WO1998055673A1 - Corps moule cellulosique regenere - Google Patents

Corps moule cellulosique regenere Download PDF

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Publication number
WO1998055673A1
WO1998055673A1 PCT/AT1998/000139 AT9800139W WO9855673A1 WO 1998055673 A1 WO1998055673 A1 WO 1998055673A1 AT 9800139 W AT9800139 W AT 9800139W WO 9855673 A1 WO9855673 A1 WO 9855673A1
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WO
WIPO (PCT)
Prior art keywords
polygalactomannan
viscose
weight
cellulose
solution
Prior art date
Application number
PCT/AT1998/000139
Other languages
German (de)
English (en)
Inventor
Susanna Schiemer
Jörg Schlangen
Original Assignee
Lenzing Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lenzing Aktiengesellschaft filed Critical Lenzing Aktiengesellschaft
Priority to AU76296/98A priority Critical patent/AU7629698A/en
Publication of WO1998055673A1 publication Critical patent/WO1998055673A1/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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • 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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose

Definitions

  • the invention relates to a regenerated cellulosic molding obtained by the viscose process, in particular viscose fibers, according to the preamble of claim 1, a process for their production and the use of the molding according to the invention.
  • regenerated cellulosic moldings is to be understood to mean all cellulosic moldings which are produced by dissolving the cellulose xanthate in alkali (viscose), shaping and coagulating in a precipitation bath while restoring the pure cellulose (e.g. viscose fibers).
  • viscose fibers result, which have a greatly increased absorption capacity compared to unmodified viscose fibers, which is expressed in most cases in increased swelling values or sometimes also in increased values for the water retention capacity.
  • the methods mentioned have not yet become commercially successful. This is due to the fact that either the feed products are too expensive or the modified viscose fibers produced still leave something to be desired in terms of their absorption properties or other fiber properties.
  • cellulose moldings containing polygalactomannans have a very strongly increased absorption capacity with good usage properties, such as e.g. Have strength and elongation values.
  • the polygalactomannans are based on an inexpensive raw material and therefore enable the molded articles according to the invention to be produced economically, even on an industrial scale.
  • Suitable cellulose moldings according to the invention are, in particular, fibers, but also films or, for example, particles obtained by extrusion and fluidization.
  • the dimensional stability is obtained through the high crystallinity and strength of the cellulose, which is why the present invention speaks of a cellulosic backbone even at high levels of polygalactomannans.
  • molded bodies according to the invention in fiber form are particularly suitable as components because of their higher strength and dimensional stability of absorbent nonwoven articles or tampons.
  • Shaped bodies according to the invention with a proportion of polygalactomannan of 30% by weight to 70% by weight, preferably 40% by weight to 50% by weight, based on cellulose, are particularly suitable for use in the area of highly absorbent polymers (super Absorbent Polymers), such as as an absorbent component in diapers.
  • highly absorbent polymers super Absorbent Polymers
  • molded articles according to the invention with a polygalactomannan content of 10% by weight to 30% by weight, based on cellulose, are also outstandingly suitable for various fields of application.
  • the polygalactomannan even if it is not crosslinked, is not or only insignificantly washed out of the molded body in all post-treatment steps and, after drying, can be detected in yields of up to 90% to 100% in the molded body.
  • the polygalactomannan can also be crosslinked with preferably bi- or polyvalent cations or preferably with borate ions.
  • a crosslinked polygalactomannan obviously has the advantage that the polygalactomannan is washed out even less during the aftertreatment of the molded body.
  • An already crosslinked polygalactomannan can be used for the production of the molded body, or the crosslinking takes place in the course of the production of the molded body, e.g. held in the precipitation bath.
  • guar gum contained in guar gum has proven to be particularly suitable for use as polygalactomannan.
  • suitable polygalactomannans are e.g. the carabin obtained from the locust bean gum.
  • a further polysaccharide is contained within the cellulosic framework.
  • Suitable polysaccharides are in particular those that also have an increased absorption capacity and show synergistic viscosity effects with the polygalactomannans used.
  • agar, carraghenan, xanthan or starch have proven to be particularly favorable. With these polysaccharides, the polygalactomannan is embedded in the double helix of the other polysaccharide, whereby gel formation is achieved.
  • polyvinyl alcohol can advantageously also be contained in the molded body according to the invention within the cellulosic framework.
  • Polyvinyl alcohol carries - as well as possibly additionally contained polysaccharides or the use of cross-linked! Polygalactomannan - to ensure that the polygalactomannan is practically not washed out in the aftertreatment of the molded body.
  • a method is used to produce the moldings according to the invention, in which an aqueous solution of the polygalactomannan, in which the polygalactomannan is present in a proportion of up to 10% by weight, typically up to 5% by weight, is prepared, the aqueous solution in the desired mixing ratio a viscose is added, optionally further polysaccharides and / or polyvinyl alcohol are added and the mixed solution is extruded in a manner known per se via a shaping tool into a precipitation bath, insoluble constituents, for example, from the aqueous solution of the polygalactomannan and / or the mixed solution be separated by filtration.
  • the native raw material e.g. Guar gum dissolved.
  • Solutions of polygalactomannans are compared to solutions of other polysaccharides, e.g. Alginates, highly viscous.
  • the native raw material e.g. Guar gum
  • Viscosities of 1% aqueous solutions at 2 to 10 Pas are quite surprising that these viscous solutions can be mixed excellently with the cellulose solution and that it is possible to produce molded articles which contain the polygalactomannans homogeneously distributed.
  • the desired mixing ratio of the polygalactomannan solution to the cellulose solution results from the desired content of polygalactomannan in the resulting molded article, since essentially no polygalactomannan is washed out in the aftertreatment of the cellulosic molded article known from the prior art.
  • insoluble constituents remain in the aqueous medium when the native raw materials of the polygalactomannans are dissolved, it is necessary to remove these constituents from the aqueous Separate solution and or the mixed solution before shaping.
  • a filtration step is particularly suitable for this.
  • the other polysaccharides or polyvinyl alcohol can e.g. can be added to the mixed solution in a dissolved form, but can also be dissolved at the same time with the polygalactomannan.
  • Viscose is an alkaline solution of cellulose xanthate. It is particularly advantageous if the aqueous solution of the polygalactomannane is alkaline and preferably has an alkali content of up to 15% by weight.
  • the polygalactomannan can e.g. already dissolved in dilute sodium hydroxide solution or the alkali content can only be adjusted after the polygalactomannan has dissolved.
  • polygalactomannan If used in an alkaline aqueous solution, it is oxidatively degraded under the influence of air, the viscosity of the solution decreasing. Surprisingly, molded articles which contain non-degraded polygalactomannan do not differ in their properties from those which contain partially degraded polygalactomannan. This makes it possible to simplify the method according to the invention, since solutions with a lower viscosity can be used.
  • An advantageous embodiment of the method according to the invention is accordingly characterized in that the aqueous solution before being added to the viscose at least 30 minutes of exposure to an oxidative medium, e.g. Exposed to air.
  • the aqueous solution can preferably be exposed for 1 hour to 24 hours.
  • the solution can optionally be stirred at elevated temperature.
  • composition of the viscose in terms of cellulose concentration, alkali and sulfur content can be in the range of the common values known from the prior art.
  • polygalactomannan in particular from about 20% by weight based on cellulose, it proves to be advantageous to use in the precipitation bath either as an additional component or as an essential component of organic solvents, e.g. Provide isopropanol or other alcohols.
  • Bi- or polyvalent cations or borates can also be provided in the precipitation bath in order to crosslink the polygalactomannan contained in the molded body.
  • the moldings according to the invention are completely biodegradable and toxicologically harmless due to the use of polygalactomannans.
  • the shaped bodies according to the invention have a greatly increased swelling value in comparison to both unmodified and shaped bodies modified according to the prior art, even with low contents of polygalactomannan.
  • viscose fibers according to the invention e.g. Depending on the guaran content, the following swelling values were measured:
  • the swelling value also called water retention capacity (WRV) indicates the amount of moisture that water-soaked fibers can retain if the wet fiber is spun off at high speeds of rotation.
  • the amount of water determined is essentially within the fibers.
  • the swelling value about 0.5 g of the fiber was placed in a centrifugal vessel and the vessel was filled with an aqueous solution containing 1.5% by weight of a surfactant (Nekal BX, manufacturer BASF). The filled vessel was left to stand for 2 hours and then centrifuged for 10 minutes at 3500 revolutions per minute. The fibers were then weighed (gives measured value Ml), then dried at 105 ° C. for 16-18 hours and weighed again (gave measured value M2).
  • a surfactant Nakal BX, manufacturer BASF
  • the molded article according to the invention in particular fibers, are particularly suitable as a component of absorbent products.
  • the invention accordingly also relates to an absorbent product which contains a molded body according to the invention.
  • the mixture was stirred for a further 15 minutes and then filtered first through a polypropylene filter fleece with a pore size of 10 ⁇ m and then through a polypropylene filter fleece with a pore size of 3 ⁇ m.
  • the filtered mixture was deaerated in vacuo and then spun into a spinning bath with the following composition by means of two nozzles, each with 800 spinning holes with a diameter of 80 ⁇ m:
  • the spun fibers were passed through a second bath in a known manner and desulfurized, washed and dried in further baths.
  • the fibers obtained had a guarane content of 2.71% by weight. Assuming a guar gum content of 80% in guar gum, this corresponds to a yield of 89%.
  • the fibers had a strength of 18 cN / tex and a swelling value of 103% according to the method described above.
  • the fibers according to the invention thus show a significant increase in the swelling value with only a slight decrease in the fiber strength.
  • a guar gum solution was produced as in Example 1, this time using 20 g guar gum / kg NaOH solution.
  • Commercial guar gum from Fim a ALDAG was used in this experiment.
  • This guar gum solution was added to a spinning viscose as described in Example 1 in an amount such that, assuming a content of 100% guar gum in the guar gum, a theoretical content of 4% guar gum based on cellulose resulted.
  • the mixed solution obtained was filtered by means of a filter pot, a polypropylene nonwoven having a pore size of 5 ⁇ m and a polypropylene nonwoven having a pore size of 10 ⁇ m being located on the filter base.
  • the mixture was stirred for a further 15 minutes and then filtered first through a polypropylene filter fleece with a pore size of 10 ⁇ m and then through a polypropylene filter fleece with a pore size of 3 ⁇ m.
  • the filtered mixture was deaerated in vacuo and then spun into a spinning bath with the following composition by means of two nozzles, each with 800 spinning holes with a diameter of 80 ⁇ m:
  • the spun fibers were passed through a second bath in a known manner and desulfurized, washed and dried in further baths.
  • the fibers obtained had a guar gum content of 3.80% by weight. This corresponds to a yield of 98.8%.
  • the fibers had a strength of 19 cN / tex, an elongation of 17% and a swelling value according to the method described above of 103%>.
  • the fibers according to the invention thus show a significant increase in the swelling value with only a slight decrease in the fiber strength.
  • a guar gum solution was produced as in Example 3, this time using 25 g guar gum / kg NaOH solution. Commercial guar gum from ALDAG was used in this experiment. After standing for 24 hours, the solution was stirred in air for 1 hour.
  • This guar gum solution was added to a spinning viscose as described in Example 3 in an amount that, assuming a guar gum content of 100% guar gum in the viscose, resulted in a theoretical content of 14% guar gum based on cellulose.
  • the mixed solution obtained was filtered by means of a filter pot, a polypropylene nonwoven having a pore size of 5 ⁇ m and a polypropylene nonwoven having a pore size of 10 ⁇ m being located on the filter base.
  • the fibers obtained had a swelling value of 139% with only a slight drop in fiber strength to 18 cN / tex.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un corps moulé cellulosique régénéré, obtenu par procédé à la viscose, notamment des fibres de viscose, avec une structure de base en cellulose régénérée. Ces corps moulés se caractérisent en ce qu'une polygalactomannane est comprise dans la structure de base cellulosique. La polygalactomannane est de préférence du guarana. Selon l'invention, ces corps moulés sont obtenus par mélange d'une viscose avec une solution de galactomannane et par démoulage. Ces corps moulés s'utilisent notamment dans des produits absorbants.
PCT/AT1998/000139 1997-06-05 1998-06-04 Corps moule cellulosique regenere WO1998055673A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU76296/98A AU7629698A (en) 1997-06-05 1998-06-04 Regenerated cellulosic moulded body

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT96697A AT405949B (de) 1997-06-05 1997-06-05 Regenerierter cellulosischer formkörper
ATA966/97 1997-06-05

Publications (1)

Publication Number Publication Date
WO1998055673A1 true WO1998055673A1 (fr) 1998-12-10

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ID=3503909

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1998/000139 WO1998055673A1 (fr) 1997-06-05 1998-06-04 Corps moule cellulosique regenere

Country Status (3)

Country Link
AT (1) AT405949B (fr)
AU (1) AU7629698A (fr)
WO (1) WO1998055673A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014201483A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide et leur procédé de production
WO2014201484A1 (fr) 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide à fort pouvoir absorbant et leur utilisation
US10030323B2 (en) 2013-04-05 2018-07-24 Lenzing Aktiengesellschaft Method for the production of polysaccharide fibers with an increased fibrillation tendency
US10196758B2 (en) 2013-06-18 2019-02-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for producing same
US10221502B2 (en) 2013-04-05 2019-03-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for the production thereof
EP3074555B1 (fr) 2013-11-26 2019-03-27 Lenzing AG Procédé pour prétraiter des fibres de coton récupérées destinées à être utilisées dans la production de corps moulés à partir de cellulose régénérée

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3036415A1 (de) * 1979-10-18 1981-04-30 Chemiefaser Lenzing Ag, Lenzing Mischfaser mit hoher saugfaehigkeit und hohem fluessigkeitsrueckhaltevermoegen auf basis regenerierter cellulose, verfahren zu deren herstellung sowie deren verwendung
DE19544097C1 (de) * 1995-11-27 1997-07-10 Thueringisches Inst Textil Verfahren zur Herstellung von Formkörpern aus Polysaccharidmischungen, daraus hergestellte Formkörper sowie deren Verwendung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3036415A1 (de) * 1979-10-18 1981-04-30 Chemiefaser Lenzing Ag, Lenzing Mischfaser mit hoher saugfaehigkeit und hohem fluessigkeitsrueckhaltevermoegen auf basis regenerierter cellulose, verfahren zu deren herstellung sowie deren verwendung
DE19544097C1 (de) * 1995-11-27 1997-07-10 Thueringisches Inst Textil Verfahren zur Herstellung von Formkörpern aus Polysaccharidmischungen, daraus hergestellte Formkörper sowie deren Verwendung

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10030323B2 (en) 2013-04-05 2018-07-24 Lenzing Aktiengesellschaft Method for the production of polysaccharide fibers with an increased fibrillation tendency
US10221502B2 (en) 2013-04-05 2019-03-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for the production thereof
WO2014201483A1 (fr) * 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide et leur procédé de production
WO2014201484A1 (fr) 2013-06-17 2014-12-24 Lenzing Ag Fibres de polysaccharide à fort pouvoir absorbant et leur utilisation
CN105745370A (zh) * 2013-06-17 2016-07-06 连津格股份公司 多糖纤维及其制备方法
US10220111B2 (en) 2013-06-17 2019-03-05 Lenzing Aktiengesellschaft Highly absorbent polysaccharide fiber and use thereof
CN105745370B (zh) * 2013-06-17 2020-12-08 杜邦工业生物科学美国有限责任公司 多糖纤维及其制备方法
US10196758B2 (en) 2013-06-18 2019-02-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for producing same
EP3074555B1 (fr) 2013-11-26 2019-03-27 Lenzing AG Procédé pour prétraiter des fibres de coton récupérées destinées à être utilisées dans la production de corps moulés à partir de cellulose régénérée

Also Published As

Publication number Publication date
ATA96697A (de) 1998-04-15
AT405949B (de) 1999-12-27
AU7629698A (en) 1998-12-21

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