US3112986A - Process for the production of crimpable regenerated cellulose fibers and yarn - Google Patents
Process for the production of crimpable regenerated cellulose fibers and yarn Download PDFInfo
- Publication number
- US3112986A US3112986A US169988A US16998862A US3112986A US 3112986 A US3112986 A US 3112986A US 169988 A US169988 A US 169988A US 16998862 A US16998862 A US 16998862A US 3112986 A US3112986 A US 3112986A
- Authority
- US
- United States
- Prior art keywords
- viscoses
- yarn
- viscose
- sodium
- regenerated cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000004627 regenerated cellulose Substances 0.000 title claims description 10
- 229920003043 Cellulose fiber Polymers 0.000 title description 6
- 229920000297 Rayon Polymers 0.000 claims description 52
- 239000003607 modifier Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 21
- 238000005345 coagulation Methods 0.000 claims description 19
- 230000015271 coagulation Effects 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000001112 coagulating effect Effects 0.000 claims description 13
- 230000001172 regenerating effect Effects 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- -1 tetrapropylammonium hydroxide tetrabutylammonium chloride Chemical compound 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 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 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- XDUJLWKIAVPQDH-UHFFFAOYSA-M sodium;n-cyclohexyl-n-methylcarbamodithioate Chemical compound [Na+].[S-]C(=S)N(C)C1CCCCC1 XDUJLWKIAVPQDH-UHFFFAOYSA-M 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical compound [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- IIHAWQOFHTYWGM-UHFFFAOYSA-N 1,4-diethoxybutane Chemical compound CCOCCCCOCC IIHAWQOFHTYWGM-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- SXYRTDICSOVQNZ-UHFFFAOYSA-N 1-(2-methoxyethoxy)ethanol Chemical compound COCCOC(C)O SXYRTDICSOVQNZ-UHFFFAOYSA-N 0.000 description 1
- JMYBSSVCXVQZFN-UHFFFAOYSA-N 1-(2-phenoxyethoxy)ethanol Chemical compound CC(O)OCCOC1=CC=CC=C1 JMYBSSVCXVQZFN-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- LUNOYBIKPTXWOW-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOC(C)O LUNOYBIKPTXWOW-UHFFFAOYSA-N 0.000 description 1
- GTYAZGDJULEKHS-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound C(CCC)OCCOCCOCCOC(C)O GTYAZGDJULEKHS-UHFFFAOYSA-N 0.000 description 1
- MBDJXHDBQNHQFE-UHFFFAOYSA-N 1-amino-2-methylhexan-2-ol Chemical compound CCCCC(C)(O)CN MBDJXHDBQNHQFE-UHFFFAOYSA-N 0.000 description 1
- ZRUPXAZUXDFLTG-UHFFFAOYSA-N 1-aminopentan-2-ol Chemical compound CCCC(O)CN ZRUPXAZUXDFLTG-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- QATXMCVRIZSPJU-UHFFFAOYSA-N 2-[2-hydroxyethyl(pentyl)amino]ethanol Chemical compound CCCCCN(CCO)CCO QATXMCVRIZSPJU-UHFFFAOYSA-N 0.000 description 1
- GIACMWUKBLHAAG-UHFFFAOYSA-N 2-[hexyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCN(CCO)CCO GIACMWUKBLHAAG-UHFFFAOYSA-N 0.000 description 1
- MSIAFRBGOYFCND-UHFFFAOYSA-N 2-amino-1-cyclohexylethanol Chemical compound NCC(O)C1CCCCC1 MSIAFRBGOYFCND-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 1
- OWRGRHKXXGTEHA-UHFFFAOYSA-N 3,3-dimethylhexane-1,6-diamine Chemical compound NCCC(C)(C)CCCN OWRGRHKXXGTEHA-UHFFFAOYSA-N 0.000 description 1
- ZFWPGRUTHAZDBK-UHFFFAOYSA-N 4-n,4-n-diethylcyclohexane-1,4-diamine Chemical compound CCN(CC)C1CCC(N)CC1 ZFWPGRUTHAZDBK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DZQZHHICNKWYBD-UHFFFAOYSA-N C(N)(SC1CCCCC1)=S.[Li] Chemical compound C(N)(SC1CCCCC1)=S.[Li] DZQZHHICNKWYBD-UHFFFAOYSA-N 0.000 description 1
- ZMISHVGIBUUCJV-UHFFFAOYSA-N C(N)(SCCCCCCCCCCCC)=S.[Na] Chemical compound C(N)(SCCCCCCCCCCCC)=S.[Na] ZMISHVGIBUUCJV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- HXIJGAYEJUZUFA-UHFFFAOYSA-N O(C1=CC=CC=C1)CCOCCOCCOC(C)O Chemical compound O(C1=CC=CC=C1)CCOCCOCCOC(C)O HXIJGAYEJUZUFA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005520 cutting process 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
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- NRKKJMFAXXHDEG-UHFFFAOYSA-N n',n'-bis(2-methylpropyl)hexane-1,6-diamine Chemical compound CC(C)CN(CC(C)C)CCCCCCN NRKKJMFAXXHDEG-UHFFFAOYSA-N 0.000 description 1
- UUWPMNGNEAEOIR-UHFFFAOYSA-N n'-hexylpropane-1,3-diamine Chemical compound CCCCCCNCCCN UUWPMNGNEAEOIR-UHFFFAOYSA-N 0.000 description 1
- GJYJPJFYKNOGEK-UHFFFAOYSA-N n'-methylnonane-1,9-diamine Chemical compound CNCCCCCCCCCN GJYJPJFYKNOGEK-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- MIHRVCSSMAGKNH-UHFFFAOYSA-M n-ethylcarbamodithioate Chemical compound CCNC([S-])=S MIHRVCSSMAGKNH-UHFFFAOYSA-M 0.000 description 1
- UQJQVUOTMVCFHX-UHFFFAOYSA-L nabam Chemical compound [Na+].[Na+].[S-]C(=S)NCCNC([S-])=S UQJQVUOTMVCFHX-UHFFFAOYSA-L 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- LAHATCIHENQQOP-UHFFFAOYSA-M sodium;n,n-dioctylcarbamodithioate Chemical compound [Na+].CCCCCCCCN(C([S-])=S)CCCCCCCC LAHATCIHENQQOP-UHFFFAOYSA-M 0.000 description 1
- RJAXVDQEAVACNL-UHFFFAOYSA-M sodium;n-cyclohexylcarbamodithioate Chemical compound [Na+].[S-]C(=S)NC1CCCCC1 RJAXVDQEAVACNL-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/32—Side-by-side structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/26—Composite fibers made of two or more materials
Definitions
- PROCESS FOR THE PRODUCTION OF CRIMPABLE REGENERATED CELLULOSE FIBERS AND YARN Original Filed Oct. 50, 1958 INVENTOR RUDLOPH WOODELL BY /?M W ATTORNEY United States Patent 3,112,086 PROES FQR THE PRODUCTHON 0F CRIMPABLE REGENERATED CELLULUSE FIBERS AND YARN Rudolph Woodell, Kinston, Nil, assignor to Beaunit Corporation, a corporation of New York Original application 0st. 30, 1958, Ser. No. 770,761. Divided and this appiication Jan. 8, 1962, Ser. No.
- crirnpa'ble filaments by extruding two or more viscoses having different shrinkage potentials through the same spinneret hole is known. While these multi-compone-nt filaments are superior in certain respects to single component filaments, i.e. in case of crimping and crimp retention, further improvement in the degree of crimping and crimp reversibility on wetting and drying, particularly in high denier per filament yarns, is desirable.
- Another object is to provide a crimpable fiber which crimps to a high degree in water, which has high bulk and improved crimp reversibility.
- a further object is to provide a process for producing these fibers.
- an integral rayon fiber having a transverse cross section consisting of two longitudinal ribbon-like components, disposed side-by-side a first component having a heavy, preferably at least 80 skin and a second component having an elongated narrow shape and a substantially thinner skin than the first component, one component of the fiber being wrinkled.
- the second component has at least 20% less skin than the first component, i.e., not over 64% of the cross-sectional area.
- the process comprises preparing two viscoses, A and B, adding to viscose A a small amount of coagulation modifier, extruding the two streams of viscoses simultaneously in side-by-side relationship through narrow, elongated spinneret openings into a coagulating and regenerating bath containing from about 6.5 to about 10% sulfuric acid, from about 12 to about 23% sodium sulfate, and at least about 3% zinc sulfate, viscose A having a salt index of at least about 5, viscose B having a salt index of at least about 2, the long axis of the spinneret openings being at least about 8 to 10 times the lenth of the short axis, and thereafter stretching the yarn.
- the salt index of viscose A is at least about 3 units higher than that of viscose B.
- FTGURE 1 is an exploded view of a device useful in the extrusion of the yarn of the present invention.
- FIGURE 2 is a rear view of the equalizer and separator section of the device illustrated in FIGURE 1.
- FTGURE 3 is an illustration of the yarn cross section produced as described in Example 1.
- the yarn produced is extruded through this orifices of the spinneret plate 2, the said plate being positioned against the equalizer and separator section 3 by means of internally threaded spinneret adapter 4, flange 5 of the spinneret plate being held against the front face of the equalizer and separator sec tion by the face 6 of the said spinneret adapter.
- Concentric cylindrical separator rings 7 extend through the equalizer and separator section, the said rings being supported by the pressure equalizer plate 8 (shown in FIG- URE 2) which holds them in fixed relation to the circumference of the said equalizer and separator section.
- the concentric cylindrical separator rings are beveled to a sharp edge which extends beyond the engaging threads of the equalizer and separator section to such an extent that when the spinneret plate 2 is positioned as previously described the sharp edges of the separator rings are immediately adjacent to the back face of spinneret plate 2. and so arranged that each edge bisects each orifice in a particular ring of the said orifices.
- Pressure equalizer plate 8 (FIGURE 2) contains concentrically arranged holes 9 fitting into spaces between the concentric separator rings previously described and act to control the pressure of, and prevent pressure surges in, viscose delivered to the spinneret plate. Pressure equalizer plate 8 fits by threaded means onto a concentric conduit 10 which contains openings 11 through which various viscoses may be pres sure fed to the system.
- the spinneret openings are narrow, elongated slits, preferably rectangular in shape although the openings may be rounded at the ends if desired.
- the long axes of the spinneret openings are at least about 8 to l0 times the length of the short axes and preferably about 16 times the length of the short axes. It is preferable that the long axis of the spinneret opening be situated radially with respect to the circular spinneret face since this greatly facilitates the extrusion of two viscoses simultaneously through the opening.
- Example I Two viscoses, A and B are prepared in the conventional manner. Viscose A containing 5.0% recoverable cellulose and 6.11% alkali, calculated as sodium hydroxide, is prepared from cotton linters pulp using 40% carbon disulfide based on the air dry weight of the pulp. Sufficient sodium N-methylcyclohexyldithiocarbamate is added during the mixing operation to give a concentration of 0.61% by weight. The viscose is filtered, deaerated, and ripened to a viscosity of 39 poises and a salt index of 14.4.
- Viscose B containing 8.60% recoverable cellulose and 5.28% alkali is prepared using 30% carbon disulfide and is filtered, deaerated, and ripened to a viscosity of 46 poises and a salt index of 3.0. Viscoses A and B are then supplied to the .spinneret, which has rectangular shaped openings, by means of separate gear pumps, viscose A being supplied .at a rate of 48.4 -g.p.m. and viscose B at 28.4 g.p.m. so that substantially equivalent amounts of recoverable cellulose are supplied by each pump.
- the viscoses are extruded through a spinneret of inch diameter having 50 openings of 0.002 inch width and 0.036 inch length equidistantly spaced in a ring whose diameter is inch.
- the long axes of the spinneret openings are disposed radially with respect to the spinneret face.
- the two viscoses are extruded through each of the spinneret holes in side-by-side relationship by means of the separator rings and pressure equalizer assembly previously described.
- the viscoses are extruded into a coagulating and regenerating bath containing 8.0% sulfuric acid, 17.5% sodium sulfate, 9.5% zinc sulfate and maintained at a temperature of 60 C.
- the filaments are led for a distance of 20 inches through the bath, then over a Y convergence guide and then for a further distance of inches, the yarn being confined in the bath by means of a series of roller guides.
- the yarn in given a sufficient number of passes around the feed wheels .to give the yarn a travel of 120 inches in this area.
- the yarn is led from the second feed wheel which has a peripheral speed of 50 y.p.m. downwardly to a centrifugal spinning bucket where it is wound into a cake in the conventional manner.
- the yarn is purified and dried in the conventional manner.
- the yarn denier is 1,000.
- the yarn filaments are examined by cutting thin transverse cross sections in the conventional manner, dyeing these cross sections and examining them under high magnification.
- Cross sections are dyed following the method described by Morehead and Sisson, Textile Research Journal, 15, 444- (1945) except that pontamine yellow dye is substituted for calcimine yellow dye. Examination of the dyed cross section shows that one end has a heavy skin while the remainder, as shown in FIGURE 3, is narrow and elongated and has a much thinner skin.
- the yarn is placed in water at 90l00 C. in a relaxed state followed by drying in a relaxed state, it is found that the yarn has an excellent spiral type of crimp.
- the essential factor in producing the fibers of this invention is the extrusion of two streams of viscoses, one containing a coagulation modifier and the other containing no modifier, in side-by-side relationship through elongated spinneret openings to produce filaments having narrow, elongated cross sections.
- the modified viscose must be spun at a salt index of at least about 5 and preferably the index is at least about 10.
- the unmodified viscose must be spun at an index of at least about 2 and is preferably spun at an index in the range of about 2 to about 5 although high indices may be employed in some cases. If higher indices are employed with the unmodified viscose, then the amount of modifier which is allowed to accumulate in the spinning bath due to the modifier being leached from the spinning filaments must to kept at a very low level in order to obtain the desired filament cross section.
- composition of the viscoses used in the process of this invention is not critical. Viscoses produced with from about 27 ltO about 43% carbon disulfide based on the dry weight of the pulp are satisfactory. Preferably the modified viscose is produced with at least about 35% carbon disulfide. The viscose may contain from about 5.5 to about 9.5% recoverable cellulose and from about 4 to about 8% alkali.
- Coagulating ⁇ and regenerating baths suitable for use in the present invention contain from about 6.5 to about 10% sulfuric acid, from about 12 to about 23% sodium sulfate, and at least about 3% zinc sulfate in addition to the coagulation modifier. Other metal salts which may supplement the action of the Zinc sulfate may be added if desired.
- the acidity of the bath should be regulated to as low a level as is commensurate with satisfactory spinning.
- a group of preferred coagulation modifiers which are suitable for use in the process of this invention are as follows:
- the use of these compounds is disclosed in United States Patent 2,536,014.
- Suitable compounds in this group which may be mentioned are benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium chloride, phenyltrimethylammonium hydroxide, tetraethanolammonium hydroxide, tetraethylammonium bromide, tetramet-hylammonium iodide, tetrapropylammonium hydroxide tetrabutylammonium chloride, tributylpropylammonium hydroxide, tri(beta hydroxyethyl)methylammonium hydroxide, tributyl(betahydroxyethyDammonium iodide, etc.
- the preferred agents of this class are those in which all four organic groups attached to the nitrogen atom are hydrocarbon groups or hydroxyl-substituted hydrocarbon groups and in which the radical X is hydroxyl or halogen of atomic weight above 19, i.e., chlorine, bromine or iodine.
- the most useful modifiers of this group are the quaternary ammonium hydroxides having a total of not more than ten carbon atoms in the molecule and in which all organic groups are hydrocaroon or hydroxyl-substituted hydrocarbon.
- Aliphatic monoamines having at least four carbon atoms but containing no radical of more than six carbon atoms.
- the use of these compounds is disclosed in United States Patent 2,535,044.
- Suitable compounds in this group which may be mentioned are triethanolamine, triethylamine, diethanolamine, butylmonoethanolamine, diethylaminoethanol, n-amylamine, diethylamine, dipropylamine, n-butylamine, ethyldiethanol amine, dipropanolamine, propylpropano-lamine, hex'anolamine, amyldiethanolamine, butylmethylethanolamine, propylethanolamine, cyclohexylethanolamine, N methylcyolohexyl amine, hexarnethyleneimine, piperidine, hexyldiethanolamine, etc.
- the preferred modifiers of this group are those in which the amino nitrogen is attached to hydrocarbon groups, preferably alkyl
- aliphatic diamines may be mentioned the following: hexamethylenediamine, tetramethylenediamine, N-methyltrimethylenediamine, N,N'-dimethylethylenediamine, N,N- diisobutylhexamethylenediamine, N,N'-dimethyltrimethylenediarnine, 4,4-dimethylhexamethylenediamine, N,N-diethyl-1,4-cyclohexanediamine, 3-ethoxyethoxyhexamethylenediamine, pentamethylenediamine, octamethylenediamine, N-cyolohexyltetramethylenediamine, N,N-diallylhexamethylenediamine, N-methylnonamethylenediamine, N hexyltrimethylenediamine, N,N dimethylpiperazine, N-butylhexamethylenediarnine, etc.
- the preferred agents of this class are the Wholly aliphatic, including cycloaliphatic, diamines which contain only carbon and hydrogen besides the two amino nitrogens and which have a total number of carbon atoms between 4 and 14, inclusive, in addition to fulfilling the other requirements stated above. Still more preferred are the polymethylenediamines of 4 to 14 total carbon atoms having from 4 to 8 methylene groups between the amino groups, and their N-alkyl substituted derivatives where the N-alkyl groups have from 1 to 4 carbon atoms inclusive.
- N-substituted dithiocarbamic acids The use of these compounds is disclosed in United States Patent 2,696,423.
- salts of N-substituted dithiocarbamic acids may be mentioned, sodium amyl dithiocarbamate, sodium bu-tyl monoethanol dithiocarbarnate, sodium hexamethylene bis (dithiocarbamate), potassium pentamethylene dithiooarbamate, sodium methyl dithiocarbamate, sodium benzyl dit-hiocarbama-te, sodium ethylene bis(dithiocarbamate), sodium 1,3-cyclohexane bis(dithiocarbamate), sodium dibutyl dithiooarbamate, sodium dimethyl dithiooarbamate, sodium dioctyl dithiocarbamate, sodium lauryl dithiocarbamate, sodium cyclohexyldithiocarbamate, lithium cyclohexyl dithiocarbamate
- ethers may be mentioned phenoxyethanol, ethoxyethanol, butox-yethanol, methoxyethoxyethanol, butoxyethoxyethanol, phenoxyethoxyethanol, ethoxye-thoxyethoxyethanol, butoxyethoxyethoxyethanol, phenoxyethoxyethoxyethanol, butoxyethoxyethoxyethoxyethanol, phenoxyethoxyethoxyethoxyethanol, 1-ethenyloxy-2-methoxyethylene, ethylene glycol diethyl ether, triethylene glycol diethyl ether, tetramethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.
- this class of coagulation modifiers it has been found that those compounds which, in addition to being soluble in viscose, are difficultly soluble in the coagulating bath, i.e., to the extent of less than 0.5%, give the best results.
- the use of these compounds is disclosed in Italian Patent 561,552.
- the polyethylene glycols of formula HO(CH CH O),,H (ethylene oxide polymers) include all such compounds where n is at least equal to 4, i.e., polymers which have a molecular weight of at least 200, and which in addition have the required solubility in viscose. Such compounds are available commercially in various molecular weight ranges, such as 600, 1500 or 2500.
- the polyethylene glycols having molecular weights between abount 300 and about 1000 are preferred.
- coagulation modifiers as are known in the art, may also be employed in place of the listed compounds.
- Various suitable ones are described in United States Patents 2,777,775; 2,792,278; 2,792,279; 2,792,280 and 2,792,281; British Patents 723,435; 730,541; 748,147 and 765,905, and French Patents 1,102,898 and 1,111,580.
- the yarn should be stretched at least about 40% while passing through the bath.
- the stretch may be concentrated in this bath or it may be divided between the two baths as desired. If a hot secondary bath is not employed, then all of the stretch is imposed on the yarn while passing through the coagulating and regenerating bath by means of tension-type roller guides.
- the ratio of the yarn draw-off speed to the linear speed at which the viscose is extruded is at least 1.0. This is particularly true where the denier per filament is low (below 8) since under these conditions the desired elongated shape of the filament cross section may not be realized if the ratio is too low. Likewise, the ratio should be at least 1.0 if the ratio of length to width of the spinneret opening is below about 8.
- the yarn After the yarn leaves the bath, it is wound into a cake in a centrifugal spinning bucket or wound on a bobbin and thereafter purified and dried in the conventional manner.
- the yarn is preferably given additional stretch after thorough wetting and is then dried in the stretched condition.
- the stretching is conveniently applied by passing the yarn through a slashing machine of the type used in the production of tire cord yarn. If the customary aqueous finish is applied to the yarn, the yarn is wetted with this before stretching.
- the yarn erim-ps readily when allowed to relax in hot water followed by drying in a relaxed state.
- various aqueous solutions as are well known in the art may be used in the crimping operation.
- the fibers of this invention may be used wherever rayon fibers are customarily employed, however, they are particularly suitable for the production of tufted carpets and cut pile fabrics.
- a process for the production of regenerated cellulose fibers comprising essentially extruding through elongated spinneret openings having long axes at least about 8 times longer than the short axes into a coagulating and regenerating bath containing from about 6.5 to about 10% sulfuric acid, from about 12 to about 23% sodium sulfate and at least about 3% zinc sulfate, pairs of streams of viscoses in side-by-side relationship, the first of said viscoses containing a small amount of a coagulation modifier and having a salt index of at least about 5, the second of said viscoses containing no coagulation modifier and having a salt index at least about 3 units lower than the salt index of said first viscose, coagulating and regenerating said pairs of streams of viscoses to form integral regenerated cellulose fibers containing two longitudinal ribbon-like components disposed side-byside, and stretching the integral fibers at least about 40% during coagulation and regeneration.
- a process for the production of regenerated cellulose fibers comprising essentially extruding through substantially rectangular spinneret openings having longer axes at least about 8 to 10 times the length of the shorter axes into a coagulating and regenerating bath containing from about 6.5 to about 10% sulfuric acid, from about 12 to about 23 to sodium sulfate and at least about 3% zinc sulfate, pairs of streams of viscoses in side-by-side relationship, the first of said viscoses containing a small amount of a coagulation modifier and having a salt index of at least about 10, the second of said viscoses containing no coagulation modifier and having a.
- a process for the production of regenerated cellulose ttibers consisting of extruding through a plurality of elongated openings radially disposed with respect to their long axes in a spinneret face, each opening having a Width of about 0.002 inch and a length of about 0.036 inch, into a coagulating and regenerating bath maintained at about 60 C.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
Description
Dec. 3, 1963 R. WOODELL 3,112,986
PROCESS FOR THE PRODUCTION OF CRIMPABLE REGENERATED CELLULOSE FIBERS AND YARN Original Filed Oct. 50, 1958 INVENTOR RUDLOPH WOODELL BY /?M W ATTORNEY United States Patent 3,112,086 PROES FQR THE PRODUCTHON 0F CRIMPABLE REGENERATED CELLULUSE FIBERS AND YARN Rudolph Woodell, Kinston, Nil, assignor to Beaunit Corporation, a corporation of New York Original application 0st. 30, 1958, Ser. No. 770,761. Divided and this appiication Jan. 8, 1962, Ser. No.
7 Claims. (Cl. 18-54) This invention relates to novel and useful crimpable rayon fibers and a process for their production.
The production of crirnpa'ble filaments by extruding two or more viscoses having different shrinkage potentials through the same spinneret hole is known. While these multi-compone-nt filaments are superior in certain respects to single component filaments, i.e. in case of crimping and crimp retention, further improvement in the degree of crimping and crimp reversibility on wetting and drying, particularly in high denier per filament yarns, is desirable.
It is an object of this invention to provide a new and useful crimpable viscose rayon fiber.
Another object is to provide a crimpable fiber which crimps to a high degree in water, which has high bulk and improved crimp reversibility.
A further object is to provide a process for producing these fibers.
These and other objects will become apparent in the course of the following specification and claims.
In accordance with the present invention an integral rayon fiber is provided having a transverse cross section consisting of two longitudinal ribbon-like components, disposed side-by-side a first component having a heavy, preferably at least 80 skin and a second component having an elongated narrow shape and a substantially thinner skin than the first component, one component of the fiber being wrinkled. Preferably the second component has at least 20% less skin than the first component, i.e., not over 64% of the cross-sectional area.
The process comprises preparing two viscoses, A and B, adding to viscose A a small amount of coagulation modifier, extruding the two streams of viscoses simultaneously in side-by-side relationship through narrow, elongated spinneret openings into a coagulating and regenerating bath containing from about 6.5 to about 10% sulfuric acid, from about 12 to about 23% sodium sulfate, and at least about 3% zinc sulfate, viscose A having a salt index of at least about 5, viscose B having a salt index of at least about 2, the long axis of the spinneret openings being at least about 8 to 10 times the lenth of the short axis, and thereafter stretching the yarn. Preferably, the salt index of viscose A is at least about 3 units higher than that of viscose B.
FTGURE 1 is an exploded view of a device useful in the extrusion of the yarn of the present invention.
FIGURE 2 is a rear view of the equalizer and separator section of the device illustrated in FIGURE 1.
FTGURE 3 is an illustration of the yarn cross section produced as described in Example 1.
Referring particularly to the figures the yarn produced is extruded through this orifices of the spinneret plate 2, the said plate being positioned against the equalizer and separator section 3 by means of internally threaded spinneret adapter 4, flange 5 of the spinneret plate being held against the front face of the equalizer and separator sec tion by the face 6 of the said spinneret adapter. Concentric cylindrical separator rings 7 extend through the equalizer and separator section, the said rings being supported by the pressure equalizer plate 8 (shown in FIG- URE 2) which holds them in fixed relation to the circumference of the said equalizer and separator section. The concentric cylindrical separator rings are beveled to a sharp edge which extends beyond the engaging threads of the equalizer and separator section to such an extent that when the spinneret plate 2 is positioned as previously described the sharp edges of the separator rings are immediately adjacent to the back face of spinneret plate 2. and so arranged that each edge bisects each orifice in a particular ring of the said orifices. Pressure equalizer plate 8 (FIGURE 2) contains concentrically arranged holes 9 fitting into spaces between the concentric separator rings previously described and act to control the pressure of, and prevent pressure surges in, viscose delivered to the spinneret plate. Pressure equalizer plate 8 fits by threaded means onto a concentric conduit 10 which contains openings 11 through which various viscoses may be pres sure fed to the system.
The spinneret openings are narrow, elongated slits, preferably rectangular in shape although the openings may be rounded at the ends if desired. The long axes of the spinneret openings are at least about 8 to l0 times the length of the short axes and preferably about 16 times the length of the short axes. It is preferable that the long axis of the spinneret opening be situated radially with respect to the circular spinneret face since this greatly facilitates the extrusion of two viscoses simultaneously through the opening.
The following example is cited to illustrate the invention. It is not intended to limit it in any manner.
Example I Two viscoses, A and B are prepared in the conventional manner. Viscose A containing 5.0% recoverable cellulose and 6.11% alkali, calculated as sodium hydroxide, is prepared from cotton linters pulp using 40% carbon disulfide based on the air dry weight of the pulp. Sufficient sodium N-methylcyclohexyldithiocarbamate is added during the mixing operation to give a concentration of 0.61% by weight. The viscose is filtered, deaerated, and ripened to a viscosity of 39 poises and a salt index of 14.4. Viscose B containing 8.60% recoverable cellulose and 5.28% alkali is prepared using 30% carbon disulfide and is filtered, deaerated, and ripened to a viscosity of 46 poises and a salt index of 3.0. Viscoses A and B are then supplied to the .spinneret, which has rectangular shaped openings, by means of separate gear pumps, viscose A being supplied .at a rate of 48.4 -g.p.m. and viscose B at 28.4 g.p.m. so that substantially equivalent amounts of recoverable cellulose are supplied by each pump. The viscoses are extruded through a spinneret of inch diameter having 50 openings of 0.002 inch width and 0.036 inch length equidistantly spaced in a ring whose diameter is inch. The long axes of the spinneret openings are disposed radially with respect to the spinneret face. The two viscoses are extruded through each of the spinneret holes in side-by-side relationship by means of the separator rings and pressure equalizer assembly previously described.
The viscoses are extruded into a coagulating and regenerating bath containing 8.0% sulfuric acid, 17.5% sodium sulfate, 9.5% zinc sulfate and maintained at a temperature of 60 C. The filaments are led for a distance of 20 inches through the bath, then over a Y convergence guide and then for a further distance of inches, the yarn being confined in the bath by means of a series of roller guides.
bination with each feed Wheel, the yarn in given a sufficient number of passes around the feed wheels .to give the yarn a travel of 120 inches in this area. The yarn is led from the second feed wheel which has a peripheral speed of 50 y.p.m. downwardly to a centrifugal spinning bucket where it is wound into a cake in the conventional manner. The yarn is purified and dried in the conventional manner. The yarn denier is 1,000.
The yarn filaments are examined by cutting thin transverse cross sections in the conventional manner, dyeing these cross sections and examining them under high magnification. Cross sections are dyed following the method described by Morehead and Sisson, Textile Research Journal, 15, 444- (1945) except that pontamine yellow dye is substituted for calcimine yellow dye. Examination of the dyed cross section shows that one end has a heavy skin while the remainder, as shown in FIGURE 3, is narrow and elongated and has a much thinner skin. When the yarn is placed in water at 90l00 C. in a relaxed state followed by drying in a relaxed state, it is found that the yarn has an excellent spiral type of crimp. Retention of the crimp on repeated wetting and drying is found to be superior to that of two-component yarns made outside the scope of the present invention. Further examination of the yarn filaments at high magnification shows that the filaments are wrinkled or wavy on one component while the other component is substantially straight. In addition, the yarn is more bulky than other yarns having the same crimp.
The essential factor in producing the fibers of this invention is the extrusion of two streams of viscoses, one containing a coagulation modifier and the other containing no modifier, in side-by-side relationship through elongated spinneret openings to produce filaments having narrow, elongated cross sections.
The modified viscose must be spun at a salt index of at least about 5 and preferably the index is at least about 10. The unmodified viscose must be spun at an index of at least about 2 and is preferably spun at an index in the range of about 2 to about 5 although high indices may be employed in some cases. If higher indices are employed with the unmodified viscose, then the amount of modifier which is allowed to accumulate in the spinning bath due to the modifier being leached from the spinning filaments must to kept at a very low level in order to obtain the desired filament cross section.
The composition of the viscoses used in the process of this invention is not critical. Viscoses produced with from about 27 ltO about 43% carbon disulfide based on the dry weight of the pulp are satisfactory. Preferably the modified viscose is produced with at least about 35% carbon disulfide. The viscose may contain from about 5.5 to about 9.5% recoverable cellulose and from about 4 to about 8% alkali.
Coagulating \and regenerating baths suitable for use in the present invention contain from about 6.5 to about 10% sulfuric acid, from about 12 to about 23% sodium sulfate, and at least about 3% zinc sulfate in addition to the coagulation modifier. Other metal salts which may supplement the action of the Zinc sulfate may be added if desired. The acidity of the bath should be regulated to as low a level as is commensurate with satisfactory spinning.
Addition of a coagulation modifier to the viscose is necessary in order to produce the desired filament structure.
A group of preferred coagulation modifiers which are suitable for use in the process of this invention are as follows:
A. Quaternary ammonium compounds of the formula wherein the Rs are organic groups which contain no more than four aliphatic carbon atoms, at least three of the said groups containing only aliphatic carbon atoms and the fourth of the said groups containing no more than one phenyl radical, and where X- in an anion having substantially no surface activity. The use of these compounds is disclosed in United States Patent 2,536,014. Suitable compounds in this group which may be mentioned are benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium chloride, phenyltrimethylammonium hydroxide, tetraethanolammonium hydroxide, tetraethylammonium bromide, tetramet-hylammonium iodide, tetrapropylammonium hydroxide tetrabutylammonium chloride, tributylpropylammonium hydroxide, tri(beta hydroxyethyl)methylammonium hydroxide, tributyl(betahydroxyethyDammonium iodide, etc. The preferred agents of this class are those in which all four organic groups attached to the nitrogen atom are hydrocarbon groups or hydroxyl-substituted hydrocarbon groups and in which the radical X is hydroxyl or halogen of atomic weight above 19, i.e., chlorine, bromine or iodine. The most useful modifiers of this group are the quaternary ammonium hydroxides having a total of not more than ten carbon atoms in the molecule and in which all organic groups are hydrocaroon or hydroxyl-substituted hydrocarbon.
B. Aliphatic monoamines having at least four carbon atoms but containing no radical of more than six carbon atoms. The use of these compounds is disclosed in United States Patent 2,535,044. Suitable compounds in this group which may be mentioned are triethanolamine, triethylamine, diethanolamine, butylmonoethanolamine, diethylaminoethanol, n-amylamine, diethylamine, dipropylamine, n-butylamine, ethyldiethanol amine, dipropanolamine, propylpropano-lamine, hex'anolamine, amyldiethanolamine, butylmethylethanolamine, propylethanolamine, cyclohexylethanolamine, N methylcyolohexyl amine, hexarnethyleneimine, piperidine, hexyldiethanolamine, etc. The preferred modifiers of this group are those in which the amino nitrogen is attached to hydrocarbon groups, preferably alkyl groups, and/or to hydroxyalkyl groups.
C. Aliphatic diamines containing two amino nitrogen atoms separated only by carbon atoms and containing a total of at least three carbon atoms, said diamines having the amino groups attached to aliphatic carbon atoms, any monovalent substituent on the amino nitrogens being alkyl groups of 1 to 6 carbon atoms. The use of these compounds is disclosed in British Patent 762,772. Among the aliphatic diamines may be mentioned the following: hexamethylenediamine, tetramethylenediamine, N-methyltrimethylenediamine, N,N'-dimethylethylenediamine, N,N- diisobutylhexamethylenediamine, N,N'-dimethyltrimethylenediarnine, 4,4-dimethylhexamethylenediamine, N,N-diethyl-1,4-cyclohexanediamine, 3-ethoxyethoxyhexamethylenediamine, pentamethylenediamine, octamethylenediamine, N-cyolohexyltetramethylenediamine, N,N-diallylhexamethylenediamine, N-methylnonamethylenediamine, N hexyltrimethylenediamine, N,N dimethylpiperazine, N-butylhexamethylenediarnine, etc. The preferred agents of this class are the Wholly aliphatic, including cycloaliphatic, diamines which contain only carbon and hydrogen besides the two amino nitrogens and which have a total number of carbon atoms between 4 and 14, inclusive, in addition to fulfilling the other requirements stated above. Still more preferred are the polymethylenediamines of 4 to 14 total carbon atoms having from 4 to 8 methylene groups between the amino groups, and their N-alkyl substituted derivatives where the N-alkyl groups have from 1 to 4 carbon atoms inclusive.
D. The salts of N-substituted dithiocarbamic acids. The use of these compounds is disclosed in United States Patent 2,696,423. Among the salts of N-substituted dithiocarbamic acids may be mentioned, sodium amyl dithiocarbamate, sodium bu-tyl monoethanol dithiocarbarnate, sodium hexamethylene bis (dithiocarbamate), potassium pentamethylene dithiooarbamate, sodium methyl dithiocarbamate, sodium benzyl dit-hiocarbama-te, sodium ethylene bis(dithiocarbamate), sodium 1,3-cyclohexane bis(dithiocarbamate), sodium dibutyl dithiooarbamate, sodium dimethyl dithiooarbamate, sodium dioctyl dithiocarbamate, sodium lauryl dithiocarbamate, sodium cyclohexyldithiocarbamate, lithium cyclohexyl dithiocarbamate, sodium N-methyl-cyclohexyldithiocarbamate, the sodium dithiooarbarnates of a mixture of hexadecylamine, 10% octadecylamine, 25% octadecenylamine and 45% octadecadienylamine, sodium hexamet-hylene bis(methyl dithiocarbamate), sodium ethylene bis(methyldithiocarbarnate), sodium 1,4-cyclohexane bis(ethyl dithiocarbamate), sodium xylene bis(dithiocarbarnate), etc. The preferred modifiers of this class are the alkali metal salts of monoor di-N-substituted dithiocarbamic acids containing no more than 10 carbon atoms in any radical and in which the nitrogen is attached to aliphatic carbon.
E. The others of the formula RO-(CH CH O),,R', where R is alkyl or aryl, n is an integer from 1 to 4 inclusive; and R is hydrogen, alkyl or aryl. The use of these compounds as coagulation modifiers is disclosed in British Patent 741,728. Among the ethers may be mentioned phenoxyethanol, ethoxyethanol, butox-yethanol, methoxyethoxyethanol, butoxyethoxyethanol, phenoxyethoxyethanol, ethoxye-thoxyethoxyethanol, butoxyethoxyethoxyethanol, phenoxyethoxyethoxyethanol, butoxyethoxyethoxyethoxyethanol, phenoxyethoxyethoxyethoxyethanol, 1-ethenyloxy-2-methoxyethylene, ethylene glycol diethyl ether, triethylene glycol diethyl ether, tetramethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc. With this class of coagulation modifiers, it has been found that those compounds which, in addition to being soluble in viscose, are difficultly soluble in the coagulating bath, i.e., to the extent of less than 0.5%, give the best results.
F. The polyethylene glycols of formula HO CH CH O) H where n is an integer greater than 3. The use of these compounds is disclosed in Italian Patent 561,552. The polyethylene glycols of formula HO(CH CH O),,H (ethylene oxide polymers) include all such compounds where n is at least equal to 4, i.e., polymers which have a molecular weight of at least 200, and which in addition have the required solubility in viscose. Such compounds are available commercially in various molecular weight ranges, such as 600, 1500 or 2500. For use as coagulation modifiers, the polyethylene glycols having molecular weights between abount 300 and about 1000 are preferred.
Other coagulation modifiers, as are known in the art, may also be employed in place of the listed compounds. Various suitable ones are described in United States Patents 2,777,775; 2,792,278; 2,792,279; 2,792,280 and 2,792,281; British Patents 723,435; 730,541; 748,147 and 765,905, and French Patents 1,102,898 and 1,111,580.
The yarn should be stretched at least about 40% while passing through the bath. Where a hot secondary bath is used, the stretch may be concentrated in this bath or it may be divided between the two baths as desired. If a hot secondary bath is not employed, then all of the stretch is imposed on the yarn while passing through the coagulating and regenerating bath by means of tension-type roller guides.
Preferably the ratio of the yarn draw-off speed to the linear speed at which the viscose is extruded is at least 1.0. This is particularly true where the denier per filament is low (below 8) since under these conditions the desired elongated shape of the filament cross section may not be realized if the ratio is too low. Likewise, the ratio should be at least 1.0 if the ratio of length to width of the spinneret opening is below about 8.
After the yarn leaves the bath, it is wound into a cake in a centrifugal spinning bucket or wound on a bobbin and thereafter purified and dried in the conventional manner.
After purification, the yarn is preferably given additional stretch after thorough wetting and is then dried in the stretched condition. The stretching is conveniently applied by passing the yarn through a slashing machine of the type used in the production of tire cord yarn. If the customary aqueous finish is applied to the yarn, the yarn is wetted with this before stretching.
The yarn erim-ps readily when allowed to relax in hot water followed by drying in a relaxed state. Instead of water, various aqueous solutions as are well known in the art may be used in the crimping operation.
The fibers of this invention may be used wherever rayon fibers are customarily employed, however, they are particularly suitable for the production of tufted carpets and cut pile fabrics.
Many modifications of the invention described herein will be apparent to those skilled in the art from a reading of the above without a departure from the inventive concept.
This application is a division of my copending application, Serial No. 770,761, filed October 30, 1958, now US. Patent No. 3,050.823.
What is claimed is:
l. A process for the production of regenerated cellulose fibers comprising essentially extruding through elongated spinneret openings having long axes at least about 8 times longer than the short axes into a coagulating and regenerating bath containing from about 6.5 to about 10% sulfuric acid, from about 12 to about 23% sodium sulfate and at least about 3% zinc sulfate, pairs of streams of viscoses in side-by-side relationship, the first of said viscoses containing a small amount of a coagulation modifier and having a salt index of at least about 5, the second of said viscoses containing no coagulation modifier and having a salt index at least about 3 units lower than the salt index of said first viscose, coagulating and regenerating said pairs of streams of viscoses to form integral regenerated cellulose fibers containing two longitudinal ribbon-like components disposed side-byside, and stretching the integral fibers at least about 40% during coagulation and regeneration.
2. The process of claim 1 wherein the long axes of the narrow spinneret openings are about 16 times longer than the short axes.
3. The process of claim 1 wherein said first viscose has a salt index of at least about 10.
4. The process of claim 1 wherein the second viscose has a salt index of from about 2 to about 5.
5. The process of claim 1 wherein the narrow elongated spinneret openings are substantially rectangular in shape.
6. A process for the production of regenerated cellulose fibers comprising essentially extruding through substantially rectangular spinneret openings having longer axes at least about 8 to 10 times the length of the shorter axes into a coagulating and regenerating bath containing from about 6.5 to about 10% sulfuric acid, from about 12 to about 23 to sodium sulfate and at least about 3% zinc sulfate, pairs of streams of viscoses in side-by-side relationship, the first of said viscoses containing a small amount of a coagulation modifier and having a salt index of at least about 10, the second of said viscoses containing no coagulation modifier and having a. salt index of from about 2 to about 5, coagulating and regenerating said pairs of streams of viscoses to form integral regenerated cellulose fibers containing two longitudinal ribbon-like components disposed side-by-side, and stretching the integral fibers at least about 40% during coagulation and regeneration.
7. A process for the production of regenerated cellulose ttibers consisting of extruding through a plurality of elongated openings radially disposed with respect to their long axes in a spinneret face, each opening having a Width of about 0.002 inch and a length of about 0.036 inch, into a coagulating and regenerating bath maintained at about 60 C. and containing about 8% sulfuric acid, about 17.5% sodium sulfate, and about 9.5% zinc sulfate, a pairs of streams of viscoses in side-by-side relationship, the first of said viscoses prepared using about 40% carbon bisulfide based on the air dry weight of the pulp and containing about 5.0% recoverable cellulose and about 6.1% alkali, calculated as sodium hydroxide, and about 0.6% by weight sodium N-methylcyclo-hexyldithiocarbamate coagulation modifier and ripened to a viscosity of about 39 poises and a salt index of about 14.4, the second the second of said viscoses prepared using about 30% carbon bisulfide based on the air dry weight of the pulp and containing about 8.6% recoverable cellulose and about 5.3% alkali, calculated as sodium hydroxide, and ripened to a viscosity of about 46 poises and a salt index of about 3.0, coagulating and regenerating said pairs of streams of viscoscs to form integral regenerated cellulose fibers containing two longitudinal ribbon-like components disposed side-by-side, and stretching the integral fibers about 50% while treating them with an aqueous solution at about 0, containing about 2% sulfuric acid, about 4% sodium sulfate, and about 2% zinc sulfate.
References Cited in the file of this patent UNITED STATES PATENTS 1,964,659 Brumberger June 26, 1934 2,013,688 Kinsel la Sept. 10, 1935 2,428,046 Sisson et al. Sept. 30, 1947 2,535,044 Oox Dec. 26, 1950 2,535,945 Cox Dec. 26, 1950 FOREIGN PATENTS 132,043 Japan Oct. 14, 1939 514,638 Great Britain Nov. 14. 1939
Claims (1)
1. A PROCESS FOR THE PRODUCTION OF REGENERATED CELLULOSE FIBERS COMPRISING ESSENTIALLY EXTRUDING THROUGH ELONGATED SPINNERET OPENINGS HAVING LONG AXES AT LEAST ABOUT 8 TIMES LONGER THAN THE SHORT AXES INTO A COAGULATING AND REGENERATING BATH CONTAINING FROM ABOUT 6.5 TO ABOUT 10% SULFURIC ACID, FROM ABOUT 12 TO ABOUT 23% SODIUM SULFATE AND AT LEAST ABOUT 3% ZINC SULFATE, PAIRS OF STREAMS OF VISCOSES IN SIDE-BY-SIDE RELATIONSHIP, THE FIRST OF SAID VISCOSES CONTAINING A SMALL AMOUNT OF A COAGULATION MODIFIER AND HAVING A SALT INDEX OF AT LEAST ABOUT 5, THE SECOND OF SAID VISCOSES CONTAINING NO COAGULATION MODIFIER AND HAVING A SALT INDEX AT LEAST ABOUT 3 UNITS LOWER THAN THE SALT INDEX OF SAID FIRST VISCOSE, COAGULATING AND REGENERATING SAID PAIRS OF STREAMS OF VISCOSES TO FORM INTEGRAL REGENERATED CELLULOSE FIBERS CONTAINING TWO LONGITUDINAL RIBBON-LIKE COMPONENTS DISPOSED SIDE-BYSIDE, AND STRETCHING THE INTEGRAL FIBERS AT LEAST ABOUT 40% DURING COAGULATION AND REGENERATION.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US169988A US3112986A (en) | 1958-10-30 | 1962-01-08 | Process for the production of crimpable regenerated cellulose fibers and yarn |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US77076158 US3050823A (en) | 1958-10-30 | 1958-10-30 | Crimpable regenerated cellulose fibers and yarn |
US169988A US3112986A (en) | 1958-10-30 | 1962-01-08 | Process for the production of crimpable regenerated cellulose fibers and yarn |
Publications (1)
Publication Number | Publication Date |
---|---|
US3112986A true US3112986A (en) | 1963-12-03 |
Family
ID=26865570
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US169988A Expired - Lifetime US3112986A (en) | 1958-10-30 | 1962-01-08 | Process for the production of crimpable regenerated cellulose fibers and yarn |
Country Status (1)
Country | Link |
---|---|
US (1) | US3112986A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3209402A (en) * | 1962-03-07 | 1965-10-05 | Celanese Corp | Apparatus for producing multicom-ponent filaments and yarns |
US3248466A (en) * | 1958-10-30 | 1966-04-26 | Beaunit Corp | Process for producing two component crimpable regenerated cellulose fiber |
US3277225A (en) * | 1963-02-13 | 1966-10-04 | Western Electric Co | Methods and apparatus for multiple extrusion of plastics |
US3303252A (en) * | 1963-03-19 | 1967-02-07 | Philadelphia Insulated Wire Co | Method of forming products extruded from plastic material |
US4364890A (en) * | 1978-11-14 | 1982-12-21 | Svenska Rayon Ab | Procedure for the preparation of crimped high-wet-modulus staple fibres |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1964659A (en) * | 1933-02-09 | 1934-06-26 | Delaware Rayon Company | Spinnerette |
US2013688A (en) * | 1929-01-02 | 1935-09-10 | Celanese Corp | Apparatus for the manufacture of artificial filaments or the like |
GB514638A (en) * | 1937-05-11 | 1939-11-14 | Ig Farbenindustrie Ag | Improvements in the manufacture of artificial silk |
US2428046A (en) * | 1943-08-03 | 1947-09-30 | Wayne A Sisson | Artificial filaments |
US2535044A (en) * | 1947-04-26 | 1950-12-26 | Du Pont | Spinning of viscose |
US2535045A (en) * | 1947-04-26 | 1950-12-26 | Du Pont | Spinning of viscose |
-
1962
- 1962-01-08 US US169988A patent/US3112986A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2013688A (en) * | 1929-01-02 | 1935-09-10 | Celanese Corp | Apparatus for the manufacture of artificial filaments or the like |
US1964659A (en) * | 1933-02-09 | 1934-06-26 | Delaware Rayon Company | Spinnerette |
GB514638A (en) * | 1937-05-11 | 1939-11-14 | Ig Farbenindustrie Ag | Improvements in the manufacture of artificial silk |
US2428046A (en) * | 1943-08-03 | 1947-09-30 | Wayne A Sisson | Artificial filaments |
US2535044A (en) * | 1947-04-26 | 1950-12-26 | Du Pont | Spinning of viscose |
US2535045A (en) * | 1947-04-26 | 1950-12-26 | Du Pont | Spinning of viscose |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3248466A (en) * | 1958-10-30 | 1966-04-26 | Beaunit Corp | Process for producing two component crimpable regenerated cellulose fiber |
US3209402A (en) * | 1962-03-07 | 1965-10-05 | Celanese Corp | Apparatus for producing multicom-ponent filaments and yarns |
US3277225A (en) * | 1963-02-13 | 1966-10-04 | Western Electric Co | Methods and apparatus for multiple extrusion of plastics |
US3303252A (en) * | 1963-03-19 | 1967-02-07 | Philadelphia Insulated Wire Co | Method of forming products extruded from plastic material |
US4364890A (en) * | 1978-11-14 | 1982-12-21 | Svenska Rayon Ab | Procedure for the preparation of crimped high-wet-modulus staple fibres |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2535044A (en) | Spinning of viscose | |
US2852333A (en) | Viscose spinning process | |
US2535045A (en) | Spinning of viscose | |
US2852334A (en) | Method of producing viscose rayon | |
US3112986A (en) | Process for the production of crimpable regenerated cellulose fibers and yarn | |
US2439813A (en) | Artificial filament | |
US3050823A (en) | Crimpable regenerated cellulose fibers and yarn | |
US2860480A (en) | Regenerated cellulose structures and process for producing them | |
US2892729A (en) | Process of producing viscose rayon | |
US3026169A (en) | Manufacture of viscose rayon | |
US2895787A (en) | Process of producing all skin rayon | |
US3019509A (en) | Crimped regenerated cellulose fibers | |
US2910341A (en) | Spinning viscose | |
US3097414A (en) | Woodell | |
US2962341A (en) | Viscose modification | |
US3539678A (en) | High speed spinning method of viscose rayon filaments having high wet modulus | |
US2792281A (en) | Viscose composition and method of spinning | |
US2904446A (en) | Process of producing viscose rayon | |
US2849274A (en) | Producing all skin viscose rayon | |
US3182107A (en) | Method of producing all-skin viscose rayon | |
US2906634A (en) | Method of producing viscose rayon | |
US2893820A (en) | Process for the production of regenerated cellulose filaments | |
US2845327A (en) | Method of producing viscose rayon | |
US2307864A (en) | Method of spinning artificial filaments | |
US2986446A (en) | Crimped regenerated cellulose fibres |