EP1334223B1 - Method for producing synthetic threads from polymer mixtures - Google Patents

Method for producing synthetic threads from polymer mixtures Download PDF

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Publication number
EP1334223B1
EP1334223B1 EP01992807A EP01992807A EP1334223B1 EP 1334223 B1 EP1334223 B1 EP 1334223B1 EP 01992807 A EP01992807 A EP 01992807A EP 01992807 A EP01992807 A EP 01992807A EP 1334223 B1 EP1334223 B1 EP 1334223B1
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polymer
additive
additive polymer
fibers
speed
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French (fr)
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EP1334223A1 (en
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Dietmar Wandel
Alexander Klein
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Roehm GmbH Darmstadt
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ZiAG Plant Engineering GmbH
Roehm GmbH Darmstadt
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides

Definitions

  • the invention relates to a method for producing synthetic threads a polymer blend consisting of a base polymer and at least one Additive polymer consists, wherein the polymer mixture as a polymer melt with Spray speeds (s) in the range of 18 to 160 m / min through nozzle openings presses and the filaments thus formed cools, to threads together, the threads peel off and wound up to form at least one bobbin.
  • Spray speeds s
  • polyamide 6 threads typically only at speeds between 4000 and 5200 m / min and Elongation at break of less than 70% to stable thread bobbins with good coil construction be wound up.
  • the winding of polyamide threads at speeds> 5000 m / min requires additional equipment for the input of heat, to get a good stable coil structure.
  • the invention is based on the object, the aforementioned method so perform that the relaxation processes favorable inside the thread be influenced so that the threads show a good Aufwickel . At the same time, the threads produced are well suited for further processing be.
  • the object is achieved in that the base polymer is polyamide (PA), that the content of additive polymer in the polymer mixture is at least M wt .-% and at most 2.5 wt .-%, wherein M from 10 -4 • v -0.4, where v is the draw speed of the yarn, where v is in the range of 4500 to 8000 m / min, that the additive polymer is amorphous and practically insoluble in the polymer melt, the additive polymer in the wound yarn in the base polymer having a fibril structure and that the ratio s: v ranges from 1:50 to 1: 250.
  • the take-off speed is the peripheral speed of the first godet; in galettenlosem spinning the take-off speed is given by the peripheral speed of the driver roller of the winder.
  • the additive polymer is at the processing temperature of the base material thermoplastically processable and its glass transition temperature is 90 to 170 ° C and mostly 100 to 140 ° C.
  • the glass transition temperature is determined in a known manner by differential scanning calorimetry (described: eg. in WO 99/07927).
  • the added additive polymer is not with the base polymer compatible, d. H. it is practically insoluble in the base polymer, leaving two form microscopically distinguishable phases in the solidified thread.
  • Melt viscosity becomes in a known manner by means of oscillation rheometer at an oscillation frequency of 2.4 Hz and a temperature equal to the melting temperature of the base polymer plus 48 ° C, measured, see WO99 / 07927 for details.
  • the Melt viscosity of the additive polymer is always higher than that of the base polymer.
  • the ratio of the melt viscosities of additive polymer and Base polymer in the range of 2: 1 to 9: 1.
  • the inclusions have cigar shape with its longitudinal axis parallel to the filament axis.
  • Tests showed a middle Particle diameter of the additive polymer, measured parallel to the filament cross-section, immediately after exiting the spinneret, for the most part a maximum of 0.3 ⁇ m, with less than 1% of the inclusions contained in the mixture Particle diameter of more than 1.0 micron had.
  • the base polymer was in this case Polyamide 6th
  • the amount of additive polymer to be added to the base polymer can be kept relatively low in order to achieve good strength and favorable further processing properties of the thread.
  • 0.1 to 1.5% by weight of the additive polymer is added to the base polymer.
  • the desired improvements in the yarn already occur with the addition of less than 1 wt .-% additive polymer.
  • an additive polymer having the above properties for. B. homopolymers of the substance groups polymethyl methacrylate and its derivatives and polystyrene and its derivatives into consideration.
  • the additive polymer may also be a polymer of a monomer unit where R 1 and R 2 are substituents consisting of the optional atoms C, H, O, S, P and halogen atoms, the sum of the molecular weights of R 1 and R 2 being at least 40.
  • base polymers are mentioned here only as examples: Polyamide-6 and polyamide-66, nylon 6, nylon 66 and their copolymers. Suitable base polymers are especially those which have a melting point of 200 to 265 ° C and preferably contain at least 80 wt .-% of polyamide units.
  • the relative solution viscosity for filaments for textile applications is suitably in the range of 2.2 to 3.0.
  • the mixture of base polymer and additive polymer to be spun can also Additives, eg. As dyes, matting agents, stabilizers, antistatic agents, Lubricants, branching agents, UV or IR absorbers, which themselves Polymers may be included.
  • Additives eg. As dyes, matting agents, stabilizers, antistatic agents, Lubricants, branching agents, UV or IR absorbers, which themselves Polymers may be included.
  • the mixing of the additive polymer with the Base polymer can be carried out in a known manner, for. As in DE-A-10022889 described.
  • the polymer mixture by means of a Spun customary spun.
  • the diameter of the nozzle holes is chosen so that the ratio of the exit velocity of the melt mixture from the bore (Spraying speed s) to the drawing speed (v) of the thread 1: 50 to 1: 250 and preferably 1: 80 to 1: 160.
  • the filaments After pressing out of the nozzle bores, the filaments are air cooled below its solidification temperature, then bundled, provided with preparation, combined into threads, stripped and optionally swirled.
  • Peeling may occur in the production of POY yarns with at least one driven galette or galettelos be performed. Galettenlos can also be used in the production of stretched, smooth threads (HOY), or you can reach the stretching in a godet system.
  • HOY stretched, smooth threads
  • a POY yarn (“partially oriented yarn”) with an elongation at break of produce at least 50%, which is wound without stretching.
  • the winding speed is 1.0 to 0.95 times the Off speed. If you have a hidden smooth thread with one Elongation at break of less than 50%, the take-up speed is suitably 1.0 to 1.5 times the take-off speed. In both In applications, the specific winding tension is 0.04 to 0.2 g / dtex, measured immediately before the winder.
  • the measurements are of course the same Process conditions, especially with regard to withdrawal and Winding speed and temperature to comply.
  • Examples 1, 2, 9 and 10 described below are comparative examples; at the other examples are worked according to the invention. In all examples, this will same polyamide used as a base polymer.
  • the Spinneret package contained, as viewed in the melt flow direction, defined shear and Filtration agent of the following structure: Steel sand volume of a grain size 250 to 350 microns and a height of 30 mm, fabric filter with Feinstfilter 20 microns, support plate, second Fabric filter with 40 ⁇ m, spinneret plate with 24 holes, bore diameter 0.25 mm, bore length 0.5 mm and a plate diameter of 65 mm.
  • the extruded filaments were made by means of a conventional cross-flow blowing cooled, the air velocity was 0.35 m / s.
  • the threads were bundled with an oiler and with a spin finish oil-water emulsion, wherein the applied Preparation amount about 0.4 wt .-% was.
  • the thread bundle was by means of two Withdrawn in an S-shaped looped godets and with a winding unit of the Barmag AG, Remscheid / DE, type SW7, wound on tubes into thread bobbins.
  • the Withdrawal speed defined by the peripheral speed of the first Galette was set according to Table 1 and the winder speed became set about 1% lower than the take-off speed, such that the Yarn tension before the wrapping unit was 8 g.
  • Spinning speeds became the polymer throughput through the spinneret so adjusted that the titer of the wound yarn was about 102 dtex.
  • Example 1 shows that it was not possible due to the relaxation and shrinkage processes without the addition of a suitable polymeric additive to wind a PA6 yarn at a take-off speed of 5500 m / min for a large technical relevant time to form a bobbin.
  • a PMMA polymethyl methacrylate; Plexiglas 7N of Röhm GmbH, Darmstadt (DE) the base polyamide from Example 1 in a concentration of 0.05 wt .-% added.
  • the melt viscosity of Plexiglas 7N was 330 Pas (2.4 Hz, 270 ° C), whereby the ratio of additive and Polyamide melt viscosity (viscosity ratio) is 4.1: 1.
  • the Flow activation energy of the PMMA is 140 kJ / mol and the Glass transition temperature was determined to be 111 ° C.
  • the added amount of additive was too low to significantly increase the Elongation at break compared to the unmodified produced at 5500 m / min To achieve base polymer of Comparative Example 1. Also, the threads were again not to thread bobbins with industrially relevant weight of Wind up the bobbin; after a winding time of 60 minutes, it recurred Shrink the bobbin on the spool.
  • the PMMA from Example 2 was the Base polyamide from Example 1 in a concentration of 0.3 or 0.6 wt .-% added.
  • the polymer blends were under otherwise the same conditions as spun in Example 2, wherein the textile characteristics given in Table 1 were achieved.
  • Example 4 has an approximately equal elongation at break as a conventional without Additive polymer at 4500 m / min spun yarn. This will work with the way of working of Example 4 over the conventional method Productivity increase of about 22%.
  • a polymaleimide was (Laboratory product of Röhm GmbH, Darmstadt / DE), d. h., An additive polymer of the type e) the base polyamide from Example 1 in the specified in Table 1 Added concentrations.
  • the PMI was a copolymer with 8.8 wt% styrene, 86.2 Wt .-% of methyl methacrylate and 5 wt .-% N-Cyclohxylmaleinimid with a Melt viscosity of 600 Pas (2.4 Hz, 270 ° C) viscosity ratio 7.5: 1, a Flow activation energy of 120 kJ / mol and glass transition temperature of 121 ° C.
  • the polymer blends were at take-off speeds of 5500 m / min (Examples 6 and 7) and 6000 m / min (Example 8) spun, wherein the in Table 1 specified textile characteristics were achieved.
  • the injection speed was 41.45 m / min and the distortion was 1: 145.
  • Examples 6 and 7 show that the PMI, which is a particularly favorable viscosity ratio has a particularly high specific activity and already at comparatively low addition a high increase in elongation at break and a good Has winding behavior.
  • the bobbin could turn easily after a Spooling time of 180 minutes with a thread weight of 10 kg from the mandrel be removed and with good processing properties as POY are processed.
  • Example 8 was over a winding time of 90 min a Thread bobbin of 5.4 kg thread weight produced, which easily from the winding mandrel removed.
  • Example 2 For these comparative examples, two were used as a duo in the exhaust system of Example 1 arranged godet pairs instead of the two arranged in S-beat godets used.
  • the bundled thread was in 6-fold looped through the first pair of take-off godets (duo 1) with a take-off speed of 4500 m / min peeled off and by means of a second, 10-fold looped pair of godets (Duo 2), which was heated to a temperature of 180 ° C, with two different Stretch ratios stretched and finally wound up.
  • the take-off speed and speed of the second duo are shown in Table 2 along with indicated the characteristics of the threads.
  • the winding speed was about 1% less than the speed of the second duo, so that the Thread tension before the winder 7g was.
  • the polymer throughput was in each case so adjusted that the wound thread had a denier of 77 dtex.
  • the Spraying speed was between 30 - 33 m / min, the delay between 1: 143 and 1: 153.
  • the PMMA from Example 2 was added to the base polyamide by means of the metering and mixing device described there.
  • the additive concentrations, take-off speeds and the second godet speed are given in Table 2 together with the characteristics of the yarns.
  • the polymer throughput was again adjusted in each case so that the wound thread had a denier of 77 dtex.
  • all coils produced according to the invention could be easily removed from the mandrel.
  • no yarn defects were measured over the measuring length, so that the threads can be processed outstandingly well.

Abstract

The synthetic threads are produced from a polymer mixture consisting of polyamide as base polymer and at least one additive polymer, the polymer mixture being pressed through nozzle openings as polymer melt with extrusion speeds (s) in the range from 18 to 160 m/min. The filaments thus formed are cooled, combined to threads, drawn off and spooled by forming at least one thread spool. The content of additive polymer in the polymer mixture is not less than M wt-% and not more than 2.5 wt-%, where M is derived from 0.0001.v-0.4, where v is the draw-off speed of the thread, and v lies in the range from 4500 to 8000 m/min. The additive polymer is amorphous and virtually insoluble in the polymer melt. In the spooled thread, the additive polymer is present in the base polymer in a fibril structure, the ratio s:v lies in the range from 1:50 to 1:250. Upon spooling, the thread spool preferably has a weight of the spooled thread of at least 4 kg.

Description

Die Erfindung betrifft ein Verfahren zum Herstellen von synthetischen Fäden aus einer Polymermischung, die aus einem Basispolymer und mindestens einem Additivpolymer besteht, wobei man die Polymermischung als Polymerschmelze mit Spritzgeschwindigkeiten (s) im Bereich von 18 bis 160 m/min durch Düsenöffnungen drückt und die so gebildeten Filamente kühlt, zu Fäden zusammen fasst, die Fäden abzieht und unter Bildung mindestens einer Fadenspule aufwickelt.The invention relates to a method for producing synthetic threads a polymer blend consisting of a base polymer and at least one Additive polymer consists, wherein the polymer mixture as a polymer melt with Spray speeds (s) in the range of 18 to 160 m / min through nozzle openings presses and the filaments thus formed cools, to threads together, the threads peel off and wound up to form at least one bobbin.

Die Verarbeitung von Polymermischungen zum Erzeugen von synthetischen Fäden ist bekannt und z. B. in EP-A-0860524, DE-A-19747867 und DE-A-10022889 beschrieben. Daraus ist bekannt, dass man die Reißdehnung des aufgewickelten Fadens durch Additivpolymere verändern kann. Beim Spinnen, Abziehen, optionalen Verstecken und Aufwickeln eines Polyamidfadens besteht das Problem, dass sich die mikroskopische Struktur des Fadens nach dem Aufwickeln verändert. Bei hohen Wickelgeschwindigkeiten neigt der Faden dazu, auf der Spule zu schrumpfen, d. h. sich zu verkürzen. Daraus resultiert eine Zerstörung der Fadenspule, so dass die Weiterverarbeitung nicht möglich ist. The processing of polymer blends to produce synthetic threads is known and z. In EP-A-0860524, DE-A-19747867 and DE-A-10022889 described. It is known that one wound up the elongation at break of the Can change thread by additive polymers. When spinning, peeling, optional Hiding and winding a polyamide thread is the problem that the changed microscopic structure of the thread after winding. At high Winding speeds, the thread tends to shrink on the bobbin, d. H. to shorten. This results in a destruction of the bobbin, so that the Further processing is not possible.

Ohne zusätzliche thermische Behandlung können z. B. Polyamid-6-Fäden typischerweise nur mit Geschwindigkeiten zwischen 4000 und 5200 m/min und Reißdehnungen von unter 70 % zu stabilen Fadenspulen mit gutem Spulenaufbau aufgewickelt werden. Das Aufwickeln von Polyamidfäden mit Geschwindigkeiten > 5000 m/min erfordert zusätzliche apparative Maßnahmen zum Eintragen von Wärme, um einen guten stabilen Spulenaufbau zu erhalten.Without additional thermal treatment z. B. polyamide 6 threads typically only at speeds between 4000 and 5200 m / min and Elongation at break of less than 70% to stable thread bobbins with good coil construction be wound up. The winding of polyamide threads at speeds> 5000 m / min requires additional equipment for the input of heat, to get a good stable coil structure.

Der Erfindung liegt die Aufgabe zugrunde, das eingangs genannte Verfahren so durchzuführen, dass die Relaxationsprozesse im Inneren des Fadens günstig beeinflusst werden, so dass die Fäden ein gutes Aufwickelverhalten zeigen. Gleichzeitig sollen die erzeugten Fäden für die Weiterverarbeitbarkeit gut geeignet sein.The invention is based on the object, the aforementioned method so perform that the relaxation processes favorable inside the thread be influenced so that the threads show a good Aufwickelverhalten. At the same time, the threads produced are well suited for further processing be.

Erfindungsgemäß wird die Aufgabe dadurch gelöst, dass das Basispolymer Polyamid (PA) ist, dass der Gehalt an Additivpolymer in der Polymermischung minimal M Gew.-% und maximal 2,5 Gew.-% beträgt, wobei sich M aus 10-4 • v -0,4 ergibt, dabei ist v die Abzugsgeschwindigkeit des Fadens, wobei v im Bereich von 4500 bis 8000 m/min liegt, dass das Additivpolymer amorph und in der Polymerschmelze praktisch unlöslich ist, wobei das Additivpolymer im aufgewickelten Faden im Basispolymer in einer Fibrillenstruktur vorliegt und dass das Verhältnis s : v im Bereich von 1 : 50 bis 1 : 250 liegt. Die Abzugsgeschwindigkeit ist die Umfangsgeschwindigkeit der ersten Galette; bei galettenlosem Spinnen ist die Abzugsgeschwindigkeit durch die Umfangsgeschwindigkeit der Treiberwalze des Wicklers gegeben.According to the invention, the object is achieved in that the base polymer is polyamide (PA), that the content of additive polymer in the polymer mixture is at least M wt .-% and at most 2.5 wt .-%, wherein M from 10 -4 • v -0.4, where v is the draw speed of the yarn, where v is in the range of 4500 to 8000 m / min, that the additive polymer is amorphous and practically insoluble in the polymer melt, the additive polymer in the wound yarn in the base polymer having a fibril structure and that the ratio s: v ranges from 1:50 to 1: 250. The take-off speed is the peripheral speed of the first godet; in galettenlosem spinning the take-off speed is given by the peripheral speed of the driver roller of the winder.

Das Additivpolymer ist bei der Verarbeitungstemperatur des Basismaterials thermoplastisch verarbeitbar und seine Glasumwandlungstemperatur beträgt 90 bis 170 °C und zumeist 100 bis 140 °C. Die Glasumwandlungstemperatur bestimmt man in bekannter Weise durch die Differential-Scanning-Calorimetrie (beschrieben: z. B. in WO 99/07927). Das zugesetzte Additivpolymer ist mit dem Basispolymer nicht kompatibel, d. h. es ist im Basispolymer praktisch nicht löslich, so dass sich zwei mikroskopisch unterscheidbare Phasen im verfestigten Faden ausbilden. The additive polymer is at the processing temperature of the base material thermoplastically processable and its glass transition temperature is 90 to 170 ° C and mostly 100 to 140 ° C. The glass transition temperature is determined in a known manner by differential scanning calorimetry (described: eg. in WO 99/07927). The added additive polymer is not with the base polymer compatible, d. H. it is practically insoluble in the base polymer, leaving two form microscopically distinguishable phases in the solidified thread.

Vorzugsweise beträgt das Verhältnis der Schmelzeviskosität des Additivpolymers zur Schmelzeviskosität des Basispolymers 1,2 : 1 bis 12 : 1. Die Schmelzeviskosität wird in bekannter Weise mittels Oszillations-Rheometer bei einer Oszillationsfrequenz von 2,4 Hz und einer Temperatur, die gleich der Schmelztemperatur des Basispolymers plus 48 °C ist, gemessen, Einzelheiten finden sich in WO 99/07927. Die Schmelzeviskosität des Additivpolymers ist stets höher als die des Basispolymers.Preferably, the ratio of the melt viscosity of the additive polymer to Melt viscosity of base polymer 1.2: 1 to 12: 1. Melt viscosity becomes in a known manner by means of oscillation rheometer at an oscillation frequency of 2.4 Hz and a temperature equal to the melting temperature of the base polymer plus 48 ° C, measured, see WO99 / 07927 for details. The Melt viscosity of the additive polymer is always higher than that of the base polymer.

Bevorzugt liegt das Verhältnis der Schmelzeviskositäten von Additivpolymer und Basispolymer im Bereich von 2 : 1 bis 9 : 1. Damit erzeugt man eine enge Teilchengrößenverteilung der Einschlüsse des Additivpolymers in der Mischung unmittelbar nach dem Austritt aus der Spinndüse. Die Einschlüsse haben Zigarrenform mit ihrer Längsachse parallel zur Filamentachse. Versuche ergaben einen mittleren Teilchendurchmesser des Additivpolymers, gemessen parallel zum Filamentquerschnitt, unmittelbar nach Austritt aus der Spinndüse von größtenteils maximal 0,3 µm, wobei weniger als 1 % der in der Mischung enthaltenen Einschlüsse einen Teilchenmesser von mehr als 1,0 µm aufwiesen. Das Basispolymer war in diesem Fall Polyamid-6.Preferably, the ratio of the melt viscosities of additive polymer and Base polymer in the range of 2: 1 to 9: 1. This creates a close Particle size distribution of the inclusions of the additive polymer in the mixture immediately after exiting the spinneret. The inclusions have cigar shape with its longitudinal axis parallel to the filament axis. Tests showed a middle Particle diameter of the additive polymer, measured parallel to the filament cross-section, immediately after exiting the spinneret, for the most part a maximum of 0.3 μm, with less than 1% of the inclusions contained in the mixture Particle diameter of more than 1.0 micron had. The base polymer was in this case Polyamide 6th

Bedingt durch die im Vergleich zum Basispolymer (PA) hohe Fließaktivierungsenergie des Additivpolymers erhöht sich das Viskositätsverhältnis nach Austritt der Polymermischung aus den Spinndüsen und dem Verziehen weiter, so dass im aufgewickelten Faden aus den zigarrenförmigen Einschlüssen die erwünschten Fibrillen des Additivpolymers geworden sind. Diese Fibrillenstruktur ist zur Aufnahme eines Teils der Spinnspannung und zur Stabilisierung der Fadenstruktur geeignet, womit das Relaxationsverhalten in der gewünschten Weise beeinflusst wird. So erreicht man, dass die Fäden zu Fadenspulen mit gutem, stabilem Spulenaufbau aufgewickelt werden, die sich gut weiterverarbeiten lassen. Dadurch wird es überhaupt erst möglich, große Fadenspulen mit einem Fadengewicht von mindestens 4 kg störungsfrei herzustellen und dies ist eine Grundvoraussetzung für eine produktiv arbeitende Spinnanlage.Due to the high flow activation energy compared to the base polymer (PA) of the additive polymer increases the viscosity ratio after exit of the Polymer mixture from the spinnerets and warping further, so that in the Coiled thread from cigar-shaped inclusions desirable Fibrils of the additive polymer have become. This fibril structure is for Picking up a part of the spinning tension and stabilizing the thread structure suitable, whereby the relaxation behavior is influenced in the desired manner. Thus one achieves that the threads to thread bobbins with good, stable coil construction be wound up, which can be processed well. That's what it's all about only possible, large bobbins with a thread weight of at least 4 kg Produce trouble-free and this is a prerequisite for a productive working spinning plant.

Allgemein kann man sagen, dass die dem Basispolymer zuzusetzende Menge an Additivpolymer relativ niedrig gehalten werden kann, um gute Festigkeiten und günstige Weiterverarbeitungseigenschaften des Fadens zu erzielen. Bevorzugt werden dem Basispolymer 0,1 bis 1,5 Gew.-% des Additivpolymers zugegeben. Für viele Anwendungen stellen sich die gewünschten Verbesserungen im Faden bereits bei Zugabe von weniger als 1 Gew.-% Additivpolymer ein.
Als Additivpolymer mit den oben genannten Eigenschaften kommen z. B. Homopolymere der Stoffgruppen Polymethylmethacrylat und dessen Derivate sowie Polystyrol und dessen Derivate in Betracht. Das Additivpolymer kann auch ein Polymer aus einer Monomereinheit

Figure 00040001
sein, dabei sind R1 und R2 Substituenten bestehend aus den optionalen Atomen C, H, O, S, P und Halogenatomen, wobei die Summe der Molekulargewichte von R1 und R2 mindestens 40 beträgt. sein:In general, it can be said that the amount of additive polymer to be added to the base polymer can be kept relatively low in order to achieve good strength and favorable further processing properties of the thread. Preferably, 0.1 to 1.5% by weight of the additive polymer is added to the base polymer. For many applications, the desired improvements in the yarn already occur with the addition of less than 1 wt .-% additive polymer.
As an additive polymer having the above properties, for. B. homopolymers of the substance groups polymethyl methacrylate and its derivatives and polystyrene and its derivatives into consideration. The additive polymer may also be a polymer of a monomer unit
Figure 00040001
where R 1 and R 2 are substituents consisting of the optional atoms C, H, O, S, P and halogen atoms, the sum of the molecular weights of R 1 and R 2 being at least 40. be:

Ferner können die Additivpolymere Copolymere sein und aus folgenden Monomereinheiten aufgebaut sein:

  • a) Styrol oder C1-3-alkylsubstituierte Styrole,
  • b) Acrylsäure oder Methacrylsäure oder
  • c) Cyclohexylmaleinimid
  • d) Das Additivpolymer kann folgende Monomereinheiten enthalten:
  • A = Styrol oder C1-3-alkylsubstituierte Styrole,
  • B = eines oder mehrere Monomere der Formel I, II oder III
    Figure 00050001
    • wobei R1, R2 und R3 jeweils ein H-Atom oder ein C1-15-Alkylrest oder ein C5-12-Cycloalkylrest oder ein C6-14-Arylrest ist, und wobei das Copolymer aus 15 bis 95 Gew.- % A und 2 bis 80 Gew.-% B besteht, dabei ist A+B=100 Gew.-%, vorzugsweise ist A=70 bis 85 Gew.-%, B=30 bis 15 Gew.-% und A+B=100 Gew.-%.
  • e) Das Additivpolymer kann ferner aus folgenden Monomereinheiten gebildet sein:
  • C = Acrylsäure, Methacrylsäure oder CH2=CR-COOR', wobei R ein H-Atom oder eine CH3-Gruppe und R' ein C1-15-Alkylrest oder ein C5-12-Cycloalkylrest oder ein C6-14-Arylrest ist,
  • D = Styrol oder C1-3-alkylsubstituierte Styrole,
  • E = eines oder mehrere Monomere der Formel I, II oder III
    Figure 00050002
    wobei R1, R2 und R3 jeweils ein H-Atom oder ein C1-15-Alkylrest oder ein C5-12-Cycloalkylrest oder ein C6-14-Arylrest sind,
  • F = eines oder mehrere ethylenisch ungesättigte, mit C und/oder mit D und/oder E copolymerisierbare Monomere aus der Gruppe, welche aus α-Methylstyrol, Vinylacetat, Acrylsäureestern, Methacrylsäureestern, die von C verschieden sind, Vinylchlorid, Vinylidenchlorid, halogensubstituierten Styrolen, Vinylethern, Isopropenylethern und Dienen besteht, wobei das Additivpolymer aus 30 bis 99 Gew.-% (vorzugsweise 60 bis 94 Gew.-%) C, 0 bis 50 Gew.-% (vorzugsweise 0 bis 20 Gew.-%) D, > 0 bis 50 Gew.-% (vorzugsweise 6 bis 30 Gew.-%) E und 0 bis 50 Gew.-% (vorzugsweise 0 bsi 20 Gew.-%) F besteht und wobei die Summe C+D+E+F=100 Gew.-% ergibt.
  • f) Das Additivpolymer kann auch aus folgenden Monomereinheiten gebildet sein:
  • G = Acrylsäure, Methacrylsäure oder CH2 = CR - COOR', wobei R ein H-Atom oder eine CH3-Gruppe und R' ein C1-15-Alkylrest oder ein C5-12-Cycloalkylrest oder ein C6-14-Arylrest ist,
  • H = Styrol oder C1-3-akylsubstituierte Styrole, wobei das polymere Additiv aus 60 bis 98 Gew.-% G (bevorzugt 90 bis 98 Gew.-% G) und 2 bis 40 Gew.-% H (bevorzugt 10 bis 20 Gew.-% H) besteht (Summe = 100 Gew.-%).
    • Furthermore, the additive polymers may be copolymers and be composed of the following monomer units:
  • a) styrene or C 1-3 -alkyl-substituted styrenes,
  • b) acrylic acid or methacrylic acid or
  • c) cyclohexylmaleimide
  • d) The additive polymer may contain the following monomer units:
  • A = styrene or C 1-3 alkyl-substituted styrenes,
  • B = one or more monomers of the formula I, II or III
    Figure 00050001
    •  wherein R 1 , R 2 and R 3 are each an H atom or a C 1-15 alkyl group or a C 5-12 cycloalkyl group or a C 6-14 aryl group, and wherein the copolymer of 15 to 95 wt. % A and 2 to 80 wt.% B, where A + B = 100 wt.%, Preferably A = 70 to 85 wt.%, B = 30 to 15 wt.% And A + B = 100% by weight.
  • e) The additive polymer can furthermore be formed from the following monomer units:
  • C = acrylic acid, methacrylic acid or CH 2 = CR-COOR ', wherein R is H or CH 3 and R' is C 1-15 alkyl or C 5-12 cycloalkyl or C 6-14 Aryl radical is,
  • D = styrene or C 1-3 alkyl-substituted styrenes,
  • E = one or more monomers of the formula I, II or III
    Figure 00050002
    where R 1 , R 2 and R 3 are each an H atom or a C 1-15 -alkyl radical or a C 5-12 -cycloalkyl radical or a C 6-14 -aryl radical,
  • F = one or more ethylenically unsaturated monomers copolymerizable with C and / or with D and / or E from the group consisting of α-methylstyrene, vinyl acetate, acrylic esters, methacrylates other than C, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, Vinyl ethers, isopropenyl ethers and dienes, wherein the additive polymer comprises from 30 to 99% by weight (preferably 60 to 94% by weight) C, 0 to 50% by weight (preferably 0 to 20% by weight) D ,. 0 to 50 wt .-% (preferably 6 to 30 wt .-%) E and 0 to 50 wt .-% (preferably 0 to 20 wt .-%) F and wherein the sum C + D + E + F = 100 wt .-% results.
  • f) The additive polymer can also be formed from the following monomer units:
  • G = acrylic acid, methacrylic acid or CH 2 = CR - COOR ', where R is an H atom or a CH 3 group and R' is a C 1-15 -alkyl radical or a C 5-12 -cycloalkyl radical or a C 6-14 Aryl radical is,
  • H = styrene or C 1-3 -acyl-substituted styrenes, wherein the polymeric additive of 60 to 98 wt .-% G (preferably 90 to 98 wt .-% G) and 2 to 40 wt .-% H (preferably 10 to 20 Wt.% H) (total = 100 wt.%).

    • Als Basispolymere werden hier nur beispielsweise genannt:
    Polyamid-6 und Polyamid-66, Nylon 6, Nylon 66 und deren Copolymere. Als Basispolymere eignen sich vor allem solche, die einen Schmelzpunkt von 200 bis 265 °C aufweisen und vorzugsweise mindestens 80 Gew.-% an Polyamid-Einheiten enthalten. Die relative Lösungsviskosität für Fäden für textile Anwendungen liegt zweckmäßigerweise im Bereich von 2,2 bis 3,0.    As base polymers are mentioned here only as examples:
    Polyamide-6 and polyamide-66, nylon 6, nylon 66 and their copolymers. Suitable base polymers are especially those which have a melting point of 200 to 265 ° C and preferably contain at least 80 wt .-% of polyamide units. The relative solution viscosity for filaments for textile applications is suitably in the range of 2.2 to 3.0.

    Die zu verspinnende Mischung aus Basispolymer und Additivpolymer kann auch noch Zusatzstoffe, z. B. Farbstoffe, Mattierungsmittel, Stabilisatoren, Antistatika, Gleitmittel, Verzweigungsmittel, UV- oder IR-Absorber, welche selbst wieder Polymere sein können, enthalten. Die Vermischung des Additivpolymers mit dem Basispolymer kann in bekannter Weise erfolgen, z. B. wie in DE-A-10022889 beschrieben. The mixture of base polymer and additive polymer to be spun can also Additives, eg. As dyes, matting agents, stabilizers, antistatic agents, Lubricants, branching agents, UV or IR absorbers, which themselves Polymers may be included. The mixing of the additive polymer with the Base polymer can be carried out in a known manner, for. As in DE-A-10022889 described.

    Zum Erzeugen der synthetischen Fäden wird die Polymermischung mittels einer üblichen Spinneinrichtung versponnen. Hierbei presst man die geschmolzene Polymermischung zunächst durch die Bohrungen einer Düsenplatte und erzeugt zahlreiche Filamente. Der Durchmesser der Düsenbohrungen wird so gewählt, dass das Verhältnis der Austrittsgeschwindigkeit der Schmelzemischung aus der Bohrung (Spritzgeschwindigkeit s) zur Abzugsgeschwindigkeit (v) des Fadens 1 : 50 bis 1 : 250 und bevorzugt 1 : 80 bis 1 : 160 beträgt.To produce the synthetic threads, the polymer mixture by means of a Spun customary spun. Here you press the molten Polymer mixture first through the holes of a nozzle plate and generated numerous filaments. The diameter of the nozzle holes is chosen so that the ratio of the exit velocity of the melt mixture from the bore (Spraying speed s) to the drawing speed (v) of the thread 1: 50 to 1: 250 and preferably 1: 80 to 1: 160.

    Nach dem Auspressen aus den Düsenbohrungen werden die Filamente mittels Luft unter ihre Erstarrungstemperatur abgekühlt, dann gebündelt, mit Präparation versehen, zu Fäden zusammengefasst, abgezogen und optional verwirbelt.After pressing out of the nozzle bores, the filaments are air cooled below its solidification temperature, then bundled, provided with preparation, combined into threads, stripped and optionally swirled.

    Das Abziehen kann bei der Herstellung von POY-Fäden mit mindestens einer angetriebenen Galette oder aber galettenlos durchgeführt werden. Galettenlos kann auch bei der Herstellung von verstreckten, glatten Fäden (HOY) gearbeitet werden, oder aber man erreicht die Verstreckung in einem Galettensystem.Peeling may occur in the production of POY yarns with at least one driven galette or galettelos be performed. Galettenlos can also be used in the production of stretched, smooth threads (HOY), or you can reach the stretching in a godet system.

    Man kann so einen POY-Faden ("partly oriented yarn") mit einer Reißdehnung von mindestens 50 % erzeugen, welcher ohne Verstreckung aufgewickelt wird. Dabei beträgt die Aufwickelgeschwindigkeit das 1,0- bis 0,95-fache der Abzugsgeschwindigkeit. Wenn man einen versteckten glatten Faden mit einer Reißdehnung von weniger als 50 % erzeugt, beträgt die Aufwickelgeschwindigkeit zweckmäßigerweise das 1,0- bis 1,5-fache der Abzugsgeschwindigkeit. In beiden Anwendungsfällen beträgt die spezifische Aufwickelspannung 0,04 bis 0,2 g/dtex, gemessen unmittelbar vor dem Wickler.You can thus a POY yarn ("partially oriented yarn") with an elongation at break of produce at least 50%, which is wound without stretching. there The winding speed is 1.0 to 0.95 times the Off speed. If you have a hidden smooth thread with one Elongation at break of less than 50%, the take-up speed is suitably 1.0 to 1.5 times the take-off speed. In both In applications, the specific winding tension is 0.04 to 0.2 g / dtex, measured immediately before the winder.

    Durch Verwenden das Additivpolymers neben dem PA-Basispolymer sorgt man insbesondere dafür, dass die relative Dehnungszunahme D im aufgewickelten Faden mindestens 1,02 beträgt, dabei ist D = a/b mit a = Reißdehnung des aus der Polymermischung bestehenden Fadens, und b = Reißdehnung des Fadens, der nur aus dem Basispolymer besteht. Bei den Messungen sind hierbei natürlich gleiche Prozessbedingungen insbesondere auch bezüglich Abzugs- und Aufwickelgeschwindigkeit und Temperatur einzuhalten. By using the additive polymer besides the PA base polymer one provides in particular, that the relative increase in elongation D in the wound thread is at least 1.02, where D = a / b with a = elongation at break of the Polymer blend existing thread, and b = elongation at break of the thread, which only out the base polymer. The measurements are of course the same Process conditions, especially with regard to withdrawal and Winding speed and temperature to comply.

    Die nachfolgend beschriebenen Beispiele 1, 2, 9 und 10 sind Vergleichsbeispiele; bei den anderen Beispielen wird erfindungsgemäß gearbeitet. In allen Beispielen wird das gleiche Polyamid als Basispolymer verwendet.Examples 1, 2, 9 and 10 described below are comparative examples; at the other examples are worked according to the invention. In all examples, this will same polyamide used as a base polymer.

    Beispiel 1:Example 1:

    Auf etwa 0,07 % Restfeuchte getrocknetes Polyamid-6 mit einer relativen Viskosität (RV) von 2,44, einer Schmelztemperatur von 222 °C und einer Schmelzeviskosität von 80 Pas (gemessen bei 2,4 Hz und 270 °C) wurde mittels eines Extruders aufgeschmolzen und bei einer Schmelzetemperatur von 270 °C entlang einer Einspeise- und Mischeinrichtung einem Spinnpaket, welches auf eine Temperatur von 270 °C aufgeheizt wurde, zugeführt und dort extrudiert. Die Dosier- und Mischeinrichtung sowie das Spinnsystem sind in WO 99/07927 beschrieben. Das Spinndüsenpaket enthielt, in Schmelzeflussrichtung betrachtet, definierte Scher- und Filtrationsmittel folgenden Aufbaus: Stahlsandvolumen einer Körnung 250 bis 350 µm und einer Höhe von 30 mm, Gewebefilter mit Feinstfilter 20 µm, Stützplatte, zweites Gewebefilter mit 40 µm, Spinndüsenplatte mit 24 Bohrungen, Bohrungsdurchmesser 0,25 mm, Bohrungslänge 0,5 mm und einem Plattendurchmesser von 65 mm.At about 0.07% residual moisture dried polyamide-6 having a relative viscosity (RV) of 2.44, a melt temperature of 222 ° C and a melt viscosity of 80 Pas (measured at 2.4 Hz and 270 ° C) was determined by means of an extruder melted and at a melt temperature of 270 ° C along a Feeding and mixing device a spin pack, which to a temperature of 270 ° C was heated, fed and extruded there. The dosing and Mixing device and the spinning system are described in WO 99/07927. The Spinneret package contained, as viewed in the melt flow direction, defined shear and Filtration agent of the following structure: Steel sand volume of a grain size 250 to 350 microns and a height of 30 mm, fabric filter with Feinstfilter 20 microns, support plate, second Fabric filter with 40 μm, spinneret plate with 24 holes, bore diameter 0.25 mm, bore length 0.5 mm and a plate diameter of 65 mm.

    Die extrudierten Filamente wurden mittels einer konventionellen Querstromanblasung abgekühlt, wobei die Luftgeschwindigkeit 0,35 m/s betrug. In einem Abstand von 1800 mm zur Düsenoberfläche wurden die Fäden mit einem Öler gebündelt und mit einer Präparationsöl-Wasser-Emulsion versehen, wobei die aufgebrachte Präparationsmenge etwa 0,4 Gew.-% betrug. Das Fadenbündel wurde mittels zweier S-förmig umschlungener Galetten abgezogen und mit einem Wickelaggregat der Barmag AG, Remscheid/DE, Typ SW7, auf Hülsen zu Fadenspulen aufgewickelt. Die Abzugsgeschwindigkeit, definiert durch die Umfangsgeschwindigkeit der ersten Galette, wurde gemäß Tabelle 1 eingestellt und die Wicklergeschwindigkeit wurde etwa 1 % geringer als die Abzugsgeschwindigkeit eingestellt, derart, dass die Fadenzugkraft vor dem Wickelaggregat 8 g betrug. Für die unterschiedlichen Spinngeschwindigkeiten wurde der Polymerdurchsatz durch die Spinndüse so eingestellt, dass der Titer des aufgewickelten Fadens etwa 102 dtex betrug. Bei dem gewählten Düsenbohrungsdurchmesser ergibt sich eine Spritzgeschwindigkeit von 39,6 m/min und ein Verzugsverhältnis s : v = 1 : 139. Zunächst wurde mit einer Spulzeit von nur 10 min eine kurze Fadenspule hergestellt und die textilen Kenndaten des ersponnenen Fadens wie in Tabelle 1 angegeben ermittelt.The extruded filaments were made by means of a conventional cross-flow blowing cooled, the air velocity was 0.35 m / s. At a distance of 1800 mm to the nozzle surface, the threads were bundled with an oiler and with a spin finish oil-water emulsion, wherein the applied Preparation amount about 0.4 wt .-% was. The thread bundle was by means of two Withdrawn in an S-shaped looped godets and with a winding unit of the Barmag AG, Remscheid / DE, type SW7, wound on tubes into thread bobbins. The Withdrawal speed, defined by the peripheral speed of the first Galette was set according to Table 1 and the winder speed became set about 1% lower than the take-off speed, such that the Yarn tension before the wrapping unit was 8 g. For the different ones Spinning speeds became the polymer throughput through the spinneret so adjusted that the titer of the wound yarn was about 102 dtex. In which selected nozzle bore diameter results in an injection speed of 39.6 m / min and a draft ratio s: v = 1: 139. First, with a Spooling time of only 10 min a short bobbin produced and the textile characteristics of the spun yarn as indicated in Table 1.

    Beispiel 1 zeigt, dass es aufgrund der Relaxations- und Schrumpfprozesse ohne Zugabe eines geeigneten polymeren Additivs nicht möglich war, ein PA6-Garn bei einer Abzugsgeschwindigkeit von 5500 m/min über eine großtechnisch relevante Zeit zu einer Fadenspule aufzuwickeln. Ein Versuch, den Faden über eine Spulzeit von 60 min zu einer Fadenspule von 3,3 kg Fadengewicht aufzuwickeln, scheiterte: Es zeigte sich, dass die Schrumpfkräfte derart groß waren, dass die Fadenspule nicht mehr vom Wickeldorn zu entfernen war. Beispiel Additiv-Polymer Viskositäts-Verhältnis Additiv-Anteil
    [Gew.%]     Abzugsgeschwindigkeit
    [m/min]     Reißdehnung
    [%]     Reißfestigkeit
    [cN/tex]     Spulfadengewicht
    [kg]         1 --- --- 0 5500 57,7 44,3 <3,3 2 PMMA 4,1 0,05 5500 58,1 43,9 <3,3 3 PMMA 4,1 0,30 5500 60,2 43,4 10 4 PMMA 4,1 0,60 5500 63,6 43,5 10 5 PS 3,5 0,75 5500 60,5 42,1 10 6 PMI 7,5 0,30 5500 70,3 43,3 10 7 PMI 7,5 0,60 5500 73,5 43,0 10 8 PMI 7,5 0,60 6000 72,5 40,9 5,4     Example 1 shows that it was not possible due to the relaxation and shrinkage processes without the addition of a suitable polymeric additive to wind a PA6 yarn at a take-off speed of 5500 m / min for a large technical relevant time to form a bobbin. An attempt to wind the yarn over a winding time of 60 minutes to a yarn package of 3.3 kg thread weight failed: It was found that the shrinkage forces were so large that the yarn package was no longer removed from the winding mandrel. example Additive polymer Viscosity ratio Additive component
    [% Wt.]     off speed
    [M / min]     elongation at break
    [%]     tear strength
    [CN / tex]     Spulfadengewicht
    [Kg]     1 --- --- 0 5500 57.7 44.3 <3.3 2 PMMA 4.1 0.05 5500 58.1 43.9 <3.3 3 PMMA 4.1 0.30 5500 60.2 43.4 10 4 PMMA 4.1 0.60 5500 63.6 43.5 10 5 PS 3.5 0.75 5500 60.5 42.1 10 6 PMI 7.5 0.30 5500 70.3 43.3 10 7 PMI 7.5 0.60 5500 73.5 43.0 10 8th PMI 7.5 0.60 6000 72.5 40.9 5.4

    Beispiel 2:Example 2:

    In diesem Vergleichsbeispiel wurde ein PMMA (Polymethylmethacrylat; Handelstyp Plexiglas 7N der Röhm GmbH, Darmstadt (DE) dem Basispolyamid aus Beispiel 1 in einer Konzentration von 0,05 Gew.-% zugesetzt. Die Schmelzeviskosität von Plexiglas 7N betrug 330 Pas (2,4 Hz; 270 °C), womit das Verhältnis aus Additiv- und Polyamidschmelzeviskosität (Viskositätsverhältnis) 4,1 : 1 beträgt. Die Fließaktivierungsenergie des PMMA beträgt 140 kJ/mol und die Glasübergangstemperatur wurde zu 111 °C bestimmt.In this comparative example, a PMMA (polymethyl methacrylate; Plexiglas 7N of Röhm GmbH, Darmstadt (DE) the base polyamide from Example 1 in a concentration of 0.05 wt .-% added. The melt viscosity of Plexiglas 7N was 330 Pas (2.4 Hz, 270 ° C), whereby the ratio of additive and Polyamide melt viscosity (viscosity ratio) is 4.1: 1. The Flow activation energy of the PMMA is 140 kJ / mol and the Glass transition temperature was determined to be 111 ° C.

    Das auf eine Restfeuchte von weniger als 0,1 % getrocknete Additivpolymer wurde mittels eines Extruders aufgeschmolzen und mit einer Zahnraddosierpumpe der Einspeiseeinrichtung zugeführt und dort durch eine Injektionsdüse in den Schmelzestrom der Polyamidkomponente eingespeist. Durch die nachfolgend angeordnete Mischstrecke, bestehend aus 15 statischen Mischern vom Typ SMX mit der Nennweite DN15 der Sulzer AG, Zürich/CH, wurde die Additivschmelze mit der Polyamidschmelze vermischt und bei einer Temperatur von 270 °C bei einer Abzugsgeschwindigkeit von 5500 m/min unter ansonsten gleichen Bedingungen wie in Beispiel 1 versponnen, wobei die in Tabelle 1 widergegebenen Kenndaten bei einem Titer von etwa 102 dtex über eine Spulzeit von 10 min erzielt wurden. Die zugegebene Additivmenge war zu gering, um eine signifikante Steigerung der Reißdehnung gegenüber dem bei 5500 m/min produzierten unmodifizierten Basispolymer aus Vergleichsbeispiel 1 zu erreichen. Auch ließen sich die Fäden wiederum nicht zu Fadenspulen mit großtechnisch relevantem Gewicht der Fadenspule aufwickeln; nach einer Spulzeit von 60 min trat wieder ein Festschrumpfen der Fadenspule auf dem Spuldom ein.The dried to a residual moisture content of less than 0.1% additive polymer was melted by means of an extruder and with a Zahnraddosierpumpe the Feeding supplied and there by an injection nozzle in the Melt flow of the polyamide component fed. By the following arranged mixing section, consisting of 15 static mixers of type SMX The nominal diameter DN15 of Sulzer AG, Zurich / CH, became the additive melt with the Polyamide melt mixed and at a temperature of 270 ° C at a Withdrawal speed of 5500 m / min under otherwise identical conditions as Spun in Example 1, wherein the reproduced in Table 1 characteristics at a titer of about 102 dtex over a winding time of 10 min were achieved. The added amount of additive was too low to significantly increase the Elongation at break compared to the unmodified produced at 5500 m / min To achieve base polymer of Comparative Example 1. Also, the threads were again not to thread bobbins with industrially relevant weight of Wind up the bobbin; after a winding time of 60 minutes, it recurred Shrink the bobbin on the spool.

    Beispiel 3 und 4:Example 3 and 4:

    Bei erfindungsgemäßer Arbeitsweise wurde das PMMA aus Beispiel 2 dem Basispolyamid aus Beispiel 1 in einer Konzentration von 0,3 bzw. 0,6 Gew.-% zugesetzt. Die Polymermischungen wurden unter ansonsten gleichen Bedingungen wie im Beispiel 2 versponnen, wobei die in Tabelle 1 angegebenen textilen Kenndaten erreicht wurden.When working according to the invention, the PMMA from Example 2 was the Base polyamide from Example 1 in a concentration of 0.3 or 0.6 wt .-% added. The polymer blends were under otherwise the same conditions as spun in Example 2, wherein the textile characteristics given in Table 1 were achieved.

    Für beide Zugabemengen wurde eine signifikante Erhöhung der Produktivität gegenüber den unter gleichen Bedingungen ohne Additivzugabe produzierten Fadenspulen erzielt, wobei sich alle aufgespulten Fäden (POY) durch ein gutes Weiterverarbeitungsverhalten auszeichneten. Überraschender Weise ließen sich für beide Zugabemengen die Fäden ohne Einschränkung über großtechnisch relevante Spulzeiten von etwa 180 min zu stabilen Fadenspulen von 10 kg Spulfadengewicht aufwickeln, die problemlos vom Spuldorn entfernt werden konnten. Die tatsächlich gegenüber dem herkömmlichen Verfahren erzielte Produktivitätssteigerung ergibt sich nicht allein aus der relativen Reißdehnungserhöhung (relative Erhöhung des Verstreckungsverhältnisses in dem textilen Folgeprozess) gegenüber dem bei gleicher Geschwindigkeit gesponnen reinen Polyamid, sondern es wird ein bislang nicht zugänglicher Bereich der Produktionsgeschwindigkeit erschlossen. Das bei 5500 m/min Abzugsgeschwindigkeit und 0,6 Gew.-% Additivzugabe produzierte Garn aus Beispiel 4 hat eine etwa gleiche Reißdehnung wie ein konventionell ohne Additivpolymer bei 4500 m/min gesponnenes Garn. Damit wird mit der Arbeitsweise des Beispiels 4 gegenüber dem herkömmlichen Verfahren eine Produktivitätssteigerung von etwa 22 % erzielt.For both additions, there was a significant increase in productivity compared to those produced under the same conditions without additive addition Fadenspulen scored, with all wound threads (POY) by a good Further processing behavior distinguished. Surprisingly, settled for both additions of the threads without restriction on industrially relevant Spooling times of about 180 minutes to stable bobbins of 10 kg Spulfadengewicht Wind up, which could be easily removed from the Spuldorn. Actually The increase in productivity compared with the conventional method results not only from the relative increase in elongation at break (relative increase of the Draw ratio in the textile follow-up process) compared to the same Speed spun pure polyamide, but it will not be one so far accessible range of production speed. That at 5500 m / min take-off speed and 0.6 wt% additive addition produced yarn Example 4 has an approximately equal elongation at break as a conventional without Additive polymer at 4500 m / min spun yarn. This will work with the way of working of Example 4 over the conventional method Productivity increase of about 22%.

    Beispiel 5:Example 5:

    Es wurde ein Polystyrol (PS) (Handelstyp Vertyron 136 der Hüls AG, Marl/DE) dem Basispolyamid aus Beispiel 1 in einer Konzentration von 0,75 Gew.-% zugesetzt. Die Schmelzeviskosität des PS betrug 280 Pas (2,4 Hz; 270 °C), d. h. das Viskositätsverhältnis betrug 3,5 : 1. Die Fließaktivierungsenergie des PS betrug 106 kJ/mol und die Glasübergangstemperatur 106 °C. Die Polymermischung wurde unter ansonsten gleichen Bedingungen wie im Beispiel 2 versponnen, wobei die in Tabelle 1 angegebenen textilen Kenndaten erreicht wurden. Die Fadenspule konnte wiederum problemlos nach einer Spulzeit von etwa 180 min mit einem Fadengewicht von 10 kg vom Wickeldorn abgenommen und als POY weiterverarbeitet werden.It was a polystyrene (PS) (trade type Vertyron 136 of Hüls AG, Marl / DE) the Base polyamide from Example 1 added in a concentration of 0.75 wt .-%. The Melt viscosity of the PS was 280 Pas (2.4 Hz, 270 ° C), d. H. the viscosity ratio was 3.5: 1. The flow activation energy of the PS was 106 kJ / mol and the glass transition temperature is 106 ° C. The polymer mixture was under otherwise spun the same conditions as in Example 2, wherein the in Table 1 specified textile characteristics were achieved. The bobbin could turn easily after a winding time of about 180 minutes with a thread weight of 10 kg from Winding mandrel removed and processed as POY.

    Beispiel 6 bis 8:Example 6 to 8:

    In diesen Anwendungen der Erfindung wurde ein Polymaleinimid (PMI) (Laborprodukt der Röhm GmbH, Darmstadt/DE), d. h., ein Additivpolymer vom Typ e) dem Basispolyamid aus Beispiel 1 in den in Tabelle 1 angegebenen Konzentrationen zugesetzt. Das PMI war ein Copolymer mit 8,8 Gew.-% Styrol, 86,2 Gew.-% Methylmethacrylat und 5 Gew.-% N-Cycloehxylmaleinimid mit einer Schmelzeviskosität von 600 Pas (2,4 Hz; 270 °C) Viskositätsverhältnis 7,5 : 1, einer Fließaktivierungsenergie von 120 kJ/mol und Glasübergangstemperatur von 121 °C. Die Polymermischungen wurden bei Abzugsgeschwindigkeiten von 5500 m/min (Beispiele 6 und 7) bzw. 6000 m/min (Beispiel 8) versponnen, wobei die in Tabelle 1 angegebenen textilen Kenndaten erreicht wurden. Bei 6000 m/min Geschwindigkeit betrug die Spritzgeschwindigkeit 41,45 m/min und der Verzug 1 : 145. Beispiele 6 und 7 zeigen, dass das PMI, welches ein besonders günstiges Viskositätsverhältnis aufweist, eine besonders hohe spezifische Wirksamkeit hat und schon bei vergleichsweise geringer Zugabe eine hohe Reißdehnungszunahme und ein gutes Spulverhalten aufweist. Die Fadenspule konnte wiederum problemlos nach einer Spulzeit von 180 min mit einem Fadengewicht von 10 kg vom Wickeldorn abgenommen werden und mit guten Weiterverarbeitungseigenschaften als POY verarbeitet werden. Im Beispiel 8 wurde über eine Spulzeit von 90 min eine Fadenspule von 5,4 kg Fadengewicht produziert, die sich problemlos vom Wickeldorn entfernen ließ.In these applications of the invention, a polymaleimide (PMI) was (Laboratory product of Röhm GmbH, Darmstadt / DE), d. h., An additive polymer of the type e) the base polyamide from Example 1 in the specified in Table 1 Added concentrations. The PMI was a copolymer with 8.8 wt% styrene, 86.2 Wt .-% of methyl methacrylate and 5 wt .-% N-Cyclohxylmaleinimid with a Melt viscosity of 600 Pas (2.4 Hz, 270 ° C) viscosity ratio 7.5: 1, a Flow activation energy of 120 kJ / mol and glass transition temperature of 121 ° C. The polymer blends were at take-off speeds of 5500 m / min (Examples 6 and 7) and 6000 m / min (Example 8) spun, wherein the in Table 1 specified textile characteristics were achieved. At 6000 m / min speed the injection speed was 41.45 m / min and the distortion was 1: 145. Examples 6 and 7 show that the PMI, which is a particularly favorable viscosity ratio has a particularly high specific activity and already at comparatively low addition a high increase in elongation at break and a good Has winding behavior. The bobbin could turn easily after a Spooling time of 180 minutes with a thread weight of 10 kg from the mandrel be removed and with good processing properties as POY are processed. In Example 8 was over a winding time of 90 min a Thread bobbin of 5.4 kg thread weight produced, which easily from the winding mandrel removed.

    Beispiel 9 und 10:Example 9 and 10:

    Für diese Vergleichsbeispiele wurden im Abzugssystem des Beispiels 1 zwei als Duo angeordnete Galettenpaare anstelle der beiden in S-Schlag angeordneten Galetten verwendet. Der gebündelte Faden wurde dabei in 6-facher Umschlingung durch das erste Abzugs-Galettenpaar (Duo 1) mit einer Abzugsgeschwindigkeit von 4500 m/min abgezogen und mittels eines zweiten, 10-fach umschlungenen Galettenpaares (Duo 2), welches auf eine Temperatur von 180 °C aufgeheizt war, mit zwei unterschiedlichen Verstreckverhältnissen verstreckt und schließlich aufgewickelt. Die Abzugsgeschwindigkeit und Geschwindigkeit des zweiten Duos sind in Tabelle 2 zusammen mit den Kenndaten der Fäden angegeben. Die Aufwickelgeschwindigkeit wurde etwa 1 % geringer als die Geschwindigkeit des zweiten Duos eingestellt, so dass die Fadenspannung vor dem Wickler 7g betrug. Der Polymerdurchsatz wurde jeweils so eingestellt, dass der aufgewickelte Faden einen Titer von 77 dtex hatte. Die Spritzgeschwindigkeit lag zwischen 30 - 33 m/min, der Verzug zwischen 1 : 143 und 1 : 153. Nach dem zweiten Galettenduo wurden Garnfehler (Kapillarbrüche) am laufenden Faden mittels eines Sensors mit Kamera aufgenommen und durch visuelle Analyse der Bilder ermittelt. Nach einer Spulzeit von 80 min konnten bei beiden Abzugsgeschwindigkeiten die Fadenspulen nicht mehr vom Wickeldorn abgezogen werden. Weiter wiesen die Fäden ohne Zusatz von Additivpolymer Fehler auf, welche eine Weiterverarbeitung ausschließen. For these comparative examples, two were used as a duo in the exhaust system of Example 1 arranged godet pairs instead of the two arranged in S-beat godets used. The bundled thread was in 6-fold looped through the first pair of take-off godets (duo 1) with a take-off speed of 4500 m / min peeled off and by means of a second, 10-fold looped pair of godets (Duo 2), which was heated to a temperature of 180 ° C, with two different Stretch ratios stretched and finally wound up. The take-off speed and speed of the second duo are shown in Table 2 along with indicated the characteristics of the threads. The winding speed was about 1% less than the speed of the second duo, so that the Thread tension before the winder 7g was. The polymer throughput was in each case so adjusted that the wound thread had a denier of 77 dtex. The Spraying speed was between 30 - 33 m / min, the delay between 1: 143 and 1: 153. After the second galette duo, yarn faults (capillary breaks) were observed ongoing thread by means of a sensor with camera and recorded by visual Analysis of the images determined. After a winding time of 80 min both could Withdrawal speeds the thread bobbins are no longer removed from the winding mandrel become. Furthermore, the filaments without the addition of additive polymer had errors, which exclude further processing.

    Beispiel 11 bis 13:Example 11 to 13:

    Es wurde das PMMA aus Beispiel 2 dem Basispolyamid mittels der dort beschriebenen Dosier- und Mischeinrichtung zugesetzt. Die Additivkonzentrationen, Abzugsgeschwindigkeiten und die Geschwindigkeit des zweiten Galettenduos sind in Tabelle 2 zusammen mit den Kenndaten der Fäden angegeben. Der Polymerdurchsatz wurde wiederum jeweils so eingestellt, dass der aufgewickelte Faden einen Titer von 77 dtex hatte. Bei einer Fadenspannung vor dem Wickler von 7. g wurden Fadenspulen über eine Spulzeit von 100 min mit einem Fadengewicht von jeweils mehr als 4 kg auf der Spule hergestellt. Überraschenderweise konnten alle erfindungsgemäß produzierten Spulen problemlos vom Wickeldorn abgezogen werden. Darüber hinaus wurden über die Messlänge keine Garnfehler gemessen, so dass sich die Fäden hervorragend weiterverarbeiten lassen. Beispiel Additiv-Polymer Additiv-Anteil
    [Gew.%]     Abzugsgeschwindigkeit
    [m/min]     Duo2-Geschwindigkeit
    [m/min]     Reißdehnung
    [%]     Reißfestigkeit
    [cN/tex]     Garnfehler
    [pro 350 km]     Spulfadengewicht
    [kg]         9 --- 0 4500 5600 29 50 2 <3,4 10 --- 0 4500 5800 27 51 5 <3,5 11 PMMA 0,15 4500 5600 34 51 0 4,3 12 PMMA 0,30 4500 5800 33 52 0 4,4 13 PMMA 0,30 5000 6000 39 50 0 4,6     The PMMA from Example 2 was added to the base polyamide by means of the metering and mixing device described there. The additive concentrations, take-off speeds and the second godet speed are given in Table 2 together with the characteristics of the yarns. The polymer throughput was again adjusted in each case so that the wound thread had a denier of 77 dtex. With a yarn tension in front of the winder of 7. g, bobbins were produced on the bobbin over a winding time of 100 minutes with a thread weight of more than 4 kg each. Surprisingly, all coils produced according to the invention could be easily removed from the mandrel. In addition, no yarn defects were measured over the measuring length, so that the threads can be processed outstandingly well. example Additive polymer Additive component
    [% Wt.]     off speed
    [M / min]     Duo2 speed
    [M / min]     elongation at break
    [%]     tear strength
    [CN / tex]     yarn faults
    [per 350 km]     Spulfadengewicht
    [Kg]     9 --- 0 4500 5600 29 50 2 <3.4 10 --- 0 4500 5800 27 51 5 <3.5 11 PMMA 0.15 4500 5600 34 51 0 4.3 12 PMMA 0.30 4500 5800 33 52 0 4.4 13 PMMA 0.30 5000 6000 39 50 0 4.6

    Claims (12)

    1. A method for the manufacture of synthetic fibers from a polymer mixture, which comprises one base polymer and at least one additive polymer, wherein the polymer mixture is pressed through nozzle openings as a polymer melt at spraying speeds (s) in the range from 18 to 160 m/min and the filaments thus formed are cooled, combined to fibers, the fibers are withdrawn and wound up with the formation of at least one take-up reel, characterized in that the base polymer is a polyamide (PA), which has a minimal additive polymer content in the polymer mixture of M wt% and a maximal content of 2.5 wt%, wherein M is given by 0.0001•v-0.4, where v is the fiber output speed, and where v is in the range from 4500 to 8000 m/min, that the additive polymer is amorphous and practically insoluble in the polymer melt, wherein the additive polymer in the wound-up fibers is present in the base polymer in a fibrillar structure and that the ratio s:v lies in the range from 1:50 to 1:250.
    2. The method according to Claim 1, characterized in that the specific windup tension, measured immediately before the winder, amounts to 0.04 to 0.2 g/dtex.
    3. The method according to Claim 1 or 2, characterized in that after the windup the fiber reel has a wound-up fiber weight of at least 4 kg.
    4. The method according to claim 1 or one of the following, characterized in that the relative lengthening (D) of the wound up fibers amounts to at least 1.02, in which D = a/b, and where a = elongation at break of fibers from the polymer mixture and b = elongation at break of fibers comprised only of the base polymer.
    5. The method according to claim 1 or one of the following, characterized in that the ratio of the melt viscosities of the additive polymer and the base polymer amounts to between 1.2:1 and 12:1.
    6. The method according to Claim 1 or one of the following, characterized in that the additive polymer is an addition polymerization product from at least one unsaturated ethylenic monomer.
    7. The method according to Claim 6, characterized in that the additive polymer is a polymer of the following monomer unit:
      Figure 00180001
      Where R1 and R2 are optional substituent atoms comprising C, H, O, S, P and halogen atoms and the sum of the molecular weights of R1 and R2 is at least 40.
    8. The method according to Claim 7, characterized in that the additive polymer is a polystyrene.
    9. The method according to Claim 7, characterized in that the additive polymer is a polymethylmethacrylate.
    10. The method according to Claims 1 through 6, characterized in that the additive polymer is a copolymer, which contains at least one of the monomers acrylic acid, methacrylic acid or CH2 = CR - COOR', wherein R is an H-atom or CH3, and R' is a C1-15 alkyl group or a C5-12 cycloalkyl group or a C6-14 aryl group.
    11. The method according to Claim 1 or one of the following, characterized in that a POY fiber with an elongation at break of at least 50 % is produced which is wound up without stretching, wherein the wind-up speed is 1.0 to 0.95 times the fiber output speed.
    12. The method according to one of Claims 1 through 10, characterized in that a stretched smooth fiber with an elongation at break of less than 50 % is produced, wherein the wind-up speed amounts to 1.0 to 1.5 times the fiber output speed.
    EP01992807A 2000-11-04 2001-11-05 Method for producing synthetic threads from polymer mixtures Expired - Lifetime EP1334223B1 (en)

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    DE10054758A DE10054758A1 (en) 2000-11-04 2000-11-04 Process for the production of synthetic threads from polymer blends
    DE10054758 2000-11-04
    PCT/EP2001/012793 WO2002036863A1 (en) 2000-11-04 2001-11-05 Method for producing synthetic threads from polymer mixtures

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    EP2108193B1 (en) 2006-12-28 2018-08-15 Genband US LLC Methods, systems, and computer program products for silence insertion descriptor (sid) conversion
    CN101781813B (en) * 2010-03-05 2012-08-22 四川辉腾科技有限公司 Aramid fiber containing fluorine and preparation method thereof
    JP6422952B2 (en) * 2013-06-06 2018-11-14 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Compositions and methods for producing fine denier polyamide fibers
    CN107402222A (en) * 2017-09-07 2017-11-28 苏州艾乐蒙特机电科技有限公司 A kind of spinning equipment the end of a thread scanning software
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