EP0000740A1 - Process for the manufacture of hydrophilic fibres and filaments by the dry-jet wet spinning process - Google Patents

Process for the manufacture of hydrophilic fibres and filaments by the dry-jet wet spinning process Download PDF

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Publication number
EP0000740A1
EP0000740A1 EP78100522A EP78100522A EP0000740A1 EP 0000740 A1 EP0000740 A1 EP 0000740A1 EP 78100522 A EP78100522 A EP 78100522A EP 78100522 A EP78100522 A EP 78100522A EP 0000740 A1 EP0000740 A1 EP 0000740A1
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Prior art keywords
threads
steam
retention capacity
water retention
fibers
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EP78100522A
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German (de)
French (fr)
Inventor
Ulrich Dr. Reinehr
Frank Dr. Druschke
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Bayer AG
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Bayer AG
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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent

Definitions

  • the invention relates to a process for the production of threads or fibers having a hydrophilic core / sheath structure from thread-forming polymers, in particular from acrylonitrile homo- or copolymers according to the dry-nozzle wet-spinning method in the presence of steam as the first precipitation medium for polyacrylonitrile threads.
  • the dry-jet wet spinning process is generally used to facilitate the stretching of the threads, to reduce the porosity of the fiber structure (cf. DT-OS 1 660 463), or else as described in US Pat. No. 3,415,922 to improve the raw tone of the threads.
  • the distance between the nozzle and the bath surface must not be more than 11.4 cm in order to prevent the individual filaments from converging and sticking together.
  • This maximum distance of 11.4 cm is achieved by reinforcing the initial coagulation of the sprayed thread-forming material through a mist atmosphere of water, the spinning solvent or a mixture of the two, which by means of air supply from nozzles is sprayed very finely in a chamber, before the threads are completely coagulated in the precipitation bath.
  • the invention accordingly relates to a process for the production of threads or fibers having a hydrophilic core-shell structure from thread-forming synthetic polymers with a porosity of at least 10% and a water retention capacity of at least 10% with a fiber swelling which is less than the water retention capacity Spinning a polymer solution according to the dry-wet wet spinning process, characterized in that the threads are brought into contact with water vapor or the vapor of another liquid coagulating the threads immediately after emerging from the spinneret and before the actual coagulation process in the precipitation bath.
  • the maximum distance between the nozzle and the precipitation bath surface of 11.4 cm known from the patent literature also plays no significant role.
  • the distance between the nozzle and Rällbad can be, for example, 50 cm and more without the threads converging and sticking.
  • polymers which are normally not hydrophilic, preferably acrylonitrile polymers and particularly preferably those with at least 50% by weight, in particular with at least 85% by weight, of acrylonitrile units are spun.
  • vapors suitable according to the invention for pre-coagulation of the threads which have not yet solidified are all vapors of substances which are non-solvents for the spun polymers, in particular acrylonitrile polymers, for example in the case of acrylonitrile polymers, mono- and polysubstituted alkyl ethers and esters of polyhydric alcohols , such as diethylene glycol, tripropylene glycol, glycol ether acetates. Alcohols such as 2 ethylcyclohexanol, glycerol, esters or ketones or mixtures, e.g. from ethylene glycol acetates, suitable.
  • substances which can be easily evaporated whose flash point is high and whose flammability is low, for example methylene chloride and carbon tetrachloride.
  • both the cross-sectional structure and the width of the outer surface and the hydrophilicity of the threads can be controlled.
  • the thickness and thus the hem width of the lateral surface can be selected by the choice of the ratio of air to steam mixture or only the amount of steam Control that core / sheath fibers with large hem width of the outer surface, which can account for up to approximately 75% of the total fiber cross-sectional area, are preferably produced at high steam quantities.
  • core / sheath fibers are obtained in reverse, which more and more approach the cross-sectional structure customary in the wet spinning process and which have a correspondingly low water retention capacity.
  • the cross-sectional structure of the core / sheath fibers was determined on the basis of electron micrographs. To determine the proportion of core or outer surface of the fibers, approximately 100 fiber cross sections were evaluated by quantitative analysis using the "Classimat" image analysis device from LEITZ.
  • the steam is preferably blown in above the spinneret in the direction of the thread take-off.
  • the threads and fibers produced by the process according to the present invention show a high absorbency, water absorption without swelling, rapid moisture transport and high moisture absorption and, also due to the porous structure, a low density due to their porous core-shell structure.
  • the sum of these positive properties in a single fiber product thus provides a fiber from which textile structures, in particular items of clothing, can be produced convey excellent comfort to the wearer.
  • the Hg density (mean apparent density) is determined by volume measurements in mercury at an overpressure of 10 bar.
  • the helium density (“true density”) is determined by measuring the volume in helium with a gas comparison pycnometer.
  • the cladding thickness on the fiber surface is determined as the distance from the outside of the fiber (stepping vertically inwards from the outside) to the point at which the described structural difference can be seen.
  • the water retention capacity is determined on the basis of DIN regulation 53814 (cf. Melliand Textile Reports 4 1973, page 350).
  • the threads were then drawn 1: 6 times in boiling water at 80 ° C., washed in water and dried at 100 ° C.
  • the individual threads with a final titer of 3.3 dtex had a water retention capacity according to DIN 53 814 of 42%.
  • the threads had a pronounced core / jacket structure with an irregular, multi-serrated cross-sectional shape.
  • the surface area of the jacket was approximately 20% of the total cross-sectional area.
  • Example 2 An acrylonitrile copolymer with the chemical composition of Example 1 was spun in a manner similar to that described in Example 1.
  • the steam temperature was 105 ° C.
  • Example 2 An acrylonitrile copolymer with the chemical composition of Example 1 was spun, stretched and post-treated as described in Example 2.
  • the coagulation bath consisted of pure water.
  • the individual threads with a final titer of 3.3 dtex had a water retention capacity of 43%.
  • the threads again had a core / shell structure with a bean-shaped to trilobal cross-sectional shape. Area share of the jacket approx. 30%.
  • Example 2 Part of the spinning solution from Example 1 was spun as described there and aftertreated.
  • the amount of steam fed was 5 kg per hour.
  • the steam temperature was 110 ° C.
  • the coagulation bath consisted of 40% DMF and 60% water.
  • the precipitation bath section was 50 cm long.
  • the single. threads with a final titer of 3.3 dtex had a water retention capacity of 36%.
  • the threads again had a core / sheath structure with an irregular trilobal to mushroom-shaped cross section form.
  • the surface area of the jacket was approximately 15% of the total cross-sectional area.
  • Example 2 Another part of the spinning solution from Example 1 was spun as described there. Instead of steam, air at 115 ° C. was blown through the tube and the threads were coagulated, drawn and post-treated in a precipitation bath analogously to that described in Example 1.
  • the individual threads with a final titer of 3.3 dtex have a bean-shaped to oval cross-sectional shape, but no core / shell structure.
  • the water retention capacity is 6%.

Abstract

Die Erfindung betrifft ein Verfahren zur Herstellung von hydrophilen, eine Kernmantelstruktur aufweisenden Fäden oder Fasern mit einer Porosität von mindestens 10 % und einem Wasserrückhaltevermögen von mindestens 10 % bei einer Faserquellung, die geringer ist als das Wasserrückhalte-vermögen. Das Verfahren wird durchgeführt durch Verspinnen einer Lösung eines synthetischen fadenbildenden Polymers, insbesondere von Acryinitril- Polymerisaten nach dem Trockendüsen - Naßspinnverfahren, indem man die Fäden unmittelbar nach Austritt aus der Spinndüse und vor dem eigentlichen Koagulationsprozeß im Fällbad mit Wasserdampf oder dem Dampf einer anderen, die Fäden koagulierenden Flüssigkeit in Berührung bringt.The invention relates to a process for the production of hydrophilic threads or fibers having a core jacket structure with a porosity of at least 10% and a water retention capacity of at least 10% with a fiber swelling which is less than the water retention capacity. The process is carried out by spinning a solution of a synthetic thread-forming polymer, in particular acrylonitrile polymers, after the drying nozzle - wet spinning process, by threading the threads immediately after emerging from the spinneret and before the actual coagulation process in the coagulation bath with steam or the steam of another Threads in contact with coagulating liquid.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von hydrophilen Kern/Mantelstruktur aufweisenden Fäden oder Fasern aus fadenbildenden Polymeren, insbesondere aus Acrylnitrilhomo- oder Copolymerisaten nach der Trocken-Düsen-Naßspinnmethode in Gegenwart von Wasserdampf als erstes Fällmedium für Polyacrylnitrilfäden.The invention relates to a process for the production of threads or fibers having a hydrophilic core / sheath structure from thread-forming polymers, in particular from acrylonitrile homo- or copolymers according to the dry-nozzle wet-spinning method in the presence of steam as the first precipitation medium for polyacrylonitrile threads.

Das Trocken-Düsen-Naßspinnverfahren wird im allgemeinen angewendet, um die Verstreckung der Fäden zu erleichtern, die Porosität der Faserstruktur zu verringern (vergl. die DT-OS 1 660 463), oder aber auch wie in der US-PS 3 415 922 beschrieben, um den Rohton der Fäden zu verbessern. Der Abstand zwischen Düse und Badoberfläche darf nach der DT-OS 1 660 463 nicht mehr als 11,4 cm betragen, um ein Zusammenlaufen und Verkleben der einzelnen Spinnfäden zu verhindern. Dieser maximale Abstand von 11,4 cm wird verwirklicht, indem man zur Verstärkung der anfänglichen Koagulierung des ausgespritzten fadenbildenden Materials die Fäden durch eine Nebelatmosphäre aus Wasser, dem Spinnlösungsmittel oder einem Gemisch der beiden, welches mittels Luftzufuhr aus Düsen in einer Kammer feinst versprüht wird, geleitet werden, ehe die Fäden im Fällbad vollständig koaguliert werden.The dry-jet wet spinning process is generally used to facilitate the stretching of the threads, to reduce the porosity of the fiber structure (cf. DT-OS 1 660 463), or else as described in US Pat. No. 3,415,922 to improve the raw tone of the threads. According to DT-OS 1 660 463, the distance between the nozzle and the bath surface must not be more than 11.4 cm in order to prevent the individual filaments from converging and sticking together. This maximum distance of 11.4 cm is achieved by reinforcing the initial coagulation of the sprayed thread-forming material through a mist atmosphere of water, the spinning solvent or a mixture of the two, which by means of air supply from nozzles is sprayed very finely in a chamber, before the threads are completely coagulated in the precipitation bath.

Es wurde nun überraschenderweise gefunden, daß man anstelle von unporösen Fasern Kern/Mantelstruktur aufweisende Acrylfasern hoher Hydrophilie nach der Trocken-Düsen-Naßspinnmethode erhält, wenn man Wasserdampf statt fein zerstäubter Wasser-Luftgemische bzw. Wasser-Luft-Lösungsmittelgemische als erstes Fällmedium einsetzt.Surprisingly, it has now been found that instead of non-porous fibers, core fibers / shell structures having high hydrophilicity, acrylic fibers having the dry-nozzle wet-spinning method are obtained if steam is used as the first precipitation medium instead of finely atomized water-air mixtures or water-air solvent mixtures.

Gegenstand der Erfindung ist demgemäß ein Verfahren zur Herstellung von hydrophilen Kern-Mantel-Struktur aufweisenden Fäden oder Fasern aus fadenbildenden synthetischen Polymeren mit einer Porosität von mindestens 10 % und einem Wasserrückhaltevermögen von mindestens 10 % hei einer Faserquellung, die geringer ist als das Wasserrückhaltevermögen, durch Verspinnen einer Polymerlösung nach dem Trocken-Dtisen-NaBspinnverfahren, dadurch gekennzeichnet, daß man die Fäden unmittelbar nach Austritt aus der Spinndüse und vor dem eigentlichen Koagulationsprozeß im Fällbad mit Wasserdampf oder dem Dampf einer anderen die Fäden koagulierenden Flüssigkeit in Berührung bringt.The invention accordingly relates to a process for the production of threads or fibers having a hydrophilic core-shell structure from thread-forming synthetic polymers with a porosity of at least 10% and a water retention capacity of at least 10% with a fiber swelling which is less than the water retention capacity Spinning a polymer solution according to the dry-wet wet spinning process, characterized in that the threads are brought into contact with water vapor or the vapor of another liquid coagulating the threads immediately after emerging from the spinneret and before the actual coagulation process in the precipitation bath.

Bei dieser Technik, d.h. bei der Verwendung von Wasserdampf spielt auch der aus der Patentliteratur bekannte maximal einzuhaltende Abstand zwischen Düse und Fällbadoberfläche von 11,4 cm keine wesentliche Rolle. Der Abstand zwischen Düse und Rällbad kann beispielsweise 50 cm und mehr betragen, ohne daß die Fäden zusammenlaufen und verkleben.With this technique, i.e. When using water vapor, the maximum distance between the nozzle and the precipitation bath surface of 11.4 cm known from the patent literature also plays no significant role. The distance between the nozzle and Rällbad can be, for example, 50 cm and more without the threads converging and sticking.

Zwedkmäßigerweise wird der Wasserdampf oberhalb der Düse in den Spinnschacht zentral eingeblasen. Es können auch Dampf/Luftgemische eingesetzt werden. Im allgemeinen reichen Dampfmengen von ca. 1 kg Dampf pro kg Spinngut aus, um bereits hydrophile Kern/Mantelstruktur aufweisende Acrylfasern zu erzeugen, wenn man von einer Polyacrylnitrilspinnlösung der Konzentration ca. 30 % ausgeht.The water vapor is inevitably blown into the spinning shaft above the nozzle. Steam / air mixtures can also be used. Generally enough Steam quantities of approx. 1 kg steam per kg spun material in order to produce acrylic fibers which already have a hydrophilic core / shell structure if one assumes a concentration of approx. 30% of a polyacrylonitrile spinning solution.

Nach dem erfindungsgemäßen Verfahren werden Polymerisate, die normalerweise nicht hydrophil sind, vorzugsweise Acrylnitrilpolymerisate und besonders bevorzugt.solche mit mindestens 50 Gew.-%, insbesondere mit mindestens 85 Gew.-% AcrylnitrilEinheiten, versponnen.In the process according to the invention, polymers which are normally not hydrophilic, preferably acrylonitrile polymers and particularly preferably those with at least 50% by weight, in particular with at least 85% by weight, of acrylonitrile units are spun.

Erfindungsgemäß geeignete Dämpfe zur Vorkoagulation der noch nicht verfestigten Fäden sind neben Wasserdampf alle Dämpfe von Substanzen, die für die versponnenen Polymerisate, insbesondere Acrylnitrilpolymerisate, ein Nichtlösungsmittel darstellen wie beispielsweise im Falle von Acrylnitrilpoly- merisaten,ein- und mehrfach substituierte Alkyläther und -ester mehrwertiger Alkohole, wie Diäthylenglykol, Tripropylenglykol, Glykolätheracetate. Ferner sind Alkohole wie 2 Äthylcyclohexanol, Glycerin, Ester oder Ketone oder Gemische, z.B. aus Äthylenglykolacetaten, geeignet. Besonders bevorzugt sind neben Wasser solche Substanzen, die sich leicht verdampfen lassen, deren Flammpunkt hoch liegt und deren Brennbarkeit gering ist, beispielsweise Methylenchlorid und Tetrachlorkohlenstoff.In addition to water vapor, vapors suitable according to the invention for pre-coagulation of the threads which have not yet solidified are all vapors of substances which are non-solvents for the spun polymers, in particular acrylonitrile polymers, for example in the case of acrylonitrile polymers, mono- and polysubstituted alkyl ethers and esters of polyhydric alcohols , such as diethylene glycol, tripropylene glycol, glycol ether acetates. Alcohols such as 2 ethylcyclohexanol, glycerol, esters or ketones or mixtures, e.g. from ethylene glycol acetates, suitable. In addition to water, particular preference is given to substances which can be easily evaporated, whose flash point is high and whose flammability is low, for example methylene chloride and carbon tetrachloride.

Je nach Intensität der Dampfeinblasung auf die Polymer fäden lassen sich sowohl die Querschnittsstruktur als auch die Breite der Mantelfläche und die Hydrophilie der Fäden steuern.Depending on the intensity of the steam injection onto the polymer threads, both the cross-sectional structure and the width of the outer surface and the hydrophilicity of the threads can be controlled.

Die Dicke und somit die Saumbreite der Mantelfläche läßt sich erfindungsgemäß durch die Wahl des Verhältnisses von Luft zu Dampfgemisch oder auch nur der Dampfmenge derart steuern, daß bei hohen Dampfmengen vorzugsweise Kern/Mantelfasern mit großer Saumbreite der Mantelfläche,'die bis zu ca. 75 % der gesamten Faserquerschnittfläche ausmachen können, erzeugt werden. - According to the invention, the thickness and thus the hem width of the lateral surface can be selected by the choice of the ratio of air to steam mixture or only the amount of steam Control that core / sheath fibers with large hem width of the outer surface, which can account for up to approximately 75% of the total fiber cross-sectional area, are preferably produced at high steam quantities. -

Setzt man bein Spinnprozeß nur wenig Dampf ein, so erhält man ungekehrt Kern/Mantelfasern, die sich mehr und mehr der beim Naßspinnprozeß üblichen Querschnittsstruktur nähern und die ein entsprechend niedriges Wasserrückhaltevermögen aufweisen.If only a little steam is used in the spinning process, core / sheath fibers are obtained in reverse, which more and more approach the cross-sectional structure customary in the wet spinning process and which have a correspondingly low water retention capacity.

Die Querschnittsstruktur der Kern/Mantelfasern wurde anhand von elektronenmikroskopischen Aufnahmen bestimmt. Zur Bestimmung des Kern- bzw. Mantelflächenanteils der Fasern wurden jeweils ca. 100 Faserquerschnitte durch quantitative Analyse mit dem Bildanalysengerät "Classimat" der Firma LEITZ ausgewertet.The cross-sectional structure of the core / sheath fibers was determined on the basis of electron micrographs. To determine the proportion of core or outer surface of the fibers, approximately 100 fiber cross sections were evaluated by quantitative analysis using the "Classimat" image analysis device from LEITZ.

Bei dem erfindungsgemäßen Verfahren wird der Dampf bevorzugt oberhalb der Spinndüse in Richtung des Fadenabzuges eingeblasen. Es ist jedoch eine Anblasung quer zu den Fäden auch unterhalb der Düse möglich, wenn die Anblasung so erfolgt, daß keine zu starke Turbulenz auftritt.In the method according to the invention, the steam is preferably blown in above the spinneret in the direction of the thread take-off. However, it is also possible to blow transversely to the threads below the nozzle if the blowing is carried out in such a way that excessive turbulence does not occur.

Die Fäden und Fasern hergestellt nach dem Verfahren gemäß der vorliegenden Erfindung zeigen durch ihre poröse Kern-Mantel-Struktur eine hohe Saugfähigkeit, Wasseraufnahme ohne Quellung, schnellen Feuchtigkeitstransport und hohe Feuchteaufnahme sowie, ebenfalls bedingt durch die poröse Struktur, eine niedrig Dichte. Durch die Summe dieser positiven Eigenschaften in einem einzigen Faserprodukt wird somit eine Faser zur Verfügung gestellt, aus der sich textile Gebilde, insbesondere Kleidungsstücke, fertigen lassen, die ihrem Träger einen hervorragenden Tragekomfort vermitteln.The threads and fibers produced by the process according to the present invention show a high absorbency, water absorption without swelling, rapid moisture transport and high moisture absorption and, also due to the porous structure, a low density due to their porous core-shell structure. The sum of these positive properties in a single fiber product thus provides a fiber from which textile structures, in particular items of clothing, can be produced convey excellent comfort to the wearer.

Die Bestimmung der zur Charakterisierung der Fäden dienenden physikalischen Größen wurde wie nachstehend beschrieben, ausgeführt. Diese Meßmethoden beziehen sich auf gefärbte bzw. blindgefärbte von Präparation befreite Fasern, Garne oder Textilflächengebilde.The determination of the physical quantities used to characterize the threads was carried out as described below. These measurement methods relate to dyed or blind-dyed fibers, yarns or textile fabrics removed from the preparation.

Meßmethoden:Measurement methods: Quecksilber-Dichte-Bestimmung (ϕ Hg)Mercury density determination (ϕ Hg)

Nach Ausheizen der Probe bei 50°C unter Vakuum (10-2 mbar) wird die Hg-Dichte (mittlere scheinbare Dichte) durch Volumenmessungen in Quecksilber bei einem Überdruck von 10 bar festgestellt.After heating the sample at 50 ° C under vacuum (10 -2 mbar), the Hg density (mean apparent density) is determined by volume measurements in mercury at an overpressure of 10 bar.

Helium-Dichte-Bestimmung (ϕHe)Helium density determination (ϕHe)

Nach Ausheizen der Probe bei 50°C unter Vakuum (10-2 bar) wird die Helium-Dichte ("wahre Dichte) durch Volumenmessung in Helium mit einem Gasvergleichspyknometer festgestellt.After heating the sample at 50 ° C under vacuum (10 -2 bar), the helium density ("true density") is determined by measuring the volume in helium with a gas comparison pycnometer.

Definition der Porosität (P)Definition of porosity (P)

Figure imgb0001
Figure imgb0001

Definition der Kern-Mantel-StrukturDefinition of the core-shell structure

Im Rasterelektronenmikroskop nach üblichen Techniken - mit Gefrierbruch, Ionenätzung und Goldbedampfung - präparierte Proben lassen im Faserquerschnitt eine Kern-Mantel-Struktur erkennen, dadurch gekennzeichnet, daß die im Kern erkennbaren Poren im Mittel deutlich größer sind als die Poren im Mantel. Der Mantel kann insbesondere kompakt erscheinen, d.h. im wesentlichen keine Poren über 300 Å Durchmesser aufweisen.In the scanning electron microscope using conventional techniques - with freeze fracture, ion etching and gold vapor deposition - prepared samples leave a core-sheath in the fiber cross section Recognize structure, characterized in that the pores recognizable in the core are significantly larger on average than the pores in the jacket. In particular, the jacket can appear compact, ie essentially have no pores over 300 Å in diameter.

Die Manteldicke an der Faseroberfläche wird bestimmt als der Abstand des Faser-Äußeren (von außen senkrecht nach innen schreitend) bis zu der Stelle,an der der geschilderte Strukturunterschied erkennbar wird.The cladding thickness on the fiber surface is determined as the distance from the outside of the fiber (stepping vertically inwards from the outside) to the point at which the described structural difference can be seen.

Bestimmung des Wasserrückhaltevermöqens (WR):Determination of the water retention capacity (WR):

Das Wasserrückhaltevermögen wird in Anlehnung an die DIN-Vorschrift 53814 (vgl. Melliand Textilberichte 4 1973, Seite 350) bestimmt.The water retention capacity is determined on the basis of DIN regulation 53814 (cf. Melliand Textile Reports 4 1973, page 350).

Die Faserproben werden 2 Stunden in Wasser getaucht, das 0;1 % Netzmittel enthält. Danach werden die Fasern 10 Minuten zentrifugiert mit einer Beschleunigung von 10 000 m/sec2 und die Wassermenge gravimetrisch ermittelt, die in und zwischen den Fasern zurückgehalten wird. Zur Bestimmung des Trockengewichtes werden die Fasern bis zur Feuchtekonstanz bei 105°C getrocknet. Das Wasserrückhaltevermögen (WR), in Gewichtsprozent ist:

Figure imgb0002

  • mf = Gewicht des feuchten Fasergutes
  • mtr = Gewicht des trockenen Fasergutes.
The fiber samples are immersed in water containing 0.1% wetting agent for 2 hours. The fibers are then centrifuged for 10 minutes at an acceleration of 10,000 m / sec 2 and the amount of water which is retained in and between the fibers is determined gravimetrically. To determine the dry weight, the fibers are dried to constant moisture at 105 ° C. The water retention capacity (WR), in weight percent, is:
Figure imgb0002
  • m f = weight of the moist fiber material
  • m tr = weight of the dry fiber material.

Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung. Teil- und Prozentangaben beziehen sich, wenn nicht anders vermerkt, auf das Gewicht.The following examples serve to further explain the invention. Unless otherwise noted, parts and percentages relate to weight.

Beispiel 1example 1

Ein Acrylnitrilcopolymerisat aus 93,6 % Acrylnitril, 5,7 % Acrylsäuremethylester und 0,7 % Natriummethallylsulfonat wurde in Dimethylformamid (DMF) bei 80°C gelöst. Die filtrierte Spinnlösung, die eine Endkonzentration von ca. 30 Gew.-% aufwies, wurde aus einer 24 Loch-Ringdüse vertikal durch eine Dampfatmosphäre in ein wäßriges Koagulationsbad gesponnen. Im Zentrum der Düse wurde ein siebförmiger Verteiler eingebaut, über den der Dampf in ein 50 cm langes Rohr vom Durchmesser 275 mm, welches ca. 2 cm über dem wäßrigen Fällbad endete, durchgeleitet wurde. Die Dampftemperatur betrug 1120C. Es wurde 9,5 kg Dampf pro Stunde durch das Rohr geschickt. Als Badflüssigkeit wurde ein Wasser/DMF-Gemisch im Verhältnis 1:1 verwendet. Die Filamente wurden mit 61,5 m/Minute abgezogen und durchliefen dabei nach der Dampfzone insgesamt eine Fällbadstrecke von 60 cm.An acrylonitrile copolymer of 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate was dissolved in dimethylformamide (DMF) at 80 ° C. The filtered spinning solution, which had a final concentration of approximately 30% by weight, was spun vertically from a 24-hole ring nozzle through a steam atmosphere into an aqueous coagulation bath. A sieve-shaped distributor was installed in the center of the nozzle, through which the steam was passed into a 50 cm long tube with a diameter of 275 mm, which ended about 2 cm above the aqueous precipitation bath. The steam temperature was 112 ° C. 9.5 kg of steam were passed through the tube per hour. A water / DMF mixture in a ratio of 1: 1 was used as the bath liquid. The filaments were drawn off at 61.5 m / minute and in the process passed through a precipitation bath section of 60 cm after the steam zone.

Anschließend wurden die Fäden in kochendem Wasser 1:6fach verstreckt bei 80°C, in Wasser gewaschen und bei 100°C getrocknet. Die Einzelfäden vom Endtiter 3,3 dtex hatten ein Wasserrückhaltevermögen nach DIN 53 814 von 42 %. Die Fäden besaßen eine ausgesprochene Kern/Mantelstruktur bei unregelmäßiger, mehrfach gezackter Querschnittsform. Der Flächenanteil des Mantels betrug ca. 20 % der gesamten Querschnittsfläche. Die Porosität betrug 31,8 % ϕHe = 1,175 ; ϕHg = 0,802). tThe threads were then drawn 1: 6 times in boiling water at 80 ° C., washed in water and dried at 100 ° C. The individual threads with a final titer of 3.3 dtex had a water retention capacity according to DIN 53 814 of 42%. The threads had a pronounced core / jacket structure with an irregular, multi-serrated cross-sectional shape. The surface area of the jacket was approximately 20% of the total cross-sectional area. The porosity was 31.8% ϕHe = 1.175; ϕHg = 0.802). t

Beispiel 2Example 2

Ein Acrylnitrilcopolymerisat mit der chemischen Zusammensetzung von Beispiel 1 wurde ähnlich wie in Beispiel 1 beschrieben versponnen. Die Dampftemperatur betrug 105°C.An acrylonitrile copolymer with the chemical composition of Example 1 was spun in a manner similar to that described in Example 1. The steam temperature was 105 ° C.

Es wurde 11 kg Dampf pro Stunde durch das Rohr geschickt. Im Koagulationsbad befand sich ein Gemisch aus 35 % DMF und 65 % Wasser. Die Fällbadstrecke war 80 cm lang. Die Filamente wurden wieder mit 61,5 m/Minute aus der Düse angezogen, analog verstreckt, gewaschen und getrocknet. Die Einzelfäden vom Endtiter 3,3 dtex hatten ein Wasserrückhaltevermögen von 43 %. Die Fäden besaßen wieder eine ausgesprochene Kern/Mantelstruktur bei bohnenförmiger bis ovaler Querschnittsform. Der Flächenanteil des Mantels betrug ca. 30 % der gesamten Querschnittsfläche. Die Porosität betrug 31,7 % (ϕ He = 1,170: ϕHg = 0,799).11 kg of steam was passed through the tube per hour. A mixture of 35% DMF and 65% water was in the coagulation bath. The precipitation bath line was 80 cm long. The filaments were drawn out of the nozzle again at 61.5 m / minute, stretched analogously, washed and dried. The individual threads with a final titer of 3.3 dtex had a water retention capacity of 43%. The threads again had a pronounced core / shell structure with a bean-shaped to oval cross-sectional shape. The surface area of the jacket was approximately 30% of the total cross-sectional area. The porosity was 31.7% (ϕ He = 1.170: ϕHg = 0.799).

Beispiel 3Example 3

Ein Acrylnitrilcopolymerisat mit der chemischen Zusammensetzung von Beispiel 1 wurde wie in Beispiel 2 beschrieben versponnen, verstreckt und zu Fäden nachbehandelt. Das Koagulationsbad bestand aus reinem Wasser. Die Einzelfäden vom Endtiter 3,3 dtex hatten ein Wasserrückhaltevermögen von 43 %. Die Fäden besaßen wiederum Kern/Mantelstruktur bei bohnenförmiger bis trilobaler Querschnittsform. Flächenanteil des Mantels ca. 30 %. Die Porosität betrug 32,0 % (ϕ He = 1,180; ϕ Hg = 0,803).An acrylonitrile copolymer with the chemical composition of Example 1 was spun, stretched and post-treated as described in Example 2. The coagulation bath consisted of pure water. The individual threads with a final titer of 3.3 dtex had a water retention capacity of 43%. The threads again had a core / shell structure with a bean-shaped to trilobal cross-sectional shape. Area share of the jacket approx. 30%. The porosity was 32.0% (ϕ He = 1.180; ϕ Hg = 0.803).

Beispiel 4Example 4

Ein Teil der Spinnlösung aus Beispiel 1 wurde wie dort beschrieben versponnen und nachbehandelt. Die eingespeiste Dampfmenge betrug 5 kg pro Stunde. Die Dampftemperatur lag bei 1100C. Das Koagulationsbad bestand aus 40% DMF und 60 % Wasser. Die Fällbadstrecke war 50 cm lang. Die Einzel- . fäden vom Endtiter 3,3 dtex hatten ein Wasserrückhaltevermögen von 36 %. Die Fäden besaßen wieder Kern/Mantelstruktur bei unregelmäßiger trilobaler bis pilzförmiger Querschnittsform. Der Flächenanteil des Mantels betrug ca. 15 % der gesamten Querschnittsfläche. Die Porosität betrug 28,4 % (ϕHe = 1,180; ϕHg = 0.845).Part of the spinning solution from Example 1 was spun as described there and aftertreated. The amount of steam fed was 5 kg per hour. The steam temperature was 110 ° C. The coagulation bath consisted of 40% DMF and 60% water. The precipitation bath section was 50 cm long. The single. threads with a final titer of 3.3 dtex had a water retention capacity of 36%. The threads again had a core / sheath structure with an irregular trilobal to mushroom-shaped cross section form. The surface area of the jacket was approximately 15% of the total cross-sectional area. The porosity was 28.4% (ϕ He = 1.180; ϕHg = 0.845).

Beispiel 5 (Vergleich)Example 5 (comparison)

Ein weiterer Teil der Spinnlösung aus Beispiel 1 wurde wie dort beschrieben versponnen. Anstelle von Dampf wurde Luft von 115°C durch das Rohr geblasen und die Fäden analog wie in Beispiel 1 beschrieben in ein Fällbad koaguliert, verstreckt und nachbehandelt. Die Einzelfäden vom Endtiter 3,3 dtex haben eine bohnenförmige bis ovale Querschnittsform, jedoch keine Kern/Mantelstruktur. Das Wasserrückhaltevermögen beträgt 6 %. Die Porosität betrug 4,5 % (ϕ He- 1,180:ϕ H9 = 1,128).Another part of the spinning solution from Example 1 was spun as described there. Instead of steam, air at 115 ° C. was blown through the tube and the threads were coagulated, drawn and post-treated in a precipitation bath analogously to that described in Example 1. The individual threads with a final titer of 3.3 dtex have a bean-shaped to oval cross-sectional shape, but no core / shell structure. The water retention capacity is 6%. The porosity was 4.5% (ϕ He-1.180: ϕ H9 = 1.128).

Claims (3)

1. Verfahren zur Herstellung von hydrophilen Kern-Mantel-Struktur aufweisenden Fäden oder Fasern aus fadenbildenden synthetischen Polymeren mit einer Porosität von mindestens 10 % und einem Wasserrückhaltevermögen von mindestens 10 % bei einer Faserquellung, die geringer ist als das Wasserrückhaltevermögen, durch Verspinnen einer Polymerlösung nach dem Trocken-Düsen-Naßspinnverfahren, dadurch gekennzeichnet, daß man die Fäden unmittelbar nach Austritt aus der Spinndüse und vor dem eigentlichen Koagulationsprozeß im Fällbad mit Wasserdampf,oder dem Dampf einer anderen die Fäden koaguliernden Flüssigkeit,in Berührung bringt.1. A process for producing hydrophilic core-sheath structure threads or fibers from thread-forming synthetic polymers with a porosity of at least 10% and a water retention capacity of at least 10% with a fiber swelling that is less than the water retention capacity, by spinning a polymer solution the dry-nozzle wet spinning process, characterized in that the threads are brought into contact with water vapor or the vapor of another liquid coagulating the threads immediately after emerging from the spinneret and before the actual coagulation process in the precipitation bath. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Polymere ein Acrylnitrilpolymerisat ist.2. The method according to claim 1, characterized in that the polymer is an acrylonitrile polymer. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß das Acrylnitrilpolymerisat zu mindestens 50 Gew.-% aus Acrylnitrileinheiten besteht.3. The method according to claim 2, characterized in that the acrylonitrile polymer consists of at least 50 wt .-% of acrylonitrile units.
EP78100522A 1977-08-10 1978-07-27 Process for the manufacture of hydrophilic fibres and filaments by the dry-jet wet spinning process Withdrawn EP0000740A1 (en)

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DE19772736065 DE2736065A1 (en) 1977-08-10 1977-08-10 PROCESS FOR MANUFACTURING HYDROPHILIC FIBERS AND FIBERS BY THE DRY-THEN-WET SPINNING PROCESS

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332765A (en) * 1977-11-26 1982-06-01 Bayer Aktiengesellschaft Process for spinning hydrophilic acrylic fibres of low density
EP0047798B1 (en) * 1980-09-15 1983-10-05 Firma Carl Freudenberg Filtering material

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2755341C2 (en) 1977-12-12 1983-09-08 Akzo Gmbh, 5600 Wuppertal Hydrophilic polyester fibers
DE2947824A1 (en) 1979-11-28 1981-07-23 Bayer Ag, 5090 Leverkusen CROSS-SECTION STABLE, HYGROSCOPIC CORE / SHEATH STRUCTURE, FIBERS AND THREADS AND METHOD FOR THE PRODUCTION THEREOF
US4851521A (en) * 1985-07-08 1989-07-25 Fidia, S.P.A. Esters of hyaluronic acid
US5202431A (en) * 1985-07-08 1993-04-13 Fidia, S.P.A. Partial esters of hyaluronic acid
US5759926A (en) * 1995-06-07 1998-06-02 Kimberly-Clark Worldwide, Inc. Fine denier fibers and fabrics made therefrom
BR9611827A (en) 1995-11-30 1999-09-28 Kimberly Clark Co non-woven weave of superfine microfibers.
US20100125963A1 (en) * 2008-11-21 2010-05-27 E. I. Du Pont De Nemours And Company Monofilament comprising hydrophilic agent
CN104862818A (en) * 2015-06-09 2015-08-26 江南大学 Preparation method of keratin complex fiber
JP7448414B2 (en) 2020-01-28 2024-03-12 ナブテスコ株式会社 Rudder control device and ship

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH397949A (en) * 1958-12-29 1965-08-31 Monsanto Chemicals Process for spinning acrylonitrile polymers
DE1660463A1 (en) * 1964-10-12 1970-12-17 Monsanto Co Process for spinning endless threads, in particular acrylonitrile threads
US3650884A (en) * 1967-02-17 1972-03-21 Du Pont Polyamide monofilament having a microporous surface layer
FR2221542A1 (en) * 1973-01-19 1974-10-11 Rhone Poulenc Textile

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2032606A (en) * 1934-02-20 1936-03-03 Celanese Corp Manufacture of artificial materials
US2303340A (en) * 1939-05-16 1942-12-01 Celanese Corp Production of artificial materials
US2303528A (en) * 1939-10-23 1942-12-01 Celanese Corp Production of artificial materials
US2367493A (en) * 1940-12-19 1945-01-16 Eastman Kodak Co Cellulose derivative extrusion process
US2425782A (en) * 1944-03-04 1947-08-19 Celanese Corp Preparation of filaments
US2688010A (en) * 1950-06-06 1954-08-31 Chemstrand Corp Polymers of acrylonitrile and nu-substituted amides
NL97529C (en) * 1952-05-17
NL96514C (en) * 1954-07-31
US3415922A (en) * 1965-07-02 1968-12-10 Monsanto Co Mist spinning
CS160281B1 (en) * 1971-12-22 1975-03-28

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH397949A (en) * 1958-12-29 1965-08-31 Monsanto Chemicals Process for spinning acrylonitrile polymers
DE1660463A1 (en) * 1964-10-12 1970-12-17 Monsanto Co Process for spinning endless threads, in particular acrylonitrile threads
US3650884A (en) * 1967-02-17 1972-03-21 Du Pont Polyamide monofilament having a microporous surface layer
FR2221542A1 (en) * 1973-01-19 1974-10-11 Rhone Poulenc Textile

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332765A (en) * 1977-11-26 1982-06-01 Bayer Aktiengesellschaft Process for spinning hydrophilic acrylic fibres of low density
EP0047798B1 (en) * 1980-09-15 1983-10-05 Firma Carl Freudenberg Filtering material

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US4257999A (en) 1981-03-24
FR2416960B1 (en) 1981-03-27
JPS6047923B2 (en) 1985-10-24
NL7815008A (en) 1979-07-31
DE2736065A1 (en) 1979-02-22
IT1098362B (en) 1985-09-07
GB2041288A (en) 1980-09-10
IT7826602A0 (en) 1978-08-08
CA1117265A (en) 1982-02-02
BE18T1 (en) 1979-12-07
ATA576378A (en) 1982-07-15
JPS5430934A (en) 1979-03-07
IE47289B1 (en) 1984-02-08
FR2416960A1 (en) 1979-09-07
IE781621L (en) 1979-02-10

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