EP0795052B2 - 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 PDFInfo
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- EP0795052B2 EP0795052B2 EP95939293A EP95939293A EP0795052B2 EP 0795052 B2 EP0795052 B2 EP 0795052B2 EP 95939293 A EP95939293 A EP 95939293A EP 95939293 A EP95939293 A EP 95939293A EP 0795052 B2 EP0795052 B2 EP 0795052B2
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- Prior art keywords
- air
- solution
- process according
- cellulose
- filaments
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- 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
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- 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
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- 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
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- 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 molded bodies, wherein a solution of cellulose in a tertiary amine N-oxide and optionally water is formed in a hot state and the molded solution is cooled before introduction into a coagulation bath with air, and a Gam cellulosic filaments.
- the air gap is the area between the shaping element and the coagulation bath in which the cellulose is precipitated.
- the temperature in the air gap is lower than in the spinneret, but is significantly higher than room temperature due to the heat radiation through the spinneret and resulting from the Enthalpiestrom the moldings heating of the air. Due to the permanent evaporation of water, which is usually used as a coagulation bath, so humid conditions are present in the air gap.
- WO 93/19230 to cool the molded solution immediately after molding, faster cooling is effected so that the tackiness of the molded solution decreases correspondingly faster.
- Post-published application WO 98/28218 describes a process for producing cellulose filaments with a solution of cellulose in an organic solvent, wherein the solution is extruded through a die having a plurality of holes to form a plurality of strands, the strands via a gas gap in directs a spin bath containing water to form the filaments and introduces a forced gas flow through the gap parallel to the water surface in the spin bath.
- the air can have a temperature of 0 ° C to 50 ° C.
- the dew point in WO 98/28218 is preferably in the range of 4 to 10 ° C (water vapor content 5 to 7.5 g / kg).
- the temperature of the air is then in the range of 5 ° C to 30 ° C, but the air at 10 ° C may also have a relative humidity of 100%. It is also preferable to use air having a temperature of 10 ° C to 40 ° C and a relative humidity in the dew point range of 4 ° C to 10 ° C, using air having a typical temperature of 20 ° C.
- the object of the present invention is to improve such a method but in particular also the properties of the shaped bodies produced therewith, preferably filaments, or of a filament yarn.
- This object is achieved by a method for producing cellulosic molded bodies, wherein a solution of cellulose in a tertiary amine N-oxide and optionally water is formed in a hot state and the molded solution is cooled before introduction into a coagulation bath with air, wherein the Cooling conditioned air is used, which has a water content of 0.1 to 2 g of water vapor per kg of dry air and their relative humidity is less than 85%.
- This water content of conditioned air corresponds to a dew point range of -8 ° C (2 g of steam per kg of dry air) to about -50 ° C (0.1 g of steam per kg of dry air) and is thus well outside the scope of WO 98/28218 ,
- the water content of the conditioned air is 0.7 (dew point -24 ° C) to 2 g of steam per kg of dry air.
- the cooling can be done with flowing air, which is blown against the formed solution or sucked from this.
- the aspiration may be accomplished by providing conditioned air and soaking it through, for example, a bundle of freshly spun fibers or filaments. Particularly advantageous is a combination of blowing and suction.
- the shaped solution may be exposed to the conditioned air all the way to the coagulation bath, or only over part of that length, it being advantageous to apply the air in the first part, that is, it is advantageous. H. in the region of the air gap, which adjoins directly to the shaping element.
- the conditioned air should flow at an angle of 0 to 120 °, preferably 90 °, relative to the direction of movement of the formed solution, the angle of 0 ° corresponding to an incident flow opposite to the direction of travel of the formed solution.
- fibers in particular filaments, films, hollow fibers, membranes, for example for use in dialysis, oxygenation or filtration can be produced in an advantageous manner.
- the formation of the solution into a desired cellulosic molding can be carried out with known spinnerets for the production of fibers, slot dies or hollow thread spinnerets. Following formation, i. before introducing the shaped solution into the coagulation bath, it can be stretched.
- a yarn of cellulosic filaments prepared from a solution of cellulose in a tertiary amine N-oxide and optionally water, is characterized in that the cross-sectional areas of the filaments have a coefficient of variation of less than 6%.
- the influence of the water content or of the mixing ratio is manifested during filament production, in particular in irregularities of the filament cross sections.
- the coefficient of variation of the filament cross-sectional areas is 30% in a yarn with 50 individual filaments.
- the coefficient of variation at the same temperature lowered to 5.8%.
- Even when using warmer air, 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%, which is thus a factor of 2.7 lower than when using cooler air with higher humidity.
- it is therefore essential to carry out a conditioning of the air gap with dry air.
- the temperature of the cooling air plays rather a minor role.
- the filaments were stretched in the air gap by a factor of 16 and dried after passing through a water bath for coagulation and washed washing baths to remove the NMMO.
- the take-off speed was 420 m / min.
- the respectively obtained filament bundles were cut through at a distance of one meter 2 times perpendicular to the bundle axis.
- the cross-sectional areas of the filaments were transferred by means of a light microscope (magnification 570: 1) and a video camera in a computer-image analysis system (Quantimet 970) and evaluated.
- the area of each filament was determined. From the mean value of the filament cross sections of each bundle examined, where two sectional images were evaluated per bundle, and the standard deviation, the coefficient of variation of the filament cross section area was calculated as the ratio of standard deviation to mean value.
- the resulting air stream was then cooled to the desired temperature with a heat exchanger.
- the relative humidity and the water content were determined with a psychrometer (ALME-MO 2290-2 with psychrometer AN 846 or humidity / temperature probe AFH 9646-2).
- ambient air was cooled until it had a relative humidity of 100%. Subsequently, a further cooling, and the auskondensierende water was deposited. With this procedure, the air was allowed to dry to a water content of about 4 g / kg. Subsequently, the air was reheated to the desired temperature. The relative humidity and water content were measured with the psychrometer.
- the air previously predried by condensation was further dried using a dehumidifier (Model 120 KS from Munters GmbH).
- the reheating of the dry air was also carried out with a heat exchanger.
- the determination of the relative humidity and the water content of the air, which was dried to a water content of less than 4 g / kg, was carried out with a mirror-cooled dew point meter (S4000 RS from MI-CHELL Instruments).
- Table I clearly shows that the lowest coefficients of variation of the filament cross-sectional areas result, almost independently of the temperature of the conditioned air, when the conditioned air has a low water content, as in Examples No. 2. 3. 9. 10 and 11, in which at water contents below 2 g / kg, the coefficient of variation is only of the order of 5 to 6%. The relative humidity in these examples was below 30%.
- Example 22 shows the conditions of 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, although the relative humidity in the claimed area, but not the water content, and there is a coefficient of variation of 23.4%.
Abstract
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 Gam aus cellulosischen Filamenten.The invention relates to a method for producing cellulosic molded bodies, wherein a solution of cellulose in a tertiary amine N-oxide and optionally water is formed in a hot state and the molded solution is cooled before introduction into a coagulation bath with air, and a Gam 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, wherein the cooling is to take place immediately after molding. With this method is to be achieved that the stickiness of the freshly extruded moldings is reduced, so that in the production of cellulosic filaments a spinneret with high hole density can be used. For cooling, the shaped solution is preferably exposed to a gas stream.
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.Cooling of the warm-shaped solution already takes place when the shaped solution leaves the shaping element, for example a spinneret, in which temperatures typically above 90 ° C. are present, and passes into the so-called air gap. The air gap is the area between the shaping element and the coagulation bath in which the cellulose is precipitated. The temperature in the air gap is lower than in the spinneret, but is significantly higher than room temperature due to the heat radiation through the spinneret and resulting from the Enthalpiestrom the moldings heating of the air. Due to the permanent evaporation of water, which is usually used as a coagulation bath, so humid conditions are present in the air gap. With the measure proposed in WO 93/19230 to cool the molded solution immediately after molding, faster cooling is effected so that the tackiness of the molded solution decreases correspondingly faster.
Die nachveröffentlichte Anmeldung WO 98/28218 beschreibt ein Verfahren zur Erzeugung von Cellulosefilamenten mit einer Lösung von Cellulose in einem organischen Lösungsmittel, wobei man die Lösung durch eine Düse mit einer Vielzahl von Löchern zur Bildung einer Vielzahl von Strängen extrudiert, die Stränge über einen Gasspalt in ein Wasser enthaltenes Spinnbad zur Bildung der Filamente leitet und einen Zwangsgasstrom durch den Spalt parallel zu Wasseroberfläche im Spinnbad zuführt. Das Gas ist vorzugsweise Luft mit einem Taupunkt von 10 °C (Wasserdampfgehalt = 7,5 g/kg) oder darunter, wodurch die Feuchtigkeit der Luft kontrolliert werden kann. Die Luft kann dabei eine Temperatur von 0 °C bis 50 °C aufweisen. Der Taupunkt in der WO 98/28218 liegt bevorzugt im Bereich von 4 bis 10 °C (Wasserdampfgehalt 5 bis 7,5 g/kg). Die Temperatur der Luft liegt dann im Bereich von 5 °C bis 30 °C, jedoch kann die Luft bei 10 °C auch eine relative Feuchtigkeit von 100 % aufweisen. Weiterhin bevorzugt verwendet man Luft mit einer Temperatur von 10 °C bis 40 °C und einer relativen Feuchtigkeit im Taupunktsbereich von 4 °C bis 10 °C, wobei Luft mit einer typischen Temperatur von 20 °C eingesetzt wird.Post-published application WO 98/28218 describes a process for producing cellulose filaments with a solution of cellulose in an organic solvent, wherein the solution is extruded through a die having a plurality of holes to form a plurality of strands, the strands via a gas gap in directs a spin bath containing water to form the filaments and introduces a forced gas flow through the gap parallel to the water surface in the spin bath. The gas is preferably air with a dew point of 10 ° C (water vapor content = 7.5 g / kg) or below, whereby the humidity of the air can be controlled. The air can have a temperature of 0 ° C to 50 ° C. The dew point in WO 98/28218 is preferably in the range of 4 to 10 ° C (water vapor content 5 to 7.5 g / kg). The temperature of the air is then in the range of 5 ° C to 30 ° C, but the air at 10 ° C may also have a relative humidity of 100%. It is also preferable to use air having a temperature of 10 ° C to 40 ° C and a relative humidity in the dew point range of 4 ° C to 10 ° C, using air having a typical temperature of 20 ° C.
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 object of the present invention is to improve such a method but in particular also the properties of the shaped bodies produced therewith, preferably filaments, or of a filament yarn.
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 2 g Wasserdampf je kg trockene Luft aufweist und deren relative Feuchtigkeit weniger als 85% beträgt.This object is achieved by a method for producing cellulosic molded bodies, wherein a solution of cellulose in a tertiary amine N-oxide and optionally water is formed in a hot state and the molded solution is cooled before introduction into a coagulation bath with air, wherein the Cooling conditioned air is used, which has a water content of 0.1 to 2 g of water vapor per kg of dry air and their relative humidity is less than 85%.
Dieser Wassergehalt konditionierter Luft entspricht einem Taupunktbereich von -8 °C (2 g Wasserdampf je kg trockene Luft) bis etwa -50 °C (0,1 g Wasserdampf je kg trockene Luft) und liegt damit deutlich außerhalb des Bereiches der WO 98/28218.This water content of conditioned air corresponds to a dew point range of -8 ° C (2 g of steam per kg of dry air) to about -50 ° C (0.1 g of steam per kg of dry air) and is thus well outside the scope of WO 98/28218 ,
Vorzugsweise beträgt der Wassergehalt der konditionierten Luft 0,7 (Taupunkt -24 °C) bis 2 g Wasserdampf je kg trockene Luft.Preferably, the water content of the conditioned air is 0.7 (dew point -24 ° C) to 2 g of steam per kg of dry air.
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 cooling can be done with flowing air, which is blown against the formed solution or sucked from this. The aspiration may be accomplished by providing conditioned air and soaking it through, for example, a bundle of freshly spun fibers or filaments. Particularly advantageous is 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 may be exposed to the conditioned air all the way to the coagulation bath, or only over part of that length, it being advantageous to apply the air in the first part, that is, it is advantageous. H. in the region of the air gap, which adjoins directly to the shaping element. The conditioned air should flow at an angle of 0 to 120 °, preferably 90 °, relative to the direction of movement of the formed solution, the angle of 0 ° corresponding to an incident flow opposite to the direction of travel of the formed 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.With the method according to the invention, fibers, in particular filaments, films, hollow fibers, membranes, for example for use in dialysis, oxygenation or filtration can be produced in an advantageous manner. The formation of the solution into a desired cellulosic molding can be carried out with known spinnerets for the production of fibers, slot dies or hollow thread spinnerets. Following formation, i. before introducing the shaped solution into the coagulation bath, it can be stretched.
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 6% aufweisen.A yarn of cellulosic filaments, prepared from a solution of cellulose in a tertiary amine N-oxide and optionally water, is characterized in that the cross-sectional areas of the filaments have a coefficient of variation of less than 6%.
Wie bereits ausgeführt, ist eine Abkühlung der frischextrudierten Formkörper im Luftspalt von Vorteil, um so deren Klebrigkeit rascher zu verringem. Um Oberhaupt 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, it is advantageous to cool the freshly extruded moldings in the air gap, in order to reduce their stickiness more rapidly. In order to cool head, the gas flow must naturally have a temperature which is below that of the molded solution. According to WO 93/19230, a gas stream is used which has a 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.However, it has now been found that not the temperature as such, but the water content of the air and their relative humidity on the properties of the cellulosic molded body have a significant influence. The water content of air in g of water vapor per kg of dry air is often referred to as the mixing ratio. In the following, the unit g / kg is simplified for this purpose. In particular, in the production of filaments, it has been found that it is important to create in the air gap as constant as possible climatic conditions, ie turn off usually occurring fluctuations in the ambient climate. In particular, it is important that fluctuations in the humidity are avoided, and that the air has only a low water content. Even in the presence of air conditioners can seasonal fluctuations and sometimes daily Fluctuations in rooms are not sufficiently suppressed. Furthermore, the conditioning should be carried out as evenly as possible, since even small instabilities in terms of Anblasstärke and blowing direction the strength. Elongation and titer constancy of filaments negatively 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 Gam 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 of the mixing ratio is manifested during filament production, in particular in irregularities of the filament cross sections. When cooled with air at 20 ° C and a water content of 14 g / kg and a relative humidity of 94%, the coefficient of variation of the filament cross-sectional areas is 30% in a yarn with 50 individual filaments. When reducing the water content to 1.2 g / kg and a relative humidity of 8.5%, the coefficient of variation at the same temperature lowered to 5.8%. Even when using warmer air, 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%, which is thus a factor of 2.7 lower than when using cooler air with higher humidity. According to the invention it is therefore essential to carry out a conditioning of the air gap with dry air. The temperature of the cooling air plays rather a minor role.
Die Erfindung wird im folgenden anhand von weiteren Beispielen näher erläutert und beschrieben.The invention will be explained and described in more detail below with reference to further examples.
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 Luttspatt 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 the examples set out below were obtained by dissolving a solution of 14% by weight of Viscokraft ELV pulp (International Paper Company) having a degree of polymerization of 680. about 76% by weight of N-methylmorpholine N-oxide (NMMO ) - a tertiary amine N-oxide, 10 wt.% Water and 0.14 wt.% Gallic acid propyl ester was spun as a stabilizer through a spinneret plate with 50 nozzle holes of 130 .mu.m nozzle hole diameter to a filament yarn. The filaments formed in the spinneret (T = 110 ° C) were cooled in a latte of 18 cm in length. In the air gap, a blowing with air at a blowing speed of 0.8 m / s was perpendicular to the bundle of fibers. The air was blown on one side of the bundle, and the homogeneous distribution of the air was done with very fine-meshed sieves with a width of 10 cm, and the blowing took place over a distance of 10 cm from the nozzle exit.
Die Filamente wurden im Luftspalt um einen Faktor 16 verstreckt und nach Durchlaufen eines Wasserbades zur Koagulation und nachgeschafteten Waschbädem zur Entfemung des NMMO getrocknet. Die Abzugsgeschwindigkeit betrug 420 m/min.The filaments were stretched in the air gap by a factor of 16 and dried after passing through a water bath for coagulation and washed washing baths to remove the NMMO. The take-off 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 Filamentquerschniffsfläche in Prozent als das Verhältnis von Standardabweichung zu Mittelwert berechnet.The respectively obtained filament bundles were cut through at a distance of one meter 2 times perpendicular to the bundle axis. The cross-sectional areas of the filaments were transferred by means of a light microscope (magnification 570: 1) and a video camera in a computer-image analysis system (Quantimet 970) and evaluated. The area of each filament was determined. From the mean value of the filament cross sections of each bundle examined, where two sectional images were evaluated per bundle, and the standard deviation, the coefficient of variation of the filament cross section area was calculated as the ratio of standard deviation to mean value.
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:
Der resultierende Luftstrom wurde anschließend auf die gewünschte Temperatur mit einem Wärmeaustauscher abgekühlt. Die relative Feuchtigkeit und der Wassergehalt wurde mit einem Psychrometer (ALME-MO 2290-2 mit Psychrometergeber AN 846 bzw. Feuchte-/ Temperaturfühler AFH 9646-2) bestimmt.The resulting air stream was then cooled to the desired temperature with a heat exchanger. The relative humidity and the water content were determined with a psychrometer (ALME-MO 2290-2 with psychrometer AN 846 or humidity / temperature probe 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.To reduce the water content, ambient air was cooled until it had a relative humidity of 100%. Subsequently, a further cooling, and the auskondensierende water was deposited. With this procedure, the air was allowed to dry to a water content of about 4 g / kg. Subsequently, the air was reheated to the desired temperature. The relative humidity and water content were measured with the psychrometer.
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 MI-CHELL Instruments).To obtain conditioned air with a water content of less than 4 g / kg, the air previously predried by condensation was further dried using a dehumidifier (Model 120 KS from Munters GmbH). The reheating of the dry air was also carried out with a heat exchanger. The determination of the relative humidity and the water content of the air, which was dried to a water content of less than 4 g / kg, was carried out with a mirror-cooled dew point meter (S4000 RS from MI-CHELL 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.
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%.Table I clearly shows that the lowest coefficients of variation of the filament cross-sectional areas result, almost independently of the temperature of the conditioned air, when the conditioned air has a low water content, as in Examples No. 2. 3. 9. 10 and 11, in which at water contents below 2 g / kg, the coefficient of variation is only of the order of 5 to 6%. The relative humidity in these examples was below 30%.
Tabelle II verdeutlicht, daß außerhalb des erfindungsgemäßen Bereichs die Variationskoeffizienten der Filamentquerschnittsflächen oberhalb von 6% liegen und sogar Werte von über 30% erreicht werden. Derart hohe Schwankungen sind bei der Herstellung von Filamentgam unerwünscht, da sich diese bei der Verarbeitung zu textilen Flächengebilden negativ auswirken und insbesondere zu einer uneinheilichen Färbung des Flächengebildes führen. Ebenso kann es aufgrund unterschiedlicher Festigkeiten der Einzellilamente untereinander und in bezug auf das Garn zu Verarbeitungsproblemen kommen. 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.
Claims (10)
- 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 conditioned air before introducing it into a coagulation bath, characterized in that the conditioned air exhibits a water content of 0.1 to 2 g water vapor per kg dry air and whose relative humidity amounts to less than 85 %.
- Process according to claim 1, characterized in that the water content amounts to between 0.7 to 2 g water vapor per kg dry air.
- 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.
- 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.
- 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.
- Process according to Claim 5, characterized in that the formed solution is subjected to the conditioned air in the first part of the pathway.
- 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.
- 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.
- 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.
- Yarn of cellulose filaments produced fro a solution of cellulose I 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 6%.
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DE4442890 | 1994-12-02 | ||
DE4442890 | 1994-12-02 | ||
PCT/EP1995/004634 WO1996017118A1 (en) | 1994-12-02 | 1995-11-24 | Method of producing shaped cellulose bodies, and yarn made of cellulose filaments |
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EP0795052B1 EP0795052B1 (en) | 1998-06-24 |
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EP95939293A Expired - Lifetime EP0795052B2 (en) | 1994-12-02 | 1995-11-24 | Method of producing shaped cellulose bodies, and yarn made of cellulose filaments |
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US (2) | US5902532A (en) |
EP (1) | EP0795052B2 (en) |
JP (1) | JPH10510011A (en) |
KR (1) | KR100398294B1 (en) |
CN (1) | CN1066214C (en) |
AT (1) | ATE167709T1 (en) |
AU (1) | AU695212B2 (en) |
CA (1) | CA2205466A1 (en) |
CZ (1) | CZ288742B6 (en) |
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ES (1) | ES2120243T5 (en) |
HU (1) | HU220367B (en) |
PL (1) | PL183097B1 (en) |
SK (1) | SK67697A3 (en) |
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GB9605504D0 (en) * | 1996-03-15 | 1996-05-15 | Courtaulds Plc | Manufacture of elongate members |
AT405531B (en) | 1997-06-17 | 1999-09-27 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC FIBERS |
AT408656B (en) * | 1998-06-04 | 2002-02-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES |
US6773648B2 (en) | 1998-11-03 | 2004-08-10 | Weyerhaeuser Company | Meltblown process with mechanical attenuation |
DE19954152C2 (en) * | 1999-11-10 | 2001-08-09 | Thueringisches Inst Textil | Method and device for producing cellulose fibers and cellulose filament yarns |
AT408355B (en) * | 2000-06-29 | 2001-11-26 | Chemiefaser Lenzing Ag | Process for producing cellulosic fibres |
DE10043297B4 (en) * | 2000-09-02 | 2005-12-08 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Process for the production of cellulose fibers and cellulose filament yarns |
CN1240890C (en) * | 2001-08-11 | 2006-02-08 | 坦塞尔有限公司 | Process for prepn. of cellulosic shaped bodies |
DE10200406A1 (en) * | 2002-01-08 | 2003-07-24 | Zimmer Ag | Spinning device and process with turbulent cooling blowing |
DE10200405A1 (en) * | 2002-01-08 | 2002-08-01 | Zimmer Ag | Cooling blowing spinning apparatus and process |
DE10206089A1 (en) | 2002-02-13 | 2002-08-14 | Zimmer Ag | bursting |
DE202005002863U1 (en) | 2005-02-21 | 2006-06-29 | Cordenka Gmbh | airbag fabrics |
US7905721B2 (en) * | 2007-06-05 | 2011-03-15 | Husky Injection Molding Systems Ltd. | Air source device and a method for use in a molding system |
TWI667378B (en) | 2014-01-03 | 2019-08-01 | 奧地利商蘭精股份有限公司 | Cellulosic fibre |
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US4416698A (en) † | 1977-07-26 | 1983-11-22 | Akzona Incorporated | Shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent and a process for making the article |
DD277289A1 (en) † | 1988-11-24 | 1990-03-28 | Schwarza Chemiefaser | METHOD OF DISPENSING VISCOELASTIC POLYMER SOLUTIONS |
WO1994028218A1 (en) † | 1993-05-24 | 1994-12-08 | Courtaulds Fibres (Holdings) Limited | Spinning cell |
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US4246221A (en) * | 1979-03-02 | 1981-01-20 | Akzona Incorporated | Process for shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent |
US4144080A (en) * | 1977-07-26 | 1979-03-13 | Akzona Incorporated | Process for making amine oxide solution of cellulose |
US4324593A (en) * | 1978-09-01 | 1982-04-13 | Akzona Incorporated | Shapeable tertiary amine N-oxide solution of cellulose, shaped cellulose product made therefrom and process for preparing the shapeable solution and cellulose products |
AT395862B (en) * | 1991-01-09 | 1993-03-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
AT395863B (en) * | 1991-01-09 | 1993-03-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
ATA53792A (en) * | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSIC MOLDED BODIES, DEVICE FOR IMPLEMENTING THE METHOD AND USE OF A SPINNING DEVICE |
TW257811B (en) * | 1993-04-21 | 1995-09-21 | Chemiefaser Lenzing Ag | |
GB2307203B (en) * | 1993-04-21 | 1997-09-10 | Chemiefaser Lenzing Ag | Process for the production of cellulose fibres having a reduced tendency to fibrillation |
AT401271B (en) * | 1993-07-08 | 1996-07-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSE FIBERS |
JP3445865B2 (en) * | 1995-04-06 | 2003-09-08 | 花王株式会社 | Cellulosic fiber modification method |
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US4416698A (en) † | 1977-07-26 | 1983-11-22 | Akzona Incorporated | Shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent and a process for making the article |
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TW300924B (en) | 1997-03-21 |
PL183097B1 (en) | 2002-05-31 |
ATE167709T1 (en) | 1998-07-15 |
ES2120243T3 (en) | 1998-10-16 |
WO1996017118A1 (en) | 1996-06-06 |
US5902532A (en) | 1999-05-11 |
ES2120243T5 (en) | 2006-11-16 |
HU220367B (en) | 2001-12-28 |
CN1066214C (en) | 2001-05-23 |
SK67697A3 (en) | 1997-10-08 |
HUT77266A (en) | 1998-03-02 |
CZ167497A3 (en) | 1997-10-15 |
CZ288742B6 (en) | 2001-08-15 |
AU4117796A (en) | 1996-06-19 |
KR100398294B1 (en) | 2003-12-31 |
AU695212B2 (en) | 1998-08-06 |
DE59502659D1 (en) | 1998-07-30 |
PL320507A1 (en) | 1997-10-13 |
EP0795052B1 (en) | 1998-06-24 |
JPH10510011A (en) | 1998-09-29 |
US6042944A (en) | 2000-03-28 |
EP0795052A1 (en) | 1997-09-17 |
CA2205466A1 (en) | 1996-06-06 |
CN1168701A (en) | 1997-12-24 |
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