Gew.-% beträgt, vorzugsweise zwischen 10 Gew.-% und 90 Gew.-%, und wobei die Komponenten (a) , (b) und (c) und ihre Anteile and der Behandlungslösung derart ausgewählt sind, dass eine Quellung der Cellulosefasern vorwiegend in a- morphen Bereichen bewirkt wird.(c) water, wherein the cellulosic fiber-containing material, especially the textile web containing cellulosic fibers, is substantially, preferably completely, free from regenerated cellulose based yarns and fibers, wherein the proportion of hydrophilic component (a) in the treatment solution is at least 10 wt %, preferably between 10% and 90% by weight, and wherein components (a), (b) and (c) and their proportions in the treatment solution are selected such that swelling of the cellulose fibers predominantly in amorphous areas.
2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass das Cellulosefasern enthaltende Material, insbesondere die textile Warenbahn im wesentlichen ausschliesslich Cellulosefasern umfasst.2. The method according to claim 1, characterized in that the cellulosic fiber-containing material, in particular the textile web essentially comprises exclusively cellulose fibers.
3. Verfahren gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass als eine wasserbindende Komponente (a) ein Alkohol, insbesondere ein mehrwertiger, vorzugsweise aliphatischer Alkohol, verwendet wird, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus Metha- nol, Ethanol, 1-Propanol, 2-Propanol, 1, 3-Propandiol,3. The method according to any one of claims 1 or 2, characterized in that as a water-binding component (a) an alcohol, in particular a polyhydric, preferably aliphatic alcohol, is used, more preferably selected from the group consisting of methane nol, ethanol, 1-propanol, 2-propanol, 1, 3-propanediol,
1, 2-Propandiol, 1, 2, 3-Propantriol, 1-Butanol, 2-Butanol, tert . -Butylalkohol, 1, 2-Butandiol, 1, 3-Butandiol,1, 2-propanediol, 1, 2, 3-propanetriol, 1-butanol, 2-butanol, tert. Butyl alcohol, 1, 2-butanediol, 1, 3-butanediol,
1, 4-Butandiol, 2, 3-Butandiol und Mischungen hiervon.1, 4-butanediol, 2, 3-butanediol and mixtures thereof.
4. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass als eine wasserbindende Komponente (a) ein Feststoff der Behandlungslösung beigegeben wird, welcher ausgewählt ist aus der Gruppe bestehend aus Kohlenhydraten, Harnstoff, anorganischen Salzen und Mischungen hiervon .4. The method according to any one of claims 1 to 3, characterized in that as a water-binding component (a) a solid of the treatment solution is added, which is selected from the group consisting of carbohydrates, urea, inorganic salts and mixtures thereof.
5. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als wasserbindende Komponente (a)5. The method according to any one of claims 1 to 4, characterized in that as water-binding component (a)
1, 2 , 3-Propantriol, NaCl und Mischungen hiervon verwendet werden.1, 2, 3-propanetriol, NaCl and mixtures thereof.
6. Verfahren gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung derart ausgewählt ist, dass ein verfügbarer, freier Wasseranteil der Behandlungslösung von höchstens 35 mol/1, vorzugsweise von höchstens 25 mol/1, besonders bevorzugt von höchstens 15 mol/1 resultiert.6. The method according to any one of claims 1 to 5, characterized in that the proportion of the water-binding component (a) is selected on the treatment solution such that an available, free water content of the treatment solution of at most 35 mol / 1, preferably of at most 25 mol / 1, more preferably at most 15 mol / 1 results.
7. Verfahren gemäss einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass als Quellmittel (b) eine Chemikalie oder eine Mischung von Chemikalien verwendet wird, welche insbesondere bei einer Konzentration von mindestens 1 mol/1 in der Behandlungslösung in einem pH Wert von7. The method according to any one of claims 1 to 6, characterized in that as the swelling agent (b) a chemical or a mixture of chemicals is used, which in particular at a concentration of at least 1 mol / 1 in the treatment solution in a pH of
>= 9, vorzugsweise von >= 11, besonders bevorzugt von >= 13 resultiert. > = 9, preferably of> = 11, particularly preferably of> = 13 results.
8. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass als Quellmittel (b) mindestens eine Chemikalie eingesetzt wird, welche ausgewählt ist aus der Gruppe bestehend aus Alkalimetallhydroxiden, Erdalkalimetallhydroxiden, Aminen, Thiocyanaten, Iodiden, Metallkomplexen, Ammoniak-Lösung, und Mischungen hiervon.8. The method according to any one of claims 1 to 7, characterized in that as swelling agent (b) at least one chemical is used which is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, amines, thiocyanates, iodides, metal complexes, ammonia solution, and mixtures thereof.
9. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Stabilisierung bei einer Temperatur zwischen -1O0C und 18O0C, bevorzugt bei einer Temperatur zwischen 150C und 1050C durchgeführt wird.9. The method according to any one of claims 1 to 8, characterized in that the stabilization at a temperature between -1O 0 C and 18O 0 C, preferably at a temperature between 15 0 C and 105 0 C is performed.
10. Verfahren gemäss einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass nach der Quellbehandlung eine Hochveredelung der Cellulosefasern oder des insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materials durchgeführt wird, insbesondere ein Schock- Trocknung-Kondensationsverfahren oder bevorzugt ein Verfahren der Feuchtvernetzung.10. The method according to any one of claims 1 to 9, characterized in that after the swelling treatment, a refining of cellulose fibers or in particular essentially exclusively cellulose fibers comprehensive material is performed, in particular a shock-drying condensation process or preferably a method of wet crosslinking.
11. Verfahren gemäss Anspruch 10, dadurch gekennzeichnet, dass in Abhängigkeit von einer nach der Hochveredelung zu erzielenden Eigenschaft die Komponenten (a) , (b) und (c) der Behandlungslösung ausgewählt und/oder in ihren Anteilen an der Behandlungslösung aufeinander abgestimmt werden.11. The method according to claim 10, characterized in that depending on a property to be achieved after the refining property, the components (a), (b) and (c) of the treatment solution selected and / or matched in their proportions of the treatment solution.
12. Verfahren gemäss einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die Stabilisierung in einem kontinuierlichen Prozess und mit ungebundener Warenführung, insbesondere mit ungebundener Warenführung erfolgt. 3. Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulose- fasern, oder von insbesondere im wesentlichen aus- schliesslich Cellulosefasern umfassenden Materialien, zur Erhöhung des resultierenden Anteils der in amorphen Bereichen gequollenen Cellulosefasern und/oder zur Verringerung des resultierenden Anteils der in kristallinen Bereichen gequollenen Cellulosefasern, wobei die Cellulosefasern im wesentlichen, vorzugsweise vollständig, frei sind von auf regenerierter Cellulose basierenden Garnen und Fasern, und wobei der Anteil der wasserbindenden Komponente an der Behandlungslösung mindestens 10 Gew.-%, vorzugsweise zwischen 10 Gew.-% und 90 Gew.-% beträgt. 12. The method according to any one of claims 1 to 11, characterized in that the stabilization takes place in a continuous process and with unbound merchandise management, in particular with unbound merchandise management. 3. 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 cellulose fibers swollen in crystalline areas, the cellulose fibers being essentially, preferably completely, free of regenerated cellulose-based yarns and fibers, and wherein the proportion of the water-binding component in the treatment solution is at least 10% by weight, preferably between 10% by weight and 90% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0609467-8A BRPI0609467A2 (en) | 2005-03-24 | 2006-03-21 | a method for stabilizing cellulose fibers, especially of a textile web comprising cellulose fibers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05102374A EP1705285B1 (en) | 2005-03-24 | 2005-03-24 | Process for the stabilisation of cellulosic fibres, especially of a textile web comprising cellulosic fibres |
| EP05102374.5 | 2005-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006100249A1 true WO2006100249A1 (en) | 2006-09-28 |
Family
ID=35530806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2006/060924 WO2006100249A1 (en) | 2005-03-24 | 2006-03-21 | Method for stabilizing cellulose fibers, especially of a textile web that comprises cellulose fibers |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1705285B1 (en) |
| CN (1) | CN101146949A (en) |
| AT (1) | ATE490367T1 (en) |
| BR (1) | BRPI0609467A2 (en) |
| DE (1) | DE502005010612D1 (en) |
| RU (1) | RU2007139334A (en) |
| WO (1) | WO2006100249A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103549692A (en) * | 2013-09-25 | 2014-02-05 | 桐乡市中龙纺业有限责任公司 | Production method of fibroin foreign fiber fabric |
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 (en) * | 1973-02-14 | 1974-08-29 | Heberlein & Co Ag | METHOD AND DEVICE FOR IMPROVING THE FIBER STRUCTURE OF TEXTILE MATERIAL CONTAINING CELLULOSE FIBERS |
| WO2003050346A1 (en) * | 2001-12-11 | 2003-06-19 | Kimberly-Clark Worldwide, Inc. | High wet resiliency curly cellulose fibers |
-
2005
- 2005-03-24 DE DE502005010612T patent/DE502005010612D1/en active Active
- 2005-03-24 EP EP05102374A patent/EP1705285B1/en not_active Not-in-force
- 2005-03-24 AT AT05102374T patent/ATE490367T1/en active
-
2006
- 2006-03-21 WO PCT/EP2006/060924 patent/WO2006100249A1/en not_active Application Discontinuation
- 2006-03-21 CN CNA2006800089038A patent/CN101146949A/en active Pending
- 2006-03-21 BR BRPI0609467-8A patent/BRPI0609467A2/en not_active Application Discontinuation
- 2006-03-21 RU RU2007139334/04A patent/RU2007139334A/en not_active Application Discontinuation
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 (en) * | 1973-02-14 | 1974-08-29 | Heberlein & Co Ag | METHOD AND DEVICE FOR IMPROVING THE FIBER STRUCTURE OF TEXTILE MATERIAL CONTAINING CELLULOSE FIBERS |
| WO2003050346A1 (en) * | 2001-12-11 | 2003-06-19 | Kimberly-Clark Worldwide, Inc. | High wet resiliency curly cellulose fibers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103549692A (en) * | 2013-09-25 | 2014-02-05 | 桐乡市中龙纺业有限责任公司 | Production method of fibroin foreign fiber fabric |
| CN103549692B (en) * | 2013-09-25 | 2015-11-18 | 桐乡市中龙纺业有限责任公司 | The production method of fibroin foreign fiber fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1705285B1 (en) | 2010-12-01 |
| RU2007139334A (en) | 2009-04-27 |
| BRPI0609467A2 (en) | 2010-04-13 |
| EP1705285A1 (en) | 2006-09-27 |
| ATE490367T1 (en) | 2010-12-15 |
| DE502005010612D1 (en) | 2011-01-13 |
| CN101146949A (en) | 2008-03-19 |
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