EP0795052B1 - Method of producing shaped cellulose bodies, and yarn made of cellulose filaments - Google Patents

Method of producing shaped cellulose bodies, and yarn made of cellulose filaments Download PDF

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Publication number
EP0795052B1
EP0795052B1 EP95939293A EP95939293A EP0795052B1 EP 0795052 B1 EP0795052 B1 EP 0795052B1 EP 95939293 A EP95939293 A EP 95939293A EP 95939293 A EP95939293 A EP 95939293A EP 0795052 B1 EP0795052 B1 EP 0795052B1
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Prior art keywords
air
solution
process according
cellulose
filaments
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German (de)
French (fr)
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EP0795052B2 (en
EP0795052A1 (en
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Jürgen Pitowski
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Akzo Nobel NV
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Akzo Nobel NV
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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
    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2965—Cellulosic

Definitions

  • the invention relates to a method for producing cellulosic Shaped body, being a solution of cellulose in a tertiary amine N-oxide and optionally water in is molded in a warm state and the molded solution before Placing in a coagulation bath is cooled with air, as well as a yarn made of cellulosic filaments.
  • the shaped solution is preferably one Exposed to gas flow.
  • the warm molded solution is already cooled, if the molded solution is the molding member, for example a spinneret, in which temperatures typically exceed 90 ° C exist, leaves and enters the so-called air gap.
  • the area between the forming element is used as an air gap and the coagulation bath in which the cellulose is precipitated, designated.
  • the temperature in the air gap is lower than in the spinneret, but is due to the heat radiation the spinneret and by the enthalpy flow of the moldings resulting air heating significantly higher than Room temperature. Due to the permanent evaporation of water, that is usually used as a coagulation bath thus in the air gap before warm and humid conditions. With the in of WO 93/19230 proposed measure, the shaped Cooling solution immediately after forming becomes a causes faster cooling, so that the stickiness of the molded solution decreases accordingly faster.
  • the present invention is based on the object such a method in particular also the properties the moldings thus produced, preferably Filaments, or a filament yarn to improve.
  • This task is accomplished through a manufacturing process cellulosic molded body dissolved, a solution of Cellulose in a tertiary amine N-oxide and optionally Water is shaped in the warm state and the shaped Solution before placing in a coagulation bath with air is cooled, with conditioned air used for cooling which has a water content of 0.1 to 7 g of water vapor per kg of dry air and its relative Moisture is less than 85%.
  • the water content is preferably that of the conditioned Air 0.7 to 4 g water vapor per kg dry air, in particular 0.7 to 2 g.
  • the cooling can be done with flowing air take place, these are blown against the shaped solution or is sucked off from this.
  • the suction can be done in this way take place that conditioned air is provided and this, for example, through a bundle of freshly spun Fibers or filaments is sucked through. Especially a combination of blowing and Suction.
  • the shaped solution can pass the conditioned air over the entire distance up to the introduction into the coagulation bath be suspended or only for part of this distance, it is advantageous to apply air in the first part, i.e. in the area of the air gap, which directly connects to the forming organ.
  • the conditioned air should be at an angle from 0 to 120 °, preferably 90 °, relative to the direction of movement pour the molded solution, taking the angle of 0 ° of an inflow opposite to the direction of flow corresponds to the shaped solution.
  • the method according to the invention can be advantageously used Wise fibers, especially filaments, films, hollow fibers, Membranes, for example for use in the Establish dialysis, oxygenation or filtration.
  • the Forming the solution into a desired cellulosic shaped body can be used with known spinnerets for the production of Fibers, slit nozzles or hollow thread spinning nozzles are made. in the Connection to the formation, i.e. before inserting the molded Solution in the coagulation bath, this can be stretched will.
  • a cellulosic filament yarn made from a solution of cellulose in a tertiary amine N-oxide and possibly water, is characterized in that the cross-sectional areas of the filaments have a coefficient of variation less than 12%, preferably less than 10% exhibit.
  • the freshly extruded is cooling Moldings in the air gap are an advantage, all the more so reduce their stickiness more quickly.
  • the gas stream must naturally have a temperature which is below that of the shaped solution.
  • a gas stream is used, the one Has temperature of -6 to 24 ° C.
  • the temperature is not such, but the water content of the air and its relative Moisture on the properties of the cellulosic moldings have a significant impact.
  • the water content of air in g of water vapor per kg of dry air is often also known as the mixing ratio.
  • the unit g / kg is used for this purpose.
  • fluctuations in air humidity be avoided and that the air is only one has low water content.
  • Even in the presence of Air conditioners can fluctuate seasonally and Sometimes even daytime fluctuations in rooms are not sufficient be suppressed. Conditioning should continue take place as evenly as possible, since already small Instabilities regarding blowing strength and blowing direction Strength, elongation and constancy of titer of filaments negative influence.
  • the influence of the water content or the mixing ratio is particularly evident in filament production in irregularities of the filament cross sections.
  • a Cooling with air at 20 ° C and a water content of 14 g / kg and a relative humidity of 94% Coefficient of variation of the filament cross-sectional areas 30% in a yarn with 50 individual filaments.
  • the coefficient of variation decreases by 8.5% same temperature to 5.8%.
  • the temperature of the Cooling air plays a minor role.
  • the filaments were drawn by a factor of 16 in the air gap and after going through a water bath Coagulation and downstream washing baths for removal of the NMMO dried.
  • the withdrawal speed was 420 m / min.
  • the filament bundles obtained in each case were in one Distance of one meter twice perpendicular to the bundle axis cut across.
  • the cross-sectional areas of the filaments were examined using a light microscope (magnification 570: 1) and a video camera in a computer image analysis system (Quantimet 970) transferred and evaluated. The area of each Filament was determined. From the mean of the filament cross sections each bundle examined, being per bundle two cross-sectional images were evaluated, and the standard deviation became the coefficient of variation of the filament cross-sectional area in percent as the ratio of Standard deviation to mean calculated.
  • the resulting airflow was then applied to the cooled the desired temperature with a heat exchanger.
  • the relative humidity and water content were measured with a psychrometer (ALMEMO 2290-2 with psychrometer sensor AN 846 or humidity / temperature sensor AFH 9646-2).
  • Ambient air was used to lower the water content cooled down to a relative humidity of 100% exhibited. This was followed by further cooling, and the condensing water was separated. With this Procedure let the air up to a water content of about 4 g / kg dry. This was followed by a Reheating the air to the desired temperature. The relative humidity and water content were measured with the Psychrometer measured.
  • the following tables show the examined air conditions, characterized by the temperature (T / ° C), the water content (x / (g / kg)) and the relative humidity (rH /%), as well as the variation coefficients of the filament cross-sectional areas (V /% ) specified.
  • Table I clearly shows that, irrespective of the temperature of the conditioned air, the lowest coefficients of variation of the filament cross-sectional areas result when the conditioned air has a low water content, as in Examples Nos. 2, 3, 9, 10 and 11, in those with water contents below 2 g / kg the coefficient of variation is only in the order of 5 to 6%.
  • the relative humidity in these examples was below 30%.
  • the coefficient of variation is lower even at high temperature (example 15) than outside the range according to the invention at considerably lower temperatures.
  • Table II shows that outside of the invention Range the variation coefficients of the filament cross-sectional areas are above 14% and even values of over 30% can be achieved. Such high fluctuations are in the production of filament yarn is undesirable because this negative when processing into textile fabrics affect and in particular to a non-uniform coloring of the fabric. Likewise, it can be due to different Strengths of the individual filaments with each other and there are processing problems with the yarn.
  • Examples 16 and 22 show that for the present invention both claims, i.e. a water content below 7 g water vapor per kg dry air and a relative humidity below 85% can be guaranteed have to. In example 16, the water content was in the area, but the air was higher relative humidity, and a coefficient of variation resulted of 16.1%.
  • Example 22 shows the conditions the ambient air at a temperature of 21 ° C, at a relative humidity of 60% and a water content of 9.2 g / kg.
  • the relative lies Moisture in the stressed area, but not that Water content, and a coefficient of variation results of 23.4%.
  • This example also shows that cooling with ambient air is not sufficient to make, and that it is not enough, a simple Blow with indoor air that is cooler than that temperature usually prevailing in the air gap, around a To achieve improvement in textile properties.

Abstract

Process for manufacturing cellulose formed objects, whereby a solution of cellulose is formed in the warm state in a tertiary amine N-oxide and, if necessary, water and the formed solution is cooled with air before introducing it into a coagulation bath. Conditioned air is employed for cooling which exhibits a water content of 0.1 to 7 g water vapor per kg dry air and whose relative humidity amounts to less than 85%.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung cellulosischer Formkörper, wobei eine Lösung von Cellulose in einem tertiären Amin-N-oxid und gegebenenfalls Wasser in warmem Zustand geformt wird und die geformte Lösung vor dem Einbringen in ein Koagulationsbad mit Luft gekühlt wird, sowie ein Garn aus cellulosischen Filamenten.The invention relates to a method for producing cellulosic Shaped body, being a solution of cellulose in a tertiary amine N-oxide and optionally water in is molded in a warm state and the molded solution before Placing in a coagulation bath is cooled with air, as well as a yarn made of cellulosic filaments.

Ein derartiges Verfahren wird in der WO 93/19230 beschrieben, wobei die Kühlung unmittelbar nach dem Formen erfolgen soll. Mit diesem Verfahren soll erreicht werden, daß die Klebrigkeit der frisch extrudierten Formkörper vermindert wird, so daß bei der Herstellung cellulosischer Fäden eine Spinndüse mit hoher Lochdichte eingesetzt werden kann. Zur Kühlung wird die geformte Lösung bevorzugt einem Gasstrom ausgesetzt. Such a method is described in WO 93/19230, cooling immediately after molding should be done. This procedure is intended to that the stickiness of the freshly extruded molded body is reduced, so that in the manufacture of cellulosic A spinneret with a high hole density can. For cooling, the shaped solution is preferably one Exposed to gas flow.

Eine Kühlung der warmen geformten Lösung erfolgt bereits, wenn die geformte Lösung das Formungsorgan, beispielsweise eine Spinndüse, in der typischerweise Temperaturen über 90°C vorliegen, verläßt und in den sogenannten Luftspalt gelangt. Als Luftspalt wird der Bereich zwischen dem Formungsorgan und dem Koagulationsbad, in dem die Cellulose gefällt wird, bezeichnet. Die Temperatur im Luftspalt ist niedriger als in der Spinndüse, ist aber aufgrund der Wärmestrahlung durch die Spinndüse und der durch den Enthalpiestrom der Formkörper resultierenden Erwärmung der Luft deutlich höher als Raumtemperatur. Durch die permanente Verdampfung von Wasser, das üblicherweise als Koagulationsbad verwendet wird, liegen somit im Luftspalt feuchtwarme Verhältnisse vor. Mit der in der WO 93/19230 vorgeschlagenen Maßnahme, die geformte Lösung unmittelbar nach der Formung zu kühlen, wird eine schnellere Abkühlung bewirkt, so daß die Klebrigkeit der geformten Lösung dementsprechend schneller abnimmt.The warm molded solution is already cooled, if the molded solution is the molding member, for example a spinneret, in which temperatures typically exceed 90 ° C exist, leaves and enters the so-called air gap. The area between the forming element is used as an air gap and the coagulation bath in which the cellulose is precipitated, designated. The temperature in the air gap is lower than in the spinneret, but is due to the heat radiation the spinneret and by the enthalpy flow of the moldings resulting air heating significantly higher than Room temperature. Due to the permanent evaporation of water, that is usually used as a coagulation bath thus in the air gap before warm and humid conditions. With the in of WO 93/19230 proposed measure, the shaped Cooling solution immediately after forming becomes a causes faster cooling, so that the stickiness of the molded solution decreases accordingly faster.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein derartiges Verfahren insbesondere aber auch die Eigenschaften der damit hergestellten Formkörper, vorzugsweise Filamente, bzw. einem Filamentgarn, zu verbessern.The present invention is based on the object such a method in particular also the properties the moldings thus produced, preferably Filaments, or a filament yarn to improve.

Diese Aufgabe wird durch ein Verfahren zur Herstellung cellulosischer Formkörper gelöst, wobei eine Lösung von Cellulose in einem tertiären Amin-N-oxid und gegebenenfalls Wasser in warmem Zustand geformt wird und die geformte Lösung vor dem Einbringen in ein Koagulationsbad mit Luft gekühlt wird, wobei zur Kühlung konditionierte Luft eingesetzt wird, die einen Wassergehalt von 0,1 bis 7 g Wasserdampf je kg trockene Luft aufweist und deren relative Feuchtigkeit weniger als 85% beträgt. This task is accomplished through a manufacturing process cellulosic molded body dissolved, a solution of Cellulose in a tertiary amine N-oxide and optionally Water is shaped in the warm state and the shaped Solution before placing in a coagulation bath with air is cooled, with conditioned air used for cooling which has a water content of 0.1 to 7 g of water vapor per kg of dry air and its relative Moisture is less than 85%.

Vorzugsweise beträgt der Wassergehalt der konditionierten Luft 0,7 bis 4 g Wasserdampf je kg trockene Luft, insbesondere 0,7 bis 2 g. Die Kühlung kann mit strömender Luft erfolgen, wobei diese gegen die geformte Lösung geblasen oder von dieser abgesogen wird. Das Absaugen kann derart erfolgen, daß konditionierte Luft bereitgestellt wird und diese beispielsweise durch ein Bündel frischgesponnener Fasern oder Filamente hindurchgesogen wird. Besonders vorteilhaft ist eine Kombination von Anblasung und Absaugung.The water content is preferably that of the conditioned Air 0.7 to 4 g water vapor per kg dry air, in particular 0.7 to 2 g. The cooling can be done with flowing air take place, these are blown against the shaped solution or is sucked off from this. The suction can be done in this way take place that conditioned air is provided and this, for example, through a bundle of freshly spun Fibers or filaments is sucked through. Especially a combination of blowing and Suction.

Die geformte Lösung kann der konditionierten Luft über die gesamte Strecke bis zum Einbringen in das Koagulationsbad ausgesetzt werden oder nur über einen Teil dieser Strecke, wobei es von Vorteil ist, die Beaufschlagung mit der Luft im ersten Teil vorzunehmen, d.h. in dem Bereich des Luftspalts, der sich unmittelbar an das Formungsorgan anschließt. Die konditionierte Luft sollte unter einem Winkel von 0 bis 120°, vorzugsweise 90°, relativ zur Bewegungsrichtung der geformten Lösung strömen, wobei der Winkel von 0° einer Anströmung entgegengesetzt zur Laufrichtung der geformten Lösung entspricht.The shaped solution can pass the conditioned air over the entire distance up to the introduction into the coagulation bath be suspended or only for part of this distance, it is advantageous to apply air in the first part, i.e. in the area of the air gap, which directly connects to the forming organ. The conditioned air should be at an angle from 0 to 120 °, preferably 90 °, relative to the direction of movement pour the molded solution, taking the angle of 0 ° of an inflow opposite to the direction of flow corresponds to the shaped solution.

Mit dem erfindungsgemäßen Verfahren lassen sich in vorteilhafter Weise Fasern, insbesondere Filamente, Filme, Hohlfasern, Membranen, beispielsweise zum Einsatz in der Dialyse, Oxygenation oder Filtration, herstellen. Die Formung der Lösung zu einem gewünschten cellulosischen Formkörper kann mit bekannten Spinndüsen zur Herstellung von Fasern, Schlitzdüsen oder Hohlfadenspinndüsen erfolgen. Im Anschluß an die Formung, d.h. vor dem Einbringen der geformten Lösung in das Koagulationsbad, kann diese verstreckt werden. The method according to the invention can be advantageously used Wise fibers, especially filaments, films, hollow fibers, Membranes, for example for use in the Establish dialysis, oxygenation or filtration. The Forming the solution into a desired cellulosic shaped body can be used with known spinnerets for the production of Fibers, slit nozzles or hollow thread spinning nozzles are made. in the Connection to the formation, i.e. before inserting the molded Solution in the coagulation bath, this can be stretched will.

Ein Garn aus cellulosischen Filamenten, hergestellt aus einer Lösung von Cellulose in einem tertiären Amin-N-oxid und gegebenenfalls Wasser, zeichnet sich dadurch aus, daß die Querschnittsflächen der Filamente einen Variationskoeffizienten kleiner als 12%, vorzugsweise kleiner als 10% aufweisen.A cellulosic filament yarn made from a solution of cellulose in a tertiary amine N-oxide and possibly water, is characterized in that the cross-sectional areas of the filaments have a coefficient of variation less than 12%, preferably less than 10% exhibit.

Wie bereits ausgeführt, ist eine Abkühlung der frischextrudierten Formkörper im Luftspalt von Vorteil, um so deren Klebrigkeit rascher zu verringern. Um überhaupt kühlen zu können, muß der Gasstrom naturgemäß eine Temperatur aufweisen, die unterhalb der der geformten Lösung liegt. Gemäß der WO 93/19230 wird ein Gasstrom eingesetzt, der eine Temperatur von -6 bis 24°C aufweist.As already stated, the freshly extruded is cooling Moldings in the air gap are an advantage, all the more so reduce their stickiness more quickly. To cool at all To be able to do so, the gas stream must naturally have a temperature which is below that of the shaped solution. According to WO 93/19230 a gas stream is used, the one Has temperature of -6 to 24 ° C.

Es wurde nun aber gefunden, daß nicht die Temperatur als solche, sondern der Wassergehalt der Luft und deren relative Feuchtigkeit auf die Eigenschaften der cellulosischen Formkörper einen wesentlichen Einfluß haben. Der Wassergehalt von Luft in g Wasserdampf je kg trockener Luft wird oftmals auch als das Mischungsverhältnis bezeichnet. Im folgenden wird hierfür vereinfacht die Einheit g/kg verwendet. Insbesondere bei der Herstellung von Filamenten zeigte es sich, daß es wichtig ist, im Luftspalt möglichst konstante klimatische Bedingungen zu schaffen, d.h. üblicherweise auftretende Schwankungen des Umgebungsklimas auszuschalten. Insbesondere ist dabei wichtig, daß Schwankungen in der Luftfeuchtigkeit vermieden werden, und daß die Luft nur einen geringen Wassergehalt aufweist. Selbst bei Vorhandensein von Klimaanlagen können jahreszeitliche Schwankungen und zum Teil auch tageszeitliche Schwankungen in Räumen nicht ausreichend unterdrückt werden. Weiterhin sollte die Konditionierung möglichst gleichmäßig erfolgen, da schon geringe Instabilitäten bezüglich Anblasstärke und Anblasrichtung die Festigkeit, Dehnung und Titerkonstanz von Filamenten negativ beeinflussen.It has now been found, however, that the temperature is not such, but the water content of the air and its relative Moisture on the properties of the cellulosic moldings have a significant impact. The water content of air in g of water vapor per kg of dry air is often also known as the mixing ratio. Hereinafter the unit g / kg is used for this purpose. Especially in the manufacture of filaments that it is important to keep climatic conditions as constant as possible in the air gap Creating conditions, i.e. usually occurring To eliminate fluctuations in the ambient climate. Especially It is important that fluctuations in air humidity be avoided and that the air is only one has low water content. Even in the presence of Air conditioners can fluctuate seasonally and Sometimes even daytime fluctuations in rooms are not sufficient be suppressed. Conditioning should continue take place as evenly as possible, since already small Instabilities regarding blowing strength and blowing direction Strength, elongation and constancy of titer of filaments negative influence.

Der Einfluß des Wassergehaltes bzw. des Mischungsverhältnisses zeigt sich bei der Filamentherstellung insbesondere in Unregelmäßigkeiten der Filamentquerschnitte. Bei einer Kühlung mit Luft von 20°C und einem Wassergehalt von 14 g/kg und einer relativen Feuchtigkeit von 94% beträgt der Variationskoeffizient der Filamentquerschnittsflächen 30% in einem Garn mit 50 Einzelfilamenten. Bei Reduzierung des Wassergehaltes auf 1,2 g/kg und einer relativen Feuchtigkeit von 8,5% erniedrigt sich der Variationskoeffizient bei gleicher Temperatur auf 5,8%. Selbst bei Einsatz von wärmerer Luft von beispielsweise 40°C, aber einem geringen Wassergehalt von 3,4 g/kg und einer relativen Feuchtigkeit von 7,4% resultiert ein Variationskoeffizient von 11,3%, der somit um einem Faktor 2,7 geringer ist als bei Verwendung von kühlerer Luft mit höherer Feuchtigkeit. Erfindungsgemäß ist es daher wesentlich, eine Konditionierung des Luftspaltes mit trockener Luft vorzunehmen. Die Temperatur der Kühlluft spielt dabei eher eine untergeordnete Rolle.The influence of the water content or the mixing ratio is particularly evident in filament production in irregularities of the filament cross sections. At a Cooling with air at 20 ° C and a water content of 14 g / kg and a relative humidity of 94% Coefficient of variation of the filament cross-sectional areas 30% in a yarn with 50 individual filaments. When reducing the Water content to 1.2 g / kg and a relative humidity The coefficient of variation decreases by 8.5% same temperature to 5.8%. Even when using warmer air of, for example, 40 ° C, but a low Water content of 3.4 g / kg and a relative humidity of 7.4% results in a coefficient of variation of 11.3% is therefore a factor of 2.7 less than when used of cooler air with higher humidity. According to the invention it is therefore essential to condition the air gap with dry air. The temperature of the Cooling air plays a minor role.

Die Erfindung wird im folgenden anhand von weiteren Beispielen näher erläutert und beschrieben.The invention is further illustrated below Examples explained and described in more detail.

Die obengenannten und auch die im weiteren ausgeführten Beispiele wurden erhalten, indem eine Lösung aus 14 Gew.% des Zellstoffs Viscokraft ELV (International Paper Company) mit einem Polymerisationsgrad von 680, ca. 76 Gew.% N-Methylmorpholin-N-oxid (NMMO) -einem tertiären Amin-N-oxid-, 10 Gew.% Wasser und 0,14 Gew.% Gallussäurepropylester als Stabilisator durch eine Spinndüsenplatte mit 50 Düsenlöchern von jeweils 130 µm Düsenlochdurchmesser zu einem Filamentgarn versponnen wurde. Die in der Spinndüse (T = 110°C) geformten Filamente wurden in einem Luftspalt von 18 cm Länge gekühlt. Im Luftspalt erfolgte eine Anblasung mit Luft mit einer Anblasgeschwindigkeit von 0,8 m/s rechtwinklig zum Fadenbündel. Die Luft wurde einseitig auf das Bündel geblasen, und die homogene Verteilung der Luft erfolgte mit sehr feinmaschigen Sieben mit einer Breite von 10 cm, und die Anblasung erfolgte über eine Strecke von 10 cm ab Düsenaustritt.The above and also those detailed below Examples were obtained by using a 14 wt% solution of the Viscokraft ELV (International Paper Company) pulp with a degree of polymerization of 680, approx. 76% by weight N-methylmorpholine-N-oxide (NMMO) -a tertiary amine-N-oxide-, 10% by weight of water and 0.14% by weight of propyl gallic acid as a stabilizer with a spinneret plate 50 nozzle holes of 130 µm diameter each was spun in a filament yarn. The one in the spinneret (T = 110 ° C) shaped filaments were in an air gap cooled by 18 cm in length. One took place in the air gap Air blowing at a blowing speed of 0.8 m / s perpendicular to the bundle of threads. The air became one-sided blown onto the bundle, and the homogeneous distribution the air was done with very fine-meshed sieves with one Width of 10 cm, and the blowing was carried out over a Distance of 10 cm from the nozzle outlet.

Die Filamente wurden im Luftspalt um einen Faktor 16 verstreckt und nach Durchlaufen eines Wasserbades zur Koagulation und nachgeschalteten Waschbädern zur Entfernung des NMMO getrocknet. Die Abzugsgeschwindigkeit betrug 420 m/min.The filaments were drawn by a factor of 16 in the air gap and after going through a water bath Coagulation and downstream washing baths for removal of the NMMO dried. The withdrawal speed was 420 m / min.

Die jeweils erhaltenen Filamentbündel wurden in einem Abstand von einem Meter 2 mal senkrecht zur Bündelachse durchgeschnitten. Die Querschnittsflächen der Filamente wurden mittels eines Lichtmikroskops (Vergrößerung 570 : 1) und einer Videokamera in ein Computer-Bild-Analyse-System (Quantimet 970) übertragen und ausgewertet. Die Fläche jedes Filaments wurde bestimmt. Aus dem Mittelwert der Filamentquerschnitte jedes untersuchten Bündels, wobei pro Bündel zwei Schnittbilder ausgewertet wurden, und der Standardabweichung wurde der Variationskoeffizient der Filamentquerschnittsfläche in Prozent als das Verhältnis von Standardabweichung zu Mittelwert berechnet.The filament bundles obtained in each case were in one Distance of one meter twice perpendicular to the bundle axis cut across. The cross-sectional areas of the filaments were examined using a light microscope (magnification 570: 1) and a video camera in a computer image analysis system (Quantimet 970) transferred and evaluated. The area of each Filament was determined. From the mean of the filament cross sections each bundle examined, being per bundle two cross-sectional images were evaluated, and the standard deviation became the coefficient of variation of the filament cross-sectional area in percent as the ratio of Standard deviation to mean calculated.

Zur Herstellung von konditionierter Luft wurde von Raumluft ausgegangen, die eine Temperatur von 21°C, einen Wassergehalt von 9,2 g/kg und eine relative Feuchtigkeit von 60% aufwies, und die zunächst über Filter gereinigt wurde. Zur Erhöhung des Mischungsverhältnisses wurde die Luft mit Wasserdampf gesättigter Luft (relative Feuchtigkeit 100%) von 80°C gemischt. Um einen Massenstrom m(x) konditionierte Luft mit dem Wassergehalt x zu erhalten, wurde ein Massenstrom mu Umgebungsluft mit dem Wassergehalt xu mit einem Massenstrom wasserdampfgesättigter Luft mh mit dem Wassergehalt xh gemäß m(x) = mu + mh gemischt. Das Mischungsverhältnis von mu und mh berechnet sich gemäß folgender Gleichung: mu mh = (xh - x) (1 + xu) (x - xu) (1 + xh) For the production of conditioned air, room air was assumed which had a temperature of 21 ° C, a water content of 9.2 g / kg and a relative humidity of 60%, and which was first cleaned using filters. To increase the mixing ratio, the air was mixed with water vapor saturated air (relative humidity 100%) of 80 ° C. In order to obtain a mass flow m (x) of conditioned air with the water content x, a mass flow m u of ambient air with the water content x u with a mass flow of water vapor-saturated air m h with the water content x h according to m (x) = m u + m h mixed. The mixing ratio of m u and m h is calculated according to the following equation: m u m H = (x H - x) (1 + x u ) (x - x u ) (1 + x H )

Der resultierende Luftstrom wurde anschließend auf die gewünschte Temperatur mit einem Wärmeaustauscher abgekühlt. Die relative Feuchtigkeit und der Wassergehalt wurde mit einem Psychrometer (ALMEMO 2290-2 mit Psychrometergeber AN 846 bzw. Feuchte-/ Temperaturfühler AFH 9646-2) bestimmt.The resulting airflow was then applied to the cooled the desired temperature with a heat exchanger. The relative humidity and water content were measured with a psychrometer (ALMEMO 2290-2 with psychrometer sensor AN 846 or humidity / temperature sensor AFH 9646-2).

Zur Erniedrigung des Wassergehaltes wurde Umgebungsluft abgekühlt, bis diese eine relative Feuchtigkeit von 100% aufwies. Anschließend erfolgte eine weitere Abkühlung, und das auskondensierende Wasser wurde abgeschieden. Mit dieser Vorgehensweise ließ sich die Luft bis zu einem Wassergehalt von etwa 4 g/kg trocknen. Im Anschluß daran erfolgte eine Wiedererwärmung der Luft auf die gewünschte Temperatur. Die relative Feuchtigkeit und der Wassergehalt wurden mit dem Psychrometer gemessen.Ambient air was used to lower the water content cooled down to a relative humidity of 100% exhibited. This was followed by further cooling, and the condensing water was separated. With this Procedure let the air up to a water content of about 4 g / kg dry. This was followed by a Reheating the air to the desired temperature. The relative humidity and water content were measured with the Psychrometer measured.

Um konditionierte Luft mit einem Wassergehalt unter 4 g/kg zu erhalten, wurde die zuvor durch Auskondensieren vorgetrocknete Luft mit einem Luftentfeuchter (Modell 120 KS der Firma Munters GmbH) weiter getrocknet. Die Wiedererwärmung der trockenen Luft erfolgte ebenfalls mit einem Wärmeaustauscher. Die Bestimmung der relativen Feuchtigkeit und des Wassergehaltes der Luft, die auf einen Wassergehalt von weniger als 4 g/kg getrocknet wurde, erfolgte mit einem spiegelgekühlten Taupunktsmesser (S4000 RS der Firma MICHELL Instruments).To conditioned air with a water content below 4 g / kg was obtained by condensing pre-dried air with a dehumidifier (model 120 KS from Munters GmbH) further dried. The reheating the dry air was also done with a Heat exchanger. The determination of the relative humidity and the water content of the air based on a water content of less than 4 g / kg was carried out with a Mirror-cooled dew point knife (S4000 RS from MICHELL Instruments).

In den nachfolgenden Tabellen sind die untersuchten Luftzustände, charakterisiert durch die Temperatur (T/°C), den Wassergehalt (x/(g/kg)) und die relative Feuchtigkeit (rH/%), sowie die Variationskoeffizienten der Filamentquerschnittsflächen (V/%) angegeben. Beispiele gemäß der Erfindung Beispiel T/°C x/(g/kg) rH/% V/% 1 6 4,7 80 8,1 2 6 1,8 30 5,0 3 10 1,7 22 5,0 4 10 2,3 30 6,1 5 10 3,0 39 6,6 6 10 3,8 50 6,5 7 10 4,8 62 7,7 8 10 5,4 68 8,5 9 10 0,9 11 5,0 10 20 1,2 9 5,8 11 21 1,0 7 5,4 12 21 2,1 14 8,0 13 21 3,1 20 9,8 14 31 2,1 8 8,4 15 40 3,4 7 11,3 The following tables show the examined air conditions, characterized by the temperature (T / ° C), the water content (x / (g / kg)) and the relative humidity (rH /%), as well as the variation coefficients of the filament cross-sectional areas (V /% ) specified. Examples according to the invention example T / ° C x / (g / kg) rH /% V /% 1 6 4.7 80 8.1 2nd 6 1.8 30th 5.0 3rd 10th 1.7 22 5.0 4th 10th 2.3 30th 6.1 5 10th 3.0 39 6.6 6 10th 3.8 50 6.5 7 10th 4.8 62 7.7 8th 10th 5.4 68 8.5 9 10th 0.9 11 5.0 10th 20th 1.2 9 5.8 11 21 1.0 7 5.4 12th 21 2.1 14 8.0 13 21 3.1 20th 9.8 14 31 2.1 8th 8.4 15 40 3.4 7 11.3

Tabelle I zeigt deutlich, daß quasi unabhängig von der Temperatur der konditionierten Luft die niedrigsten Variationskoeffizienten der Filamentquerschnittsflächen resultieren, wenn die konditionierte Luft einen geringen Wassergehalt aufweist, wie bei den Beispielen Nr. 2, 3, 9, 10 und 11, bei denen bei Wassergehalten unterhalb von 2 g/kg der Variationskoeffizient nur in der Größenordnung von 5 bis 6 % liegt. Die relative Feuchtigkeit lag bei diesen Beispielen unterhalb 30%. Unter Einhaltung der erfindungsgemäßen Bedingungen ist der Variationskoeffizient selbst bei hoher Temperatur (Beispiel 15) niedriger als außerhalb des erfindungsgemäßen Bereichs bei erheblich tieferen Temperaturen. Vergleichsbeispiele Beispiel T/°C x/(g/kg) rH/% V/% 16 6 5,1 87 16,1 17 10 7,5 97 14,5 18 11 8,0 97 16,8 19 12 8,2 92 20,8 20 12 8,9 100 21,9 21 20 14,0 94 30,0 22 21 9,2 60 23,4 23 21 13,7 89 26,6 24 21 15,4 100 31,6 Table I clearly shows that, irrespective of the temperature of the conditioned air, the lowest coefficients of variation of the filament cross-sectional areas result when the conditioned air has a low water content, as in Examples Nos. 2, 3, 9, 10 and 11, in those with water contents below 2 g / kg the coefficient of variation is only in the order of 5 to 6%. The relative humidity in these examples was below 30%. In compliance with the conditions according to the invention, the coefficient of variation is lower even at high temperature (example 15) than outside the range according to the invention at considerably lower temperatures. Comparative examples example T / ° C x / (g / kg) rH /% V /% 16 6 5.1 87 16.1 17th 10th 7.5 97 14.5 18th 11 8.0 97 16.8 19th 12th 8.2 92 20.8 20th 12th 8.9 100 21.9 21 20th 14.0 94 30.0 22 21 9.2 60 23.4 23 21 13.7 89 26.6 24th 21 15.4 100 31.6

Tabelle II verdeutlicht, daß außerhalb des erfindungsgemäßen Bereichs die Variationskoeffizienten der Filamentquerschnittsflächen oberhalb von 14% liegen und sogar Werte von über 30% erreicht werden. Derart hohe Schwankungen sind bei der Herstellung von Filamentgarn unerwünscht, da sich diese bei der Verarbeitung zu textilen Flächengebilden negativ auswirken und insbesondere zu einer uneinheitlichen Färbung des Flächengebildes führen. Ebenso kann es aufgrund unterschiedlicher Festigkeiten der Einzelfilamente untereinander und in bezug auf das Garn zu Verarbeitungsproblemen kommen. Zudem wird mit den Beispielen 16 und 22 gezeigt, daß für die vorliegende Erfindung beide Forderungen, d.h. ein Wassergehalt unterhalb von 7 g Wasserdampf je kg trockene Luft und eine relative Feuchtigkeit unterhalb 85% gewährleistet sein müssen. Bei Beispiel 16 lag zwar der Wassergehalt in dem beanspruchten Bereich, jedoch wies die Luft eine höhere relative Feuchtigkeit auf, und es resultierte ein Variationskoeffizient von 16,1%. Beispiel 22 zeigt die Bedingungen der Umgebungsluft bei einer Temperatur von 21°C, bei einer relativen Feuchtigkeit von 60% und einem Wassergehalt von 9,2 g/kg. Bei diesem Beispiel liegt zwar die relative Feuchtigkeit in dem beanspruchten Bereich, nicht jedoch der Wassergehalt, und es resultiert ein Variationskoeffizient von 23,4%. Dieses Beispiel verdeutlicht darüber hinaus, daß es nicht ausreichend ist, eine Kühlung mit Umgebungsluft vorzunehmen, und daß es nicht ausreichend ist, eine einfache Anblasung mit Raumluft durchzuführen, die kühler ist als die üblicherweise im Luftspalt herrschende Temperatur, um eine Verbesserung textiler Eigenschaften zu erreichen.Table II shows that outside of the invention Range the variation coefficients of the filament cross-sectional areas are above 14% and even values of over 30% can be achieved. Such high fluctuations are in the production of filament yarn is undesirable because this negative when processing into textile fabrics affect and in particular to a non-uniform coloring of the fabric. Likewise, it can be due to different Strengths of the individual filaments with each other and there are processing problems with the yarn. In addition, Examples 16 and 22 show that for the present invention both claims, i.e. a water content below 7 g water vapor per kg dry air and a relative humidity below 85% can be guaranteed have to. In example 16, the water content was in the area, but the air was higher relative humidity, and a coefficient of variation resulted of 16.1%. Example 22 shows the conditions the ambient air at a temperature of 21 ° C, at a relative humidity of 60% and a water content of 9.2 g / kg. In this example, the relative lies Moisture in the stressed area, but not that Water content, and a coefficient of variation results of 23.4%. This example also shows that cooling with ambient air is not sufficient to make, and that it is not enough, a simple Blow with indoor air that is cooler than that temperature usually prevailing in the air gap, around a To achieve improvement in textile properties.

Claims (10)

  1. Process for manufacturing cellulose formed objects, whereby a solution of cellulose is formed in the warm state in a tertiary amine N-oxide and, if necessary, water and the formed solution is cooled with air before introducing it into a coagulation bath, characterized in that conditioned air is employed for cooling which exhibits a water content of 0.1 to 7 g water vapor per kg dry air and whose relative humidity amounts to less than 85%.
  2. Process according to Claim 1, characterized in that the water content amounts to between 0.7 and 4 g water vapor per kg dry air, preferably 0.7 to 2 g.
  3. Process according to Claim 1 or 2, characterized in that the cooling is carried out with streaming air, whereby this air is blown against the formed solution and/or drawn away from it.
  4. Process according to Claim 1, 2 or 3, characterized in that the formed solution is subjected to the conditioned air throughout the entire pathway up to the introduction into the coagulation bath.
  5. Process according to Claim 1, 2 or 3, characterized in that the formed solution is subjected to the conditioned air over a portion of the pathway up to the introduction into the coagulation bath.
  6. Process according to Claim 5, characterized in that the formed solution is subjected to the conditioned air in the first part of the pathway.
  7. Process according to one or more of Claims 1 to 6, characterized in that the conditioned air streams at an angle of 0° to 120°, preferably 90° in relation to the direction of movement of the formed solution, whereby the angle of 0° corresponds to a flow opposite to the running direction of the formed solution.
  8. Process according to one or more of Claims 1 to 7 characterized in that the formed solution is drawn before the introduction into the coagulation bath.
  9. Process according to one or more of Claims 1 to 8 characterized in that fibers, in particular filaments, films, hollow filaments and membranes are produced from the solution.
  10. Yarn of cellulose filaments produced from a solution of cellulose in a tertiary amine N-oxide and if necessary water, characterized in that the cross-sectional areas of the filaments exhibit a coefficient of variation lower than 12%, preferably lower than 10%.
EP95939293A 1994-12-02 1995-11-24 Method of producing shaped cellulose bodies, and yarn made of cellulose filaments Expired - Lifetime EP0795052B2 (en)

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