EP0295271B1 - Polyurethane elastomer thread and its use - Google Patents

Polyurethane elastomer thread and its use Download PDF

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Publication number
EP0295271B1
EP0295271B1 EP19870907735 EP87907735A EP0295271B1 EP 0295271 B1 EP0295271 B1 EP 0295271B1 EP 19870907735 EP19870907735 EP 19870907735 EP 87907735 A EP87907735 A EP 87907735A EP 0295271 B1 EP0295271 B1 EP 0295271B1
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EP
European Patent Office
Prior art keywords
thread
spun
spinning
threads
elastic
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EP19870907735
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German (de)
French (fr)
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EP0295271A1 (en
Inventor
Maria Toscan
Rémy HUMBRECHT
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Viscosuisse SA
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Rhone Poulenc Viscosuisse SA
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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
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes

Definitions

  • the present invention relates to a smooth, melt-spun, multifilament elastomer thread made of polyurethanes with a hardness of 80 to 95 ° Shore and the use thereof.
  • melt-spun elastomeric polyurethane threads which consist of at least 85% by weight of segmented polyurethanes.
  • threads were practically unusable because of the sticking after spinning.
  • a remedy was achieved by chemical modification of the polyurethane.
  • polyimides are incorporated into the polymer chain or added to the polymer melt.
  • the continuous filaments produced with the polymer obtained have to be wound up at very low speeds and drawn in a second operation. No information is given about the properties of the threads obtained.
  • DE-A-19 44 507 discloses a multi-stage process which reduces the stickiness of elastomeric polyurethane threads during the spinning process.
  • melt extrusion is carried out in a first stage, the thread obtained is solidified by quenching and stretched by at least 30% in a second stage and relaxed by at least 50% in a further stage before winding.
  • a theoretical consideration is given that in the case of a small relaxation ratio, i.e. the tackiness of the thread increases with a faster winding speed.
  • the melt-spun thread is stretched and then relaxed again.
  • the process sequence indicates that the finished, completely cooled elastomer thread is already present on the take-off godet. This shows the typical properties of a polyurethane elastomer; it can no longer be stretched in the true sense, but it can be stretched considerably due to its high elasticity, and this stretching is reversible.
  • the stretching process according to DE-A-1944507 has no major influence on the thread properties.
  • Quenching the threads after melt spinning represents a further complex process step and requires different thread properties.
  • Suitable polyurethanes for producing the elastomer fiber according to the invention are preferably those which are extrudable and which consist of an aromatic diisocyanate, for example 4,4'-diphenylmethane diisocyanate (MDI) and a linear polyether e.g. Polytetramethylene glycol or an aliphatic polyester, for example polybutylene adipate or polycaprolactone diol.
  • MDI 4,4'-diphenylmethane diisocyanate
  • a linear polyether e.g. Polytetramethylene glycol or an aliphatic polyester, for example polybutylene adipate or polycaprolactone diol.
  • Block polymers of a cycloaliphatic diisocyanate such as hexahydro-MDI and a linear segmented polyether which are known to be particularly suitable for medical applications, are also suitable.
  • the softening point of the suitable polyurethane is between 180 to 130 ° C, the hardness is 80 to 95 ° Shore A and the density is 1.1 to 1.25 g / cm3. This hardness plays an important role in the stickiness of the polyurethane thread.
  • PUR such as the polyether or polyether ester or polyester amine urethanes, provided they have sufficient melt stability, can also be used and melt spun and processed into elastic threads.
  • the object of the invention is to produce a high-modulus, high-strength, multifilament elastic thread, the fibrils of which are not glued to one another, by melt spinning.
  • the object is achieved by a module of 10-40 cN / tex and an elongation at break of 80 to 300%, based on the length of the unstretched thread.
  • the resulting smooth, elastic thread is suitable for further processing immediately after winding. It has the advantage over the known elastomers that it can be used directly without spinning.
  • the process is carried out in such a way that the polyurethane granules are first melted and extruded at 190 to 240 ° C.
  • the speed of the winding should be at least 600 m / min, preferably more than 900 m / min, as a result of which a draw ratio of at least 1.5 should be present. Since the stretching and winding take place immediately after the spun thread has been drawn off, the process can practically be referred to as simultaneous, simultaneous or spinning.
  • the thread has not yet completely cooled on a first pair of rolls, which still allows actual drawing in the drawing zone.
  • This stretching and thus also greater molecular orientation in the threads is then also manifested by low elongation at break and high boiling shrinkage and in particular a greatly increased modulus.
  • the orientation of the molecules in the take-off zone depends on the take-off speed and, due to the strongly temperature-dependent viscosity of the polymers, also to a large extent on the spinning temperature. If the pre-orientation is too low, the module can no longer be increased to the highest values.
  • the winding is preferably carried out without voltage.
  • This high-modulus, spun-stretched thread can be easily processed into a flat structure. In order to avoid severe dimensional loss of the fabric in the equipment, it is advisable to fix it in front of the equipment.
  • the choice of fixing conditions allows the resulting elasticity of the goods to be controlled. Because of the shrinkage present, the thread according to the invention is also particularly suitable for fixing form.
  • the fabric can also be annealed in water of at most 130 ° C, but advantageously at temperatures below the boiling point of the water, for example 94 to 100 ° C.
  • the tempering is preferably carried out using steam, hot water or heated metal surfaces. In order to guarantee sufficient dimensional stability, the tempering should take place at temperatures> 90 ° C.
  • the elastomer thread Before tempering, the elastomer thread has a modulus of 10-40, preferably> 20, in particular 20 to 40 cN / tex, an elongation at break of 80 to 300%, preferably 90 to 200%, based on the length of the unstretched thread.
  • the stretched elastomer thread has a completely reversible elasticity up to the elongation at break.
  • the rubber-elastic elastomer thread according to the invention After tempering, the rubber-elastic elastomer thread according to the invention, depending on the type and temperature of the treatment, has an elongation at break of 100 to 800%, in particular of 300 to 600%, preferably of about 400%, based on the length of the unstretched thread (see Table 1 and 2).
  • the spun-stretched elastomer thread is expediently almost completely reversibly elastic up to the tear limit.
  • Preferred areas of application for the rubber-elastic elastomer thread according to the invention are textile fabrics. It has proven to be advantageous here to process the elastomer thread according to the invention together with at least one other non-elastic thread made of synthetic or natural fibers to form an elastic flat structure.
  • a spinning block with spinning nozzles is shown in FIG.
  • a bundle of fibrils 2 is combined on an ensemble pin or a roll 3 into a thread 2 'and guided over a godet 4 and a separating roller 4', which together form the pair of rollers 4, 4 '.
  • Another pair of rollers 5, 5 ' consists of a godet 5 and a separation roller 5'. 6 with a coil with a drive roller 7 is designated.
  • curve 1 shows the cold-spun stretched thread.
  • Curves 2 to 4 show the force-elongation of the same thread annealed at different temperatures; Curve 2 at 40 ° C, curve 3 at 60 ° C and curve 4 at 98 ° C in water.
  • Fig. 3 the hysteresis curve 1 of the spun yarn and hysteresis curve 2 of the spun yarn additionally treated at 98 ° C in water is shown.
  • UV absorbers of the Tinuvin® type from CIBA GEIGY can be polymerized or powdered onto the granulate. Fillers such as TiO2, SiO2 can be used to improve the elastic properties and gloss.
  • the granulate is melted in an extruder, for example at 210 ° C., in the absence of oxygen, pressed through a 10 ⁇ m filter screen and through spinning block 1 with a spinneret with eight holes at a pre-pressure of 60 bar, and in a spin-stretching process to form a multifilament dtex 41 f 8 spun.
  • the individual filaments 2 are cooled in a blow shaft (not shown) with air of 40 mm Wasa column and brought together and oiled by means of an ensemble pin 3.
  • the spinning speed, given by the godet 4, is 600 m / min.
  • the thread 2' is guided on the second pair of rollers 5, 5 'with five loops and 2.1 times cold hiding.
  • the cold rollers 4, 5 with a smooth surface are driven with electric motors, not shown, and the counter rollers 4 'and 5' with air. This keeps the friction resp. the thread tension so low that the thread 2 'is not distorted.
  • the thread 2 ⁇ is wound up without tension on a bobbin at a winding speed of 1250 m / min.
  • the thread is produced by the spin-stretch method.
  • thermoplastic polyurethane also based on polyester from GOODRICH, Estane 58277, which is suitable for medical use, with a hardness of 93 ° Shore A, a softening point of 185 ° C and a density of 1.19 g / cm3, was according to the example 1 spun and stretched at the same time.
  • Tables 1 and 2 summarize the thread properties of Examples 1 and 2.
  • the thread 2 ⁇ according to the invention shows the properties according to the table, 1st column. Its strength is 25 cN / tex, its elongation at break 145% and the boiling shrinkage 61% based on the length of the unstretched thread.
  • the thread can also be wound up well. It shows no tendency to stick.
  • a microscopic cross-section shows that the individual filaments are well separated from one another and have the desired round cross-section.
  • This thread shows when it is subjected to a heat treatment e.g. Is subjected to 2 min in hot water, the properties according to column 2 to 5 of the table.
  • the elongation at break in boiling water (column 5) increases to 490%.
  • the elastic properties are comparable to those of the multifilament, commercially available wet-spun polyurethane fibers glued together.
  • thermoplastic polyurethane from Example 1 10 kg were spin-stretched using our spin-stretching method with a draw of 600 m or 1600 m / min at various spinning temperatures.
  • the possible spinning speed is strongly dependent on the polymer viscosity and thus on the spinning temperature.
  • the take-off speed and thus the cost-effectiveness of thread production can be greatly increased.
  • the spun drawn original thread can e.g. knitted together with a polyamide dtex 33 f 10 to form a fabric. After fixation or after heat treatment, e.g. Coloring, this knitted fabric can be processed into a rubber-elastic sheet in a known manner.

Abstract

In a process for producing melt-spun elastomer threads with a high modulus, a maximum breaking elongation of 300 % and shrinking when boiled of at least 20 %, multifilament elastic threads are obtained by spin-drawing. A molten mass of polyurethane granulate is simultaneously drawn at a drawing factor of at least 1,5 and wound on spools at 600m/min minimum. The spun-drawn, non-adhesiveestane thread can be processed to form a flat structure, the elasticity of which can be regulated by setting or by tempering in hot water. The thread can also be tempered before being processed in order to acquire the desired elastic properties.

Description

Die vorliegende Erfindung betrifft einen glatten, schmelzgesponnenen, multifilen Elastomerfaden aus Polyurethanen mit einer Härte von 80 bis 95° Shore sowie dessen Verwendung.The present invention relates to a smooth, melt-spun, multifilament elastomer thread made of polyurethanes with a hardness of 80 to 95 ° Shore and the use thereof.

Die Herstellung von schmelzgesponnenen elastomeren Polyurethanfäden, welche aus mindestens 85 Gew.-% segmentierten Polyurethanen bestehen, ist bekannt. Solche Fäden waren wegen des Verklebens nach dem Spinnen jedoch praktisch nicht verwertbar. Eine Abhilfe wurde durch chemische Abwandlung des Polyurethans erzielt.The production of melt-spun elastomeric polyurethane threads, which consist of at least 85% by weight of segmented polyurethanes, is known. However, such threads were practically unusable because of the sticking after spinning. A remedy was achieved by chemical modification of the polyurethane.

Ein solches Verfahren, in welchem auf chemischem Weg die Verklebung von extrudierten Endlosfäden reduziert werden konnte, ist bekannt (DE-A-22 04 470).Such a method, in which the bonding of extruded continuous filaments could be reduced chemically, is known (DE-A-22 04 470).

In dem bekannten Verfahren werden Polyimide in die Polymerkette eingebaut oder der Polymerschmelze zugefügt. Die mit dem erhaltenen Polymer erzeugten Endlosfäden müssen mit sehr niedrigen Geschwindigkeiten aufgewickelt und in einem zweiten Arbeitsgang verstreckt werden. Über die Eigenschaften der erhaltenen Fäden werden keine Angaben gemacht.In the known process, polyimides are incorporated into the polymer chain or added to the polymer melt. The continuous filaments produced with the polymer obtained have to be wound up at very low speeds and drawn in a second operation. No information is given about the properties of the threads obtained.

Abgesehen davon, dass die Zugabe von Additiven eine Erniedrigung des Molekulargewichtes bewirkt, womit ein Absinken der Schmelzviskosität einhergeht, was wiederum die elastischen Eigenschaften, die Reissdehnung und Festigkeit eines resultierenden Garnes nachteilig beeinflusst, ist eine Produktivität mit den um 160 m/min genannten Aufspulgeschwindigkeiten unzureichend und unwirtschaftlich.Apart from the fact that the addition of additives causes a reduction in the molecular weight, which is accompanied by a decrease in the melt viscosity, which in turn adversely affects the elastic properties, the elongation at break and the strength of a resulting yarn, productivity with the winding speeds mentioned by 160 m / min is insufficient and uneconomical.

Aus der DE-A-19 44 507 ist ein mehrstufiges Verfahren bekannt, welches die Klebrigkeit von elastomeren Polyurethan-Fäden beim Spinnprozess vermindert. In diesem Verfahren wird in einer ersten Stufe schmelzextrudiert, der erhaltene Faden durch Abschrecken verfestigt und in einer zweiten Stufe um mindestens 30 % verstreckt und in einer weiteren Stufe um mindestens 50 % vor dem Aufwickeln relaxiert. Es wird in einer theoretischen Betrachtung ausgeführt, dass im Falle eines kleinen Entspannungsverhältnisses, d.h. bei einer rascheren Aufwickelgeschwindigkeit die Klebrigkeit des Fadens zunimmt.DE-A-19 44 507 discloses a multi-stage process which reduces the stickiness of elastomeric polyurethane threads during the spinning process. In this process, melt extrusion is carried out in a first stage, the thread obtained is solidified by quenching and stretched by at least 30% in a second stage and relaxed by at least 50% in a further stage before winding. A theoretical consideration is given that in the case of a small relaxation ratio, i.e. the tackiness of the thread increases with a faster winding speed.

Nach diesem Verfahren wird der schmelzgesponnene Faden verdehnt und anschiessend wieder relaxiert.-Der Verfahrensablauf deutet darauf hin, dass auf der Abzugsgalette bereits der fertiggestellte, völlig erkaltete Elastomerfaden vorliegt. Dieser zeigt die typischen Eigenschaften eines Polyurethanelastomeren; er lässt sich nicht mehr im eigentlichen Sinne verstrecken, aufgrund seiner hohen Elastizität wohl aber stark verdehnen, wobei diese Dehnung reversibel ist. Der Verdehnungsprozess gemäss DE-A-1944507, bleibt ohne grossen Einfluss auf die Fadeneigenschaften.After this process, the melt-spun thread is stretched and then relaxed again. - The process sequence indicates that the finished, completely cooled elastomer thread is already present on the take-off godet. This shows the typical properties of a polyurethane elastomer; it can no longer be stretched in the true sense, but it can be stretched considerably due to its high elasticity, and this stretching is reversible. The stretching process according to DE-A-1944507 has no major influence on the thread properties.

Alle Versuche, elastomere Polyurethanfäden unter wirtschaftlichen Bedingungen, d.h. bei höheren Spinngeschwindigkeiten durch Spinnen aus einer Schmelze herzustellen, sind bisher daran gescheitert, dass die extrudierten Filamente zusammenkleben sobald die Spinngeschwindigkeit über ein bestimmtes Mass erhöht wird.All attempts to make elastomeric polyurethane threads under economic conditions, i.e. To produce at higher spinning speeds by spinning from a melt have so far failed because the extruded filaments stick together as soon as the spinning speed is increased to a certain extent.

Es wurde nun in überraschender Weise, entgegen der allgemeinen Lehre gefunden, dass die bekannte Klebrigkeit der Fäden aufeinander und der Fibrillen untereinander vermieden werden und ein hochmoduliger und besser verarbeitbarer Faden hergestellt werden kann, wenn man das Polymer und die Streckbedingungen so auswählt, dass eine irreversible Verstreckung einsetzt, und wenn man auf eine Entspannung/Relaxation ganz verzichtet, und schliesslich die Abzugsgeschwindigkeit zusätzlich erhöht.It has now surprisingly been found, contrary to the general teaching, that the known stickiness of the threads to one another and of the fibrils to one another can be avoided and a high-modulus and better processable thread can be produced if the polymer and the stretching conditions are selected in such a way that an irreversible one Stretching begins, and if you do not relax completely, and finally increases the take-off speed.

Ein Abschrecken der Fäden nach dem Schmelzspinnen stellt eine weiteren aufwendigen Verfahrensschritt dar und bedingt andere Fadeneigenschaften.Quenching the threads after melt spinning represents a further complex process step and requires different thread properties.

Durch die hohen Aufspulgeschwindigkeiten bei hohen Spinntemperaturen kann die Wirtschaftlichkeit stark erhöht werden. Dabei können sehr feinfibrillige Fäden hergestellt werden.Due to the high winding speeds at high spinning temperatures, the economy can be greatly increased. Very fine fibrillated threads can be produced.

Als Polyurethane zur Herstellung der erfindungsgemässen Elastomerfaser sind bevorzugt solche geeignet, welche extrudierbar sind und aus einem aromatischen Diisocyanat, beispielsweise 4,4′-Diphenyl-Methandiisocyanat (MDI) und einem linearen Polyether z.B. Polytetramethylenglykol oder einem aliphatischen Polyester, beispielsweise Polybutylenadipat oder Polycaprolactondiol. Geeignet sind auch Blockpolymere aus einem cycloaliphatischen Diisocyanat wie Hexahydro-MDI und einem linearen segmentierten Polyether, welche bekannterweise besonders für medizinische Einsätze geeignet sind. Der Erweichungspunkt des geeigneten Polyurethans liegt zwischen 180 bis 130°C, die Härte beträgt 80 bis 95° Shore A und die Dichte 1,1 bis 1,25 g/cm³. Diese Härte spielt für die Klebrigkeit des Polyurethanfadens eine wichtige Rolle.Suitable polyurethanes for producing the elastomer fiber according to the invention are preferably those which are extrudable and which consist of an aromatic diisocyanate, for example 4,4'-diphenylmethane diisocyanate (MDI) and a linear polyether e.g. Polytetramethylene glycol or an aliphatic polyester, for example polybutylene adipate or polycaprolactone diol. Block polymers of a cycloaliphatic diisocyanate such as hexahydro-MDI and a linear segmented polyether, which are known to be particularly suitable for medical applications, are also suitable. The softening point of the suitable polyurethane is between 180 to 130 ° C, the hardness is 80 to 95 ° Shore A and the density is 1.1 to 1.25 g / cm³. This hardness plays an important role in the stickiness of the polyurethane thread.

Verwandte PUR hie die Polyether- oder Polyetherester- oder Polyesteramin-urethane können, sofern sie eine ausreichende Schmelzstabilität aufweisen, ebenfalls eingesetzt und schmelzgesponnen sowie zu elastischen Fäden verarbeitet werden.Related PUR such as the polyether or polyether ester or polyester amine urethanes, provided they have sufficient melt stability, can also be used and melt spun and processed into elastic threads.

Aufgabe der Erfindung ist es, einen hochmoduligen, hochfesten, multifilen elastischen Faden, dessen Fibrillen untereinander nicht verklebt sind, durch Schmelzspinnen wirtschaftlich herzustellen.The object of the invention is to produce a high-modulus, high-strength, multifilament elastic thread, the fibrils of which are not glued to one another, by melt spinning.

Die Aufgabe wird erfindungsgemäss nach Anspruch 1 gelöst durch einen Modul von 10 - 40 cN/tex und eine Bruchdehung von 80 bis 300 %, bezogen auf die Länge des ungedehnten Fadens.According to the invention, the object is achieved by a module of 10-40 cN / tex and an elongation at break of 80 to 300%, based on the length of the unstretched thread.

Nach dem erfindungsgemässen Verfahren ist es in überraschender Weise gelungen, aus einer Schmelze gesponnene, aufwickelbare, multifile Elastomerfäden mit einem hohen Anfangsmodul herzustellen, deren Einzelfibrillen untereinander nicht verklebt sind. Es wird in einem integrierten einstufigen Verfahren, d.h. unmittelbar nach dem Spinnen der Fäden mit bekannten Einrichtungen verstreckt aufgespult, ohne dass ein weiterer Verfahrensschritt wie beispielsweise Relaxieren erforderlich ist.According to the method according to the invention, it has surprisingly been possible to produce multifilament elastomer threads spun from a melt, which can be wound up, with a high initial modulus, the individual fibrils of which are not glued to one another. It is built in an integrated one-step process, i.e. immediately after spinning the threads with known devices, wound on without any further process step such as relaxation being necessary.

Der resultierende glatte, elastische Faden ist unmittelbar nach dem Aufwickeln zur Weiterverarbeitung geeignet. Er hat gegenüber den bekannten Elastomeren den Vorteil, dass er direkt ohne Umspinnen eingesetzt werden kann.The resulting smooth, elastic thread is suitable for further processing immediately after winding. It has the advantage over the known elastomers that it can be used directly without spinning.

In einer bevorzugten Weise wird das Verfahren so ausgeführt, dass das Polyurethan-Granulat zunächst bei 190 bis 240°C geschmolzen und extrudiert wird. Die Geschwindigkeit der Aufspulung soll wenigstens 600 m/min, bevorzugt mehr als 900 m/min betragen, wodurch ein Verstreckungsverhältnis von wenigstens 1,5 vorliegen soll. Da das Verstrecken und Aufspulen unmittelbar nach dem Abzug des gesponnenen Fadens erfolgt, kann der Vorgang praktisch als simultan, gleichzeitig oder Spinnstrecken bezeichnet werden.In a preferred manner, the process is carried out in such a way that the polyurethane granules are first melted and extruded at 190 to 240 ° C. The speed of the winding should be at least 600 m / min, preferably more than 900 m / min, as a result of which a draw ratio of at least 1.5 should be present. Since the stretching and winding take place immediately after the spun thread has been drawn off, the process can practically be referred to as simultaneous, simultaneous or spinning.

Auf einem ersten Rollenpaar ist der Faden noch nicht vollständig erkaltet, was eine tatsächliche Verstreckung in der Streckzone noch erlaubt. Diese Verstreckung und damit auch grössere Molekülorientierung in den Fäden äussert sich dann auch durch niedrige Bruchdehnung und hohen Kochschrumpf und insbesondere stark erhöhten Modul. Die Orientierung der Moleküle in der Abzugszone hängt erwartungsgemäss von der Abzugsgeschwindigkeit und aufgrund der stark temperaturabhängigen Viskosität der Polymeren auch in hohem Mass von der Spinntemperatur ab. Ist die Vororientierung zu gering, lässt sich der Modul nicht mehr auf höchste Werte steigen.The thread has not yet completely cooled on a first pair of rolls, which still allows actual drawing in the drawing zone. This stretching and thus also greater molecular orientation in the threads is then also manifested by low elongation at break and high boiling shrinkage and in particular a greatly increased modulus. As expected, the orientation of the molecules in the take-off zone depends on the take-off speed and, due to the strongly temperature-dependent viscosity of the polymers, also to a large extent on the spinning temperature. If the pre-orientation is too low, the module can no longer be increased to the highest values.

Das Aufspulen erfolgt vorzugsweise spannungslos.The winding is preferably carried out without voltage.

Dieser hochmodulige, spinngestreckte Faden lässt sich gut zu einem Flächengebilde verarbeiten. Um starke Dimensionsverluste des Flächengebildes in der Ausrüstung zu vermeiden, ist es zweckmässig, dieses vor der Ausrüstung zu fixieren. Die Wahl der Fixierbedingungen erlauben eine Steuerung der resultierenden Elastizität der Ware. Aufgrund des vorliegenden Schrumpfes eignet sich der erfindungsgemässe Faden insbesondere auch für Formfixirungen.This high-modulus, spun-stretched thread can be easily processed into a flat structure. In order to avoid severe dimensional loss of the fabric in the equipment, it is advisable to fix it in front of the equipment. The choice of fixing conditions allows the resulting elasticity of the goods to be controlled. Because of the shrinkage present, the thread according to the invention is also particularly suitable for fixing form.

Das Flächengebilde kann aber auch in Wasser von höchstens 130°C, vorteilhaft jedoch bei Temperaturen unter dem Siedepunkt des Wassers, beispielsweise 94 bis 100°C, getempert werden.However, the fabric can also be annealed in water of at most 130 ° C, but advantageously at temperatures below the boiling point of the water, for example 94 to 100 ° C.

Es ist ebenfalls zweckmässig, den verstreckten Elastomerfaden vor der Verarbeitung zu tempern, um ihm die gewünschte Elastizität zu verleihen.It is also advisable to temper the stretched elastomer thread before processing in order to give it the desired elasticity.

Das Tempern erfolgt bevorzugt mittels Dampf, Heisswasser oder beheizten Metallflächen. Um eine ausreichende Dimensionsstabilität zu garantieren, soll das Tempern bei Temperaturen >90°C erfolgen.The tempering is preferably carried out using steam, hot water or heated metal surfaces. In order to guarantee sufficient dimensional stability, the tempering should take place at temperatures> 90 ° C.

Vor dem Tempern weist der Elastomerfaden einen Modul von 10-40, bevorzugt >20, insbesondere 20 bis 40 cN/tex, eine Bruchdehnung von 80 bis 300 %, bevorzugt von 90 bis 200 % auf, bezogen auf die Länge des ungedehnten Fadens. Der verstreckte Elastomerfaden weist bis zur Bruchdehnung eine vollständig reversible Elastizität auf.Before tempering, the elastomer thread has a modulus of 10-40, preferably> 20, in particular 20 to 40 cN / tex, an elongation at break of 80 to 300%, preferably 90 to 200%, based on the length of the unstretched thread. The stretched elastomer thread has a completely reversible elasticity up to the elongation at break.

Nach dem Tempern erhält der erfindungsgemässe gummielastische Elastomerfaden je nach Art und Temperatur der Behandlung eine Reissdehnung von 100 bis 800 %, insbesondere von 300 bis 600 %, bevorzugt von etwa 400 %, bezogen auf die Länge des ungedehnten Fadens auf (s. Tabelle 1 und 2).After tempering, the rubber-elastic elastomer thread according to the invention, depending on the type and temperature of the treatment, has an elongation at break of 100 to 800%, in particular of 300 to 600%, preferably of about 400%, based on the length of the unstretched thread (see Table 1 and 2).

Der spinngestreckte Elastomerfaden ist zweckmässig bis zur Reissgrenze nahezu vollständig reversibel elastisch.The spun-stretched elastomer thread is expediently almost completely reversibly elastic up to the tear limit.

Bevorzugte Anwendungsgebiete des erfindungsgemässen gummielastischen Elastomerfadens sind textile Flächengebilde. Dabei hat es sich als vorteilhaft erwiesen, den erfindungsgemässen Elastomerfaden zusammen mit wenigstens einem anderen nicht-elastischen Faden aus synthetischen oder natürlichen Fasern zu einem elastischen Flächengebilde zu verarbeiten.Preferred areas of application for the rubber-elastic elastomer thread according to the invention are textile fabrics. It has proven to be advantageous here to process the elastomer thread according to the invention together with at least one other non-elastic thread made of synthetic or natural fibers to form an elastic flat structure.

Die Erfindung soll anhand von Zeichnungen und Beispielen näher erläutert werden.The invention will be explained in more detail with reference to drawings and examples.

Es zeigen:

  • Fig. 1 ein schematisches Fliessbild des Spinn-streck-Verfahrens
  • Fig. 2 Kraft-Dehnungsdiagramme
  • Fig. 3 Hysteresekurven
Show it:
  • Fig. 1 is a schematic flow diagram of the spin-draw process
  • Fig. 2 force-strain diagrams
  • Fig. 3 hysteresis curves

In der Figur 1 ist mit dem Bezugszeichen 1 ein Spinnblock mit Spinndüsen dargestellt. Ein Bündel von Fibrillen 2 wird an einem Ensimagestift oder einer rolle 3 zu einem Faden 2′ zusammengefasst und über eine Galette 4 und eine Trennrolle 4′ geführt, welche zusammen das Rollenpaar 4, 4′ bilden. Ein weiteres Rollenpaar 5, 5′ besteht aus einer Galette 5 und einer Trennrolle 5′. Mit 6 ist eine Spule mit einer Antriebswalze 7 bezeichnet.A spinning block with spinning nozzles is shown in FIG. A bundle of fibrils 2 is combined on an ensemble pin or a roll 3 into a thread 2 'and guided over a godet 4 and a separating roller 4', which together form the pair of rollers 4, 4 '. Another pair of rollers 5, 5 'consists of a godet 5 and a separation roller 5'. 6 with a coil with a drive roller 7 is designated.

In Fig. 2 zeigt die Kurve 1 den kalt-spinngestreckten Faden. Kurven 2 bis 4 geben die Kraft-Dehnung des gleichen Fadens bei verschiedenen Temperaturen getempert wieder; Kurve 2 bei 40°C, Kurve 3 bei 60°C und Kurve 4 bei 98°C in Wasser.In Fig. 2, curve 1 shows the cold-spun stretched thread. Curves 2 to 4 show the force-elongation of the same thread annealed at different temperatures; Curve 2 at 40 ° C, curve 3 at 60 ° C and curve 4 at 98 ° C in water.

In Fig. 3 wird die Hysteresekurve 1 des spinngestreckten Fadens und Hysteresekurve 2 des spinngestreckten Fadens zusätzlich bei 98°C in Wasser behandelt, wiedergegeben.In Fig. 3 the hysteresis curve 1 of the spun yarn and hysteresis curve 2 of the spun yarn additionally treated at 98 ° C in water is shown.

Wie aus dem Unterschied der Kurven vor und nach der thermischen Behandlung ersichtlich ist, resultiert eine bei annähernd gleicher Reisskraft, höhere Elastizität.As can be seen from the difference between the curves before and after the thermal treatment, the elasticity is greater with almost the same tensile strength.

Zwei Ausführungsbeispiele sollen die Erfindung weiter erläutern.Two exemplary embodiments are intended to explain the invention further.

Beispiel 1example 1

10 kg eines thermoplastischen Polyurehtans von GOODRICH, Estane 54351 hergestellt ab einem aromatischen Diisocyanat, einem Polycaprolactonmakrodiol und Butandiol mit einer Härte von 84° Shore A, einem Erweichungspunkt von 185°C, einer Dichte von 1,15 g/cm³ werden zuerst bei 60°C während 8h und ca. 50 mbar, dann bei 90°C während 24h und bei Hochvakuum auf eine Restfeuchtigkeit von 0,01 % getrocknet, wobei eine Grenzviskosität von 1,80, gemessen in einem Lösungsmittelgemisch von 1:1 Phenol/Tetrachlorethan mit einem Ubbelohde-Viskosimeter bei 25°C und Konzentration von 0,4 %, resultiert.10 kg of a thermoplastic polyurethane from GOODRICH, Estane 54351 made from an aromatic diisocyanate, a polycaprolactone macrodiol and butanediol with a hardness of 84 ° Shore A, a softening point of 185 ° C, a density of 1.15 g / cm³ are first at 60 ° C for 8h and approx. 50 mbar, then dried at 90 ° C for 24h and under high vacuum to a residual moisture of 0.01%, an intrinsic viscosity of 1.80, measured in a solvent mixture of 1: 1 phenol / tetrachloroethane with a Ubbelohde viscometer at 25 ° C and a concentration of 0.4%.

Zur Verbesserung der Lichtbeständigkeit können UV-Absorber des Typs Tinuvin® von CIBA GEIGY einpolymerisiert oder dem Granulat aufgepudert werden. Zur Verbesserung der elastischen Eigenschaften und des Glanzes können Füllstoffe wie TiO₂, SiO₂, eingesetzt werden.To improve light resistance, UV absorbers of the Tinuvin® type from CIBA GEIGY can be polymerized or powdered onto the granulate. Fillers such as TiO₂, SiO₂ can be used to improve the elastic properties and gloss.

Zur Fadenherstellung wird das Granulat unter Sauerstoffausschluss in einem Extruder z.B. bei 210°C aufgeschmolzen, durch ein 10 µm Filtersieb und durch den Spinnblock 1 mit einer Spinndüse mit acht Löchern bei einem Vordruck von 60 bar gepresst und in einem Spinnstreckprozess zu einem Multifilament dtex 41 f 8 versponnen. Dazu werden die einzelnen Filamente 2 in einem nicht gezeigten Blasschacht mit Luft von 40 mm Wasaersäule abgekühlt und mittels Ensimagestift 3 zusammengeführt und geölt. Die Spinngeschwindigkeit, gegeben durch die Galette 4, beträgt 600 m/min. Nach fünf Umschlingungen auf dem Rollenpaar 4, 4′ wird der Faden 2′ auf das zweite Rollenpaar 5, 5′ mit fünf Umschlingungen geführt und 2,1 Mal kalt verstfeckt. Die kalten Rollen 4, 5 mit glatter Oberfläche werden mit nicht gezeigten Elektromotoren und die Gegenrollen 4′ und 5′ mit Luft angetrieben. Dadurch bleibt die Reibung resp. die Fadenspannung so niedrig, dass der Faden 2′ nicht verzogen wird. Mittels einer angetriebenen Walze 7 wird der Faden 2˝ auf eine Spule bei einer Aufspulgeschwindigkeit von 1250 m/min spannungslos aufgewickelt.To produce the thread, the granulate is melted in an extruder, for example at 210 ° C., in the absence of oxygen, pressed through a 10 μm filter screen and through spinning block 1 with a spinneret with eight holes at a pre-pressure of 60 bar, and in a spin-stretching process to form a multifilament dtex 41 f 8 spun. For this purpose, the individual filaments 2 are cooled in a blow shaft (not shown) with air of 40 mm Wasa column and brought together and oiled by means of an ensemble pin 3. The spinning speed, given by the godet 4, is 600 m / min. After five loops on the pair of rollers 4, 4 ', the thread 2' is guided on the second pair of rollers 5, 5 'with five loops and 2.1 times cold hiding. The cold rollers 4, 5 with a smooth surface are driven with electric motors, not shown, and the counter rollers 4 'and 5' with air. This keeps the friction resp. the thread tension so low that the thread 2 'is not distorted. By means of a driven roller 7, the thread 2˝ is wound up without tension on a bobbin at a winding speed of 1250 m / min.

Die Fadenherstellung erfolgt gemäss Fig. 1 nach dem Spinn-streck-Verfahren.According to FIG. 1, the thread is produced by the spin-stretch method.

Beispiel 2Example 2

10 kg eines thermoplastischen Polyurethans ebenfalls auf Polyesterbasis von GOODRICH, Estane 58277, welches für medizinische Einsätze geeignet ist, mit einer Härte von 93° Shore A, einem Erweichungspunkt von 185°C und einer Dichte von 1,19 g/cm³, wurde gemäss Beispiel 1 gesponnen und gleichzeitig verstreckt.10 kg of a thermoplastic polyurethane, also based on polyester from GOODRICH, Estane 58277, which is suitable for medical use, with a hardness of 93 ° Shore A, a softening point of 185 ° C and a density of 1.19 g / cm³, was according to the example 1 spun and stretched at the same time.

In den folgenden Tabellen 1 und 2 sind die Fadeneigenschaften der Beispiele 1 und 2 zusammengefasst.

Figure imgb0001
Tables 1 and 2 summarize the thread properties of Examples 1 and 2.
Figure imgb0001

Der erfindungsgemässe Faden 2˝ zeigt die Eigenschaften gemäss der Tabelle, 1. Kolonne. Seine Festigkeit beträgt 25 cN/tex, seine Bruchdehnung 145 % und der Kochschrumpf 61 % bezogen auf die Länge des ungedehnten Fadens.

Figure imgb0002
The thread 2˝ according to the invention shows the properties according to the table, 1st column. Its strength is 25 cN / tex, its elongation at break 145% and the boiling shrinkage 61% based on the length of the unstretched thread.
Figure imgb0002

Der Faden kann auch gut aufgespult werden. Er zeigt keine Verklebungstendenz. Eine mikroskopische Queraufnahme zeigt, dass die einzelnen Filamente voneinander gut getrennt sind und den erwünschten runden Querschnitt aufweisen.The thread can also be wound up well. It shows no tendency to stick. A microscopic cross-section shows that the individual filaments are well separated from one another and have the desired round cross-section.

Dieser Faden zeigt, wenn er einer Wärmebehandlung z.B. 2 min in heissem Wasser unterworfen wird, die Eigenschaften gemäss Kolonne 2 bis 5 der Tabelle. Bei der Bruchdehnung in siedendem Wasser (Kolonne 5) steigt die Bruchdehnung auf 490 %. Die elastischen Eigenschaften sind mit jenen der zusammengeklebten, multifilen, kommerziell erhältlichen nassgesponnenen Polyurethanfasern vergleichbar.This thread shows when it is subjected to a heat treatment e.g. Is subjected to 2 min in hot water, the properties according to column 2 to 5 of the table. The elongation at break in boiling water (column 5) increases to 490%. The elastic properties are comparable to those of the multifilament, commercially available wet-spun polyurethane fibers glued together.

Beispiele 3 und 4Examples 3 and 4

10 kg des thermoplastischen Polyurethans von Beispiel 1 wurden nach unserem Spinnstreckverfahren bei einem Abzug von 600 m bzw. 1600 m/min bei verschiedenen Spinntemperaturen spinngestreckt.

Figure imgb0003
10 kg of the thermoplastic polyurethane from Example 1 were spin-stretched using our spin-stretching method with a draw of 600 m or 1600 m / min at various spinning temperatures.
Figure imgb0003

Wie diese Beispiele zeigen, ist die mögliche Spinngeschwindigkeit stark von der Polymerviskosität und somit von der Spinntemperatur abhängig. Bei der höheren Temperatur von Beispiel 4 kann die Abzugsgeschwindigkeit und somit die Wirtschaftlichkeit der Fadenherstellung stark erhöht werden.As these examples show, the possible spinning speed is strongly dependent on the polymer viscosity and thus on the spinning temperature. At the higher temperature of Example 4, the take-off speed and thus the cost-effectiveness of thread production can be greatly increased.

Der spinngestreckte Originalfaden kann z.B. zusammen mit einem Polyamid dtex 33 f 10 zu einem Flächengebilde gestrickt werden. Nach dem Fixieren oder nach einer Wärmebehandlung, z.B. Färben, dieses Gestricks kann das Erzeugnis zu einem gummielastischen Flächengebilde in bekannter Weise verarbeitet werden.The spun drawn original thread can e.g. knitted together with a polyamide dtex 33 f 10 to form a fabric. After fixation or after heat treatment, e.g. Coloring, this knitted fabric can be processed into a rubber-elastic sheet in a known manner.

Als besondere Anwendungsgebiete seien noch genannt medizinische Stützstrümpfe, elastische Bänder, Sportbekleidung, Badehose, Strumpfhose (feine Titer), elastische Filter, elastische Artikel für die Bekleidungsindustrie sowie für die Herstellung von elastischen Artikeln für die Medizin oder Chirurgie, insbesondere für Prothesen.Medical support stockings, elastic bands, sportswear, swimming trunks, tights (fine titer), elastic filters, elastic articles for the clothing industry and for the production of elastic articles for medicine or surgery, in particular for prostheses, may also be mentioned as special areas of application.

Claims (4)

1. Elastomeric multifilament yarn composed of polyurethane having a hardness of from 80 to 95° Shore, characterised by a modulus of 10 - 40 cN/tex and a breaking extension of 80 to 300%, based on the length of the unextended yarn.
2. Elastomeric multifilament yarn according to Claim 1, characterised in that the individual filaments are in tack-free contact.
3. Elastomeric multifilament yarn according to Claims 1 and 2, characterised by completely reversible elasticity up to the breaking extension.
4. Use of the elastomeric multifilament yarn according to Claims 1 to 3, for manufacturing elastomeric textile sheet materials.
EP19870907735 1986-12-17 1987-12-11 Polyurethane elastomer thread and its use Expired - Lifetime EP0295271B1 (en)

Applications Claiming Priority (2)

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CH5011/86 1986-12-17
CH501186 1986-12-17

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EP0295271B1 true EP0295271B1 (en) 1992-05-27

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DE3902039C1 (en) * 1989-01-25 1990-08-09 Klaus 5205 St Augustin De Bloch
DE3911725C2 (en) * 1989-04-11 1997-09-25 Basf Ag Process for the production of tack-free, highly elastic, multifilament polyurethane elastomer threads, elastomer threads produced by this process and their use
JP5895312B2 (en) 2011-05-27 2016-03-30 東レ・オペロンテックス株式会社 Elastic fabric
US11339504B2 (en) 2017-02-10 2022-05-24 Basf Se Process for producing elastic fiber, process for producing elastic fiber article, elastic fiber and elastic fiber article

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DE1944507A1 (en) * 1968-09-04 1970-07-02 Kanegafuchi Spinning Co Ltd Process for making an elastomeric continuous yarn
GB1393801A (en) * 1971-04-01 1975-05-14 Monsanto Co Helically crimped bicomponent yarn and garment made therefrom
JPS5849303A (en) * 1981-09-18 1983-03-23 Mitsui Toatsu Chem Inc Insecticidal and miticidal composition
JPS60123491A (en) * 1983-12-08 1985-07-02 Sumitomo Chem Co Ltd Organosilicon compound, its preparation, and insecticide containing it as active ingredient
JPS6153291A (en) * 1984-08-23 1986-03-17 Sumitomo Chem Co Ltd Organosilicon compound, its production, and insecticide comprising it as active ingredient
JPS6187657A (en) * 1984-10-05 1986-05-06 Kao Corp Preparation of alpha-sulfo-fatty acid ester salt
JPS6187687A (en) * 1984-10-05 1986-05-06 Yoshio Katsuta Insecticide and acaricide containing organosilicon aromatic alkane derivative and their production

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