EP0686712B1 - Fibres cellulosiques flexibles avec module et RMN-caractéristiques réduits et procédé pour leur fabrication - Google Patents

Fibres cellulosiques flexibles avec module et RMN-caractéristiques réduits et procédé pour leur fabrication Download PDF

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Publication number
EP0686712B1
EP0686712B1 EP95104358A EP95104358A EP0686712B1 EP 0686712 B1 EP0686712 B1 EP 0686712B1 EP 95104358 A EP95104358 A EP 95104358A EP 95104358 A EP95104358 A EP 95104358A EP 0686712 B1 EP0686712 B1 EP 0686712B1
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EP
European Patent Office
Prior art keywords
spinning
mass
cellulose
tex
additives
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
Application number
EP95104358A
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German (de)
English (en)
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EP0686712A2 (fr
EP0686712A3 (fr
Inventor
Peter Dr. Weigel
Konrad Dr. Frigge
Wolfgang Dr. Wagenknecht
Albrecht Dr. Habil. Bauer
Jürgen Dr. Gensrich
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP0686712A2 publication Critical patent/EP0686712A2/fr
Publication of EP0686712A3 publication Critical patent/EP0686712A3/fr
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Publication of EP0686712B1 publication Critical patent/EP0686712B1/fr
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Classifications

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

Definitions

  • the invention relates to flexible cellulose fibers with a reduced modulus and a reduced degree of NMR order for predominant use in such textile areas where flexible moldings, e.g. textile fibers and filament yarn are produced and required, hereinafter called fibers, and those that are more environmentally friendly than the viscose process N-methylmorpholine-N-oxide (NMMNO) spinning process can be produced, and a Process for their production.
  • flexible moldings e.g. textile fibers and filament yarn are produced and required
  • NMMNO N-methylmorpholine-N-oxide
  • NMMNO and caprolactam derivatives also has good solubility properties for cellulose (US Pat. No. 5,362,867, TW 210359).
  • a special feature of this process is the instability of the solvent under certain conditions at temperatures just above the processing temperature of the spinning solutions, which can lead to an uncontrolled chain reaction.
  • additives are added to the spinning solution with the aim of stabilizing the spinning solution, in particular preventing or at least limiting the breakdown of the cellulose and the decomposition of the NMMNO (DD 201 703, DD 229 708, DD158 656) .
  • a number of substances such as amines, gallates, ascorbic acid, hydroquinone and urea are mentioned by various authors. Propyl gallate has proven to be particularly effective even at low concentrations.
  • the amounts used for stabilization are in a range below 1% based on cellulose.
  • Additives are also used to prevent the threads from sticking during the process Spinning process recommended (DD 218 121) e.g. Polyethylene glycol, or as useful for that Increased tear strength and the modulus of the threads detected (Chanzy, H. et al .: polymer 31: 400-405 (1990).
  • the fibers produced by the NMMNO process are compared to viscose fibers characteristic of high strengths and moduli.
  • the tensile strengths are in general in an approximate range of approx. 20 to 50 cN / tex, where cN / tex centi Newtons per tex means, and the initial moduli in a range above about 1500 cN / tex. It means that the strengths are pleasantly high, but often higher than necessary and the moduli significantly high for an advantageous application in the area of flexible fibers with good textile usage properties in which e.g. the usual, for textile use in clothing proven viscose fibers with initial moduli well below 1500 cN / tex will.
  • the fibers produced with it also have some other disadvantages compared to those which are produced using the conventional viscose process. Among other things, they show brittleness and fibrillation resistance. The values achieved for the elongation at break cannot be satisfactory either, so that Krisoninin et al. (SU 1 224 362) and Romanov et al. (Fiber Chemistry, 21, 4 (1990), 317-320) correct this defect in place of the most commonly used Falling bath from an aqueous NMMNO solution, a solution of NMMNO in isopropanol or amyl alcohol has been described. It also proves to be disadvantageous that the range of variation of the textile-physical characteristic values is small when the production conditions change.
  • the fibers have a relatively high degree of order, which can be seen in the high-resolution 13 C-NMR solid-state spectrum at C-1, C-4 and to a certain extent also at C-6. From the ratio of the line heights (distance of the maximum of the respective line from the baseline of the spectrum) at C-4 at approx. 88 and 85 ppm, a relatively easily accessible measure, it can be seen, for example, that this ratio has a value ⁇ 1 for flexible viscose fibers , 0, while for NMMNO fibers it is above one, for example 1.35.
  • the object of the present invention is to provide such flexible cellulose fibers, all Do not have disadvantages of the prior art to specify.
  • Another procedural object of the invention is that it is proposed Process for producing the flexible cellulose fibers of the type mentioned lower Investment costs required and less polluting than the viscose process.
  • An additional object of the invention is that this to be proposed on the Process based on the NMMNO process with regard to the range of variation textile-physical parameters about changes in manufacturing conditions allows great scope.
  • the tasks on the cellulose fiber side are solved with a flexible cellulose fiber with a reduced module and a reduced degree of NMR order, especially for textile use, which is achieved by pressing solutions of cellulose in water-containing NMMNO (N-methylmorpholine-N-oxide) through spinnerets over an air gap in an NMMNO-containing aqueous and / or alcoholic precipitation bath, as well as by conventional rinsing, post-treatment and drying with strengths between 15 and 50 cN / tex.
  • NMMNO N-methylmorpholine-N-oxide
  • these flexible cellulose fibers which can be produced in this way are characterized in that they have an initial modulus of less than 1500 cN / tex and in the high-resolution 13 C-NMR solid-state spectrum the ratio of the heights of the lines at 88 ppm and 85 ppm (C-4 range ) above the spectrum baseline is ⁇ 1.
  • the initial module and the NMR order of the cellulose fibers precipitated from cellulose NMMNO water spinning solutions then drastically lower when both the cellulose spinning solution hydrophilic, low molecular weight, organic, soluble in the polymer solution
  • Additives can be added.
  • Amines and amides are suitable as additives for this or other substances containing amino groups, which is one of the nitrogen groups have a neighboring oxygen-containing group.
  • the concentration of additives in the spinning solution, based on the cellulose content of the solution should be at least 1% by mass, amount to a maximum of 200% by mass.
  • a proportion of the additives in the precipitation bath is at least 0.1 mass% and at most 20 mass%, based on the amount of Total fall bath, cheap.
  • Additives are preferably used in which the oxygen-containing group is a Is carbonyl group.
  • the oxygen-containing group is a Is carbonyl group.
  • Urea e.g. Urea, caprolactam, Aminopropanol and / or aminocarboxylic acid used.
  • Several additives can be used as individual components or as Introduce mixture.
  • the concentration of the additives in the spinning solution should be at least 10% by mass and at most 100% by mass. So it is advantageous here, for example, if the concentration of the additives in the spinning solution, based on the cellulose content of the solution at least 4% by mass, at most 75% by mass, preferably at least 10% by mass, at most 50% by mass. Against it in the precipitation bath a proportion of the additives of at least 1% by mass and at most 10% by mass, based on the amount of total precipitation bath preferred.
  • the desired effect also occurs when the water in the precipitation bath partially or completely, preferably completely, by alcohols, in particular is replaced by isopropanol or amyl alcohol, the additives up to their maximum Saturation concentration can be contained in the precipitation bath.
  • the fibers spun in a conventional manner from a nozzle through an air gap into the precipitation bath and aftertreated and dried in the usual way have an initial modulus derived in a known manner from the force / elongation diagram of well below 1500 cN / tex, preferably even below 1200 cN / tex, and / or an NMR order of magnitude of ⁇ 1 characterized by the height ratio in the maximum of the lines at 88 ppm and 85 ppm above the baseline of the high-resolution 13 C-NMR solid-state spectrum in the C-4 range.
  • a spinning solution of 9.5% cellulose in NMMNO monohydrate with 0.1% by mass, based on cellulose, propyl gallate as stabilizing agent was spun in a laboratory extruder with a 20-hole nozzle at a temperature of 90 ° C., being the spinning bath (Precipitation bath) a 10% solution of NMMNO in water was used.
  • the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 34.3 cN / tex wet: 23.2 cN / tex Elongation at break, dry: 5.1% wet: 8.1% Initial module, dry: 2117 cN / tex wet: 311 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 1.35.
  • the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 35.6 cN / tex wet: 10.5 cN / tex Elongation at break, dry: 10.0% wet: 18.1% Initial module, dry: 1922 cN / tex wet: 131 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 1.0.
  • Example 2 using a precipitation bath consisting of a 6% aqueous urea solution.
  • the fiber has the following parameters: Titer: 4.1 tex Tensile strength, dry: 33.1 cN / tex wet: 12.2 cN / tex Elongation at break, dry: 11.5% wet: 17.0% Initial module, dry: 1430 cN / tex wet: 120 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 1.0.
  • the fiber has the following parameters: Titer: 4.0 tex Tensile strength, dry: 28.0 cN / tex wet: 13.2 cN / tex Elongation at break, dry: 13.9% wet: 19.9% Initial module, dry: 446 cN / tex wet: 126 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 0.96.
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 0.98.
  • caprolactam As example 1 with an addition of 25% caprolactam, based on the cellulose content, but additionally in the spinning solution using a spinning bath (precipitation bath) consisting of a 10% aqueous caprolactam solution.
  • the fiber has the following parameters: Titer: 4.0 tex Tensile strength, dry: 31.0 cN / tex wet: 10.9 cN / tex Elongation at break, dry: 12.3% wet: 18.4% Initial module, dry: 1255 cN / tex wet: 110 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 0.95.
  • the fiber has the following parameters: Titer: 4.2 tex Tensile strength, dry: 25.4 cN / tex wet: 10.1 cN / tex Elongation at break, dry: 7.1% wet: 11.9% Initial module, dry: 1580 cN / tex wet: 278 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 0.98.
  • the fiber has the following parameters: Titer: 3.9 tex Tensile strength, dry: 18.3 cN / tex wet: 5.7 cN / tex Elongation at break, dry: 6.1% wet: 23.4% Initial module, dry: 760 cN / tex wet: 63 cN / tex
  • the ratio of the heights of the NMR lines at 88 and 85 ppm is 0.96.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Multicomponent Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (13)

  1. Fibres de cellulose souples à module diminué et degré d'ordre RMN diminué pour l'utilisation textile qu'on obtient par extrusion de solutions de cellulose dans de la solution aqueuse de N-méthyl-morpholine-N-oxyde (NMMNO) par des buses de filature via une course dans l'air dans un bain de précipitation aqueux contenant du NMMNO et/ou alcoolique ainsi que par lavage habituel, post-traitement et séchage avec des résistances à la déchirure comprises entre 15 et 50 cN/tex,
    caractérisé en ce qu'
    à l'état sec, elles possèdent un module initial inférieur à 1500 cN/tex et que dans le spectre de solide de 13C-NMR à haute résolution le rapport des hauteurs de pics à 88 ppm et 85 ppm (domaine C-4) au-dessus de la ligne de base du spectre est ≤ 1.
  2. Procédé de production de fibres de cellulose simples à module diminué et degré d'ordre RMN diminué selon la revendication 1 qu'on obtient par extrusion d'une solution de cellulose dans la solution aqueuse de (NMMNO) par des buses de filature via une course dans l'air dans un bain de précipitation aqueuse contenant du NMMNO et/ou alcoolique et ensuite lavage, post-traitement et séchage de manière habituelle,
    caractérisé en ce qu'
    on ajoute aussi bien à la solution de filature de cellulose qu'au bain de précipitation des additifs organiques hydrophiles, solubles dans la solution de polymère, de bas poids moléculaire, que les additifs sont des amines, des amides ou d'autres substances contenant des groupes amino-, où le groupe contenant l'azote est voisin d'un groupe contenant de l'oxygène, que la concentration des additifs dans la solution de filature, par rapport à la teneur en cellulose de la solution de filature correspond au moins à 1 % en masse et au plus à au moins 200 % en masse et que la teneur massique des additifs au bain de précipitation représente au moins 0,1 % en masse et au plus 20 % en masse.
  3. Procédé selon la revendication 2,
    caractérisé en ce que
    les groupes portant de l'hydrogène sont des groupes carbonyles.
  4. Procédé selon la revendication 2 ou 3,
    caractérisé en ce qu'
    on utilise comme additifs de l'urée, du caprolactame et/ou de l'acide aminocapronique.
  5. Procédé selon la revendication 2 ou 3,
    caractérisé en ce qu'
    on utilise comme additif de l'aminopropanol.
  6. Procédé selon l'une ou plusieurs des revendications 2 à 5,
    caractérisé en ce qu'
    on utilise les additifs sous forme de mélanges de ceux-ci, quand on utilise plusieurs additifs.
  7. Procédé selon l'une ou plusieurs des revendications 2 à 5,
    caractérisé en ce qu'
    on utilise les additifs sous forme de composants individuels, même quand on utilise plusieurs additifs.
  8. Procédé selon l'une ou plusieurs des revendications 2 à 7,
    caractérisé en ce que
    le ou les additifs ajoutés au bain de précipitation correspond(ent) à l'additif ou aux additifs contenu(s) dans la solution de filature.
  9. Procédé selon la revendication 2,
    caractérisé en ce que
    les quantités dans lesquelles on ajoute les additifs à la solution de filature, correspondent à une concentration des additifs dans la solution de filature, par rapport à la teneur en cellulose de la solution de filature, d'au moins 10 % en masse et d'au plus 100 % en masse.
  10. Procédé selon la revendication 2,
    caractérisé en ce que
    la teneur en masse des additifs dans le bain de précipitation représente au moins 1 % en masse et au plus 10 % en masse.
  11. Procédé selon une ou plusieurs des revendications 2 à 4,
    caractérisé en ce qu'
    on remplace en partie ou en totalité l'eau du bain de précipitation par des alcools.
  12. Procédé selon la revendication 11,
    caractérisé en ce qu'
    on remplace totalement l'eau dans le bain de précipitation par des alcools.
  13. Procédé selon la revendication 11 ou 12,
    caractérisé en ce qu'
    on utilise comme alcools l'isopropanol et/ou l'alcool amylique.
EP95104358A 1994-06-10 1995-03-24 Fibres cellulosiques flexibles avec module et RMN-caractéristiques réduits et procédé pour leur fabrication Expired - Lifetime EP0686712B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4420304 1994-06-10
DE4420304A DE4420304C1 (de) 1994-06-10 1994-06-10 Flexible Cellulosefasern mit reduziertem Modul und vermindertem NMR-Ordnungsgrad und deren Herstellung

Publications (3)

Publication Number Publication Date
EP0686712A2 EP0686712A2 (fr) 1995-12-13
EP0686712A3 EP0686712A3 (fr) 1996-05-01
EP0686712B1 true EP0686712B1 (fr) 1998-09-09

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EP95104358A Expired - Lifetime EP0686712B1 (fr) 1994-06-10 1995-03-24 Fibres cellulosiques flexibles avec module et RMN-caractéristiques réduits et procédé pour leur fabrication

Country Status (4)

Country Link
US (1) US5618483A (fr)
EP (1) EP0686712B1 (fr)
AT (1) ATE170938T1 (fr)
DE (2) DE4420304C1 (fr)

Families Citing this family (18)

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Publication number Priority date Publication date Assignee Title
DE19600572B4 (de) * 1996-01-09 2005-03-10 Fraunhofer Ges Forschung Verfahren zur Herstellung von Cellulosefasern und die mit diesem Verfahren hergestellten Fasern
US6471727B2 (en) 1996-08-23 2002-10-29 Weyerhaeuser Company Lyocell fibers, and compositions for making the same
US6331354B1 (en) 1996-08-23 2001-12-18 Weyerhaeuser Company Alkaline pulp having low average degree of polymerization values and method of producing the same
US6210801B1 (en) 1996-08-23 2001-04-03 Weyerhaeuser Company Lyocell fibers, and compositions for making same
US6306334B1 (en) 1996-08-23 2001-10-23 The Weyerhaeuser Company Process for melt blowing continuous lyocell fibers
US6235392B1 (en) 1996-08-23 2001-05-22 Weyerhaeuser Company Lyocell fibers and process for their preparation
DE19737113A1 (de) * 1997-08-27 1999-03-04 Kalle Nalo Gmbh Verfahren und Vorrichtung zur Herstellung eines nahtlosen Folienschlauches auf Cellulosebasis durch Extrudieren
DE19753190B4 (de) * 1997-11-21 2004-02-26 Gerking, Lüder, Dr.-Ing. LYOCELL-Fasern mit verringerter Neigung zum Fibrillieren
US6143884A (en) * 1998-05-09 2000-11-07 Acelon Chemicals & Fiber Corporation Manufacturing process of cellulose viscose with low viscosity
GB9810778D0 (en) * 1998-05-19 1998-07-15 Courtaulds Plc Cellulosic solutions and their uses
US6773648B2 (en) 1998-11-03 2004-08-10 Weyerhaeuser Company Meltblown process with mechanical attenuation
DE10016307C2 (de) * 2000-03-31 2002-05-08 Thueringisches Inst Textil Verfahren zur Herstellung und Verarbeitung einer Celluloselösung
DE10019628A1 (de) * 2000-04-19 2001-10-31 Fraunhofer Ges Forschung Verfahren zur Verringerung des Ordnungsgrades von Cellulose
US6749721B2 (en) 2000-12-22 2004-06-15 Kimberly-Clark Worldwide, Inc. Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition
US6916402B2 (en) * 2002-12-23 2005-07-12 Kimberly-Clark Worldwide, Inc. Process for bonding chemical additives on to substrates containing cellulosic materials and products thereof
AT413287B (de) * 2003-11-25 2006-01-15 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer fasern
US7670459B2 (en) * 2004-12-29 2010-03-02 Kimberly-Clark Worldwide, Inc. Soft and durable tissue products containing a softening agent
TWI667378B (zh) 2014-01-03 2019-08-01 奧地利商蘭精股份有限公司 纖維素纖維

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DE142898C (fr) *
DE218121C (fr) *
DE201703C (fr) *
DE229708C (fr) *
US3767756A (en) * 1972-06-30 1973-10-23 Du Pont Dry jet wet spinning process
US4142913A (en) * 1977-07-26 1979-03-06 Akzona Incorporated Process for making a precursor of a solution of cellulose
US4144080A (en) * 1977-07-26 1979-03-13 Akzona Incorporated Process for making amine oxide solution of cellulose
DD158656A1 (de) * 1981-04-27 1983-01-26 Birgitte Lukanoff Verfahren zur verringerung des celluloseabbaus in aminoxidhaltigen celluloseloesungen
SU1224362A1 (ru) * 1984-06-29 1986-04-15 Предприятие П/Я А-3844 Способ получени целлюлозных волокон
TW210359B (en) * 1992-01-22 1993-08-01 Formosa Chemicals Fibre Corp A spinning method by using spinning solution prepared from pulp cellulose which is dissolved by N-methyl morpholine N-oxide and recycled caprolactam as solvents
US5362867A (en) * 1992-05-27 1994-11-08 Formosa Chemicals & Fibre Corporation Method of making cellulose yarn solution

Also Published As

Publication number Publication date
DE59503497D1 (de) 1998-10-15
EP0686712A2 (fr) 1995-12-13
ATE170938T1 (de) 1998-09-15
EP0686712A3 (fr) 1996-05-01
DE4420304C1 (de) 1995-09-21
US5618483A (en) 1997-04-08

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