EP0083063A1 - Method and apparatus for the wet treatment of bundles - Google Patents

Abstract

In the wet treatment of fibre cables, for example dyeing in the gelled state, it is very difficult, especially with a total titre of more than 1,000,000 dtex, to obtain a uniform penetration and action of the liquor 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 gel dyeing must be considered a precondition for a marketable quality of the dyed articles produced by this process. According to the invention, these problems are solved in that the spinning material running continuously through a wet-treatment zone is forced by the action of mechanical means to allow a loosening of its material structure, in order thereby to bring about transversely to the direction of advance of the article an intensive penetration of the fibre material by the treatment liquor. The change in state of the packing density which is decisive for such penetration is obtained by means of the fulling effect which, with a modification of the pressing force or bearing pressure in particular regions during the passage of the cable strand, is brought about by (a) a system of a plurality of pairs of pinching rollers rotated relative to one another in relation to their axial direction or (b) a system of a plurality of centrally and/or eccentrically rotating rollers of differing spatial arrangement. <IMAGE>

Description

The present invention relates to a method and an apparatus for uniform wet treatment, i.e. Washing, possibly bleaching, dyeing and rinsing, of cables made from synthetic or regenerated fibers in the gel state produced by a conventional wet spinning process; it is carried out or applied in the course of the manufacturing process for the spinning material. In the case of dyeing polyacrylonitrile fiber gel cables with cationic dyes, the procedure according to the invention is of particular importance.

According to the conventional methods for continuous gel dyeing following the extrusion of the spun material, fiber cables with a diameter of more than 30 mm have so far been dyed by means of a dip passage through the dyeing liquor, but each time only uneven dyeing is achieved due to poor penetration of the material over the cable cross-section could. Despite in-depth efforts, this incomplete penetration of the bundle could not be remedied by any physical measure such as venting, modified immersion, HT steaming or the like, nor by adding any chemical products to the dyebath. On the other hand, however, a production of yarn skeins with, for example, only 50 threads, which is specifically geared to the inadequacies of the dyeing conditions introduced in practice, produces a production output which is too low in comparison to the thousands of threads in a technical cable, which also requires expensive equipment and considerable energy losses due to this minimal quantities of material occur, so that such a procedure is uneconomical.

The difficulties with regard to the implementation of the dyeing process, which occur in all of these prior art processes, are primarily due to the freshly spun material itself, in particular due to the gel state of the polyacrylonitrile fiber cable. In this condition, the fiber cable just created can already be deformed by an excessively violent liquor flow, overstretched or stretched too much by a force that is too powerful, or the elasticity or strength of the individual thread can be adversely affected by an added textile auxiliary.

The measures according to the instructions in DE-OS 21 32 030 to guide the cable through a spatially restricted zone during the liquid treatment and to press the heated liquor within this zone at a specific flow speed through the continuously running fiber material do not lead to usable results . This is because the equipment conditions do not allow control of the fleet flow that covers all areas of the goods. Therefore, the liquid pressed into the interior of the cable searches for the path of least resistance and flows through uncontrollable channels, such as gaps, along the fiber cable with or against the direction of the cable run to the two outlets for the fleet. The result of this is an uneven flow through the goods, which, although the diameter of the material is very small, results in uneven polyacrylonitrile gel colorations.

The present invention is based on the object, while maintaining the favorable aspects of gel coloring, to avoid the disadvantageous flow influences shown in this connection and thus to create the basis for good coloring results. The problem for such an improvement is - how already hinted - in the fact that in the course of the coloring of fiber cables 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 a uniform penetration and effect over the entire fiber cable cross section.

This object is achieved in that, after the coagulation process, the spun material is guided continuously in the form of a strand through the wet treatment room and is forced there - at least once within a spatially restricted zone - by the action of mechanical means over the length of the distance intended for the transport of goods to loosen the material structure (packing density) of the strand of goods resulting from the spinning process several times alternately on different sides and largely perpendicular to the direction of travel and thereby allow an intensive penetration of the running textile goods through the fleet, which may have a treatment agent, over the entire cable cross-section.

The principle of the new method is based on the fact that - after you have first pressed the air out of the material - a further movement and squeezing within the densely packed fiber cable triggers a material movement of the parallel arranged filaments transversely to the goods transport direction and in this way the goods from the surrounding or the superficially applied fleet is penetrated. However, it is very important here that the goods are transported without any trains using only driven rollers.

The desired removal of the tightly packed form of the strand-like spun material, which is a hindrance to the flow of the liquor, in accordance with the present invention is accomplished, for example, by essentially placing the cable within the wet treatment zone leads linearly and almost stress-free; The mechanical influencing of the continuously running strand material transversely to its direction of travel and possibly alternately from different sides with the aim of loosening the material structure at these points then takes place with the aid of a section-wise modification of the pressing pressure, which takes the form of alternating opening and closing of the strand of goods when it is passed through the nip (pinch joint) of at least one apparatus unit, which serves as a goods guide element and, if applicable, in some cases at the same time as a transport system, is made up of two or more pinch roller pairs connected in series, parallel with respect to the alignment of their roller axes, or twisted relative to one another by up to 90 °, which are driven in the same direction of rotation as the goods run, and can optionally be arranged offset to one another.

This ensures that the fiber cable strand is kneaded and the fleet in the strand is pushed out. In this case, the penetration of the fiber cable is not achieved by a flowing liquor, but by a squeezing and flexing system. Due to the pressing pressure, the treatment liquor penetrates the entire fiber cable, which remains perfectly organized, and individual fiber balls cannot generally occur.

In this context, it has been found that in such a process, which - apart from the slow inflow in fleet replacement - actually runs without a fleet flowing at a certain speed, perfect and completely level dyeings of a polyacrylonitrile gel cable even with a diameter of the fiber cable of 100 and more millimeters. Material deformation does not occur, in particular since there is no actual liquor flow and the material is guided through the squeeze roller pairs which are to be continuously traversed. With a strong material cross section, the number of nip roller pairs must be higher.

A device for uniform wet treatment of cables in the gel state in accordance with the previously described embodiment of the method according to the invention is characterized in that in the course of a spinning line (not shown) in the direction of travel of the strand-like spun material following the coagulation bath (not shown) either in a closed or in a trough-shaped container (not shown), at least one apparatus unit is arranged, which consists of two or more series-connected squeeze roller pairs (2), which are parallel with respect to the alignment of their roller axes or rotated by up to 90 ° with respect to one another, as goods guiding element and, if appropriate, partly at the same time Transport system for the continuously passing through the wet treatment zone (Fig. 1) strand material (1), which are in contact with each other across the width of the pinch joint together with the textile material (1) carried out, which can be driven about its axis are, the rotation of the contacting, paired rollers (2) takes place in accordance with the direction of conveyance of the cable harness (1), and which can optionally be arranged offset from one another.

• a) Das gesamte Quetschwalzensystem befindet sich in einer Wanne, welche die Behandlungsflotte enthält. Daraus folgt, daß das strangförmige Textilgut (1) im Verlauf der Naßbehandlungsoperation von einer ruhenden Flotte umgeben ist.
• b) Das gesamte Quetschwalzensystem ist in einem Kanal (Rohr) angebracht, wobei die Richtung der sich langsam bewegenden Behandlungsflotte mit oder gegen den Fortbewegungssinn des Faserkabels (1) verläuft und das strangförmige Textilgut (1) von der Flotte umspült wird.
• c) Die Behandlungsflotte wird zwischen den einzelnen Quetschwerken (2) (bzw.bei nur zwei Quetschwerken direkt hinter den ersten) durch Aufsprühen auf das strangförmige Textilgut (1) appliziert.
• d) Die Behandlungsflotte wird zwischen den einzelnen Quetschwerken (2) durch Injektionsstrahl oder Injektionsnadeln ins Kabelinnere des strangförmigen Textilgutes (1) gebracht.

With regard to the spatial arrangement of the system of roller pairs (2) according to FIG. 1, the following variations are now possible:

• a) The entire nip roller system is located in a tub that contains the treatment liquor. It follows that the strand-like textile material (1) is surrounded by a resting liquor in the course of the wet treatment operation.
• b) The entire squeeze roller system is mounted in a channel (tube), the direction of the slowly moving treatment liquor running with or against the direction of travel of the fiber cable (1) and the strand-like textile material (1) being washed around by the liquor.
• c) The treatment liquor is applied between the individual squeeze units (2) (or in the case of only two squeeze units directly behind the first) by spraying onto the strand-like textile material (1).
• d) The treatment liquor is brought between the individual crushing units (2) by means of an injection jet or injection needles into the interior of the strand of the textile material (1).

The squeezing effect to be set within the scope of the wet treatment according to the method is, for example in the case of polyacrylonitrile gel fibers, 100 to 200% (based on the weight of the dry goods), preferably 120 to 170% by weight, on each individual squeezing unit; with fiber cables of other origins, more or less must be observed accordingly.

The number of squeezing units (2) in a device according to FIG. 1 is 2 to 12, preferably 4 to 8. As already mentioned, all the squeezing units (2) can be arranged with the same axis direction or preferably with a changed axis direction. The distance between the individual crushing units (2) can be almost arbitrary, preferably however 2 - 4 d (d = roll diameter). The diameter of the rollers, the nature of the roller covering and the surface hardness are also not prescribed.

In the course of a wet treatment process using a device according to FIG. 1, the tension of the fiber cable (1) should be so low that there is a good opening of the fiber cable after each squeezing (cross-sectional enlargement). As a result, the treatment liquor penetrates the fiber cable (1) very well and evenly. A high treatment uniformity (levelness) of the fiber cable is obtained (particularly important e.g. in polyacrylonitrile gel staining).

Another type or a modification of the above-described embodiment of the novel method consists in that the cable is guided within the wet treatment zone essentially linearly and almost without tension; The mechanical influencing of the continuously running strand material transversely to its direction of travel and alternately from different sides with the aim of loosening the material structure at these points then takes place with the aid of a section-by-section modification of the contact pressure, which in the form of a controlled back and forth movement of the goods strand its passage, with alternating contact between the front and back and with more or less looping in sections, via at least one apparatus unit, which serves as a goods control element and, if necessary, at the same time partly as a transport system, consisting of two or more, in a separate but parallel position and transversely to the conveyed one Textile material connected in series, centrically or eccentrically mounted, cylindrical-circular or elliptical rollers, which are driven in the same direction of rotation as the goods run, possibly offset from each other and / or can be arranged in pairs. The device used to carry out this variant of the method according to the invention for uniform wet treatment of cables in the gel state is characterized in that in the course of a spinning line (not shown) in the direction of travel of the strand-like spun material following the coagulation bath (not shown) either in a closed or in a trough-shaped container (not shown) is arranged at least one apparatus unit, which consists of two or more cylindrical, circular or elliptical rollers (3), which are arranged in a separate, but parallel to one another, and connected in series, transversely to the flow of goods, in a centric or eccentric manner, as goods guide element and if necessary in part also as a transport system for the strand material (1) continuously passing through the wet treatment zone (Fig. 2 or Fig. 3), which can be driven about its axis, the rotation taking place according to the direction of conveyance of the cable strand (1) lgt, and possibly offset and / or in pairs (Fig. 3) can be arranged.

According to this embodiment of the invention, the flow through the fiber cable (1) will be very high as a result of the back and forth movement (up and down movement) of the textile material (1) in the liquor. The contact pressure on the roller (3) acts here in the same way as the pressing pressure in the case of the use of crushing units (2) according to FIG. 1.

The centrally mounted rollers or the eccentric rollers (3) can have a closed or perforated (perforated) outer surface. The shape, scope and eccentricity of these rollers (3) are such that the fiber cable (1) is optimally impregnated by the liquor. The number of such rollers (3) per wet treatment unit is 2 to 10; but they are also orders possible with even more rollers (3). The eccentric rollers (3) can also be arranged in pairs for the purposes of the invention.

The speed of rotation of the eccentric rollers (3) can be adapted to the cable speed (ie the same), or can be considerably higher.

The entire system of centrically or eccentrically rotatable rollers (3) can be arranged in a tub filled with a treatment liquor or in a closed channel in a horizontal position. However, it can also be arranged vertically, in which case either the entire channel is filled with liquor, or this is applied by spray devices. It is also possible to install only a single spray device in the vertical arrangement, which then moves in one direction when the fiber cable is constantly squeezed with the material.

The present invention is explained in more detail with reference to drawings. The figures shown each show a schematic side view of a wet treatment zone, the change in state of the packing density, which is decisive for the flow through the cable with the liquor, according to FIG. 1 with the aid of a squeeze roller system, and according to FIGS. 2 and 3 with the aid of eccentric rollers of different spatial arrangement is controlled. The reference symbols used here are identical to the numbers used for this purpose in the text above.

In addition to the embodiments illustrated here, other devices which differ from the models described above in terms of machine technology can be used for dyeing or treating, for example, polyacrylonitrile gel cables. Also here the principle of mutual penetration with a fleet running perpendicular to the material transport direction is mandatory.

For wet treatment, i.e. Washing, possibly bleaching, dyeing and rinsing, in the present case the undrawn fibers or threads are used, without being dried, and the respective treatment medium flows through them. The treatment liquor can consist of water, organic solvents or such mixtures with one another. It can have temperatures between 10 ° and 100 ° C and contain common additives, dyes and chemicals. The residence time in the treatment liquids is 2 to 20 seconds.

The further treatment of the fiber material takes place depending on the previous type of treatment: In washing and finishing processes, also in combination processes, drying follows, possibly with simultaneous fixing of the applied aids. After a dyeing process, the dyes applied to the fiber cable are fixed in accordance with the available options, it being immaterial in the context of the present application whether the fixing process takes place according to old methods or according to the latest knowledge. The dyed fiber cables are then stretched, finished and, if necessary, dried with the approval of shrinkage under normal conditions.

The wet treatment operation of the present invention can be applied to fiber cables made from regenerated cellulose, polyacrylonitrile fibers or other polymers. The novel process, including the device, is particularly suitable for a polyacrylonitrile gel cable, which can be washed, colored and rinsed in succession. In this way, cables of up to 10 million dtex are a continuous process control accessible.

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.

Cationic dyes of both the mono-quaternary and bis-quaternary type can be used for the process according to the invention, which belong to the most varied chemical compound classes, in particular the class of the monoazo dyes, the disazo dyes, the methine, azamethine and diazamethine dyes and the Naphthalactam dyes.

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.

example 1

An acrylonitrile copolymer of 85% acrylonitrile, 13% vinyl chloride and 2% Na allyl sulfonate is wet spun 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 , using a coagulation bath of 50 ° C, which consists of 50% dimethylformamide and 50% water.

in 250 ml Wasser von Raumtemperatur mit dem beschriebenen Quetschwalzensystem behandelt. Nach Ablauf von 20 Sekunden Kontaktzeit des Spinngutes mit der Färbeflotte beobachtet man eine praktisch vollständige Baderschöpfung. Die so behandelten Fäden werden anschließend mit Wasser gespült, wie üblich verstreckt, relaxiert und getrocknet.The thread material obtained is then run into a device according to FIG. 1 in an amount of 10 g (dry weight), corresponding to 20 g wet weight, without prior drying, and is adjusted to pH 5 during the run with good liquor movement and in the presence of an acetic acid Solution of 0.01 g of a bis-quaternary dye of the formula

treated in 250 ml of water at room temperature with the described squeeze roller system. After 20 seconds of contact between the spinning material and the dyeing liquor, practically complete bath exhaustion is observed. 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.

Example 2

An acrylonitrile copolymer from 94% acrylonitrile, 5% methyl acrylate and 1% styrene-4-sulfonic acid Na 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.

in 250 ml Wasser von Raumtemperatur über ein System von Exzenterwalzen geführt. Nach Ablauf von 30 Sekunden Verweilzeit des Spinngutes in der Färbeflotte beobachtet man eine praktisch vollständige Baderschöpfung. Die so behandelten Fäden werden anschließend mit Wasser gespült, wie üblich verstreckt, relaxiert und getrocknet.The thread material obtained is then, without prior drying, in an amount of 10 g (dry weight), corresponding to 20 g wet weight, in the course of a passage through a device according to FIG. 3 with good liquor movement and in the presence of a pH of 4.3 using acetic acid Solution of 0.01 g of a mono-quaternary dye of the formula

in 250 ml of water at room temperature over a system of eccentric rollers. After 30 seconds of spinning material in the dyeing liquor, practically complete bath exhaustion is observed. The threads treated in this way are then rinsed with water, stretched, relaxed and dried as usual.

A dyeing is obtained in a Bordo shade with excellent fastness properties, mainly particularly good wet fastness properties and very good light fastness properties.

Example 3

An acrylonitrile copolymer made from 94% acrylonitrile, 4% methyl acrylate and 2% Na methallylsulfonate is wet-spun 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 , using a coagulation bath of 50 ° C, which consists of 50% dimethylformamide and 50% water.

in 250 ml Wasser von Raumtemperatur gebracht und dort über eine Anordnung von Quetschwalzen entsprechend Fig. 1 geleitet. Nach Ablauf von 5 Sekunden Behandlungszeit des Spinngutes in der Färbeflotte beobachtet man eine praktisch vollständige Baderschöpfung. Die so gefärbten Fäden werden anschließend mit Wasser gespült, wie üblich verstreckt, relaxiert und getrocknet.The thread material obtained is then, without prior drying, in an amount of 10 g (dry weight), corresponding to 20 g wet weight, with good liquor agitation into a solution of 0.01 g of a bis-quaternary dye of the formula adjusted to pH 4.6 using acetic acid

brought in 250 ml of water from room temperature and passed there over an arrangement of squeeze rollers according to FIG. 1. After 5 seconds of treatment of the spinning material in the dyeing liquor, practically complete bath exhaustion is observed. The threads thus dyed are then rinsed with water, stretched, relaxed and dried as usual.

A bluish red color is obtained with excellent fastness properties, mainly particularly good wet fastness properties and very good light fastness properties.

Claims (11)

1. A method for uniform wet treatment in the course of the manufacturing process of cables produced by a conventional wet spinning process from synthetic or regenerated fibers in the gel state, characterized in that the spun material is passed continuously after the coagulation process in strand form through the wet treatment room and there - at least once within a spatially restricted zone - due to the action of mechanical means, loosens the material structure (packing density) of the strand of goods resulting from the spinning process and thereby intensively penetrates it over the length of the route intended for the transport of goods several times alternately on different sides and largely perpendicular to the direction of travel of the running textile goods over the entire cable cross-section by the fleet, which may have a treatment agent. 2. The method according to claim 1, characterized in that the cable is guided within the wet treatment zone almost without tension, and that the mechanical influencing of the continuously running strand material is carried out transversely to its direction of travel and optionally alternately from different sides with the aid of a section-wise modification of the pressing pressure, which in the form of alternating opening and closing of the goods strand as it passes through the nip (pinch joint) of at least one apparatus unit serving as a goods guide element and possibly also at the same time partly as a transport system, consisting of two or more series-connected units which are parallel or in relation to the alignment of their roller axes an angle of up to 90 ° relative to each other is caused by pairs of squeezing rollers which are driven in the same direction of rotation as the goods run and which can optionally be arranged offset from one another. 3. The method according to claim 1, characterized in that the cable within the wet treatment zone is almost stress-free, and that the mechanical influencing of the continuously running strand material transversely to its direction of travel and alternately from different sides with the aid of a section-wise modification of the contact pressure, which in the form of a controlled to-and-fro movement of the line of goods as it passes, alternately touching the front and back as well as with more or less looping in sections, via at least one apparatus unit consisting of two or more serving as a goods guiding element and possibly also partly as a transport system, in a separate, but mutually parallel position and transversely to the conveyed textile goods connected in series, centrically or eccentrically mounted, cylindrical-circular or elliptical rollers, which are in the same direction of rotation as the goods are run-in, optionally offset from one another and / or arranged in pairs. 4. The method according to claims 1 to 3, characterized in that the strand-like textile material is surrounded by a resting liquor in the course of the wet treatment operation. 5. The method according to claims 1 to 3, characterized in that the strand-like textile material is washed by a moving liquor in the course of the wet treatment operation. 6. The method according to claims 1 to 3, characterized in that the liquor is applied by spraying onto the strand-like textile material in the course of the wet treatment operation between the individual rolls or roll systems. 7. The method according to claims 1 to 3, characterized in that the fleet is brought in the course of the wet treatment operation by injection jet or needles between the individual rollers or roller systems in the cable interior of the strand-like textile material. 8. Process according to Claims 1 to 7, characterized in that a dyeing liquid with a temperature in the range from 10 ° to 100 ° C is used as the liquor. 9. Process according to Claims 1 to 8, characterized in that cables made from polyacrylonitrile fibers in the gel state are colored with cationic dyes. 10.Device for uniform wet treatment of cables in the gel state for the purpose of carrying out the method according to claim 2, characterized in that at least one apparatus unit is arranged in the course of a spinning line in the direction of travel of the strand-like spun material following the coagulation bath, which consists of two or more, connected in series , regarding the orientation of their There are parallel roller axes or pairs of nip rollers rotated relative to one another by an angle of up to 90 °, which are in contact with one another over the width of the nip joint, together with the textile material being carried through, which can be driven about their axis and which can optionally be offset from one another. 11. Device for uniform wet treatment of cables in the gel state for the purpose of carrying out the method according to claim 3, characterized in that at least one apparatus unit is arranged in the course of a spinning line in the direction of movement of the strand-like spun material following the coagulation bath, which consists of two or more, in There is a separate, but parallel position, as well as centrically or eccentrically mounted, cylindrical or circular or elliptical rollers connected in series to one another transversely to the flow of goods, which can be driven about their axis, and which can optionally be offset and / or arranged in pairs.

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