EP0083066A2 - Process and apparatus for the fixation of cationic dyes on polyacrylonitrile fibres in the gel state - Google Patents

Process and apparatus for the fixation of cationic dyes on polyacrylonitrile fibres in the gel state Download PDF

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Publication number
EP0083066A2
EP0083066A2 EP82111874A EP82111874A EP0083066A2 EP 0083066 A2 EP0083066 A2 EP 0083066A2 EP 82111874 A EP82111874 A EP 82111874A EP 82111874 A EP82111874 A EP 82111874A EP 0083066 A2 EP0083066 A2 EP 0083066A2
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Prior art keywords
goods
store
zone
dyeing
fiber cable
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EP82111874A
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German (de)
French (fr)
Inventor
Helmut Dr. Beutler
Manfred Dr. Hähnke
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Hoechst AG
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Hoechst AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B21/00—Successive treatments of textile materials by liquids, gases or vapours
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70—Material containing nitrile groups
    • D06P3/702—Material containing nitrile groups dyeing of material in the gel state
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/04—Supporting filaments or the like during their treatment
    • D01D10/0436—Supporting filaments or the like during their treatment while in continuous movement
    • 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
    • D01D11/00—Other features of manufacture
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • D06B15/02—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours by squeezing rollers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B17/00—Storing of textile materials in association with the treatment of the materials by liquids, gases or vapours

Definitions

  • the present invention relates to the continuous fixing of cationic dyes in the course of the manufacturing process on cables made from polyacrylonitrile fibers in the gel state produced by a conventional wet spinning process, in accordance with a dip dyeing / dwelling technique.
  • anionically modified polyacrylonitrile fibers in the gel state are immersed in a liquor with cationic dyes for dyeing, left in the dye bath for a dye fixation with continuous operation for a period of between 5 and 20 seconds and then to complete the dyeing rinsed with or without squeezing the fiber material.
  • a large amount of particles entrained in the d ll rch transporting goods dye liquor contained dye is usually washed out again, it ie resulting strongly colored washing water and therefore to suffer a significant loss of dye.
  • the fastness properties of dyeings obtained in this way also leave much to be desired as a result of insufficient dye fixation.
  • the object of the present invention is now to eliminate the problems identified in this connection while maintaining the favorable aspects of gel coloring and to avoid the aforementioned disadvantages of this method of working.
  • it is very difficult particularly in the case of a total titer of more than 1,000,000 dtex, to achieve uniform penetration and rapid and uniform fixation over the entire cross section of the fiber cable to achieve.
  • An improvement of the known dyeing technique should therefore be developed on the basis of a short dwell process, but without questioning the continuous process principle.
  • the spinning material which runs continuously in the form of a strand and is then soaked with dye liquor, after intensive squeezing off of the excess liquid for dye fixation, is placed in a goods store by lingering, during the passage, e.g. in the stored state or guided over rollers, sieve belts or sieve drums, exposed to moist heat and finally continuously removed from the store, after which the fiber cable thus dyed is rinsed and further processed.
  • the concept of the measures applied according to the invention is thus based on the fact that the goods, which are relatively saturated with dye liquor, are introduced after sufficient squeezing into a dwell zone in which the Dye is given a reasonable time to fix. If necessary, the goods are heated up immediately before entering the dwell zone, which shortens the fixing time. Since the process runs continuously, the colored fiber cable can be rinsed and washed immediately after leaving the dwelling zone. Instead of a very cumbersome and time-consuming dyeing process, a continuously running, easily visible and controllable dyeing process has taken place. By using the residence method for dye fixation in accordance with the new process, the cationic dyes are not only fixed on the gel fibers continuously, but also extremely gently and quickly. The dye fixation is complete, the fastness properties of the dyed fibers are good.
  • the dye liquor is normally applied at room temperature or moderately elevated temperature.
  • the fiber cable soaked with the dye preparation is heated to 50 ° to 100 ° C. after being squeezed, but immediately before entering the goods store during a passage through a heating channel, and brought it to approximately the fixing temperature.
  • the moist strand material is fed to a dwelling zone which it passes through more or less quickly in accordance with the time required for dye fixation. Only when the fixation of the dye is finished, do the rinsing of the colored fiber cable with water, as well as the measures for further treatment such as stretching, relaxing, drying etc. follow.
  • the goods store itself i.e. the dwelling zone can be operated with or without separate heating, for example at 20 ° to 60 ° C, but the goods are preferably left at elevated temperature, i.e. stay at 50 ° to 100 ° C.
  • the temperature control in the goods store, as well as in a possibly preceding heating zone, can be done by means of high frequency radiators (microwaves), by means of direct steam or by means of indirect steam, e.g. done by heated deflection rollers.
  • microwaves microwaves
  • indirect steam e.g. done by heated deflection rollers.
  • the colored spinning material stays in the dwell zone for 5 to 120 seconds, preferably 10 to 60 seconds.
  • the effectiveness of the dwell operation in the method according to the invention can be increased further by repeatedly squeezing the fiber cable strongly, possibly also alternately, from different sides during the passage through the warmed goods store.
  • a device suitable for carrying out the novel immersion dyeing / dwelling method, to which the present invention also relates consists essentially of an impregnation zone (2) containing a chassis for immersion, each designated in the direction of travel of the continuously running cable harness (1). or impregnation bath (not shown), including the subsequent pair of rollers (3), transverse to the goods run, for dewatering the spun material (1) soaked with excess dyeing liquor by squeezing pressure; a heating zone (4), essentially for applying radiation energy, steam or contact heat to the goods; and a dwelling zone (5) which is designed as a goods store (6) and has means for passing the strand material (1) through the stress-relieving phase during the dwelling phase for dye fixation.
  • This dwell zone (5) is characterized in accordance with the invention in that (5), in addition to the direction of travel of the goods - at least at the goods inlet and at the goods outlet - a plurality of crushing units / roller pairs (7) for that transported through the goods store (G) Cables (1) are arranged in a parallel position to one another or advantageously in a position rotated relative to one another by an angle of up to 90 °, optionally alternately in combination with heating fields (8).
  • the goods store which is used to hold the fiber cable soaked with dye liquor and often already preheated, can be designed quite differently: In the simplest case, it is a heatable chamber with an inclined floor, on which, due to the oblique position, the spun material is roughly de-laminated after Exit to slides. Systems in a kind of roller skids can also be used for this purpose, and chambers with sieve drums can also be used. Finally, endless circulating sieve belts are suitable for material transport through the goods store, optionally divided into several individual belts and arranged one above the other, on which the strand material is deposited.
  • heating zone (4) and dwell zone (5) i.e. Goods store (6) together with squeeze rollers (7) and heating fields (8)] are accommodated in a common container (9) which is closed by means of the goods inlet and goods outlet.
  • Dwell zones with heated chambers which are spacious enough to offer squeezing mechanisms at the entrance and exit, as well as a storage facility, are therefore extremely efficient.
  • a dwell chamber is attached to a microwave heater, which heats the material to the desired temperature and there is another heater in the chamber to prevent the fiber cable from cooling.
  • the dwell time is short in such systems, and as a result the speed of goods is relatively high.
  • FIG. 2 contains a variant of such a device, according to which the goods store is alternately interrupted by squeezing mechanisms and heating fields over the length of the dwell path.
  • the reference symbols used here are identical to the numbers used for this purpose in the text above.
  • cationic dyes of both mono-quaternary and bis-quaternary type can be used, which belong to the most diverse classes of chemical compounds, in particular the class of monoazo dyes, disazo dyes, methine, azamethine and diazamethine dyes and naphthalactam Dyes.
  • copolymers of acrylonitrile with other vinyl compounds can be used as substrates to be spun for the claimed process, these copolymers having at least 50% by weight, preferably at least 85% by weight, of acrylonitrile units.
  • the homopolymers of acrylonitrile or their copolymers used are mostly acid-modified.
  • the undrawn fibers or threads - without being dried - are treated at temperatures between 10 ° and 100 ° C., preferably between 20 ° and 80 ° C., with the dyes dissolved in aqueous or solvent-containing dyeing medium.
  • the dyeing time is generally between 0.5 and 20 seconds, preferably between 2 and 20 seconds.
  • the stated dyeing time corresponds to the contact time (residence time) of the polymer with the dye solution after spinning.
  • the dyeing operation itself is carried out according to the method continuously in the course of the manufacturing process of the fiber cable, ie as long as the freshly spun acrylonitrile polymers exist in g g elarti he form. It can be carried out during or shortly after the polymer coagulation process.
  • the colored fiber cables are then fixed under normal conditions with steam or hot air, stretched, finished and, if necessary, dried with the approval of shrinkage.
  • An acrylonitrile copolymer made of 85% acrylonitrile, 14.5% vinyl acetate and 0.5% Na vinyl sulfonate is in the form of a 28% spinning solution in dimethylformamide according to standard conditions at 80 ° C using a 100-hole spinneret with a hole diameter of 80 ⁇ m wet spun, using a coagulation bath at 50 ° C, which consists of 50% dimethylformamide and 50% water.
  • the thread material obtained passes through an impregnation zone in which a solution of 0.1 g of a mono-quaternary dye of the formula brought to pH 4.5 by means of acetic acid in 25 liters of water at room temperature.
  • the spun material is then squeezed off, heated to 80 ° C. by microwaves and introduced into a chamber, where it passes through 4 pairs of squeezing rollers standing horizontally and vertically, then deposited briefly, squeezed twice and finally led out of the 80 ° C. warm chamber.
  • the total dwell time during the passage of goods is 40 seconds.
  • the threads treated in this way are then rinsed with water, stretched, relaxed and dried as usual.
  • a blue color is obtained with excellent fastness properties, mainly particularly good wet fastness properties and very good light fastness properties.
  • An acrylonitrile copolymer made from 94% acrylonitrile, 4% vinyl acetate, 1% itaconic acid Na and 1% Na methallylsulfonate is wet-spun in the form of a 28% spinning solution in dimethylformamide according to standard conditions as in Example 1 and passed through a coagulation bath.
  • the thread material obtained is squeezed out and passes through an impregnation zone without prior drying, in which a solution of 0.1 g of a bis-quaternary dye of the formula adjusted to pH 4.3 by means of acetic acid is passed in 2.5 l of water at room temperature to act on the material.
  • the spun material is then squeezed off, heated to approximately 70 ° C. with the aid of indirect steam and, at approximately the same temperature, passes through a chamber in which it is continuously exposed to the action of squeeze rollers.
  • the passage of goods under these conditions takes place without a train, so that the material opens again after every crushing.
  • the material remains in the chamber for a total of 10 seconds.
  • the threads treated in this way are rinsed with water, then stretched, relaxed and dried as usual.
  • M an receives a reddish yellow on the fiber cable with excellent fastness properties, mainly particularly good wet fastness properties and very good light fastness properties.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Coloring (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Abstract

In the dyeing of PAC gel fibre cables, it is very difficult, especially with a total titre of more than 1,000,000 dtex, to achieve a uniform penetration of the dye liquor and a uniform fixing of the dyestuff over the entire cross-section of the fibre cable. In addition to the propagation of suitable dyestuffs and the colouring knowhow, therefore, the mastery of the mechanical technology of PAC gel dyeing must be considered a precondition for a marketable quality of the PAC dyed article produced by this process. According to the invention, these problems are solved according to a dip-dyeing/dwell technique in that the spinning material saturated with dyestuff solution and cleared of excess liquor is introduced in the form of a strand into a store, where, in the course of its continuous passage, it is exposed to the action of damp heat and is repeatedly and, if appropriate, alternately pinched to bring about a dyestuff fixing which is uniform over the entire gel cable. <IMAGE>

Description

Die vorliegende Erfindung betrifft das kontinuierliche Fixieren von kationischen Farbstoffen im Zuge des Herstellungsprozesses auf nach einem üblichen Naßspinnverfahren erzeugten Kabeln aus Polyacrylnitrilfasern im Gelzustand entsprechend einer Tauchfärbe-/Verweil-Technik.The present invention relates to the continuous fixing of cationic dyes in the course of the manufacturing process on cables made from polyacrylonitrile fibers in the gel state produced by a conventional wet spinning process, in accordance with a dip dyeing / dwelling technique.

Nach den in der Praxis bisher geläufigen Methoden werden anionisch-modifizierte Polyacrylnitrilfasern im Gelzustand zum Färben in eine Flotte mit kationischen Farbstoffen getaucht, für eine Farbstoff-Fixierung bei kontinuierlicher Arbeitsweise während einer Verweilzeit zwischen 5 und 20 Sekunden im Färbebad belassen und anschließend zur Fertigstellung der Färbung mit oder ohne vorheriges Abquetschen des Fasermaterials gespült. Dabei wird meistens eine große Menge von in der dllrch den Warentransport mitgerissenen Färbeflotte enthaltener Farbstoff wieder ausgewaschen, d.h. es resultieren stark farbige Waschwässer und man erleidet daher einen merklichen Farbstoffverlust. Abgesehen von den stark verschmutzten Abwässern, die zur Umweltbelastung beitragen, lassen auch die Echtheitseigenschaften von in solcher Weise erhaltenen Färbungen infolge'ungenügender Farbstoff-Fixierung viel zu wünschen übrig.According to the methods which have been used in practice up to now, anionically modified polyacrylonitrile fibers in the gel state are immersed in a liquor with cationic dyes for dyeing, left in the dye bath for a dye fixation with continuous operation for a period of between 5 and 20 seconds and then to complete the dyeing rinsed with or without squeezing the fiber material. In this case, a large amount of particles entrained in the d ll rch transporting goods dye liquor contained dye is usually washed out again, it ie resulting strongly colored washing water and therefore to suffer a significant loss of dye. In addition to the heavily polluted wastewater that contributes to environmental pollution, the fastness properties of dyeings obtained in this way also leave much to be desired as a result of insufficient dye fixation.

Um in dieser Hinsicht bessere färberische Ergebnisse zu erzielen, ist man in vielen Fällen dazu übergegangen, dem mit der Färbeflotte behandelten Textilgut durch eine gewisse Periode des Verweilens mehr Zeit zur Verfügung zu stellen, eine ausreichende Fixierung der Farbstoffe herbeizuführen. Ein derartiger Verweilvorgang unter Warenablage kann beim Färben einer Warenbahn wohl ohne weiteres in den Färbeprozeß eingeschaltet werden, bei Garnen und Fäden ist dieser jedoch schon nur noch schwer zu bewerkstelligen, bei Gelfasern hat man indessen wegen der Empfindlichkeit dieses Materials ein solches Vorgehen bisher für nicht möglich gehalten, ganz abgesehen davon, daß ein kontinuierliches Verweilen von Gelfasern unbekannt ist.In order to achieve better dyeing results in this regard, in many cases it has been decided to provide the textile material treated with the dyeing liquor with more time through a certain period of time to achieve adequate fixation of the dyes. Such a dwell process under the storage of goods can probably be easily switched into the dyeing process when dyeing a web, but this is already difficult to accomplish in the case of yarns and threads Given the sensitivity of this material, such an approach has so far not been possible, quite apart from the fact that a continuous residence of gel fibers is unknown.

Die Aufgabe der vorliegenden Erfindung besteht nunmehr darin, unter Beibehaltung der günstigen Aspekte einer Gelfärbung die in diesem Zusammenhang aufgezeigten Probleme auszuschalten sowie die zuvor genannten Nachteile dieser Arbeitsweise zu vermeiden. Dazu kommt, daß im Rahmen der Färbung von Faserkabeln aus Acrylnitril-Polymerisaten im Gelzustand es insbesondere im Falle eines Gesamt-Titers von mehr als 1 000 000 dtex sehr schwierig ist, eine gleichmäßige Durchdringung und eine rasche und gleichmäßige Fixierung über den gesamten Faserkabel-Querschnitt zu erzielen. Eine Verbesserung der bekannten Färbetechnik sollte demzufolge auf Basis eines kurzen Verweilprozesses erschlossen werden, ohne aber das kontinuierliche Verfahrensprinzip in Frage zu stellen.The object of the present invention is now to eliminate the problems identified in this connection while maintaining the favorable aspects of gel coloring and to avoid the aforementioned disadvantages of this method of working. In addition, in the course of dyeing fiber cables made of acrylonitrile polymers in the gel state, it is very difficult, particularly in the case of a total titer of more than 1,000,000 dtex, to achieve uniform penetration and rapid and uniform fixation over the entire cross section of the fiber cable to achieve. An improvement of the known dyeing technique should therefore be developed on the basis of a short dwell process, but without questioning the continuous process principle.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man im Anschluß an den Koagulationsvorgang das kontinuierlich in Strangform laufende und sodann mit Färbeflotte getränkte Spinngut nach intensivem Abquetschen des Flüssigkeitsüberschusses zur Farbstoff-Fixierung durch Verweilen in einen Warenspeicher einbringt, dort während der Passage, z.B. im abgelegten Zustand oder über Rollen, Siebbänder bzw. Siebtrommeln geführt, der Einwirkung von feuchter Wärme aussetzt und schließlich dem Warenspeicher wieder kontinuierlich entnimmt, worauf das so gefärbte Faserkabel gespült und weiterbehandelt wird.This object is achieved according to the invention in that, after the coagulation process, the spinning material, which runs continuously in the form of a strand and is then soaked with dye liquor, after intensive squeezing off of the excess liquid for dye fixation, is placed in a goods store by lingering, during the passage, e.g. in the stored state or guided over rollers, sieve belts or sieve drums, exposed to moist heat and finally continuously removed from the store, after which the fiber cable thus dyed is rinsed and further processed.

Die Konzeption der nach der Erfindung angewandten Maßnahmen beruht somit darauf, daß man die mit Färbeflotte verhältnismäßig gesättigte Ware nach ausreichendem Abquetschen in eine Verweilzone einführt, in welcher dem Farbstoff eine angemessene Zeit zum Fixieren gegeben ist. Gegebenenfalls wird die Ware unmittelbar vor Eintritt in die Verweilzone aufgeheizt, wodurch sich die Fixierzeit verkürzt. Da der Ablauf des Prozesses kontinuierlich erfolgt, kann sofort nach dem Verlassen der Verweilzone das gefärbte Faserkabel gespült und gewaschen werden. Anstelle eines sehr umständlichen und zeitraubenden Färbeverfahrens ist also ein kontinuierlich ablaufender, gut übersehbarer und steuerbarer Färbeprozeß getreten. Durch die Ausnutzung der Verweilmethode zur Farbstoff-Fixierung entsprechend dem neuen Verfahren wird erreicht, daß das Fixieren der kationischen Farbstoffe auf den Gelfasern nicht nur kontinuierlich sondern gleichzeitig auch außerordentlich faserschonend sowie rasch erfolgt. Die Farbstoff-Fixierung ist vollständig, die Echtheitseigenschaften der gefärbten Fasern sind gut.The concept of the measures applied according to the invention is thus based on the fact that the goods, which are relatively saturated with dye liquor, are introduced after sufficient squeezing into a dwell zone in which the Dye is given a reasonable time to fix. If necessary, the goods are heated up immediately before entering the dwell zone, which shortens the fixing time. Since the process runs continuously, the colored fiber cable can be rinsed and washed immediately after leaving the dwelling zone. Instead of a very cumbersome and time-consuming dyeing process, a continuously running, easily visible and controllable dyeing process has taken place. By using the residence method for dye fixation in accordance with the new process, the cationic dyes are not only fixed on the gel fibers continuously, but also extremely gently and quickly. The dye fixation is complete, the fastness properties of the dyed fibers are good.

Im einzelnen läuft der Färbevorgang verfahrensgemäß auf folgende Weise ab:

  • Das aus dem Tauchbad bzw. aus dem Imprägnierbad kommende und mit Färbeflüssigkeit getränkte Faserkabel wird zunächst abgequetscht und von der überschüssigen Flotte befreit. Das hinter dem·Färbebad angeordnete Quetschwerk soll hierzu den Kabelstrang möglichst gut auf eine Flottenaufnahme von 100 bis 200 % (bezogen auf das Gewicht der trockenen Ware) entwässern, vorzugsweise sind 120-170 Gew.-% erwünscht. Je stärker das Material abgequetscht wird, desto schneller erfolgt alsdann die Farbstoff-Fixierung.
In detail, the dyeing process proceeds according to the process in the following way:
  • The fiber cable coming from the immersion bath or from the impregnation bath and soaked with dyeing liquid is first squeezed and freed from the excess liquor. For this purpose, the squeezing mechanism arranged behind the dye bath should drain the cable harness as well as possible to a liquor absorption of 100 to 200% (based on the weight of the dry goods), preferably 120-170% by weight. The more the material is squeezed off, the faster the dye fixation takes place.

Das Aufbringen der Färbeflotte findet normalerweise bei Raumtemperatur oder mäßig erhöhter Temperatur statt. Zur Erhöhung der Fixiergeschwindigkeit ist es prinzipiell möglich, die Färbeflüssigkeit vorgewärmt zu applizieren. Als wesentlich zweckmäßiger für dieses Vorhaben hat es sich - wie weiter oben schon erwähnt - allerdings erwiesen, das mit der Farbstoffzubereitung getränkte Faserkabel nach dem Abquetschen, jedoch unmittelbar vor dem Eintritt in den Warenspeicher während einer Passage durch einen Heizkanal auf 50° bis 100°C aufzuheizen und annähernd auf Fixiertemperatur zu bringen.The dye liquor is normally applied at room temperature or moderately elevated temperature. In principle, in order to increase the fixing speed, it is possible to apply the coloring liquid preheated. It has been found to be much more appropriate for this purpose However, as already mentioned above, it has been proven that the fiber cable soaked with the dye preparation is heated to 50 ° to 100 ° C. after being squeezed, but immediately before entering the goods store during a passage through a heating channel, and brought it to approximately the fixing temperature.

Im Anschluß an die Imprägnierbehandlung zum Farbstoffauftrag, der Reduzierung der Ware von überschüssigen Flottenmengen sowie gegebenenfalls nach zwischenzeitlichem Erhitzen wird das feuchte Strangmaterial einer Verweilzone zugeführt, die es im Einklang mit der für die Farbstoff-Fixierung erforderlichen Zeit mehr oder weniger rasch durchläuft. Erst dann, wenn die Fixierung des Farbstoffes beendet ist, schließen sich das Spülen des gefärbten Faserkabels mit Wasser, sowie die Maßnahmen zur Weiterbehandlung wie beispielsweise Verstrecken, Relaxieren, Trocknen etc. an.After the impregnation treatment for dye application, the reduction of the goods from excess liquor quantities and, if necessary, after heating in the meantime, the moist strand material is fed to a dwelling zone which it passes through more or less quickly in accordance with the time required for dye fixation. Only when the fixation of the dye is finished, do the rinsing of the colored fiber cable with water, as well as the measures for further treatment such as stretching, relaxing, drying etc. follow.

Der Warenspeicher selbst, d.h. die Verweilzone, kann mit oder ohne separate Heizung beispielsweise bei 20° bis 60°C betrieben werden, vorzugsweise läßt man die Ware jedoch bei erhöhter Temperatur, d.h. bei 50° bis 100°C verweilen.The goods store itself, i.e. the dwelling zone can be operated with or without separate heating, for example at 20 ° to 60 ° C, but the goods are preferably left at elevated temperature, i.e. stay at 50 ° to 100 ° C.

Die Temperatursteuerung im Warenspeicher, wie auch in einer gegebenenfalls vorhergehenden Aufheizzone , kann mittels Hochfrequenzstrahlern (Mikrowellen), mittels direktem Dampf oder mittels indirektem Dampf, z.B. durch beheizte Umlenkwalzen erfolgen. Je höher die Verweiltemperatur ist, umso kürzer beläuft sich die Fixierzeit für den Farbstoff. Der Aufenthalt des gefärbten Spinnguts in der Verweilzone beträgt erfindungsgemäß 5 bis 120 Sekunden, vorzugsweise 10 bis 60 Sekunden.The temperature control in the goods store, as well as in a possibly preceding heating zone, can be done by means of high frequency radiators (microwaves), by means of direct steam or by means of indirect steam, e.g. done by heated deflection rollers. The higher the residence temperature, the shorter the fixing time for the dye. According to the invention, the colored spinning material stays in the dwell zone for 5 to 120 seconds, preferably 10 to 60 seconds.

Im Rahmen der vorstehenden Maßnahmen kommt der Verweiloperation die entscheidende Bedeutung zu, daß sich die Farbstoffe über den gesamten Kabel-Querschnitt gleichmäßig fixieren lassen. Auch hohe Farbstoffmengen werden hier im Gegensatz zu bisherigen Verfahren echt fixiert. Allerdings wird man bei tiefen Färbungen nie ohne beheizte Verweilzone arbeiten.Within the framework of the above measures, the indwelling operation is of crucial importance that the Allow dyes to be fixed evenly across the entire cross-section of the cable. In contrast to previous methods, even large amounts of dye are really fixed here. However, you will never work without a heated dwell zone for deep dyeings.

Die Wirksamkeit der Verweiloperation kann beim erfindungsgemäßen Verfahren noch dadurch verstärkt werden, daß man das Faserkabel während der Passage durch den erwärmten Warenspeicher wiederholt stark, eventuell auch abwechselnd von verschiedenen Seiten her abquetscht. Es war in dieser Hinsicht außerordentlich überraschend und ist nicht vorhersehbar gewesen, daß eine derartige mechanische Behandlung in der Verweilzone, also in einer erwärmten Kammer, zu einer sehr raschen Fixierung führt.The effectiveness of the dwell operation in the method according to the invention can be increased further by repeatedly squeezing the fiber cable strongly, possibly also alternately, from different sides during the passage through the warmed goods store. In this regard, it was extremely surprising and it was not foreseeable that such mechanical treatment in the dwell zone, that is to say in a heated chamber, leads to very rapid fixation.

Eine zur Durchführung des neuartigen Tauchfärbe-/Verweil-Verfahrens geeignete Vorrichtung, auf die sich die vorliegende Erfindung ebenfalls bezieht, besteht - jeweils in Fortbewegungsrichtung des kontinuierlich laufenden Kabelstranges (1) bezeichnet - im wesentlichen aus einer Imprägnierzone (2) enthaltend Chassis für Tauch- bzw. Imprägnierbad (nicht abgebildet), samt anschließendem Walzenpaar (3), quergestellt zum Warenlauf, zur Entwässerung des mit überschüssiger Färbeflotte getränkten Spinngutes (1) durch Quetschdruck; einer Aufheizzone (4), im wesentlichen zur Beaufschlagung von Strahlungsenergie, Dampf oder Kontaktwärme auf die Ware; sowie einer Verweilzone (5), die als Warenspeicher (6) ausgebildet ist und Mittel zum spannungsarmen Hindurchführen des Strangmaterials (1) während Verweilphase zur Farbstoff-Fixierung aufweist. Diese Verweilzone (5) ist erfindungsgemäß dadurch gekennzeichnet, daß darin (5) quer zur Warenlaufrichtung - zumindestens am Wareneinlaß und am Warenauslaß - zusätzlich mehrere Quetschwerke / Walzenpaare (7) für das durch den Warenspeicher (G) transportierte Kabel (1), in paralleler Stellung zueinander oder vorteilhaft in um einen Winkel bis zu 90° gegeneinander verdrehter Stellung angeordnet sind , gegebenenfalls einander abwechselnd in Kombination mit Heizfeldern (8). Mit dieser Ausbildung der Verweilzone wird ins Auge gefaßt, daß mit Imprägnierflotte zusammengeklebte, parallel aneinanderhaftende Filamente des Stranges wieder voneinander gelöst und dadurch die Stränge gelockert und geöffnet werden, wodurch sich eine höhere Gleichmäßigkeitder Durchfärbung des Kabelstranges sowie eine bessere Effizienz der Verweiloperation ergibt.A device suitable for carrying out the novel immersion dyeing / dwelling method, to which the present invention also relates, consists essentially of an impregnation zone (2) containing a chassis for immersion, each designated in the direction of travel of the continuously running cable harness (1). or impregnation bath (not shown), including the subsequent pair of rollers (3), transverse to the goods run, for dewatering the spun material (1) soaked with excess dyeing liquor by squeezing pressure; a heating zone (4), essentially for applying radiation energy, steam or contact heat to the goods; and a dwelling zone (5) which is designed as a goods store (6) and has means for passing the strand material (1) through the stress-relieving phase during the dwelling phase for dye fixation. This dwell zone (5) is characterized in accordance with the invention in that (5), in addition to the direction of travel of the goods - at least at the goods inlet and at the goods outlet - a plurality of crushing units / roller pairs (7) for that transported through the goods store (G) Cables (1) are arranged in a parallel position to one another or advantageously in a position rotated relative to one another by an angle of up to 90 °, optionally alternately in combination with heating fields (8). With this design of the dwelling zone, it is envisaged that filaments of the strand stuck together with impregnating liquor and adhering to one another in parallel will be detached from one another again and the strands will be loosened and opened thereby, which results in a higher uniformity of the coloration of the cable strand and a better efficiency of the dwelling operation.

Der Warenspeicher, welcher zum Verweilen des mit Färbeflotte getränkten und oft schon vorgewärmten Faserkabels dient, kann recht unterschiedlich gestaltet sein: Im einfachsten Fall ist es eine heizbare Kammer mit einem geneigten Boden, auf dem infolge der schrägen Lage das Spinngut in etwa abgetafeltem Zustand nach dem Ausgang zu gleitet. Auch sind für diesen Zweck Systeme in einer Art Rollen-Kufe brauchbar, ebenfalls lassen sich Kammern mit Siebtrommeln einsetzen. Schließlich eignen sich zum Materialtransport durch den Warenspeicher endlos umlaufende Siebbänder, gegebenenfalls unterteilt auf mehrere Einzelbänder und übereinander angeordnet, auf welche das Stranggut abgelegt wird.The goods store, which is used to hold the fiber cable soaked with dye liquor and often already preheated, can be designed quite differently: In the simplest case, it is a heatable chamber with an inclined floor, on which, due to the oblique position, the spun material is roughly de-laminated after Exit to slides. Systems in a kind of roller skids can also be used for this purpose, and chambers with sieve drums can also be used. Finally, endless circulating sieve belts are suitable for material transport through the goods store, optionally divided into several individual belts and arranged one above the other, on which the strand material is deposited.

Besonders vorteilhafte Verhältnisse liegen dann vor, wenn im Rahmen der erfindungsgemäßen Vorrichtung Aufheizzone (4) und Verweilzone (5) [d.h. Warenspeicher (6) samt Quetschwalzen (7) und Heizfeldem (8)] in einem mittels Wareneinlaß und Warenauslaß verschlossenen, gemeinsamen Behälter (9) untergebracht sind. Verweilzonen mit beheizbaren Kammern, die geräumig genug sind, um sowohl Quetschwerke am Ein- und Ausgang, wie auch eine Ablagemöglichkeit bieten, haben daher den höchsten Wirkungsgrad.Particularly advantageous conditions are present if, in the context of the device according to the invention, heating zone (4) and dwell zone (5) [i.e. Goods store (6) together with squeeze rollers (7) and heating fields (8)] are accommodated in a common container (9) which is closed by means of the goods inlet and goods outlet. Dwell zones with heated chambers, which are spacious enough to offer squeezing mechanisms at the entrance and exit, as well as a storage facility, are therefore extremely efficient.

Eine weitere Variante in der Ausbildung solcher Verweilzonen besteht darin, daß am Eingang zur. Verweilkammer eine Mikrowellenheizung angebracht ist, die das Material auf die gewünschte Temperatur aufheizt und in der Kammer sich nochmals eine Heizung befindet, um eine Abkühlung des Faserkabels zu verhindern. Bei solchen Anlagen ist die Verweilzeit niedrig, infolgedessen ist die Warengeschwindigkeit verhältnismäßig hoch.Another variant in the formation of such dwellings is that at the entrance to. A dwell chamber is attached to a microwave heater, which heats the material to the desired temperature and there is another heater in the chamber to prevent the fiber cable from cooling. The dwell time is short in such systems, and as a result the speed of goods is relatively high.

Die vorliegende Erfindung wird an Hand von Zeichnungen näher erläutert. Die abgebildeten Figuren zeigen als schematische Darstellung die Seitenansicht einer Kontinuestraße, wobei entsprechend Figur 1 der Warenspeicher als Rutsche ausgebildet ist, auf der das abgetafelte Strangmaterial der Verweiloperation ausgesetzt ist. Figur 2 beinhaltet eine Variante einer solchen Vorrichtung, gemäß welcher der Warenspeicher über die Länge der Verweilstrecke abwechselnd von Quetschwerken und Heizfeldern unterbrochen ist. Die hierbei verwendeten Bezugszeichen sind mit den im obigen Text für diesen Zweck verwendeten Ziffern identisch.The present invention is explained in more detail with reference to drawings. The figures shown show a schematic representation of the side view of a continuous road, the goods store being designed as a slide, in accordance with FIG. 1, on which the strip material which has been removed is exposed to the dwell operation. FIG. 2 contains a variant of such a device, according to which the goods store is alternately interrupted by squeezing mechanisms and heating fields over the length of the dwell path. The reference symbols used here are identical to the numbers used for this purpose in the text above.

Für das erfindungsgemäße Verfahren können kationische Farbstoffe sowohl vommono-quartären als auch bis-quartären Typ eingesetzt werden, die den verschiedensten chemischen Verbindungsklassen angehören, so insbesondere der Klasse der Monoazofarbstoffe, der Disazofarbstoffe, der Methin-, Azamethin- und Diazamethin-Farbstoffe und der Naphthalactam-Farbstoffe.For the process according to the invention, cationic dyes of both mono-quaternary and bis-quaternary type can be used, which belong to the most diverse classes of chemical compounds, in particular the class of monoazo dyes, disazo dyes, methine, azamethine and diazamethine dyes and naphthalactam Dyes.

Neben den Polymeren des Acrylnitrils kommen für den Einsatz nach dem beanspruchten Verfahren als zu verspinnende Substrate Mischpolymerisate des Acrylnitrils mit anderen Vinylverbindungen in Betracht, wobei diese Mischpolymerisate mindestens 50 Gew.-%, vorzugsweise mindestens 85 Gew.-% Acrylnitril-Einheiten aufweisen. Die verwendeten Homopolymerisate von Acrylnitril oder dessen Mischpolymerisate sind meistens sauer modifiziert.In addition to the polymers of acrylonitrile, copolymers of acrylonitrile with other vinyl compounds can be used as substrates to be spun for the claimed process, these copolymers having at least 50% by weight, preferably at least 85% by weight, of acrylonitrile units. The homopolymers of acrylonitrile or their copolymers used are mostly acid-modified.

Zum Färben werden im vorliegenden Falle die unverstreckten Fasern oder Fäden - ohne getrocknet zu sein-bei Temperaturen zwischen 10° und 100°C, vorzugsweise zwischen 20° und 80°C, mit den in wäßrigem oder lösemittelhaltigem Färbemedium gelösten Farbstoffen behandelt. Die Färbezeit beträgt im allgemeinen zwischen 0,5 und 20 Sekunden, vorzugsweise wird zwischen 2 und 20 Sekunden gefärbt. Die angeführte Färbedauer entspricht der Kontaktzeit (Verweilzeit) des Polymers mit der Farbstofflösung nach der Verspinnung.For dyeing in the present case, the undrawn fibers or threads - without being dried - are treated at temperatures between 10 ° and 100 ° C., preferably between 20 ° and 80 ° C., with the dyes dissolved in aqueous or solvent-containing dyeing medium. The dyeing time is generally between 0.5 and 20 seconds, preferably between 2 and 20 seconds. The stated dyeing time corresponds to the contact time (residence time) of the polymer with the dye solution after spinning.

Die Färbeoperation selbst wird verfahrensgemäß kontinuierlich im Verlauf des Herstellungsprozesses der Faserkabel vorgenommen, d.h. solange die frisch versponnenen Acrylnitril-Polymerisate in gelartiger Form vorliegen. Sie kann während des oder kurz nach dem Koagulationsvorgang des Polymers durchgeführt werden.The dyeing operation itself is carried out according to the method continuously in the course of the manufacturing process of the fiber cable, ie as long as the freshly spun acrylonitrile polymers exist in g g elarti he form. It can be carried out during or shortly after the polymer coagulation process.

Die gefärbten Faserkabel werden anschließend unter praxisüblichen Bedingungen mit Dampf oder Heißluft fixiert, verstreckt, aviviert und gegebenenfalls unter Zulassung von Schrumpf getrocknet.The colored fiber cables are then fixed under normal conditions with steam or hot air, stretched, finished and, if necessary, dried with the approval of shrinkage.

Die nachstehenden Beispiele dienen zur Erläuterung der Erfindung. Die darin angegebenen Teile und Prozentangaben sind Gewichtsteile und Gewichtsprozente, sofern nichts anderes vermerkt ist.The following examples serve to illustrate the invention. The parts and percentages given therein are parts by weight and percentages by weight, unless stated otherwise.

Beispiel 1example 1

Ein Acrylnitril-Mischpolymerisat aus 85 % Acrylnitril, 14,5 % Vinylacetat und 0,5 % Na-Vinylsulfonat wird in Form einer 28%igen Spinnlösung in Dimethylformamid nach Standardbedingungen bei 80°C unter Einsatz einer 100-Loch-Spinndüse mit einem Lochdurchmesser von 80 µm naß versponnen, wobei man ein Koagulationsbad von 50°C verwendet, welches aus 50 % Dimethylformamid und 50 % Wasser besteht.An acrylonitrile copolymer made of 85% acrylonitrile, 14.5% vinyl acetate and 0.5% Na vinyl sulfonate is in the form of a 28% spinning solution in dimethylformamide according to standard conditions at 80 ° C using a 100-hole spinneret with a hole diameter of 80 µm wet spun, using a coagulation bath at 50 ° C, which consists of 50% dimethylformamide and 50% water.

Das erhaltene Fadenmaterial durchläuft nach einem Quetschvorgang ohne vorherige Trocknung eine Imprägnierzone, in der eine mittels Essigsäure auf pH 4,5 gestellte Lösung von 0,1 g eines mono-quartären Farbstoffes der Formel

Figure imgb0001
in 25 1 Wasser bei Raumtemperatur auf das Material einwirkt. Danach wird das Spinngut abgequetscht, durch Mikrowellen auf 80°C aufgeheizt und in eine Kammer eingeleitet, wo es 4 horizontal und vertikal stehende Quetschwalzenpaare durchläuft, sodann kurz abgelegt, zweimal gequetscht und schließlich wieder aus der 80°C warmen Kammer geführt wird. Die Gesamtverweilzeit während der Warenpassage beträgt 40 Sekunden. Die so behandelten Fäden werden anschließend mit Wasser gespült, wie üblich verstreckt, relaxiert und getrocknet.After a squeezing process and without prior drying, the thread material obtained passes through an impregnation zone in which a solution of 0.1 g of a mono-quaternary dye of the formula brought to pH 4.5 by means of acetic acid
Figure imgb0001
 in 25 liters of water at room temperature. The spun material is then squeezed off, heated to 80 ° C. by microwaves and introduced into a chamber, where it passes through 4 pairs of squeezing rollers standing horizontally and vertically, then deposited briefly, squeezed twice and finally led out of the 80 ° C. warm chamber. The total dwell time during the passage of goods is 40 seconds. The threads treated in this way are then rinsed with water, stretched, relaxed and dried as usual.

Man erhält eine blaue Färbung mit ausgezeichneten Echtheiten, hauptsächlich besonders guten Naßechtheiten und sehr guten Lichtechtheiten.A blue color is obtained with excellent fastness properties, mainly particularly good wet fastness properties and very good light fastness properties.

Beispiel 2Example 2

Ein Acrylnitril-Mischpolymerisat aus 94 % Acrylnitril, 4 % Vinylacetat, 1 % Itaconsäure-Na und 1 % Na-Methallylsulfonat wird in Form einer 28%igen Spinnlösung in Dimethylformamid nach Standardbedingungen wie in Beispiel 1 naß versponnen und durch ein Koagulationsbad geführt.An acrylonitrile copolymer made from 94% acrylonitrile, 4% vinyl acetate, 1% itaconic acid Na and 1% Na methallylsulfonate is wet-spun in the form of a 28% spinning solution in dimethylformamide according to standard conditions as in Example 1 and passed through a coagulation bath.

Das erhaltene Fadenmaterial wird abgequetscht und durchläuft ohne vorherige Trocknung eine Imprägnierzone, in der man eine mittels Essigsäure auf pH 4,3 gestellte Lösung von 0,1 g eines bis-quartären Farbstoffes der Formel

Figure imgb0002
in 2,5 1 Wasser von Raumtemperatur auf das Material einwirken läßt. Danach wird das Spinngut abgequetscht, mit Hilfe von indirektem Dampf auf ca. 70°C aufgeheizt und durchläuft bei etwa gleicher Temperatur eine Kammer, in der es kontinuierlich der Einwirkung von Quetschwalzen ausgesetzt ist. Die Warenpassage unter diesen Bedingungen erfolgt ohne Zug, so daß sich das Material nach jeder Quetschung wieder öffnet. Das Material verweilt insgesamt 10 Sekunden in der Kammer. Nach Verlassen der Kammer werden die so behandelten Fäden mit Wasser gespült, anschließend wie üblich verstreckt, relaxiert und getrocknet.The thread material obtained is squeezed out and passes through an impregnation zone without prior drying, in which a solution of 0.1 g of a bis-quaternary dye of the formula adjusted to pH 4.3 by means of acetic acid is passed
Figure imgb0002
 in 2.5 l of water at room temperature to act on the material. The spun material is then squeezed off, heated to approximately 70 ° C. with the aid of indirect steam and, at approximately the same temperature, passes through a chamber in which it is continuously exposed to the action of squeeze rollers. The passage of goods under these conditions takes place without a train, so that the material opens again after every crushing. The material remains in the chamber for a total of 10 seconds. After leaving the chamber, the threads treated in this way are rinsed with water, then stretched, relaxed and dried as usual.

Man erhält auf dem Faserkabel ein rotstichiges Gelb mit ausgezeichneten Echtheiten, hauptsächlich besonders guten Naßechtheiten und sehr guten Lichtechtheiten. M an receives a reddish yellow on the fiber cable with excellent fastness properties, mainly particularly good wet fastness properties and very good light fastness properties.

Claims (7)

1. Verfahren zum.kontinuierlichen Fixieren von kationischen Farbstoffen im Zuge des Herstellungsprozesses auf nach einem üblichen Naßspinnverfahren erzeugten Kabeln aus Polyacrylnitrilfasern im Gelzustand, dadurch gekennzeichnet, daß man im Anschluß an den Koagulationsvorgang das kontinuierlich in Strangform laufende und sodann mit Färbeflotte getränkte Spinngut nach intensivem Abquetschen des Flüssigkeitsüberschusses zur Farbstoff-Fixierung durch Verweilen in einen Warenspeicher einbringt, dort während der Passage der Einwirkung von feuchter Wärme aussetzt und schließlich dem Warenspeicher wieder kontinuierlich entnimmt, worauf das so gefärbte Faserkabel gespült und weiterbehandelt wird.1. A process for the continuous fixation of cationic dyes in the course of the manufacturing process on cables made from polyacrylonitrile fibers in the gel state produced according to a conventional wet spinning process, characterized in that after the coagulation process, the continuously running strand material and then soaked with dye liquor after intensive squeezing introduces the excess liquid for dye fixation by lingering in a goods store, exposes it to the action of moist heat during the passage and finally removes it continuously from the goods store, whereupon the fiber cable dyed in this way is rinsed and further processed. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Faserkabel unmittelbar vor dem Eintritt in den Warenspeicher während der Passage durch einen Heizkanal auf 50° bis 100°C aufgeheizt wird.2. The method according to claim 1, characterized in that the fiber cable is heated immediately before entering the goods store during the passage through a heating channel to 50 ° to 100 ° C. 3. Verfahren nach dem Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Faserkabel während der Passage durch den Warenspeicher noch zusätzlich beheizt wird.3. The method according to claim 1 or 2, characterized in that the fiber cable is additionally heated during the passage through the goods store. 4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß das Faserkabel während der Passage durch den Warenspeicher wiederholt stark sowie gegebenenfalls wechselseitig abgequetscht wird.4. The method according to claims 1 to 3, characterized in that the fiber cable is repeatedly squeezed strongly and optionally mutually during the passage through the goods store. 5. Verfahren nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß die Verweilzeit des Faserkabels im Warenspeicher 5 bis 120 Sekunden, vorzugsweise 10 bis 60 Sekunden beträgt.5. The method according to claims 1 to 4, characterized in that the residence time of the fiber cable in the goods store is 5 to 120 seconds, preferably 10 to 60 seconds. 6. Vorrichtung zur Durchführung des Verfahrens nach Ansprüchen 1 bis 5, bestehend - jeweils in Fortbewegungsrichtung des zu behandelnden Kabelstranges bezeichnet - aus einer Imprägnierzone samt anschließendem Quetschwalzenpaar, quergestellt zum Warenlauf; einer Aufheizzone; sowie einer Verweilzone, die als Warenspeicher ausgebildet ist und Transportmittel für das durchzuschleusende Strangmaterial aufweist, dadurch gekennzeichnet, daß in der Verweilzone (5) quer zur Warenlaufrichtung - zumindestens am Wareneinlaß und am Warenauslaß - zusätzlich mehrere Quetschwerke (7) für das durch den Warenspeicher (6) geführte Kabel (1), in paralleler Stellung zueinander oder vorteilhaft in um einen Winkel bis zu 90° gegeneinander verdrehter Stellung angeordnet sind, gegebenenfalls einander abwechselnd in Kombination mit Heizfeldern (8).6. Device for carrying out the method according to claims 1 to 5, consisting - each designated in the direction of travel of the cable harness to be treated - from an impregnation zone including a subsequent pair of squeeze rollers, transverse to the flow of goods; a heating zone; and a dwell zone, which is designed as a goods store and has transport means for the strand material to be passed through, characterized in that in the dwell zone (5) transverse to the direction of the goods flow - at least at the goods inlet and at the goods outlet - a plurality of crushing units (7) for the through the goods store ( 6) guided cables (1) are arranged in a parallel position to one another or advantageously in a position rotated relative to one another by an angle of up to 90 °, optionally alternately in combination with heating fields (8). 7. Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, daß Aufheizzone (4) und Verweilzone (5) [Warenspeicher (6) samt Quetschwalzen (7) und Heizfeldern (8)_7 in einem mittels Wareneinlaß und Warenauslaß verschlossenen, gemeinsamen Behälter (9) untergebracht sind.7. The device according to claim 6, characterized in that heating zone (4) and dwell zone (5) [goods store (6) together with squeeze rollers (7) and heating fields (8) _7 in a closed by means of goods inlet and goods outlet, common container (9) are.
EP82111874A 1981-12-24 1982-12-21 Process and apparatus for the fixation of cationic dyes on polyacrylonitrile fibres in the gel state Withdrawn EP0083066A2 (en)

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DE3151466 1981-12-24
DE19813151466 DE3151466A1 (en) 1981-12-24 1981-12-24 "METHOD AND DEVICE FOR FIXING CATIONIC DYES ON POLYACRYLNITRILE FIBERS IN THE GEL STATE"

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0151374A1 (en) * 1983-12-30 1985-08-14 Ciatti Angiolo s.a.s. di Roberto Benassai &amp; C. Apparatus for removing a process liquid from tubolar knit fabrics
EP1342936A1 (en) 2002-03-07 2003-09-10 Morse Tec Europe S.r.l. Hydraulic tensioner of the hollow piston type with a screw-type retaining device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0151374A1 (en) * 1983-12-30 1985-08-14 Ciatti Angiolo s.a.s. di Roberto Benassai &amp; C. Apparatus for removing a process liquid from tubolar knit fabrics
EP1342936A1 (en) 2002-03-07 2003-09-10 Morse Tec Europe S.r.l. Hydraulic tensioner of the hollow piston type with a screw-type retaining device

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JPS58115165A (en) 1983-07-08
DE3151466A1 (en) 1983-07-21

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