EP0295271A1 - Polyurethane elastomer thread and its use. - Google Patents

Polyurethane elastomer thread and its use.

Info

Publication number
EP0295271A1
EP0295271A1 EP19870907735 EP87907735A EP0295271A1 EP 0295271 A1 EP0295271 A1 EP 0295271A1 EP 19870907735 EP19870907735 EP 19870907735 EP 87907735 A EP87907735 A EP 87907735A EP 0295271 A1 EP0295271 A1 EP 0295271A1
Authority
EP
European Patent Office
Prior art keywords
thread
spun
elastomer
stretched
melt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19870907735
Other languages
German (de)
French (fr)
Other versions
EP0295271B1 (en
Inventor
Maria Toscan
Remy Humbrecht
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Viscosuisse SA
Original Assignee
Viscosuisse SA
Societe de la Viscose Suisse SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Viscosuisse SA, Societe de la Viscose Suisse SA filed Critical Viscosuisse SA
Publication of EP0295271A1 publication Critical patent/EP0295271A1/en
Application granted granted Critical
Publication of EP0295271B1 publication Critical patent/EP0295271B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 process for the production of a smooth, melt-spun, multifilament elastomer filament a polyurethane and the elastomer filament produced by the process and its use.
  • polyimides are incorporated into the polymer chain or added to the polymer melt.
  • the continuous filaments produced with the polymer obtained must be wound up at very low speeds and stretched in a second operation, and no information is given about the properties of the filaments 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. From a theoretical point of view, it is stated that in the case of a low relaxation ratio, ie at a faster winding speed, the stickiness of the thread increases.
  • the melt-spun thread is stretched and then relaxed again.
  • the course of the process 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 actual sense, but it can be greatly stretched due to its high elasticity
  • the stretching process according to DE-A-1944507 remains without a great influence on the thread properties.
  • Preferred polyurethanes for producing the elastomer fiber according to the invention are those which are extrudable and which consist of an aromatic diisocyanate, for example 4,4'-diphenylmethane diisocyanate (MDI) and a linear polyether, for example polytetramethylene glycol or an aliphatic polyester for example polybutylene adipate or polycaprolactone diol.
  • MDI 4,4'-diphenylmethane diisocyanate
  • a linear polyether for example 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 230 ° C., the hardness is 80 to 95 ⁇ Shore A and the density is 1.1 to 1.25 g / cm 3. This hardness plays an important role in the tackiness 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 according to the invention in that the polyurethane is melt-spun, at the same time irreversibly stretched and wound directly at at least 600 m / min.
  • the process according to the invention has surprisingly succeeded in producing 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.
  • an integrated one-step process ie immediately after spinning the threads, it is wound up with known devices without the need for a further process step, such as relaxing.
  • 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 / in, so that a draw ratio of at least 1.5 should be present. Since the drawing 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 an actual stretching 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 cooking 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 large dimensional losses 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 shape fixation.
  • the fabric can also in water of at most 130 # C, but advantageously sers at temperatures below the boiling point of the Was ⁇ , for example 94 to 100 C ⁇ are annealed.
  • 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 at least 10, 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 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 tearing limit.
  • Preferred areas of application for the rubber-elastic elastomer thread according to the invention are textile fabrics. It has proven to be advantageous 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 sheet-like structure.
  • FIG. 1 shows a schematic flow diagram of the spin-stretching method.
  • FIG. 2 force-strain diagrams.
  • FIG. 3 hysteresis curves
  • a spinning block with spinnerets is shown in FIG.
  • a bundle of fibrils 2 is combined into a thread 2 ' on an ensemble pin or a roll 3 and guided over a godet 4 and a separating roll 4', which together form the pair of rolls 4, 4 1 .
  • Another pair of rollers 5, 5 ' consists of a godet 5 and a separating 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.
  • hysteresis curve 1 of the spun yarn and hysteresis curve 2 of the spun yarn additionally treated at 98 * C in water is shown.
  • the elasticity is greater with approximately the same tractive force.
  • 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 / cm 3 are the first dried at 6.0 * C for 8h and approx. 50 mbar, then at 90 * C for 24h and under high vacuum to a residual moisture of 0.01%, with an intrinsic viscosity of 1.80, measured in a solvent mixture of 1: 1 phenol / Tetrachloroethane with an Ubbelohde viscometer at 25 * C and concentration of 0.4% results.
  • UV absorbers of the Tinuvinvfy type from CIBA GEIGY can be polymerized or powdered onto the granulate. Fillers such as TiO 2 , SiO 2 can be used to improve the elastic properties and the gloss.
  • the granulate is melted in the absence of oxygen in an extruder, for example at 210 * C, through a 10 ⁇ m filter sieve 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 a multifilament dtex 41 f 8 spun.
  • the individual filaments 2 are cooled in a blow shaft (not shown) with air of 40 mm water 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 onto the second pair of rolls 5, 5 'with five loops and cold stretched 2.1 times.
  • 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 is 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. - 8th -
  • the thread is produced by the spin-stretch method.
  • thermoplastic polyurethane also based on GOODRICH polyester, Estane 58277, which is suitable for medical applications, with a hardness of 93 "Shore A, a softening point of 185 ° C. and a density of 1.19 g / cm 3 , was spun according to Example 1 and stretched at the same time.
  • Tables 1 and 2 summarize the thread properties of Examples 1 and 2.
  • ** Module is understood to mean the force at 100% elongation based on the initial titer - 9 -
  • the inventive caden 2 '' 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 transverse image shows that the individual filaments are well separated from one another and have the desired round cross section.
  • this thread shows the properties according to columns 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 spun-stretched original thread can, for example, be knitted together with a polyamide dtex 33 f 10 to form a fabric. After fixing or after a heat treatment, for example dyeing, of this knitted fabric, the product can be processed into a rubber-elastic flat structure in a known manner.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)

Abstract

Le procédé permet la fabrication par étirage à chaud de fils en élastomère ayant un module élevé, un allongement à la rupture maximum de 300 %, un rétrécissement à la cuisson supérieur à 20 %. A cet effet, un mélange en fusion de granulés de polyuréthane est étiré d'au moins 1,5 et simultanément filé à une vitesse d'au moins 600m/min. Le filé obtenu peut être travaillé sous forme de surface plane, son élasticité étant déterminée par fixage ou trempage dans de l'eau chaude. Le filé peut être également trempé avant la phase de travail textile pour lui conférer les propriétes élastiques désirées.The process allows the manufacture by stretching of elastomeric yarns having a high modulus, a maximum elongation at break of 300%, a shrinkage during baking greater than 20%. For this purpose, a molten mixture of polyurethane granules is stretched by at least 1.5 and simultaneously spun at a speed of at least 600m / min. The yarn obtained can be worked in the form of a flat surface, its elasticity being determined by fixing or soaking in hot water. The yarn can also be soaked before the textile working phase to give it the desired elastic properties.

Description

Verfahren zur Herstellung eines glatten, multifilen Polyurethan-Elastomerfadens, Elastomerfaden herge¬ stellt nach dem Verfahren und dessen Verwendung Process for producing a smooth, multifilament polyurethane elastomer thread, elastomer thread produced according to the method and its use
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellun eines glatten, εchmelzgesponnenen, multifilen Elastomerfadens a Polyurethanen sowie den nach dem Verfahren hergestellten Elasto merfaden und dessen Verwendung.The present invention relates to a process for the production of a smooth, melt-spun, multifilament elastomer filament a polyurethane and the elastomer filament produced by the process and its use.
Die Herstellung von schraelzgesponnenen elasto eren Polyurethan¬ fäden, welche aus mindestens 85 Gew.-% segmentierten Polyuretha nen bestehen, ist bekannt. Solche Fäden waren wegen des Verkle- bens nach dem Spinnen jedoch praktisch nicht verwertbar. Eine A hilfe wurde durch chemische Abwandlung des Polyurethans erzieltIt is known to produce elastomeric polyurethane threads spun from Israel, which consist of at least 85% by weight segmented polyurethanes. However, such threads were practically unusable because of the sticking after spinning. Aid was achieved by chemical modification of the polyurethane
Ein solches Verfahren, in welchem auf chemischem Weg die Verkle bung 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 Polymerεchmelze zugefügt. Die mit dem erhalt nen Polymer erzeugten Endlosfäden müssen mit sehr niedrigen Ge¬ schwindigkeiten 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 must be wound up at very low speeds and stretched in a second operation, and no information is given about the properties of the filaments obtained.
Abgesehen davon, dass die Zugabe von Additiven eine Erniedrigun des Molekulargewichtes bewirkt, womit ein Absinken der Schmelz¬ viskosität einhergeht, was wiederum die elastischen Eigenschaf¬ ten, die Reissdehnung und Festigkeit eines resultierenden Garne nachteilig beeinflusst, ist eine Produktivität mit den um 160 m/min genannten Aufspulgeεchwindigkeiten unzureichend und unwir schaftlich. 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 % ver¬ streckt und in einer weiteren Stufe um mindestens 50 % vor dem Aufwickeln relaxiert. Es wird in einer theoretischen Betrachtung ausgeführt, dass im Falle eines kleinen Entspannungsverhältnis¬ ses, d.h. bei einer rascheren Aufwickelgeschwindigkeit die Kleb¬ rigkeit des Fadens zunimmt.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 around 160 m / min winding speeds inadequate and inefficient. 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. From a theoretical point of view, it is stated that in the case of a low relaxation ratio, ie at a faster winding speed, the stickiness of the thread increases.
Nach diesem Verfahren wird der schmelzgesponnene Faden verdehnt und anschiessend wieder relaxiert. "Der Verfahrensablauf deutet darauf hin, dass auf der Abzugsgalette bereits der fertiggestell¬ te, völlig erkaltete Elastomerfaden vorliegt. Dieser zeigt die typischen Eigenschaften eines Polyurethanelastomeren; er lässt sich nicht mehr im eigentlichen Sinne verstrecken, aufgrund sei¬ ner hohen Elastizität wohl aber stark verdehnen, wobei diese Deh¬ nung reversibel ist. Der Verdehnungsprozess gemäss DE-A-1944507, bleibt ohne grossen Einfluss auf die Fadeneigenschaften.According to this process, the melt-spun thread is stretched and then relaxed again. " The course of the process 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 actual sense, but it can be greatly stretched due to its high elasticity The stretching process according to DE-A-1944507 remains without a great influence on the thread properties.
Alle Versuche, elastomere Polyurethanfäden unter wirtschaftlichen Bedingungen, d.h. bei höheren Spinngeschwindigkeiten durch Spin¬ nen aus einer Schmelze herzustellen, sind bisher daran geschei¬ tert, 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 has so far failed that 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 aufeinan¬ der 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. Ein Abschrecken der Fäden nach dem Schmelzspinnen stellt einen weiteren aufwendigen Verfahrensschritt dar und bedingt andere Fadeneigenschaften.It has now surprisingly been found, contrary to the general teaching, that the known stickiness of the threads on one another and of the fibrils with 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 stretching begins, and if one completely does not relax / unwind, and finally increases the take-off speed additionally. Quenching the threads after melt spinning represents a further complex process step and requires different thread properties.
Durch die hohen AufSpulgeschwindigkeiten bei hohen Spinntempera¬ turen kann die Wirtschaftlichkeit stark erhöht werden. Dabei kön¬ nen sehr feinfibrillige Fäden hergestellt werden.The economy can be greatly increased by the high winding speeds at high spinning temperatures. Very fine-fibrillated threads can be produced here.
Als Polyurethane zur Herstellung der erfindungsgemässen Elasto¬ merfaser sind bevorzugt solche geeignet, welche extrudierbar sind und aus einem aromatischen Diisocyanat, beispielsweise 4,4'-Di- phenyl-Methandiisocyanat (MDI) und einem linearen Polyether z.B. Polytetramethylenglykol oder einem aliphatischen Polyester, bei¬ spielsweise 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 geeig¬ net sind. Der Erweichungspunkt des geeigneten Polyurethans liegt zwischen 180 bis 230"C, die Härte beträgt 80 bis 95βShore A und die Dichte 1,1 bis 1,25 g/cm3. Diese Härte spielt für die Kleb¬ rigkeit des Polyurethanfadens eine wichtige Rolle.Preferred polyurethanes for producing the elastomer fiber according to the invention are those which are extrudable and which consist of an aromatic diisocyanate, for example 4,4'-diphenylmethane diisocyanate (MDI) and a linear polyether, for example 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 230 ° C., the hardness is 80 to 95 β Shore A and the density is 1.1 to 1.25 g / cm 3. This hardness plays an important role in the tackiness of the polyurethane thread .
Verwandte PUR wie die Polyether- oder Polyetherester- oder Poly- esteramin-urethane können, sofern sie eine ausreichende Schmelz¬ stabilität 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 herzu¬ stellen.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 dadurch gelöst, dass das Polyurethan schmelzgesponnen, gleichzeitig irreversibel verstreckt und direkt mit wenigstens 600 m/min aufgespult wird. Nach dem erfindungsgemässen Verfahren ist es in überraschender Weise gelungen, aus einer Schmelze gesponnene, aufwickelbare, multifile Elastomerfäden mit einem hohen Anfangsmodul herzustel¬ len, deren Einzelfibrillen untereinander nicht verklebt sind. Es wird in einem integrierten einstufigen Verfahren, d.h. unmittel¬ bar nach dem Spinnen der Fäden mit bekannten Einrichtungen ver¬ streckt aufgespult, ohne dass ein weiterer Verfahrensschritt wie beispielsweise Relaxieren erforderlich ist.The object is achieved according to the invention in that the polyurethane is melt-spun, at the same time irreversibly stretched and wound directly at at least 600 m / min. The process according to the invention has surprisingly succeeded in producing 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. In an integrated one-step process, ie immediately after spinning the threads, it is wound up with known devices without the need for a further process step, such as relaxing.
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 Um¬ spinnen 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 we¬ nigstens 600 m/min, bevorzugt mehr als 900 m/inin betragen, wo¬ durch 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 / in, so that a draw ratio of at least 1.5 should be present. Since the drawing 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 Molekül¬ orientierung in den Fäden äussert sich dann auch durch niedrige Bruchdehnung und hohen Kochschrumpf und insbesondere stark erhöh¬ ten 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 ge¬ ring, 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 an actual stretching 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 cooking 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. Dieser hochmodulige, spinngestreckte Faden lässt sich gut zu einem Flächengebilde verarbeiten. Um starke Dimensionsverluste des Flächengebildes in der Ausrüstung zu vermeiden, ist es zweck¬ mässig, dieses vor der Ausrüstung zu fixieren. Die Wahl der Fi¬ xierbedingungen erlauben eine Steuerung der resultierenden Ela¬ stizität der Ware. Aufgrund des vorliegenden Schrumpfes eignet sich der erfindungsgemässe Faden insbesondere auch für Formfixi- rungen.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 large dimensional losses 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 shape fixation.
Das Flächengebilde kann aber auch in Wasser von höchstens 130#C, vorteilhaft jedoch bei Temperaturen unter dem Siedepunkt des Was¬ sers, beispielsweise 94 bis 100βC, getempert werden.But the fabric can also in water of at most 130 # C, but advantageously sers at temperatures below the boiling point of the Was¬, for example 94 to 100 C β are annealed.
Es ist ebenfalls zweckmässig, den verstreckten Elastomerfaden vor der Verarbeitung zu tempern, um ihm die gewünschte Elastizität zu verleihen.It is also expedient to temper the stretched elastomer thread before processing in order to give it the desired elasticity.
Das Tempern erfolgt bevorzugt mittels Dampf, Heisswasser oder be¬ heizten 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 minde¬ stens 10, 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 rever¬ sible Elastizität auf.Before tempering, the elastomer thread has a modulus of at least 10, 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 300 to 600%, preferably of about 400%, based on the length of the unstretched thread (see Table 1 and 2).
Der εpinngestreckte Elastomerfaden ist zweckmässig bis zur Reiεs- grenze nahezu vollständig reversibel elastisch. Bevorzugte Anwendungsgebiete des erfindungsgemässen gummiela¬ stischen Elastomerfadens sind textile Flächengebilde. Dabei hat es sich als vorteilhaft erwiesen, den erfindungsgemässen Elasto¬ merfaden zusammen mit wenigstens einem anderen nicht-elastischen Faden aus synthetischen oder natürlichen Fasern zu einem elasti¬ schen Flächengebilde zu verarbeiten.The spun-stretched elastomer thread is expediently almost completely reversibly elastic up to the tearing limit. Preferred areas of application for the rubber-elastic elastomer thread according to the invention are textile fabrics. It has proven to be advantageous 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 sheet-like 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 zeigenrIt shows no
Fig. 1 ein schematisches Fliessbild des Spinn-streck-Verfahrens Fig. 2 Kraft-Dehnungsdiagramme Fig. 3 Hysteresekurven1 shows a schematic flow diagram of the spin-stretching method. 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 ' zusammenge- fasst und über eine Galette 4 und eine Trennrolle 4' geführt, welche zusammen das Rollenpaar 4, 41 bilden. Ein weiteres Rollen¬ paar 5, 5' besteht aus einer Galette 5 und einer Trennrolle 5'. Mit 6 ist eine Spule mit einer Äntriebswalze 7 bezeichnet.A spinning block with spinnerets is shown in FIG. A bundle of fibrils 2 is combined into a thread 2 ' on an ensemble pin or a roll 3 and guided over a godet 4 and a separating roll 4', which together form the pair of rolls 4, 4 1 . Another pair of rollers 5, 5 'consists of a godet 5 and a separating roller 5'. 6 with a coil with a drive roller 7 is designated.
In Fig. 2 zeigt die Kurve 1 den kalt-spinngestreckten Faden. Kur¬ ven 2 bis 4 geben die Kraft-Dehnung des gleichen Fadens bei ver¬ schiedenen Temperaturen getempert wieder; Kurve 2 bei 40*C, Kur¬ ve 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 glei¬ cher Reisεkraft, höhere Elastizität.As can be seen from the difference between the curves before and after the thermal treatment, the elasticity is greater with approximately the same tractive force.
Zwei Ausführungsbeispiele sollen die Erfindung weiter erläutern. Beispiel 1Two exemplary embodiments are intended to explain the invention further. example 1
10 kg eines thermoplastischen Polyurehtans von GOODRICH, Estane 54351 hergestellt ab einem aromatischen Diisocyanat, einem Poly- caprolactonmakrodiol und Butandiol mit einer Härte von 84'Shore A, einem Erweichungspunkt von 185*C, einer Dichte von 1,15 g/cm3 werden zuerst bei 6.0*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 / cm 3 are the first dried at 6.0 * C for 8h and approx. 50 mbar, then at 90 * C for 24h and under high vacuum to a residual moisture of 0.01%, with an intrinsic viscosity of 1.80, measured in a solvent mixture of 1: 1 phenol / Tetrachloroethane with an Ubbelohde viscometer at 25 * C and concentration of 0.4% results.
Zur Verbesserung der Lichtbeständigkeit können UV-Absorber des Typs Tinuvinvfy von CIBA GEIGY einpolymerisiert oder dem Granulat aufgepudert werden. Zur Verbesserung der elastischen Eigenschaf¬ ten und des Glanzes können Füllstoffe wie Ti02, Si02, eingesetzt werden.To improve the light resistance, UV absorbers of the Tinuvinvfy type from CIBA GEIGY can be polymerized or powdered onto the granulate. Fillers such as TiO 2 , SiO 2 can be used to improve the elastic properties and the gloss.
Zur Fadenherstellung wird das Granulat unter Sauerstoffausschluss in einem Extruder z.B. bei 210*C aufgeschmolzen, durch ein 10 ym 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 Wassersäule abgekühlt und mittels Ensimagestift 3 zusammengeführt und geölt. Die Spinngeschwindig¬ keit, 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 verstreckt. Die k lten Rollen 4, 5 mit glatter Oberflä¬ che 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 span¬ nungslos aufgewickelt. - 8 -To produce the thread, the granulate is melted in the absence of oxygen in an extruder, for example at 210 * C, through a 10 μm filter sieve 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 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 water 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 rolls 4, 4 ', the thread 2' is guided onto the second pair of rolls 5, 5 'with five loops and cold stretched 2.1 times. 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 is 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. - 8th -
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 Poly¬ esterbasis von GOODRICH, Estane 58277, welches für medizinische Einsätze geeignet ist, mit einer Härte von 93"Shore A, einem Er¬ weichungspunkt 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 GOODRICH polyester, Estane 58277, which is suitable for medical applications, with a hardness of 93 "Shore A, a softening point of 185 ° C. and a density of 1.19 g / cm 3 , was spun according to Example 1 and stretched at the same time.
In den folgenden Tabellen 1 und 2 sind die Fadeneigenschaften der Beispiele 1 und 2 zusammengefasst.Tables 1 and 2 summarize the thread properties of Examples 1 and 2.
Tabelle 1Table 1
* Markenname der Firma GOODRICH* Brand name of the company GOODRICH
** Unter Modul wird die Kraft bei 100 % Dehnung bezogen auf den Ausgangstiter verstanden - 9 -** Module is understood to mean the force at 100% elongation based on the initial titer - 9 -
Der erfindunysgemässe caden 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.The inventive caden 2 '' 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.
Tabelle 2Table 2
* Markenname der Firma GOODRICH x > Modul auf 100 % gerechnet* Brand name of the company GOODRICH x> module calculated at 100%
Der Faden kann auch gut aufgespult werden. Er zeigt keine Verkle- bungstendenz. Eine mikroskopische Queraufnahme zeigt, dass die einzelnen Filamente voneinander gut getrennt sind und den er¬ wünschten runden Querschnitt aufweisen. 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 ver¬ gleichbar.The thread can also be wound up well. It shows no tendency to stick. A microscopic transverse image shows that the individual filaments are well separated from one another and have the desired round cross section. When subjected to a heat treatment, for example 2 minutes in hot water, this thread shows the properties according to columns 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.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.
Wie diese Beispiele zeigen, ist die mögliche Spinngeschwindig¬ keit stark von der Polymerviskosität und somit von der Spinntem¬ peratur abhängig. Bei der höheren Temperatur von Beispiel 4 kann die Abzugsgeschwindigkeit und somit die Wirtschaftlichkeit der Fadenherstellung stark erhöht werden. 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.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 economy of thread production can be greatly increased. The spun-stretched original thread can, for example, be knitted together with a polyamide dtex 33 f 10 to form a fabric. After fixing or after a heat treatment, for example dyeing, of this knitted fabric, the product can be processed into a rubber-elastic flat structure 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 ela¬ stischen Artikeln für die Medizin oder Chirurgie, insbesondere für Prothesen. Medical support stockings, elastic bands, sports clothing, 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 fields of application.
BezeichnungenDesignations
SpinnblockSpinning block
Fibrillenbündel ' Faden unverstreckt « . Faden verstrecktFibril bundle ' thread undrawn'. Thread stretched
EnsimagestiftEnsemble pin
Galette r TrennrolleGalette r separation roller
Galette ' TrennrolleGalette 'separation roller
SpuleKitchen sink
Antriebswelle der Spule 6 Drive shaft of the coil 6

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung eines glatten, schmelzgesponnenen, multifilen Elastomerfadens aus thermoplastisch verformbaren Polyurethanen (TPU) mit einer Härte von 80 bis 95*Shore, da¬ durch gekennzeichnet, dass das Polyurethan schmelzgesponnen, gleichzeitig irreversibel verstreckt und direkt mit wenig¬ stens 600 m/min aufgespult wird.1. Process for the production of a smooth, melt-spun, multifilament elastomer thread from thermoplastic deformable polyurethanes (TPU) with a hardness of 80 to 95 * Shore, characterized in that the polyurethane is melt-spun, at the same time irreversibly stretched and directly with at least 600 m / min is wound up.
2. Elastomerfaden, hergestellt nach Anspruch 1, gekennzeichnet, durch einen Modul >10 cN/tex, einen Kochschrumpf von mehr als 20 % und eine Bruchdehnung von 80 bis 300 % bezogen auf die Länge des ungedehnten Fadens.2. elastomer thread, produced according to claim 1, characterized by a modulus> 10 cN / tex, a cooking shrinkage of more than 20% and an elongation at break of 80 to 300% based on the length of the unstretched thread.
3. Elastomerfaden nach Anspruch 2, dadurch gekennzeichnet, dass sich die Einzelfibrillen verklebungsfrei berühren.3. elastomer thread according to claim 2, characterized in that the individual fibrils touch without adhesion.
4. Elastomerfaden nach den Ansprüchen 2 und 3, gekennzeichnet, durch eine bis zur Reissdehnung vollständig reversiblen Elastizität.4. elastomer thread according to claims 2 and 3, characterized by an elasticity which is completely reversible up to the elongation at break.
5. Verwendung des Elastomerfadens gemäss den Ansprüchen 2 bis 4 zur Herstellung von gummielastischen textilen Flächengebilden. 5. Use of the elastomer thread according to claims 2 to 4 for the production of rubber-elastic textile fabrics.
EP19870907735 1986-12-17 1987-12-11 Polyurethane elastomer thread and its use Expired - Lifetime EP0295271B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH5011/86 1986-12-17
CH501186 1986-12-17

Publications (2)

Publication Number Publication Date
EP0295271A1 true EP0295271A1 (en) 1988-12-21
EP0295271B1 EP0295271B1 (en) 1992-05-27

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JP (1) JPH0686683B2 (en)
WO (1) WO1988004703A1 (en)

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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

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JPS5849303A (en) * 1981-09-18 1983-03-23 Mitsui Toatsu Chem Inc Insecticidal and miticidal composition
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JPH0686683B2 (en) 1994-11-02
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EP0295271B1 (en) 1992-05-27

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