EP3536831A1 - Fibre lyocell comportant une nouvelle section transversale - Google Patents

Fibre lyocell comportant une nouvelle section transversale Download PDF

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Publication number
EP3536831A1
EP3536831A1 EP18160130.3A EP18160130A EP3536831A1 EP 3536831 A1 EP3536831 A1 EP 3536831A1 EP 18160130 A EP18160130 A EP 18160130A EP 3536831 A1 EP3536831 A1 EP 3536831A1
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EP
European Patent Office
Prior art keywords
fiber
fibers
lyocell
pulp
lyocell fiber
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.)
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EP18160130.3A
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German (de)
English (en)
Inventor
Martina OPIETNIK
Gabriele Schild
Verena Silbermann
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Lenzing AG
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Lenzing AG
Chemiefaser Lenzing AG
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Priority to EP18160130.3A priority Critical patent/EP3536831A1/fr
Priority to PCT/EP2019/055516 priority patent/WO2019170714A1/fr
Priority to TW108107363A priority patent/TW201938669A/zh
Publication of EP3536831A1 publication Critical patent/EP3536831A1/fr
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts

Definitions

  • the present invention relates to a lyocell fiber with a novel cross sectional structure, a method for producing same as well as to products comprising the lyocell fiber.
  • Fiber based fibers are employed in a wide variety of applications. Due to ever increasing demands even for such fibers based on renewable resources such as wood attempts have been made to increase the variety of raw materials which may be employed for the production of such fibers. At the same time a demand exists towards a further functionalization of such fibers, targeting specific fiber properties. Another aim is to mimic properties and structure of natural fibers. Fibers based on cellulose regeneration differ in their structure from natural fibers in that they typically do not show any internal /lumen. For example viscose fibers show an oval cross section comprising a dense sheath and a sponge like core of the fiber.
  • Lyocell fibers on the other hand show a circular cross section with a three layered structure, comprising an outer compact skin with a thickness of 100 to 150 nm and a small pore size of from 2 to 5 nm, followed by a middle layer with increasing porosity and a dense, non-porous core.
  • the fiber in accordance with the present invention is a lyocell fiber with a novel structure of the cross section, as compared to standard lyocell fibers. While the three layered structure known from standard lyocell fibers is maintained, at least the inner core layer shows an increased porosity, as compared with standard lyocell fibers.
  • increased porosity refers to the fact that the novel fibers as described herein do show a staining behavior differing from standard Lyocell fibers.
  • the novel fibers in accordance with the present invention can be stained over the entire cross section with fluorescent dyes
  • a quantitative measure of this novel property can be seen in the possibility to stain the entire cross section of a fiber using the methodology as described in example 5.
  • Fibers in accordance with the present invention show a staining (using the method as described in example 5) over the entire cross section after 24 h or less, preferably 12 h or less, even more preferably 6 h or less, such as 3 h or less.
  • the surface layer may be less thick and/or the pore size, which is typically for standard lyocell fibers in the range of from 2 to 5 nm, may be larger.
  • the fiber in accordance with the present invention is a lyocell fiber.
  • the lyocell process is well known in the art and relates to a direct dissolution process of cellulose wood pulp or other cellulose-based feedstock in a polar solvent (for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids).
  • a polar solvent for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids.
  • NMMO N-methylmorpholine N-oxide
  • ionic liquids for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids.
  • the technology is used to produce a family of cellulose staple fibers (commercially available from Lenzing AG, Lenzing, Austria under the trademark TENCEL® or TENCELTM) which are widely used in the textile and nonwoven industry.
  • Other cellulose bodies from lyocell technology have also been produced.
  • the solution of cellulose is extruded in a so called dry-wet-spinning process by means of a forming tool and the moulded solution is guided for example over an air gap into a precipitation bath, where the moulded body is obtained by precipitation of the cellulose.
  • the molding is washed and optionally dried after further treatment steps.
  • Such lyocell fibers are well known in the art and the general methodology to produce same is for example disclosed in US 4,246,221 and its analytics in the BISFA ( The International Bureau for the Standardization of Man-Made Fibers) publication "Terminology of Man-Made Fibres", 2009 editi on. Both references are included herewith in their entirety by reference.
  • lyocell fiber as employed herein defines a fiber obtained by this process, as it has been found that fibers in accordance with the present invention differ greatly from fibers for example obtained from a meltblown process, even if using a direct dissolution process of cellulose wood pulp or other cellulose-based feedstock in a polar solvent (for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids) in order to produce the starting material.
  • a polar solvent for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids
  • hemicelluloses refers to materials known to the skilled person which are present in wood and other cellulosic raw material such as annual plants, i.e. the raw material from which cellulose typically is obtained. Hemicelluloses are present in wood and other plants in form of branched short chain polysaccharides built up by pentoses and/or hexoses (C5 and / or C6-sugar units). The main building blocks are mannose, xylose, glucose, rhamnose and galactose. The back bone of the polysaccharides can consist of only one unit (f.e. xylan) or of two or more units (e.g. mannan).
  • hemicelluloses as known by the skilled person and as employed herein comprises hemicelluloses in its native state, hemicelluloses degraded by ordinary processing and hemicelluloses chemically modified by special process steps (e. g. derivatization) as well as short chain celluloses and other short chain polysaccharides with a degree of polymerization (DP) of up to 500.
  • DP degree of polymerization
  • the pulps preferably employed in the present invention do show as outlined herein a high content of hemicelluloses. Compared with the standard low hemicellulose content pulp employed for the preparation of standard lyocell fibers the preferred pulps employed in accordance with the present invention do show also other differences, which are outlined below.
  • the pulps as employed herein display a more fluffy appearance, which results after milling (during preparation of starting materials for the formation of spinning solutions for the lyocell process), in the presence of a high proportion of larger particles.
  • the bulk density is much lower, compared with standard pulps having a low hemicellulose content.
  • This low bulk density requires adaptions in the dosage parameters (f.e. dosage from at least 2 storage devices).
  • the pulps employed in accordance with the present invention are more difficult to impregnate with NMMO. This can be seen by evaluating the impregnating behavior according to the Cobb evaluation.
  • the pulp employed for the preparation of the lyocell products, preferably fibers, as described herein has a scan viscosity in the range of from 300-440 ml/g, especially 320-420 ml/g, more preferably 320 to 400 ml/g.
  • the scan viscosity is determined in accordance with SCAN-CM 15:99 in a cupriethylenediamine solution, a methodology which is known to the skilled person and which can be carried out on commercially available devices, such as the device Auto PulplVA PSLRheotek available from psl-rheotek.
  • the scan viscosity is an important parameter influencing in particular processing of the pulp to prepare spinning solutions.
  • lyocell process and lyocell technology relate to a direct dissolution process of cellulose wood pulp or other cellulose-based feedstock in a polar solvent (for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids).
  • a polar solvent for example N-methylmorpholine N-oxide [NMMO, NMO] or ionic liquids.
  • the technology is used to produce a family of cellulose staple fibers (commercially available from Lenzing AG, Lenzing, Austria under the trademark TENCEL® or TENCELTM) which are widely used in the textile and nonwoven industry.
  • Other cellulose bodies from lyocell technology have also been produced.
  • the solution of cellulose is usually extruded in a so called dry-wet-spinning process by means of a forming tool and the moulded solution gets for example over an air gap into a precipitation bath, where the moulded body is obtained by precipitation of the cellulose.
  • the moulding is washed and optionally dried after further treatment steps.
  • a process for production of lyocell fibers is described, for instance, in US 4,246,221 , WO 93/19230 , WO95/02082 or WO97/38153 .
  • lyocell fibers with enhanced porosity of the core layer of a lyocell fiber show, due to the specific structure, improved properties, such as improved dyeability, increased enzymatic degradability, etc.
  • Standard lyocell fibers are currently commercially produced from high quality wood pulps with high ⁇ -cellulose content and low non-cellulose contents such as hemicelluloses.
  • Commercially available lyocell fibers such as TENCELTMfibers produced from Lenzing AG, show excellent fiber properties for non-wovens and textile applications.
  • the present invention overcomes the shortcomings of the state of the art by providing lyocell fibers as described herein.
  • these are produced from hemicellulose-rich pulps with a hemicellulose content of at least 7 wt.-%.
  • hemicellulose-rich pulps with a hemicellulose content of at least 7 wt.-%.
  • high hemicellulose content surprisingly, for lyocell fibers of the present invention, gives rise to an increased porosity of the core layer of the lyocell fiber structure, while having only minor effect on the mechanical properties of the fibers.
  • the present invention surprisingly achieves the tasks as outlined above while using cellulose based raw material with a higher hemicelluloses content, as compared for standard lyocell fibers.
  • the content of hemicelluloses in the pulps may be from 7 wt.-% up to 25 wt.-%, such as from 8 to 20, and in embodiments from 10 to 15 wt.-%.
  • the hemicellulose content may be adjusted according to procedures known in the art.
  • the hemicellulose may be the hemicelluloses originating from the woof from which the pulp is obtained, it is however also possible to add individual hemicelluloses depending on the desired fiber properties from other sources to high purity cellulose with a low original hemicellulose content.
  • the addition of individual hemicelluloses may also be employed to adjust the composition of the hemicelluloses content, for example to adjust the ratio of hexoses to pentoses.
  • the pulp enabling the preparation of the fibers in accordance with the present invention preferably shows a ratio of C5/xylan to C6/mannan of from 125:1 to 1:3, preferably in the range of 25:1 to 1:2, such as from 10:1 to 1:1.
  • the hemicellulose content may be 7 wt.-% or more, preferable 10 wt.-% or more and in embodiments up to 25 wt.-% or even 30 wt.-%.
  • the xylan content is 5 wt.-% or more, such as 8 wt.-% or more, and in embodiments 10 wt.-% or more.
  • the mannan content is 3 wt.-% or more, such as 5 wt.-% or more. In other embodiments the mannan content, preferably in combination with a high xylan content as defined above, may be 1 wt.-% or less, such as 0.2 wt.-% or 0.1 wt.-% or less.
  • the fibers in accordance with the present invention typically have a titer of 6.7 dtex or less, such as 2.2 dtex or less, such as 1.7 dtex, or even lower, such as 1.3 dtex or even lower, depending on the desired application. If the fiber is intended to be used in non-woven applications a titer of from 1.5 to 1.8 dtex typically is suitable while for textile applications lower tites such as from 1.2 to 1.5 dtex are suitable. However, the present invention also covers fibers with much lower titers, with suitable lower limits for titers being 0.5 dtex or higher, such as 0.8 dtex or higher, and in embodiments 1.3 dtex or higher.
  • the fiber in accordance with the present invention preferably shows a reduced crystallinity, preferably of 40% or less.
  • the fiber in accordance with the present invention preferably shows a WRV of 70% or more, more preferably 75% or more.
  • Illustrative ranges of WRV of the fibers of the present invention, in particular in combination with the crystallinity values described herein, are form 72% to 90%, such as from 75% to 85%.
  • the fiber in accordance with the present invention does not show any sulfuric smell so that olfactoric drawbacks of viscose fibers are overcome, while properties such as WRV and working capacity enable the use of the fibers of the present invention as viscose replacement fibers.
  • the fiber in accordance with the present invention in isolation or in any combination with features outlined above as preferred for the claimed fiber, has a crystallinity of 40 % or less, preferably 39 % or less.
  • fibers to be employed for non woven applications do show preferably a low crystallinity of for example from 39 to 30%, such as from 38 to 33 %.
  • the present invention however is not limited to these exemplary crystallinity values.
  • the fibers in accordance with the present invention do show a reduced crystallinity of 40 % or less.
  • the fiber in accordance with the present invention may be prepared using lyocell technology employing a solution of cellulose and a spinning process employing a precipitation bath according to standard lyocell processes, known to the skilled person. It is important that the process employs a solution in equilibrium state in accordance with large scale processing methods, as this enhances the properties and structures associated with the present invention, without sacrificing the mechanical properties to an extend detrimental for the intended end use.
  • the fiber in accordance with the present invention shows a novel type of distribution of the hemicelluloses over the cross section of the fiber. While for standard lyocell fibers the hemicelluloses is concentrated within the surface region of the fiber the fibers in accordance with the present invention show an even distribution of the hemicelluloses over the entire cross section of the fiber. Such a distribution enhances the functionality of the fiber, as hemicelluloses increase for example binding properties towards other additives with a matching chemical reactivity. In addition the even distribution of the hemicelluloses may also contribute towards stabilizing the novel structure of the fibers in accordance with the present invention, comprising larger pores volumes in the surface layer and a porous core layer. This novel structure enhances uptake as well as retention of other molecules, such as dyes or moisture and also contributes towards a faster degradation, in particular biological (enzymatic) degradation.
  • the fibers in accordance with the present invention may be employed for a variety of applications, such as the production of non-woven fabrics, but also textiles.
  • the fibers in accordance with the present invention may be employed as the only fiber of a desired product or they maybe mixed with other types of fibers.
  • the mixing ratio can depend from the desired end use. If for example a non-woven or textile product with enhanced coloring and color retention is desired the fibers in accordance with the present invention may be present in a higher amount, relative to other fibers according to the prior art, in order to secure the desired properties, while in other applications a lower relative amount of fibers of the present invention may be sufficient.
  • parameter values and ranges as defined herein in relation to fibers refer to properties determined with fibers derived from pulp and containing only additives, such as processing aids typically added to the dope as well as other additives, such as matting agents (TiO 2 , which often is added in amounts of 0.75 wt.-%), in a total amount of up to 1 wt.-% (based on fiber weight).
  • additives such as processing aids typically added to the dope as well as other additives, such as matting agents (TiO 2 , which often is added in amounts of 0.75 wt.-%), in a total amount of up to 1 wt.-% (based on fiber weight).
  • TiO 2 matting agents
  • the unique and particular properties as reported herein are properties of the fibers as such, and not properties obtained by addition of particular additives and/or post spinning treatments (such as fibrillation improving treatments etc.).
  • the fibers as disclosed and claimed herein may comprise additives, such as inorganic fillers etc. in usual amounts as long as the presence of these additives has no detrimental effect on dope preparation and spinning operation.
  • additives such as inorganic fillers etc.
  • the type of such additives as well as the respective addition amounts are known to the skilled person.
  • 3 different fibers were produced using 3 different types of pulp with different hemicellulose contents (table 1).
  • the lyocell fibers were produced according to WO93/19230 dissolving the pulps in NMMO and spinning them over an air-gap into a precipitation bath to receive fibers with titers from 1.3 dtex to 2.2 dtex, without and with matting agent (0.75% TiO 2 ).
  • Table 1 Sugar contents of the different pulps for the lyocell fiber production sugar [%ATS] reference pulp hemi-rich pulp 1 hemi-rich pulp 2 Glucan 95.5 82.2 82.3 Xylan 2.3 8.3 14 Mannan 0.2 5.7 ⁇ 0.2 Arabinan ⁇ 0.1 0.3 ⁇ 0.1 Rhaman ⁇ 0.1 ⁇ 0.1 ⁇ 0.1 Galactan ⁇ 0.1 0.2 ⁇ 0.1
  • Fiber 1 is produced from hemi-rich pulp 1 and fiber 2 from hemi-rich pulp 2.
  • the standard lyocell (CLY) fibers are produced from the standard lyocell reference pulp. Bright indicates a textile fiber without matting agent, whereas the dull fibers contain the matting agent identified above.
  • Table 2 Fiber properties (working capacity determined in accordance with BISFA definitions) fiber type Titer [dtex] working capacity [cN/tex*%] FFk [cN/tex] FDk [%] 1.3 dtex / 38 mm fiber 1 bright 1.33 410 31 13.2 1.3 dtex / 38 mm CLY standard bright 1.28 491 35.7 13.8 1.7 dtex / 38 mm fiber 1 bright 1.69 380 30.4 12.5 1.7 dtex / 38 mm CLY standard bright 1.65 571 38.6 14.8 2.2 dtex / 38 mm fiber 1 bright 2.12 339 28.2 12.1 2.2 dtex / 38 mm CLY standard bright 2.14 559 41.7 13.4 1.7 dtex / 38 mm fiber 1 dull 1.67 333 28.7 11.6 1.7 dtex / 38 mm CLY standard dull 1.71 384 32.1 11.9 1.7 dtex /38 mm fiber 2 dull 1.72 315 27.6 11.4 1.7 dtex /
  • the displayed results show that the fibers in accordance with the present invention may be prepared over the commercially relevant range of fiber titers, while maintaining sufficient mechanical properties, in particular working capacity, to render these fibers suitable as viscose replacement fibers.
  • Crystallinities of the fibers of Example 1 are measured using a FT/IR with a Bruker MultiRAM FT-Raman spectrometer with a Nd-Yag-laser at 1064 nm and 500mW. The fibers are pressed into pellets for a smooth surface. Fourfold determination with a spectral resolution of 4 cm -1 with 100 scans respectively. Evaluation of the measurements was done using a chemometric method (calibration with WAXS-data).
  • crystallinities of the fibers of the present invention decrease by 16 and 15% respectively compared to the standard CLY fibers.
  • Table 3 Crystallinities of the different lyocell fibers fiber type crystallinity [%] 1.3 dtex / 38 mm CLY standard bright 44 1.3 dtex / 40 mm viscose standard bright 29 1.3 dtex / 38 mm fiber 1 bright 37 1.7 dtex / 38 mm CLY standard dull 47 1.7 dtex / 40 mm viscose standard dull 34 1.7 dtex / 38 mm fiber 1 dull 40 1.7 dtex / 38 mm fiber 2 dull 39
  • a defined quantity of dry fibers is introduced into special centrifuge tubes (with an outlet for the water).
  • the fibers are allowed to swell in deionized water for 5 minutes. Then they are centrifuged at 3000 rpm for 15 minutes, whereupon the moist cellulose is weighed right away. The moist cellulose is dried for 4 hours at 105 °C, whereupon the dry weight is determined.
  • the water retention value is a measured value that indicates how much water of a moisture penetrated sample is retained after centrifuging.
  • the water retention value is expressed as a percentage relative to the dry weight of the sample.
  • Table 4 the water retention values of the fibers of the present invention (fiber 1 and 2) compared to the reference fibers are listed and an increase of the WRV by 19% and 26% respectively compared to standard CLY fibers can be observed.
  • the new fibers produced from hemi-rich pulp 1 showed a higher water retention value which indicates an increased pore size and number over the whole fiber cross section.
  • a low WRV is known combined with a very high orientation of the polymer chains described by high crystallinity.
  • the crystallinity decreased significantly underlining a lower orientation of the polymer chains and giving rise to an enhanced pore volume.
  • Table 5 Orientation and porosity of different fiber types.
  • Example 1 fiber 1 bright (1.3 dtex/ 38 mm), CLY standard bright (1.3 dtex / 38 mm) as well as standard viscose standard bright fibers (1.3 dtex / 38 mm) were subjected to staining with Uvitex BHT according to the method of Abu-Rous (J.Appl. Polym.Sci., 2007, 106:2083-2091 ).
  • the fibers obtained were evaluated after different intervals of immersion in the dye solution, at periods of from 5 min to 24 h. Due to the big size of the dye molecules the penetration is restricted to areas with bigger pore volumes. Conclusions can be drawn from the extent of dye penetration about the porous structure of the fiber cross section.
  • the intensity of the color gives indications about the number of pores and voids, their size and chemical binding of the dye molecules to the inner surface of the fiber pores. Chemical binding is mainly attributed to hemicelluloses and non-crystalline regions.
  • the fibers in accordance with the present invention showed a fast and complete staining of the entire cross section of the fiber as shown in Figure 1 .
  • the fiber is more easily penetrated indicating an increased accessibility due to a bigger pore size and number in the new fibers, a lower crystallinity as shown in Example 2 and a higher hemicellulose content over the whole fiber cross section as shown in Example 6.
  • the viscose fibers showed an uptake of the dye up to 3 h, thereafter no further uptake of dye was observed.
  • Example 1 The lyocell fibers evaluated in Example 1 were subjected to an enzymatic peeling test according to Sjöberg et al (Biomacromolecules 6:3146-3151, 2005 ). A viscose fiber with an enhanced xylan content of 7.5% was chosen for comparison from the paper by Schild and Liftinger (2014). This xylan content is close to the xylan content of the new fiber with 6.9%.
  • the test enables the generation of data concerning the hemicellulose distribution over the cross section of fibers, in particular xylan (by HPLC determination) including information relating to different densities and structures of layers (as denser layers show a slower response as well as layers with smaller pore sizes).
  • the standard lyocell fibers (1.3 dtex / 38 mm bright) as well as the xylan enriched viscose fibers (1.3 dtex / 38mm bright) showed a slow peeling rate ( fig. 2 ). This effect is even more pronounced for prolonged peeling times due to the denser cores.
  • the xylan liberation determined corresponds to fibers with high hemicellulose content at the surface of the fiber and a sharp concentration decrease towards the core ( fig. 3 ).
  • the fibers in accordance with the present invention show a peeling behavior corresponding to a fiber structure with an even distribution of the hemicellulose content over the entire cross section. Additionally, the peeling is much faster.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
EP18160130.3A 2018-03-06 2018-03-06 Fibre lyocell comportant une nouvelle section transversale Withdrawn EP3536831A1 (fr)

Priority Applications (3)

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EP18160130.3A EP3536831A1 (fr) 2018-03-06 2018-03-06 Fibre lyocell comportant une nouvelle section transversale
PCT/EP2019/055516 WO2019170714A1 (fr) 2018-03-06 2019-03-06 Fibre lyocell avec section transversale nouvelle
TW108107363A TW201938669A (zh) 2018-03-06 2019-03-06 具新穎剖面的萊纖纖維

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022139727A1 (fr) * 2020-12-21 2022-06-30 Bahcesehir Universitesi Production de fil dentaire à partir de fibres de bois

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WO1998005702A1 (fr) 1996-08-01 1998-02-12 Lenzing Aktiengesellschaft Procede de production d'une suspension de cellulose
US6042769A (en) 1994-06-22 2000-03-28 Acordis Fibres (Holdings ) Limited Lyocell fibre and a process for its manufacture
WO2001062845A1 (fr) * 2000-02-21 2001-08-30 Zimmer Ag Corps moule en cellulose et procede permettant de le produire
US6706237B2 (en) 1996-08-23 2004-03-16 Weyerhaeuser Company Process for making lyocell fibers from pulp having low average degree of polymerization values
US20090004473A1 (en) * 2007-06-29 2009-01-01 Weyerhaeuser Co. Lyocell fibers
US8420004B2 (en) 2009-12-31 2013-04-16 Acelon Chemical And Fiber Corporation Meltblown wetlaid method for producing non-woven fabrics from natural cellulose
WO2014086883A1 (fr) 2012-12-06 2014-06-12 Lenzing Aktiengesellschaft Procédé de production d'un article façonné cellulosique

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US4246221A (en) 1979-03-02 1981-01-20 Akzona Incorporated Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent
WO1993019230A1 (fr) 1992-03-17 1993-09-30 Lenzing Aktiengesellschaft Procede de fabrication d'elements moules cellulosiques et dispositif de mise en oeuvre dudit procede
WO1994028214A1 (fr) 1993-05-24 1994-12-08 Courtaulds Fibres (Holdings) Limited Tremie de stockage et de pre-melange
WO1994028217A1 (fr) 1993-05-24 1994-12-08 Courtaulds Fibres (Holdings) Limited Formation d'un premelange a base de cellulose
WO1995002082A1 (fr) 1993-07-08 1995-01-19 Lenzing Aktiengesellschaft Fibres cellulosiques
US6042769A (en) 1994-06-22 2000-03-28 Acordis Fibres (Holdings ) Limited Lyocell fibre and a process for its manufacture
WO1996033221A1 (fr) 1995-04-19 1996-10-24 Lenzing Aktiengesellschaft Procede de production d'une suspension de cellulose
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