EP1208253B1 - Hmls-fibers made of polyester and a spin-stretch process for its production - Google Patents

Hmls-fibers made of polyester and a spin-stretch process for its production Download PDF

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Publication number
EP1208253B1
EP1208253B1 EP00951438A EP00951438A EP1208253B1 EP 1208253 B1 EP1208253 B1 EP 1208253B1 EP 00951438 A EP00951438 A EP 00951438A EP 00951438 A EP00951438 A EP 00951438A EP 1208253 B1 EP1208253 B1 EP 1208253B1
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EP
European Patent Office
Prior art keywords
weight
hmls
polyester
additive
polymer
Prior art date
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EP00951438A
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German (de)
French (fr)
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EP1208253A1 (en
Inventor
Joachim Cziollek
Werner Mrose
Dietmar Wandel
Helmut Schwind
Wolfgang Janas
Werner Ude
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Roehm GmbH Darmstadt
LL Plant Engineering AG
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ZiAG Plant Engineering GmbH
Roehm GmbH Darmstadt
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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
    • D01F6/88—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
    • D01F6/92—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 polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • the invention relates to HMLS threads made of polyester with a tensile strength of> 70 cN / tex, a LASE 5 of> 35 cN / tex and a hot air shrinkage at 160 ° C of 1.5 to 3.5% and to a spin-draw method Production of HMLS threads.
  • Under HMLS threads are here multifilament drawn polyester yarns of high modulus and low shrinkage (h igh odulus m, l ow s hrinkage) to understand.
  • Multifilament polyethylene terephthalate threads with high LASE 5 (the specific force in the force-strain diagram of a strain of 5% corresponds) and low heat shrinkage and methods for their Production are known, the yarns for industrial applications, like tire cord, are used.
  • Et al are such procedures in the Patents US 5,067,538, EP 0423 213 B, US 4,101,525, USP 5,472,781.
  • the applicable one with increasing spinning take-off speed Draw ratio decreases, the slope of the force-strain diagram, d. H. the LASE 5 increases, the thermal shrinkage decreases and the achievable Strength decreases.
  • the drop in the applicable draw ratio is due to the increase in orientation in the spun yarn and characterized by an increase in the birefringence of the filament.
  • EP 0 546 859 A discloses a polyester thread at spinning take-off speeds generated from 2500 to 4000 m / min. Here, too, arise through the low drawability, even at spinning take-off speeds of 4000 m / min, in high-speed spinning End speeds of just 6000 m / min, the tear strength less than 65 cN / tex.
  • EP 0 438 421 B1 makes it clear that the High-speed spinning lines to threads with many capillary breaks leads. Therefore, there is a point of reference defining device introduced the Kapillarbruchmat of such HMLS threads in the best Fall to 20 defects / 10 km lowers.
  • Drawn yarns with tear strengths above 70 cN / tex and low Thermal shrink, produced with spinning speeds over 2500 m / min, are also described in EP 0 526 740 B. These yarns consist of a polyester raw material based on a by copolymerization modified polyethylene terephthalate. The installation of this Modification components occur in the polymer chain during the Polymer formation process, giving the flexibility of spinning operation impaired.
  • EP 0 047 464 B relates to an undrawn polyester yarn, wherein by addition of 0.2-10% by weight of a polymer of the type (CH 2 -CR 1 R 2 ) n , such as poly (4-methyl-1-pentene ) or polymethyl methacrylate, improved productivity is obtained by increasing the elongation at break of the spun yarn at speeds between 2500-8000 m / min.
  • a polymer of the type (CH 2 -CR 1 R 2 ) n such as poly (4-methyl-1-pentene ) or polymethyl methacrylate
  • improved productivity is obtained by increasing the elongation at break of the spun yarn at speeds between 2500-8000 m / min.
  • Necessary is a fine and uniform dispersion of the additive polymer by mixing, wherein the particle diameter must be ⁇ 1 micron to avoid fibril formation. Decisive for the effect, in addition to the chemical additive structure, which hardly allows a stretching of the additive molecules, the low mobility and the compatibility of polyester and additive should
  • EP 0 631 638 B describes fibers made predominantly of PET, which are 0.1-5 % By weight of a 50-90% imidized polymethacrylic acid alkyl ester contains. The obtained at speeds of 500 - 10 000 m / min and subsequently end-stretched fibers should have a higher Have initial module. In the examples of industrial yarns can be the influence on the module but not easily understand; in the In general, the achieved strengths are low, which is a considerable disadvantage for this product is.
  • the present invention has for its object to provide HMLS yarns with a tensile strength> 70 cN / tex, a LASE 5> 35 cN / tex and a hot air shrinkage at 160 ° C of 1.5 to 3.5% available, as well as to provide a spin-draw process for their production, in which final speeds of over 6000 m / min can be driven, even with very high viscosity polyester, and while minimizing the number of Kapillarbrüche.
  • the desired HMLS yarns should be able to be produced at high spinning speeds without the need for chemical modification of the polyester raw material which would reduce the flexibility of the spinning plant.
  • birefringence should be adjustable in the range of 30 ⁇ 10 -3 to 55 ⁇ 10 -3 .
  • the object underlying the invention is characterized by HMLS threads Polyester and a spin-draw process for their preparation according to the Details of the claims solved.
  • polyesters are poly (C 2-4 alkylene) terephthalates which up to 15 mol% of other dicarboxylic acids and or diols, such as.
  • isophthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, or the other C 2-4 alkylene glycols may contain to understand.
  • Preferred is polyethylene terephthalate having an intrinsic viscosity (IV) in the range of 0.8 to 1.4 dl / g, polypropylene terephthalate having an IV of 0.9 to 1.6 dl / g, and polybutylene terephthalate having an IV of 0.9 to 1 , 8 dl / g.
  • Conventional additives such as dyes, matting agents, stabilizers, antistatic agents, lubricants, branching agents can be added to the polyester or polyester additive mixture in amounts of 0 to 5.0 wt .-% without disadvantage.
  • the polyester is mixed in the melt with an amorphous, melt-processable, incompatible, polymeric additive which has a glass transition temperature of from 90 to 170 ° C., the ratio of the melt viscosity of the additive to the melt viscosity of the polyester being from 1: 1 to 7: 1 the mixture is sheared in a static mixer, the shear rate being 16 to 128 s -1 , and the product of the shear rate and the 0.8th power of the residence time set in seconds to a value of at least 250, and the mixture subsequently spun, stretched, thermally treated and wound up at ⁇ 6000 m / min with a spinning take-off speed v of 2500 to 4000 m / min.
  • an amorphous, melt-processable, incompatible, polymeric additive which has a glass transition temperature of from 90 to 170 ° C.
  • the ratio of the melt viscosity of the additive to the melt viscosity of the polyester being from 1: 1 to 7: 1
  • the mixture is shea
  • Component H is an optional component. Although the advantages to be achieved according to the invention already by Polymers comprising components from groups E to G, can be achieved, the present invention to achieve Advantages also when used in the structure of the invention Polymers other monomers from the group H are involved.
  • the component H is preferably selected so that they have no Adverse effect on the properties of the invention too has used polymer.
  • the component H can u. a. therefore be used to the properties of the polymer to desired Way to modify, for example, by increases or Improvements in flow properties when the polymer is applied to the Melting temperature is heated, or to reduce a residual color in Polymer or by using a polyfunctional monomer to this way some level of crosslinking in the polymer introduce.
  • H can also be chosen so that a Copolymerization of components E to G even possible or supported, as in the case of MSA and MMA, which are not copolymerize, but with the addition of a third component such as styrene copolymerize easily.
  • Vinylester Esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid other than methyl methacrylate, for example, butyl methacrylate and ethylhexyl methacrylate, Vinyl chloride, vinylidene chloride, styrene, ⁇ -methylstyrene and the various halogen-substituted styrenes, vinyl and Isopropenyl ethers, dienes such as 1,3-butadiene and Divinylbenzene.
  • the color reduction of the polymer may be, for example particularly preferably by using an electron-rich monomer, such as a vinyl ether, vinyl acetate, styrene or ⁇ -methylstyrene can be achieved.
  • an electron-rich monomer such as a vinyl ether, vinyl acetate, styrene or ⁇ -methylstyrene
  • Particularly preferred among the Compounds of component H are vinyl aromatic monomers, such as for example, styrene or ⁇ -methylstyrene.
  • the preparation of the polymers to be used according to the invention is on known. They can be in substance, solution, suspension or Emulsion polymerization are prepared. Find helpful hints with regard to the bulk polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Notes on solution polymerization finds one just described there on page 1149ff, while the Emulsion polymerization just run there on page 1150ff and is explained.
  • the present invention for example, by mixing in the melt of the fiber polymers to be used polymers in the form of Particles with a mean diameter of 0.1 to 1.0 mm. It but are also larger or smaller beads or granules can be used, but smaller beads have special requirements for Logistics, such as conveying and drying.
  • the imidized polymer types 2 and 3 can be both from the monomers be prepared using a monomeric imide as well by subsequent complete or preferably partial imidization a polymer containing the corresponding maleic acid derivative.
  • additive polymers are obtained for example by complete or preferably partial reaction of the corresponding polymer in the Melting phase with ammonia or a primary alkyl or arylamine, For example, aniline (Encyclopedia of Polymer Science and Engineering Vol 16 [1989], Wiley-Verlag, page 78). All inventive Polymers and, as far as given, their non-imidized Starting polymers are commercially available or according to one of the Produce expert familiar process.
  • the additive polymer is incompatible with the polyester, that is, that the additive in the polyester matrix is largely insoluble.
  • the polyester and the additive polymer form two phases, the can be distinguished microscopically.
  • the copolymer must a glass transition temperature (determined by DSC at 10 ° C / min Heating rate) from 90 to 170 ° C and thermoplastically processable his.
  • the melt viscosity of the copolymer is to be chosen so that the Ratio of its extrapolated to the zero measurement time Melt viscosity, measured at an oscillation rate of 2.4 Hz and a temperature equal to the melting temperature of the polyester plus 34.0 ° C (for polyethylene terephthalate 290 ° C) relative to that of the polyester, measured under the same conditions, between 1: 1 and 7: 1 lies.
  • the melt viscosity of the polymer is at least equal to or preferably higher than that of the polyester. Only through the election a specific viscosity ratio of additive and polyester the optimum efficiency is achieved. With such an optimized Viscosity ratio is a minimization of the amount of Additive additive possible, reducing the cost of the process becomes particularly high.
  • this is according to the invention as ideally determined viscosity ratio for the use of Polymer blends for the production of HMLS filaments above the Range, which in the literature for the mixing of two polymers is shown as cheap.
  • Polymer blends with high molecular weight additive polymers to spin were Polymer blends with high molecular weight additive polymers to spin.
  • the ratio of the melt viscosity of the copolymer is too that of the polyester under the above conditions between 1.5: 1 and 5: 1.
  • the mean particle size is of the additive polymer immediately after exit from the spinneret 120 - 300 nm, resulting in fibrils with a mean diameter of about 40 nm.
  • the mixing of the additive polymer with the matrix polymer is carried out by Add as a solid to the matrix polymer chips in the extruder inlet with Chips mixer or gravimetric dosing or alternatively by Melting of the additive polymer, metering by gear pump and Feed into the melt stream of the matrix polymer. Also called Masterbatch techniques are possible, with the additive being used as a concentrate in Polyester chips later in solid or molten state Matrix polyester are present. Also the addition to a Partial flow of the matrix polymer, which is then the main stream of the matrix polymer is admixed, is practicable.
  • a defined particle distribution is set by specific choice of the mixer and the duration of the mixing process, before the melt mixture is passed through product distribution lines to the individual spinning stations and spinnerets.
  • Mixers with a shear rate of 16 to 128 sec -1 have proven themselves.
  • the product of shear rate (s -1 ) and the power of 0.8th of the residence time (in sec) should be at least 250, preferably 350 to 1250. Values over 2500 are generally avoided in order to limit the pressure drop in the pipelines.
  • Both the mixing of the two polymers and the subsequent Spinning the polymer blend occurs at temperatures, as appropriate Matrix polymer, in the range of 220 to 320 ° C, preferably at (Melting temperature of the matrix polymer + 34) + 25 / -20 ° C.
  • temperatures of 270 to 315 ° C are set.
  • HMLS threads from the invention Polymer blends by spinning at take-off speeds of 2500 Up to 4000 m / min, stretching, thermosetting and winding happens using the known Spinnuxinraumen in the same As with polyester without additive.
  • the filter pack is after the prior art with filtering devices and / or loose Equipped with filter media.
  • the molten polymer mixture is after shearing and Filtration treatment in the nozzle package through the holes of the nozzle plate pressed.
  • the melt strands become Cooled by cooling air below its solidification temperature, so that a Glueing or upsetting on the following thread guide avoided becomes.
  • the cooling air can by transverse or radial blowing of a Air conditioning system to be supplied.
  • the filaments are with Spinnoniaparation applied, via godet systems with defined Drawn off speed, then stretched, heat-set and finally wound up.
  • thread swirling devices be included in the process.
  • HMLS polyester threads are in large Direct melt spinning plants are manufactured, in which the melt over long heated product lines on the individual spinning lines and distributed within the lines on the individual spinning systems.
  • a spinning line represents a juxtaposition of at least a number of spinning systems and a spinning system is the smallest Spinning unit with a spinner head, comprising at least one spinneret pack including spinneret plates.
  • the melt is subject in such systems a high thermal load at residence times up to 35 min.
  • the effectiveness of the polymer additive according to the invention leads due to the high thermal stability of the additive no appreciable limitations of its effect, so that a small addition amount of the additive ⁇ 2.5% and in many cases ⁇ 1.5% despite high thermal load is sufficient.
  • the properties of the additive polymer and the blending technique cause the additive polymer to form globule-like or elongated particles in the matrix polymer immediately upon exit of the polymer blend from the spinneret. Best conditions were obtained when the average particle size (arithmetic mean) d 50 ⁇ 400 nm, and the proportion of particles> 1000 nm in a sample cross-section was less than 1%.
  • the effectiveness of the additives according to this invention is a Glass transition temperature of 90 to 170 ° C, and preferably a Flow activation energy of the additive polymers of at least 80 kJ / mol, that is, a higher flow activation energy than that of the polyester matrix required. Under this condition, it is possible that the Solidify additive fibrils in front of the polyester matrix and one record a significant proportion of the applied spinning tension.
  • the preferred to apply additives are also characterized by a high Thermostability off. Thus, in the case of a large residence time and / or high temperature operated direct spinning the Efficacy losses due to additive decomposition minimized.
  • the stretching takes place in a manner known per se in at least one stage between differently heated godet systems, preferably in two stages.
  • DR is the product of the single draw ratios.
  • the winding speed is equal to Product of spinning speed v, the draw ratio DR and the Relax ratio.
  • the HMLS filaments according to the invention have at least the same Quality values, such as analog yarns without polymeric additive.
  • Additive fibrils the investigation of the microtome thin sections of the threads was carried out by transmission electron microscopy and subsequent image analysis evaluation, wherein the diameter of the fibrils was evaluated, and the length from that in samples immediately after the Spinneret diameter was estimated.
  • the intrinsic viscosity was measured on a solution of 0.5 g of polyester in 100 ml of a mixture of phenol and 1,2-dichlorobenzene (3: 2 parts by weight) at 25 ° C.
  • the measurement temperature was 290 ° C for polyethylene terephthalate and additive polymers, which are added to polyethylene terephthalate, or was equal to the melting temperature of the polyester concerned plus 34.0 ° C.
  • the measuring temperature thus determined corresponds to the typical processing or spinning temperature of the respective polyester.
  • the amount of sample was chosen so that the rheometer gap was completely filled.
  • the measurement was carried out in oscillation with the frequency 2.4 Hz (corresponding to a shear rate of 15 sec -1 ) and a deformation amplitude of 0.3, and determines the amount of the complex viscosity as a function of the measuring time. Thereafter, the initial viscosity was converted to the zero measurement time by linear regression.
  • the polyester sample was initially at Melted 310 ° C for 1 min and immediately afterwards Room temperature quenched. Subsequently, the Glass transition temperature and melting temperature by DSC measurement (Differential scanning calorimetry) at a heating rate of 10 ° C / min determined. Pretreatment and measurement were carried out under Nitrogen flow.
  • the birefringence of the spun yarn was determined by means of Polarizing microscope with tilt compensator and green filter (540 nm) determined using wedges. was measured the Path difference between proper and extraordinary beam Passage of linearly polarized light through the filaments.
  • the Birefringence is the quotient of the gait difference and the Filament diameter. In the spin draw process, the filament was after taken from the withdrawal godet.
  • the hot air shrink was using the shrinkage tester of the company Testrite / USA at 160 ° C, a preload force of 0.05 cN / dtex and a Treatment duration of 2 min determined.
  • the partial relaxation ratio between Duo 4 and Duo 3 was in all cases 0.995.
  • the other settings are shown in the table.
  • the Process parameters for the spinning process were in all examples identical. Starting from the given spinning speed and a desired birefringence was the applicable range of Additive polymer concentration calculated according to equation 1, wherein the Factor x additive-specific equal to 1 for Examples 3 to 7 and equal to 2.8 for example 8 was used. The actual Concentration was chosen within the calculated range.
  • the mean diameter of the fibrils in the threads was less than 80 nm.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

HMLS filaments consisting of a polyester, from 0.1 to 2.5% by weight of an incompatible, thermoplastic, amorphous, polymeric additive having a glass transition temperature of from 90 to 170° C. and a ratio of its melt viscosity to that of the polyester component of from 1:1 to 7:1, and from 0 to 5.0% by weight of conventional additives, where the polymeric additive is present in the filaments in the form of fibrils having a mean diameter of <=80 NM.Process for the production of these HMLS filaments by static mixing with shearing of the polyester and of the polymeric additive and, optionally, of the additives, spinning of the mixture at a spinning take-off speed of from 2500 to 4000 m/min to give spun filaments which are stretched, heat-set and wound up, where the concentration of the polymeric additive is determined as a function of the pre-specified spinning take-off speed and the desired birefringence of the spun filaments.

Description

Die Erfindung bezieht sich auf HMLS-Fäden aus Polyester mit einer Reißfestigkeit von > 70 cN/tex, einem LASE 5 von > 35 cN/tex und einem Heißluftschrumpf bei 160 °C von 1,5 - 3,5 % sowie auf ein Spinnstreckverfahren zur Herstellung der HMLS-Fäden. Unter HMLS-Fäden sind hierbei multifile verstreckte Polyesterfäden mit hohem Modul und niedrigem Schrumpf (high modulus, low shrinkage) zu verstehen.The invention relates to HMLS threads made of polyester with a tensile strength of> 70 cN / tex, a LASE 5 of> 35 cN / tex and a hot air shrinkage at 160 ° C of 1.5 to 3.5% and to a spin-draw method Production of HMLS threads. Under HMLS threads are here multifilament drawn polyester yarns of high modulus and low shrinkage (h igh odulus m, l ow s hrinkage) to understand.

Multifile Polyethylenterephthalat-Fäden mit hohem LASE 5 (die spezifische Kraft, die im Kraft-Dehnungsdiagramm einer Dehnung von 5 % entspricht) und geringem Thermoschrumpf sowie Verfahren zu deren Herstellung sind bekannt, wobei die Garne für industrielle Anwendungen, wie Reifencord, eingesetzt werden. U.a. sind solche Verfahren in den Patentschriften US 5,067,538, EP 0423 213 B, US 4,101,525, USP 5,472,781 beschrieben. In diesen Publikationen wird deutlich, daß mit zunehmender Spinnabzugsgeschwindigkeit das anwendbare Streckverhältnis sinkt, die Steilheit des Kraft-Dehnungs-Diagrammes, d. h. der LASE 5 ansteigt, der Thermoschrumpf sinkt und die erreichbare Festigkeit abnimmt. Der Abfall des anwendbaren Streckverhältnisses ist bedingt durch den Anstieg der Orientierung im Spinnfaden und charakterisiert durch einen Anstieg der Doppelbrechung des Spinnfadens.Multifilament polyethylene terephthalate threads with high LASE 5 (the specific force in the force-strain diagram of a strain of 5% corresponds) and low heat shrinkage and methods for their Production are known, the yarns for industrial applications, like tire cord, are used. Et al are such procedures in the Patents US 5,067,538, EP 0423 213 B, US 4,101,525, USP 5,472,781. In these publications it becomes clear that the applicable one with increasing spinning take-off speed Draw ratio decreases, the slope of the force-strain diagram, d. H. the LASE 5 increases, the thermal shrinkage decreases and the achievable Strength decreases. The drop in the applicable draw ratio is due to the increase in orientation in the spun yarn and characterized by an increase in the birefringence of the filament.

Im US-Patent 4,491,657 werden bei 3000 m/min Spinngeschwindigkeit, im nachgeschalteten Streckprozeß nur noch Reißfestigkeiten um 62 cN/tex erreicht. Im EP 0 423 213 B zeigen Tabelle 2 und 5, daß bei in der Praxis anwendbaren Streckverhältnissen bereits bei Spinngeschwindigkeiten von 2900 m/min gerade noch eine Reißfestigkeit von 69 cN/tex erreicht wird.In US Patent 4,491,657 are at 3000 m / min spinning speed, im Downstream stretching process only tensile strength to 62 cN / tex reached. In EP 0 423 213 B, Tables 2 and 5 show that in the Practice applicable draw ratios already at Spinning speeds of 2900 m / min just a tear strength of 69 cN / tex is achieved.

Der Abfall des anwendbaren Streckverhältnisses mit steigender Spinngeschwindigkeit wird durch höhere Spinnviskositäten noch verstärkt, wie das US-Patent 5,067,538 zeigt. Darin ist das anwendbare Streckverhältnis bei einer Intrinsic Viskosität des Polymeren von 0,88 dl/g schon so gering, daß Endgeschwindigkeiten, über 6000 m/min nicht mehr möglich sind. In der EP 0 169 415 A wird ein Polyesterspinnfaden mit einer Intrinsic-Viskosität über 0,9 dl/g beschrieben. Die für die verschiedenen Spinngeschwindigkeiten anwendbaren Streckverhältnisse sind so gering, daß erst bei sehr hohen Spinnabzugsgeschwindigkeiten von über 3500 m/min beim Spinnstrecken effiziente Endgeschwindigkeiten von über 6000 m/min möglich werden. In der EP 0 546 859 A wird ein Polyesterfaden bei Spinnabzugsgeschwindigkeiten von 2500 bis 4000 m/min erzeugt. Auch hier ergeben sich durch die geringe Verstreckbarkeit, selbst bei Spinnabzugsgeschwindigkeiten von 4000 m/min, beim Hochgeschwindigkeits-Spinnstrecken Endgeschwindigkeiten von gerade 6000 m/min, wobei die Reißfestigkeit kleiner als 65 cN/tex ist.The drop in the applicable stretch ratio with increasing Spinning speed is still due to higher spinning viscosities reinforced, as shown in US Patent 5,067,538. Therein is the applicable Draw ratio at an intrinsic viscosity of the polymer of 0.88 dl / g already so low that terminal velocities, over 6000 m / min are no longer possible. In EP 0 169 415 A is a Polyester spun yarn with an intrinsic viscosity above 0.9 dl / g described. The for the different spinning speeds applicable stretching ratios are so low that only at very high Spin-off speeds of over 3500 m / min during spinning efficient end speeds of over 6000 m / min are possible. In EP 0 546 859 A discloses a polyester thread at spinning take-off speeds generated from 2500 to 4000 m / min. Here, too, arise through the low drawability, even at spinning take-off speeds of 4000 m / min, in high-speed spinning End speeds of just 6000 m / min, the tear strength less than 65 cN / tex.

In der EP 0 438 421 B1 wird darüber hinaus deutlich gemacht, daß das Hochgeschwindigkeits-Spinnstrecken zu Fäden mit vielen Kapillarbrüchen führt. Deshalb wird dort eine den Streckpunkt festlegende Einrichtung eingeführt, welche das Kapillarbruchniveau solcher HMLS-Fäden im besten Fall auf 20 Defekte/10 km absenkt.In addition, EP 0 438 421 B1 makes it clear that the High-speed spinning lines to threads with many capillary breaks leads. Therefore, there is a point of reference defining device introduced the Kapillarbruchniveau of such HMLS threads in the best Fall to 20 defects / 10 km lowers.

Verstreckte Garne mit Reißfestigkeiten über 70 cN/tex und geringem Thermoschrumpf, hergestellt mit Spinngeschwindigkeiten über 2500 m/min, werden auch in der EP 0 526 740 B beschrieben. Diese Garne bestehen aus einem Polyesterrohstoff auf der Basis eines durch Copolymerisation modifizierten Polyethylenterephthalates. Der Einbau dieser Modifizierungskomponenten erfolgt in die Polymerkette während des Polymerbildungsprozesses, was die Flexibilität des Spinnbetriebes beeinträchtigt.Drawn yarns with tear strengths above 70 cN / tex and low Thermal shrink, produced with spinning speeds over 2500 m / min, are also described in EP 0 526 740 B. These yarns consist of a polyester raw material based on a by copolymerization modified polyethylene terephthalate. The installation of this Modification components occur in the polymer chain during the Polymer formation process, giving the flexibility of spinning operation impaired.

Des weiteren ist aus WO 99-07927A1 bekannt, daß die Reißdehnung von bei Abzugsgeschwindigkeiten von mindestens 2500 m/min ersponnenen, vororientierten Polyesterfilamenten (POY) durch Zusatz von amorphen, thermoplastisch verarbeitbaren Copolymeren auf Basis von Styrol, Acrylsäure und/oder Maleinsäure bzw. deren Derivaten gegenüber der Reißdehnung von unter gleichen Bedingungen ersponnenen Polyesterfilamenten ohne Zusatz erhöht werden kann. Angaben zur Herstellung von HMLS-Fäden im Spinnstreckprozeß sind nicht enthalten.Furthermore, it is known from WO 99-07927A1 that the elongation at break of at Abrasion speeds of at least 2500 m / min spun, Preoriented polyester filaments (POY) by addition of amorphous, thermoplastically processable copolymers based on styrene, Acrylic acid and / or maleic acid or derivatives thereof to the Elongation at break of the same conditions spun Polyester filaments can be increased without addition. notes to the Production of HMLS filaments in the spin draw process are not included.

EP 0 047 464 B betrifft ein unverstrecktes Polyester-Garn, wobei durch Zusatz von 0,2 - 10 Gew.-% eines Polymeren des Typs (CH2-CR1R2)n, wie Poly(4-methyl-1-penten) oder Polymethylmethacrylat, eine verbesserte Produktivität durch Erhöhung der Reißdehnung des Spinnfadens bei Geschwindigkeiten zwischen 2500 - 8000 m/min erhalten wird. Notwendig ist eine feine und gleichmäßige Dispersion des Additiv-Polymers durch Mischen, wobei der Teilchendurchmesser ≤ 1 µm zur Vermeidung von Fibrillenbildung sein muß. Maßgebend für die Wirkung soll neben der chemischen Additivstruktur, die ein Verdehnen der Additivmoleküle kaum zuläßt, die geringe Mobilität und die Kompabilität von Polyester und Additiv sein.EP 0 047 464 B relates to an undrawn polyester yarn, wherein by addition of 0.2-10% by weight of a polymer of the type (CH 2 -CR 1 R 2 ) n , such as poly (4-methyl-1-pentene ) or polymethyl methacrylate, improved productivity is obtained by increasing the elongation at break of the spun yarn at speeds between 2500-8000 m / min. Necessary is a fine and uniform dispersion of the additive polymer by mixing, wherein the particle diameter must be ≤ 1 micron to avoid fibril formation. Decisive for the effect, in addition to the chemical additive structure, which hardly allows a stretching of the additive molecules, the low mobility and the compatibility of polyester and additive should be.

EP 0 631 638 B beschreibt Fasern aus überwiegend PET, welches 0,1 - 5 Gew.-% eines zu 50 - 90 % imidisierten Polymethacrylsäurealkylesters enthält. Die bei Geschwindigkeiten von 500 - 10 000 m/min erhaltenen und nachfolgend endverstreckten Fasern sollen einen höheren Anfangsmodul aufweisen. In den Beispielen für Industriegarne läßt sich der Einfluß auf den Modul aber nicht ohne weiteres nachvollziehen; im allgemeinen sind die erzielten Festigkeiten niedrig, was ein erheblicher Nachteil für dieses Produkt ist.EP 0 631 638 B describes fibers made predominantly of PET, which are 0.1-5 % By weight of a 50-90% imidized polymethacrylic acid alkyl ester contains. The obtained at speeds of 500 - 10 000 m / min and subsequently end-stretched fibers should have a higher Have initial module. In the examples of industrial yarns can be the influence on the module but not easily understand; in the In general, the achieved strengths are low, which is a considerable disadvantage for this product is.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, HMLS-Fäden mit einer Reißfestigkeit > 70 cN/tex, einem LASE 5 > 35 cN/tex und einem Heißluftschrumpf bei 160 °C von 1,5 bis 3,5 % zur Verfügung zu stellen, sowie ein Spinnstreckverfahren zu deren Herstellung zu schaffen, bei dem Endgeschwindigkeiten von über 6000 m/min gefahren werden können, auch bei höchstviskosem Polyester, und unter Minimierung der Anzahl der Kapillarbrüche. Die gewünschten HMLS-Fäden sollten bei hohen Spinngeschwindigkeiten herzustellen sein, ohne daß eine chemische Modifizierung des Polyesterrohstoffes notwendig wird, welche die Flexibilität der Spinnanlage reduzieren würde. Außerdem sollte es möglich sein, die HMLS-Fäden maßgeschneidert für den jeweiligen Anwendungszweck durch Einstellung der Doppelbrechung im Spinnfaden weitgehendst unabhängig von der Spinnabzugsgeschwindigkeit zu erzeugen. Dabei sollten Doppelbrechungen im Bereich von 30 · 10-3 bis 55 · 10-3 einstellbar sein.The present invention has for its object to provide HMLS yarns with a tensile strength> 70 cN / tex, a LASE 5> 35 cN / tex and a hot air shrinkage at 160 ° C of 1.5 to 3.5% available, as well as to provide a spin-draw process for their production, in which final speeds of over 6000 m / min can be driven, even with very high viscosity polyester, and while minimizing the number of Kapillarbrüche. The desired HMLS yarns should be able to be produced at high spinning speeds without the need for chemical modification of the polyester raw material which would reduce the flexibility of the spinning plant. In addition, it should be possible to tailor the HMLS filaments for the particular application by setting the birefringence in the filament largely independent of the spinning take-off speed. In this case, birefringence should be adjustable in the range of 30 × 10 -3 to 55 × 10 -3 .

Die der Erfindung zugrundeliegende Aufgabe wird durch HMLS-Fäden aus Polyester und ein Spinnstreckverfahren zu deren Herstellung gemäß den Angaben der Patentansprüche gelöst.The object underlying the invention is characterized by HMLS threads Polyester and a spin-draw process for their preparation according to the Details of the claims solved.

Unter Polyester sind hierbei Poly(C2-4-alkylen)-terephthalate, welche bis zu 15 Mol-% anderen Dicarbonsäuren und oder Diole, wie z. B. Isophthalsäure, Adipinsäure, Diethylenglykol, Polyethylenglykol, 1,4-Cyclohexandimethanol, oder die jeweils anderen C2-4-Alkylenglykole, enthalten können, zu verstehen. Bevorzugt ist Polyethylenterephthalat mit einer Intrinsic Viskosität (I.V.) im Bereich von 0,8 bis 1,4 dl/g, Polypropylenterephthalat mit einer I.V. von 0,9 bis 1,6 dl/g und Polybutylenterephthalat mit einer I.V. von 0,9 bis 1,8 dl/g. Übliche Zusatzstoffe wie Farbstoffe, Mattierungsmittel, Stabilisatoren, Antistatika, Gleitmittel, Verzweigungsmittel, können dem Polyester- oder dem Polyester-Additiv-Gemisch in Mengen von 0 bis 5,0 Gew.-% ohne Nachteil zugesetzt werden.Among polyesters here are poly (C 2-4 alkylene) terephthalates which up to 15 mol% of other dicarboxylic acids and or diols, such as. Example, isophthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, or the other C 2-4 alkylene glycols may contain to understand. Preferred is polyethylene terephthalate having an intrinsic viscosity (IV) in the range of 0.8 to 1.4 dl / g, polypropylene terephthalate having an IV of 0.9 to 1.6 dl / g, and polybutylene terephthalate having an IV of 0.9 to 1 , 8 dl / g. Conventional additives such as dyes, matting agents, stabilizers, antistatic agents, lubricants, branching agents can be added to the polyester or polyester additive mixture in amounts of 0 to 5.0 wt .-% without disadvantage.

Erfindungsgemäß wird der Polyester in der Schmelze mit einem amorphen, thermoplastisch verarbeitbaren, inkompatiblen, polymeren Additiv, das eine Glasumwandlungstemperatur von 90 bis 170°C aufweist, versetzt, wobei das Verhältnis der Schmelzeviskosität des Additivs zur Schmelzeviskosität des Polyesters 1 : 1 bis 7 : 1 beträgt, die Mischung in einem statischen Mischer unter Scherung behandelt, wobei die Scherrate 16 bis 128 s-1 beträgt, und das Produkt aus der Scherrate und der 0,8ten Potenz der Verweilzeit in Sekunden auf einen Wert von mindestens 250 eingestellt wird und die Mischung anschließend mit einer Spinnabzugsgeschwindigkeit v von 2500 bis 4000 m/min versponnen, verstreckt, thermobehandelt und mit ≥ 6000 m/min aufgewickelt wird.According to the invention, the polyester is mixed in the melt with an amorphous, melt-processable, incompatible, polymeric additive which has a glass transition temperature of from 90 to 170 ° C., the ratio of the melt viscosity of the additive to the melt viscosity of the polyester being from 1: 1 to 7: 1 the mixture is sheared in a static mixer, the shear rate being 16 to 128 s -1 , and the product of the shear rate and the 0.8th power of the residence time set in seconds to a value of at least 250, and the mixture subsequently spun, stretched, thermally treated and wound up at ≥ 6000 m / min with a spinning take-off speed v of 2500 to 4000 m / min.

Die dem Polyester zuzusetzenden Additivpolymere können, sofern sie die genannten physikalischen Eigenschaften besitzen, eine unterschiedliche chemische Zusammensetzung aufweisen. Bevorzugt werden drei verschiedene Polymertypen, nämlich

  • 1. Ein Additiv-Polymer (Typ 1), welches folgende Monomereinheiten enthält:
  • A = 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,
  • B = Styrol oder C1-3-alkylsubstituierte Styrole,
    wobei das Polymer aus 60 bis 100 Gew.-% A und 0 bis 40 Gew.-% B, vorzugsweise aus 83 bis 98 Gew.-% A und 2 bis 17 Gew.-% B, und besonders bevorzugt aus 90 bis 98 Gew.-% A und 2 bis 10 Gew.-% B (Summe = 100 Gew.-%) besteht.
  • 2. Ein Additiv-Polymer (Typ 2), welches folgende Monomereinheiten enthält:
  • C = Styrol oder C1-3-alkylsubstituierte Styrole,
  • D = eines oder mehrere Monomere der Formel I, II oder III
    Figure 00060001
       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,
    wobei das Polymer aus 15 bis 100 Gew.-% C und 0 bis 85 Gew.-% D, vorzugsweise aus 50 bis 95 Gew.-% C und 5 bis 50 Gew.-% D und besonders bevorzugt aus 70 bis 85 Gew.-% C und 15 bis 30 Gew.-% D besteht, wobei die Summe aus C und D zusammen 100 % ergibt.
  • 3. Ein Additiv-Polymer (Typ 3), welches folgende Monomereinheiten enthält:
  • E = 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,
  • F = Styrol oder C1-3-alkylsubstituierte Styrole,
  • G = eines oder mehrere Monomere der Formel I, II oder III
    Figure 00070001
       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,
  • H = eines oder mehrerer ethylenisch ungesättigter, mit E und/oder mit F und/oder G copolymerisierbarer Monomerer aus der Gruppe, welche aus α-Methylstyrol, Vinylacetat, Acrylsäureestern, Methacrylsäureestern, die von E verschieden sind, Vinylchlorid, Vinylidenchlorid, halogensubstituierten Styrolen, Vinylestern, Isopropenylethern und Dienen besteht,
       wobei das Polymer aus 30 bis 99 Gew.-% E, 0 bis 50 Gew.-% F, > 0 bis 50 Gew.-% G und 0 bis 50 Gew.-% H, vorzugsweise aus 45 bis 97 Gew.-% E, 0 bis 30 Gew.-% F, 3 bis 40 Gew.-% G und 0 bis 30 Gew.-% H und besonders bevorzugt aus 60 bis 94 Gew.-% E, 0 bis 20 Gew.-% F, 6 bis 30 Gew.-% G und 0 bis 20 Gew.-% H besteht, wobei die Summe aus E, F, G und H zusammen 100 % ergibt.
    • The additive polymers to be added to the polyester can have a different chemical composition, provided they have the stated physical properties. Three different types of polymers are preferred, namely
  • 1. An additive polymer (type 1) which contains the following monomer units:
  • A = 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,
  • B = styrene or C 1-3 alkyl-substituted styrenes,
    wherein the polymer of 60 to 100 wt .-% A and 0 to 40 wt .-% B, preferably from 83 to 98 wt .-% A and 2 to 17 wt .-% B, and particularly preferably from 90 to 98 wt % A and 2 to 10% by weight B (total = 100% by weight).
  • 2. An additive polymer (type 2) which contains the following monomer units:
  • C = styrene or C 1-3 alkyl-substituted styrenes,
  • D = one or more monomers of the formula I, II or III
    Figure 00060001
    wherein R 1, R 2 and R 3 are each an H atom or a C 1-15 alkyl or C 5-12 -cycloalkyl radical or a C 6-14 aryl group are
    wherein the polymer of 15 to 100 wt .-% C and 0 to 85 wt .-% D, preferably from 50 to 95 wt .-% C and 5 to 50 wt .-% D and particularly preferably from 70 to 85 wt. -% C and 15 to 30 wt .-% D, wherein the sum of C and D together gives 100%.
  • 3. An additive polymer (type 3) which contains the following monomer units:
  • E = 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,
  • F = styrene or C 1-3 alkyl-substituted styrenes,
  • G = one or more monomers of the formula I, II or III
    Figure 00070001
    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,
  • H = one or more ethylenically unsaturated monomers copolymerizable with E and / or with F and / or G from the group consisting of α-methylstyrene, vinyl acetate, acrylic esters, methacrylates other than E, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, Vinyl esters, isopropenyl ethers and dienes,
    wherein the polymer consists of 30 to 99 wt.% E, 0 to 50 wt.% F,> 0 to 50 wt.% G and 0 to 50 wt.% H, preferably from 45 to 97 wt. E, 0 to 30 wt .-% F, 3 to 40 wt .-% G and 0 to 30 wt .-% H and particularly preferably from 60 to 94 wt .-% E, 0 to 20 wt .-% F, 6 to 30 wt .-% G and 0 to 20 wt .-% H, wherein the sum of E, F, G and H together gives 100%.

    • Es handelt sich bei der Komponente H um eine optionale Komponente. Obwohl die erfindungsgemäß zu erzielenden Vorteile bereits durch Polymere, welche Komponenten aus den Gruppen E bis G aufweisen, erreicht werden können, treten die erfindungsgemäß zu erzielenden Vorteile auch auf, wenn am Aufbau des erfindungsgemäß einzusetzenden Polymeren weitere Monomere aus der Gruppe H beteiligt sind.Component H is an optional component. Although the advantages to be achieved according to the invention already by Polymers comprising components from groups E to G, can be achieved, the present invention to achieve Advantages also when used in the structure of the invention Polymers other monomers from the group H are involved.

    Die Komponente H wird vorzugsweise so ausgewählt, daß sie keinen nachteiligen Effekt auf die Eigenschaften des erfindungsgemäß zu verwendenden Polymers hat. Die Komponente H kann u. a. deswegen eingesetzt werden, um die Eigenschaften des Polymeren auf erwünschte Weise zu modifizieren, beispielsweise durch Steigerungen oder Verbesserungen der Fließeigenschaften, wenn das Polymer auf die Schmelztemperatur erhitzt wird, oder zur Reduzierung einer Restfarbe im Polymer oder durch Verwendung eines polyfunktionellen Monomeren, um auf diese Art und Weise ein gewisses Maß an Vernetzung in das Polymer einzuführen. Daneben kann H auch so gewählt werden, daß eine Copolymerisation von Komponenten E bis G überhaupt erst möglich oder unterstützt wird, wie im Fall von MSA und MMA, die an sich nicht copolymerisieren, jedoch bei Zusatz einer dritten Komponente wie Styrol problemlos copolymerisieren.The component H is preferably selected so that they have no Adverse effect on the properties of the invention too has used polymer. The component H can u. a. therefore be used to the properties of the polymer to desired Way to modify, for example, by increases or Improvements in flow properties when the polymer is applied to the Melting temperature is heated, or to reduce a residual color in Polymer or by using a polyfunctional monomer to this way some level of crosslinking in the polymer introduce. In addition, H can also be chosen so that a Copolymerization of components E to G even possible or supported, as in the case of MSA and MMA, which are not copolymerize, but with the addition of a third component such as styrene copolymerize easily.

    Zu den für diesen Zweck geeigneten Monomeren gehören u. a. Vinylester, Ester der Acrylsäure, beispielsweise Methyl- und Ethylacrylat, Ester der Methacrylsäure, die sich von Methylmethacrylat unterscheiden, beispielsweise Butylmethacrylat und Ethylhexylmethacrylat, Vinylchlorid, Vinylidenchlorid, Styrol, α-Methylstyrol und die verschiedenen halogensubstituierten Styrole, Vinyl- und Isopropenylether, Diene, wie beispielsweise 1,3-Butadien und Divinylbenzol. Die Farbverminderung des Polymeren kann beispielsweise besonders bevorzugt durch Einsatz eines elektronenreichen Monomeren, wie beispielsweise eines Vinylethers, Vinylacetat, Styrol oder α-Methylstyrol, erreicht werden. Besonders bevorzugt unter den Verbindungen der Komponente H sind aromatische Vinylmonomere, wie beispielsweise Styrol oder α-Methylstyrol.Among the monomers suitable for this purpose are u. a. Vinylester, Esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid other than methyl methacrylate, for example, butyl methacrylate and ethylhexyl methacrylate, Vinyl chloride, vinylidene chloride, styrene, α-methylstyrene and the various halogen-substituted styrenes, vinyl and Isopropenyl ethers, dienes such as 1,3-butadiene and Divinylbenzene. The color reduction of the polymer may be, for example particularly preferably by using an electron-rich monomer, such as a vinyl ether, vinyl acetate, styrene or α-methylstyrene can be achieved. Particularly preferred among the Compounds of component H are vinyl aromatic monomers, such as for example, styrene or α-methylstyrene.

    Die Herstellung der erfindungsgemäß zu verwendenden Polymere ist an sich bekannt. Sie können in Substanz-, Lösungs-, Suspensions- oder Emulsionspolymerisation hergestellt werden. Hilfreiche Hinweise finden sich hinsichtlich der Substanzpolymerisation bei Houben-Weyl, Band E20, Teil 2 (1987), Seite 1145ff. Hinweise zur Lösungspolymerisation findet man eben dort auf Seite 1149ff beschrieben, während die Emulsionspolymerisation eben dort auf Seite 1150ff ausgeführt und erläutert wird.The preparation of the polymers to be used according to the invention is on known. They can be in substance, solution, suspension or Emulsion polymerization are prepared. Find helpful hints with regard to the bulk polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Notes on solution polymerization finds one just described there on page 1149ff, while the Emulsion polymerization just run there on page 1150ff and is explained.

    Besonders bevorzugt sind im Rahmen der Erfindung Perlpolymerisate, deren Teilchengröße in einem besonders günstigen Bereich liegt. Bevorzugt liegen die erfindungsgemäß durch beispielsweise Einmischen in die Schmelze der Faserpolymeren zu verwendenden Polymere in Form von Teilchen mit einem mittleren Durchmesser von 0,1 bis 1,0 mm vor. Es sind jedoch auch größere oder kleinere Perlen oder Granulate einsetzbar, wobei aber kleinere Perlen besondere Anforderungen an die Logistik, wie Fördern und Trocknen, stellen.Particularly preferred within the scope of the invention are bead polymers, whose particle size is in a particularly favorable range. Preferably, the present invention, for example, by mixing in the melt of the fiber polymers to be used polymers in the form of Particles with a mean diameter of 0.1 to 1.0 mm. It but are also larger or smaller beads or granules can be used, but smaller beads have special requirements for Logistics, such as conveying and drying.

    Die imidisierten Polymertypen 2 und 3 können sowohl aus den Monomeren unter Verwendung eines monomeren Imids hergestellt werden als auch durch nachträgliche vollständige oder bevorzugt partielle Imidisierung eines das entsprechende Maleinsäurederivat enthaltenden Polymers. The imidized polymer types 2 and 3 can be both from the monomers be prepared using a monomeric imide as well by subsequent complete or preferably partial imidization a polymer containing the corresponding maleic acid derivative.

    Erhalten werden diese Additivpolymere beispielsweise durch vollständige oder bevorzugt partielle Umsetzung des entsprechenden Polymers in der Schmelzphase mit Ammoniak oder einem primären Alkyl- oder Arylamin, beispielsweise Anilin (Encyclopedia of Polymer Science and Engineering Vol 16 [1989], Wiley-Verlag, Seite 78). Sämtliche erfindungsgemäßen Polymere als auch, soweit gegeben, deren nicht imidisierte Ausgangspolymere sind im Handel erhältlich oder nach einem für den Fachmann geläufigen Verfahren herstellbar.These additive polymers are obtained for example by complete or preferably partial reaction of the corresponding polymer in the Melting phase with ammonia or a primary alkyl or arylamine, For example, aniline (Encyclopedia of Polymer Science and Engineering Vol 16 [1989], Wiley-Verlag, page 78). All inventive Polymers and, as far as given, their non-imidized Starting polymers are commercially available or according to one of the Produce expert familiar process.

    Die Konzentration c des polymeren Additivs in Gew.-% im Polyester wird hierbei in Funktion der vorgegebenen Abzugsgeschwindigkeit v in m/min und der gewünschten Doppelbrechung des Spinnfadens Δn gemäß nachstehender Formeln bestimmt: x · f1 ≤ c ≤ x · f2 wobei f1 = 100 · (Δno - Δn) Δno (7,2589 · 10-6 · v2 - 7,7932 · 10-2 · v + 236,0755) f2 = 100 · (Δno - Δn) Δno (5,9391 · 10-6 · v2 - 6,3763 · 10-2 · v + 193,1527)

  • Δn = Doppelbrechung des erfindungsgemäßen Spinnfadens aus Polyester mit Additivzusatz,
  • Δno = Doppelbrechung von unter gleichen Spinnbedingungen, wie erfindungsgemäß, hergestellten Spinnfäden aus Polyester ohne Additivzusatz,
  • Δn < Δno
  • x = 1 für Additiv-Polymere des Typs 1 oder 3, und
  • x = 2,8 für Additiv-Polymere des Typs 2 (ohne Acrylverbindung).
    • The concentration c of the polymeric additive in% by weight in the polyester is in this case determined as a function of the predetermined take-off speed v in m / min and the desired birefringence of the spun yarn Δn according to the following formulas: x · f 1 ≤ c ≤ x · f 2 in which f 1 = 100 · (Δn O - Δn) .DELTA.n O (7.2589 · 10 -6 · V 2 - 7,7932 · 10 -2 · V + 236,0755) f 2 = 100 · (Δn O - Δn) .DELTA.n O (5.9391 · 10 -6 · V 2 - 6.3763 · 10 -2 · V + 193,1527)
  • Δn = birefringence of the polyester filament of the invention with added additive,
  • Δn o = birefringence of spun yarns made of polyester without addition of additive, produced under the same spinning conditions, according to the invention,
  • Δn <Δn o
  • x = 1 for type 1 or 3 additive polymers, and
  • x = 2.8 for Type 2 additive polymers (without acrylic compound).

    • Das Additiv-Polymer ist mit dem Polyester inkompatibel, das heißt, daß das Additiv in der Polyester-Matrix weitgehend unlöslich ist. Der Polyester und das Additiv-Polymer bilden dabei zwei Phasen, die mikroskopisch unterschieden werden können. Weiterhin muß das Copolymer eine Glasumwandlungstemperatur (bestimmt durch DSC mit 10 °C/min Aufheizrate) von 90 bis 170 °C haben und thermoplastisch verarbeitbar sein.The additive polymer is incompatible with the polyester, that is, that the additive in the polyester matrix is largely insoluble. Of the Polyester and the additive polymer form two phases, the can be distinguished microscopically. Furthermore, the copolymer must a glass transition temperature (determined by DSC at 10 ° C / min Heating rate) from 90 to 170 ° C and thermoplastically processable his.

    Die Schmelzeviskosität des Copolymeren ist dabei so zu wählen, daß das Verhältnis seiner auf die Meßzeit Null extrapolierten Schmelzeviskosität, gemessen bei einer Oszillationsrate von 2,4 Hz und einer Temperatur, die gleich der Schmelztemperatur des Polyesters plus 34,0 °C ist (für Polyethylenterephthalat 290 °C) relativ zu derjenigen des Polyesters, gemessen unter gleichen Bedingungen, zwischen 1 : 1 und 7 : 1 liegt. D. h. die Schmelzeviskosität des Polymeren ist mindestens gleich oder bevorzugt höher als die des Polyesters. Erst durch die Wahl eines spezifischen Viskositätsverhältnisses von Additiv und Polyester wird der optimale Wirkungsgrad erreicht. Bei einem derart optimierten Viskositätsverhältnis ist eine Minimierung der Menge des Additivzusatzes möglich, wodurch die Wirtschaftlichkeit des Verfahrens besonders hoch wird. Überraschenderweise liegt das erfindungsgemäß als ideal ermittelte Viskositätsverhältnis für die Verwendung von Polymermischungen zur Herstellung von HMLS-Fäden oberhalb des Bereiches, welcher in der Literatur für das Vermischen zweier Polymere als günstig ausgewiesen wird. Im Gegensatz zum Stand der Technik waren Polymermischungen mit hochmolekularen Additivpolymeren ausgezeichnet verspinnbar.The melt viscosity of the copolymer is to be chosen so that the Ratio of its extrapolated to the zero measurement time Melt viscosity, measured at an oscillation rate of 2.4 Hz and a temperature equal to the melting temperature of the polyester plus 34.0 ° C (for polyethylene terephthalate 290 ° C) relative to that of the polyester, measured under the same conditions, between 1: 1 and 7: 1 lies. Ie. the melt viscosity of the polymer is at least equal to or preferably higher than that of the polyester. Only through the election a specific viscosity ratio of additive and polyester the optimum efficiency is achieved. With such an optimized Viscosity ratio is a minimization of the amount of Additive additive possible, reducing the cost of the process becomes particularly high. Surprisingly, this is according to the invention as ideally determined viscosity ratio for the use of Polymer blends for the production of HMLS filaments above the Range, which in the literature for the mixing of two polymers is shown as cheap. In contrast to the prior art were Polymer blends with high molecular weight additive polymers to spin.

    Bedingt durch die hohe Fließaktivierungsenergie der Additivpolymere erhöht sich das Viskositätsverhältnis nach Austritt der Polymermischung aus der Spinndüse im Bereich der Fadenbildung noch drastisch. Hierbei ist die Fließaktivierungsenergie (E) ein Maß für die Änderungsrate der Nullviskosität in Abhängigkeit von der Änderung der Meßtemperatur, wobei die Nullviskosität die auf die Scherrate 0 extrapolierte Viskosität ist. (M. Pahl et al., Praktische Rheologie der Kunststoffe und Elastomere, VDI-Verlag, Düsseldorf (1995), Seiten 256 ff.). Durch die Wahl eines günstigen Viskositätsverhältnisses erzielt man eine besonders enge Teilchengrößenverteilung des Additivs in der Polyestermatrix und durch Kombination des Viskositätsverhältnisses mit einer Fließaktivierungsenergie von deutlich mehr als die des Polyesters (PET etwa 60 kJ/mol), d. h. von mehr als 80 kJ/mol erhält man die Fibrillenstruktur des Additivs im Spinnfaden. Die im Vergleich zum Polyester hohe Glasumwandlungstemperatur stellt eine schnelle Verfestigung dieser Fibrillenstruktur im Spinnfaden sicher. Die maximalen Teilchengrößen des Additiv-Polymers liegen dabei unmittelbar nach Austritt aus der Spinndüse bei etwa 1000 nm, während die mittlere Teilchengröße 400 nm oder weniger beträgt. Nach dem Verziehen unterhalb der Spinndüse und dem Verstrecken entstehen Fibrillen mit einem mittleren Durchmesser ≤ 80 nm.Due to the high flow activation energy of the additive polymers increases the viscosity ratio after exiting the polymer mixture from the spinneret in the field of thread formation still drastically. in this connection is the flow activation energy (E) a measure of the rate of change of Zero viscosity as a function of the change in the measuring temperature, where the zero viscosity extrapolated to the shear rate 0 Viscosity is. (M. Pahl et al., Practical Rheology of Plastics and elastomers, VDI-Verlag, Dusseldorf (1995), pages 256 ff.). By the choice of a favorable viscosity ratio is achieved particularly narrow particle size distribution of the additive in the Polyester matrix and by combining the viscosity ratio with a flow activation energy of significantly more than that of the polyester (PET about 60 kJ / mol), d. H. of more than 80 kJ / mol gives the Fibril structure of the additive in the filament. The compared to Polyester high glass transition temperature provides a fast Solidification of this fibril structure in the filament safely. The maximum particle sizes of the additive polymer are immediate After exiting the spinneret at about 1000 nm, while the middle Particle size is 400 nm or less. After warping below the spinneret and the stretching arise fibrils with a average diameter ≤ 80 nm.

    Bevorzugt liegt das Verhältnis der Schmelzeviskosität des Copolymers zu der des Polyesters unter oben genannten Bedingungen zwischen 1,5 : 1 und 5 : 1. Unter diesen Bedingungen beträgt die mittlere Teilchengröße des Additivpolymers unmittelbar nach Austritt aus der Spinndüse 120 - 300 nm, und es entstehen Fibrillen mit einem mittleren Durchmesser von etwa 40 nm. Preferably, the ratio of the melt viscosity of the copolymer is too that of the polyester under the above conditions between 1.5: 1 and 5: 1. Under these conditions, the mean particle size is of the additive polymer immediately after exit from the spinneret 120 - 300 nm, resulting in fibrils with a mean diameter of about 40 nm.

    Die Vermischung des Additivpolymers mit dem Matrixpolymer erfolgt durch Zugabe als Feststoff zu den Matrixpolymerchips im Extrudereinlauf mit Chipsmischer oder gravimetrischer Dosierung oder alternativ durch Aufschmelzen des Additivpolymers, Dosierung mittels Zahnradpumpe und Einspeisung in den Schmelzestrom des Matrixpolymers. Auch sogenannte Masterbatch-Techniken sind möglich, wobei das Additiv als Konzentrat in Polyesterchips, die später im festen oder geschmolzenen Zustand dem Matrix-Polyester zugesetzt werden, vorliegt. Auch der Zusatz zu einem Teilstrom des Matrix-Polymers, der dann dem Hauptstrom des Matrix-Polymers zugemischt wird, ist praktikabel.The mixing of the additive polymer with the matrix polymer is carried out by Add as a solid to the matrix polymer chips in the extruder inlet with Chips mixer or gravimetric dosing or alternatively by Melting of the additive polymer, metering by gear pump and Feed into the melt stream of the matrix polymer. Also called Masterbatch techniques are possible, with the additive being used as a concentrate in Polyester chips later in solid or molten state Matrix polyester are present. Also the addition to a Partial flow of the matrix polymer, which is then the main stream of the matrix polymer is admixed, is practicable.

    Anschließend erfolgt die Herstellung einer homogenen Verteilung durch Mischung mittels statischer Mischer. Vorteilhafterweise wird durch spezifische Wahl des Mischers und der Dauer des Mischvorgangs eine definierte Teilchenverteilung eingestellt, bevor die Schmelzemischung durch Produktverteilungsleitungen zu den einzelnen Spinnstellen und Spinndüsen weitergeleitet wird. Mischer mit einer Scherrate von 16 bis 128 sec-1 haben sich bewährt. Dabei soll das Produkt aus Scherrate (s-1) und der 0,8ten Potenz der Verweilzeit (in sec) mindestens 250, vorzugsweise 350 bis 1250 betragen. Werte über 2500 werden im allg. vermieden, um den Druckabfall in den Rohrleitungen limitiert zu halten.Subsequently, the production of a homogeneous distribution by mixing by means of static mixer. Advantageously, a defined particle distribution is set by specific choice of the mixer and the duration of the mixing process, before the melt mixture is passed through product distribution lines to the individual spinning stations and spinnerets. Mixers with a shear rate of 16 to 128 sec -1 have proven themselves. In this case, the product of shear rate (s -1 ) and the power of 0.8th of the residence time (in sec) should be at least 250, preferably 350 to 1250. Values over 2500 are generally avoided in order to limit the pressure drop in the pipelines.

    Hierbei ist die Scherrate definiert durch die Scherrate im Leerrohr (s-1) mal dem Mischerfaktor, wobei der Mischerfaktor eine charakteristische Kenngröße des Mischertyps ist. Für Sulzer-SMX-Typen beispielsweise beträgt dieser Faktor etwa 7 - 8. Die Scherrate γ im Leerrohr berechnet sich gemäß

    Figure 00130001
    und die Verweilzeit t (s) gemäß t = V2 · ε · δ · 60 F wobei

  • F = Fördermenge des Polymeren (g/min)
  • V2 = Innenvolumen des Leerrohres (cm3)
  • R = Leerrohrradius (mm)
  • ε = Leervolumenanteil (bei Sulzer-SMX-Typen 0,84 bis 0,88)
  • δ = Nenndichte der Polymermischung in der Schmelze (etwa 1,2 g/cm3)
    • Here, the shear rate is defined by the shear rate in the empty tube (s -1 ) times the mixer factor, the mixer factor being a characteristic parameter of the mixer type. For Sulzer SMX types, for example, this factor is approximately 7 - 8. The shear rate γ in the empty tube is calculated according to
    Figure 00130001
    and the residence time t (s) according to t = V 2 · Ε · δ · 60 F in which
  • F = flow rate of the polymer (g / min)
  • V 2 = inner volume of the empty tube (cm 3 )
  • R = empty pipe radius (mm)
  • ε = void volume fraction (for Sulzer SMX types 0.84 to 0.88)
  • δ = nominal density of the polymer mixture in the melt (about 1.2 g / cm 3 )

    • Sowohl das Vermischen der beiden Polymere als auch das nachfolgende Verspinnen der Polymermischung erfolgt bei Temperaturen, je nach Matrix-Polymer, im Bereich von 220 bis 320 °C, bevorzugt bei (Schmelztemperatur des Matrix-Polymer + 34) + 25/- 20 °C. Für PET werden vorzugsweise Temperaturen von 270 bis 315 °C eingestellt.Both the mixing of the two polymers and the subsequent Spinning the polymer blend occurs at temperatures, as appropriate Matrix polymer, in the range of 220 to 320 ° C, preferably at (Melting temperature of the matrix polymer + 34) + 25 / -20 ° C. For PET preferably temperatures of 270 to 315 ° C are set.

    Die Herstellung der HMLS-Fäden aus den erfindungsgemäßen Polymermischungen durch Spinnen mit Abzugsgeschwindigkeiten von 2500 bis 4000 m/min, Verstrecken, Thermofixieren und Aufwickeln geschieht unter Verwendung an sich bekannter Spinnstreckeinrichtungen in gleicher Weise wie bei Polyester ohne Additiv. Hierbei wird das Filterpaket nach dem bekannten Stand der Technik mit Filtereinrichtungen und/oder losen Filtermedien bestückt.The production of HMLS threads from the invention Polymer blends by spinning at take-off speeds of 2500 Up to 4000 m / min, stretching, thermosetting and winding happens using the known Spinnstreckeinrichtungen in the same As with polyester without additive. Here, the filter pack is after the prior art with filtering devices and / or loose Equipped with filter media.

    Die geschmolzene Polymermischung wird nach erfolgter Scher- und Filtrationsbehandlung im Düsenpaket durch die Bohrungen der Düsenplatte gepreßt. In der anschließenden Kühlzone werden die Schmelzefäden mittels Kühlluft unter ihre Erstarrungstemperatur abgekühlt, so daß ein Verkleben oder Aufstauchen an dem folgenden Fadenleitorgan vermieden wird. Die Kühlluft kann durch Quer- oder Radialanblasung aus einem Klimasystem zugeführt werden. Nach Abkühlung werden die Spinnfäden mit Spinnpräparation beaufschlagt, über Galettensysteme mit definierter Geschwindigkeit abgezogen, anschließend verstreckt, thermofixiert und schließlich aufgewickelt. Vorteilhafterweise können Fadenverwirbelungseinrichtungen in den Prozeß eingeschlossen werden.The molten polymer mixture is after shearing and Filtration treatment in the nozzle package through the holes of the nozzle plate pressed. In the subsequent cooling zone, the melt strands become Cooled by cooling air below its solidification temperature, so that a Glueing or upsetting on the following thread guide avoided becomes. The cooling air can by transverse or radial blowing of a Air conditioning system to be supplied. After cooling, the filaments are with Spinnpräparation applied, via godet systems with defined Drawn off speed, then stretched, heat-set and finally wound up. Advantageously, thread swirling devices be included in the process.

    Typisch für HMLS-Fäden aus Polyester ist es, daß sie in großen Direktschmelze-Spinnanlagen hergestellt werden, in denen die Schmelze über lange beheizte Produktleitungen auf die einzelnen Spinnlinien und innerhalb der Linien auf die einzelnen Spinnsysteme verteilt wird. Hierbei stellt eine Spinnlinie eine Aneinanderreihung von mindestens einer Reihe von Spinnsystemen dar und ein Spinnsystem die kleinste Spinneinheit mit einem Spinnkopf, der mindestens ein Spinndüsenpaket einschließlich Spinndüsenplatten enthält. Die Schmelze unterliegt in derartigen Systemen einer hohen thermischen Belastung bei Verweilzeiten bis zu 35 min. Die Effektivität des erfindungsgemäßen Polymeradditivs führt dabei infolge der hohen thermischen Stabilität des Additivs zu keinen nennenswerten Einschränkungen seiner Wirkung, so daß eine geringe Zugabemenge des Additives ≤ 2,5 % und in vielen Fällen ≤ 1,5 % trotz hoher thermischer Belastung ausreicht.Typical of HMLS polyester threads is that they are in large Direct melt spinning plants are manufactured, in which the melt over long heated product lines on the individual spinning lines and distributed within the lines on the individual spinning systems. In this case, a spinning line represents a juxtaposition of at least a number of spinning systems and a spinning system is the smallest Spinning unit with a spinner head, comprising at least one spinneret pack including spinneret plates. The melt is subject in such systems a high thermal load at residence times up to 35 min. The effectiveness of the polymer additive according to the invention leads due to the high thermal stability of the additive no appreciable limitations of its effect, so that a small addition amount of the additive ≤ 2.5% and in many cases ≤ 1.5% despite high thermal load is sufficient.

    Die Eigenschaften des Additivpolymers und die Mischtechnik bewirken, daß das Additivpolymer unmittelbar nach Austritt der Polymermischung aus der Spinndüse kugelähnliche oder länglich verformte Teilchen im Matrixpolymer bildet. Beste Bedingungen ergaben sich, wenn die mittlere Teilchengröße (arithmetisches Mittel) d50 ≤ 400 nm war, und der Anteil von Teilchen > 1000 nm in einem Probenquerschnitt unter 1 % lag. The properties of the additive polymer and the blending technique cause the additive polymer to form globule-like or elongated particles in the matrix polymer immediately upon exit of the polymer blend from the spinneret. Best conditions were obtained when the average particle size (arithmetic mean) d 50 ≤ 400 nm, and the proportion of particles> 1000 nm in a sample cross-section was less than 1%.

    Die Beeinflussung dieser Teilchen durch den Spinnverzug bzw. die Verstreckung konnte analytisch nachgewiesen werden. Neue Untersuchungen der Fäden nach dem TEM-Verfahren (Transmissions-Elektronenmikroskopie) haben gezeigt, daß dort eine fibrillenartige Struktur vorliegt. Der mittlere Durchmesser der Fibrillen wurde mit ca. 40 nm und das Längen-/Durchmesserverhältnis der Fibrillen zu > 50 abgeschätzt. Diese Fibrillen bedingen eine "Mikrorauhigkeit" der Faseroberfläche, was zu einer verbesserten Cord/Gummi-Haftung führt und bei der Verwendung des Garnes z. B. als Reifencord sehr geschätzt wird. Werden diese Fibrillen nicht gebildet oder sind die Additivteilchen nach Austritt aus der Spinndüse im Durchmesser zu groß oder ist die Größenverteilung zu ungleichmäßig, was bei ungenügendem Viskositätsverhältnis der Fall ist, so geht der Wirkungseffekt verloren.The influence of these particles by the spinning delay or the Drawing could be detected analytically. New investigations threads according to the TEM method (Transmission Electron Microscopy) have shown that there is a fibril-like structure. Of the average diameter of the fibrils was about 40 nm and the Length / diameter ratio of fibrils estimated to> 50. This Fibrils cause a "microroughness" of the fiber surface, resulting in improved cord / rubber adhesion and in the use of the Garnes z. B. is highly appreciated as a tire cord. Will these fibrils not formed or are the additive particles after leaving the Spinneret too large in diameter or is the size distribution too uneven, which is the case with insufficient viscosity ratio, so the effect is lost.

    Ferner ist für die Wirksamkeit der Additive gemäß dieser Erfindung eine Glasumwandlungstemperatur von 90 bis 170 °C, sowie vorzugsweise eine Fließaktivierungsenergie der Additiv-Polymere von mindestens 80 kJ/mol, also eine höhere Fließaktivierungsenergie als die der Polyestermatrix erforderlich. Unter dieser Voraussetzung ist es möglich, daß die Additivfibrillen vor der Polyestermatrix erstarren und einen erheblichen Anteil der anliegenden Spinnspannung aufnehmen. Die bevorzugt anzuwendenden Additive zeichnen sich zudem durch eine hohe Thermostabilität aus. So werden in den bei großer Verweilzeit und/oder hoher Temperatur betriebenen Direktspinnanlagen die Wirksamkeitsverluste durch Additivzersetzung minimiert.Further, for the effectiveness of the additives according to this invention is a Glass transition temperature of 90 to 170 ° C, and preferably a Flow activation energy of the additive polymers of at least 80 kJ / mol, that is, a higher flow activation energy than that of the polyester matrix required. Under this condition, it is possible that the Solidify additive fibrils in front of the polyester matrix and one record a significant proportion of the applied spinning tension. The preferred to apply additives are also characterized by a high Thermostability off. Thus, in the case of a large residence time and / or high temperature operated direct spinning the Efficacy losses due to additive decomposition minimized.

    Die Verstreckung erfolgt in an sich bekannter Weise in mindestens einer Stufe zwischen unterschiedlich beheizten Galettensystemen, vorzugsweise zweistufig. Bevorzugt erfolgt das Verstrecken des Spinnfadens unter Anwendung eines Streckverhältnisses DR, für das in Funktion der Abzugsgeschwindigkeit v in m/min und der Konzentration c des Additiv-Copolymers in Gew.-% gilt: f3 ≤ DR ≤ f4 wobei f3 = -5 · 10-4 · v - 1,6 · 10-4 · v · c/x + 0,98 · c/x + 3,55 f4 = -5 · 10-4 · v - 2,4 · 10-4 · v · c/x + 1,46 · c/x + 3,55 The stretching takes place in a manner known per se in at least one stage between differently heated godet systems, preferably in two stages. Preferably, the drawing of the spun yarn is carried out using a draw ratio DR, for which the following applies in terms of the withdrawal speed v in m / min and the concentration c of the additive copolymer in% by weight: f 3 ≤ DR ≤ f 4 in which f 3 = -5 · 10 -4 · V - 1.6 · 10 -4 · V · c / x + 0.98 · c / x + 3.55 f 4 = -5 · 10 -4 · V - 2.4 · 10 -4 · V · c / x + 1.46 · c / x + 3.55

    Bei mehrstufiger Verstreckung ist DR das Produkt aus den Einzel-Streckverhältnissen. Die Aufwickelgeschwindigkeit ist gleich dem Produkt aus Spinngeschwindigkeit v, dem Streckverhältnis DR und dem Relaxverhältnis.For multi-stage drawing, DR is the product of the single draw ratios. The winding speed is equal to Product of spinning speed v, the draw ratio DR and the Relax ratio.

    Die erfindungsgemäßen HMLS-Fäden besitzen zumindest die gleichen Qualitätswerte, wie analog hergestellte Garne ohne polymeres Additiv.The HMLS filaments according to the invention have at least the same Quality values, such as analog yarns without polymeric additive.

    Die in den nachfolgenden Beispielen und im vorstehenden Text angegebenen Eigenschaftswerte wurden, wie folgt, ermittelt:Those in the examples below and in the preceding text specified property values were determined as follows:

    Additivfibrillen: Die Untersuchung der Mikrotom-Dünnschnitte der Fäden erfolgte mittels Transmissions-Elektronenmikroskopie und anschließender bildanalytischer Auswertung, wobei der Durchmesser der Fibrillen bewertet wurde, und die Länge aus dem in Proben unmittelbar nach der Spinndüse ermittelten Teilchendurchmesser abgeschätzt wurde.Additive fibrils: the investigation of the microtome thin sections of the threads was carried out by transmission electron microscopy and subsequent image analysis evaluation, wherein the diameter of the fibrils was evaluated, and the length from that in samples immediately after the Spinneret diameter was estimated.

    Die Intrinsic Viskosität wurde an einer Lösung von 0,5 g Polyester in 100 ml eines Gemisches aus Phenol und 1,2-Dichlorbenzol (3 : 2 Gew.-Teile) bei 25 °C bestimmt. The intrinsic viscosity was measured on a solution of 0.5 g of polyester in 100 ml of a mixture of phenol and 1,2-dichlorobenzene (3: 2 parts by weight) at 25 ° C.

    Zur Bestimmung der Schmelzeviskosität (Anfangsviskosität) wurde das Polymer im Vakuum auf einen Wassergehalt ≤ 1000 ppm (Polyester ≤ 50 ppm) getrocknet. Anschließend wurde das Granulat in einem Kegel-Platte-Rheometer, Typ UM100, Physica Meßtechnik GmbH, Stuttgart/DE, unter Beschleierung mit Stickstoff auf die temperierte Meßplatte eingebracht. Dabei wurde der Meßkegel (MK210) nach dem Aufschmelzen der Probe, d. h. nach ca. 30 Sekunden, auf der Meßplatte positioniert. Die Messung wurde nach einer weiteren Aufheizperiode von 60 Sekunden gestartet (Meßzeit = 0 Sekunden). Die Meßtemperatur betrug 290 °C für Polyethylenterephthalat und Additiv-Polymere, welche Polyethylenterephthalat zugesetzt werden, bzw. war gleich der Schmelztemperatur des betroffenen Polyesters plus 34,0 °C. Die so festgelegte Meßtemperatur entspricht der typischen Verarbeitungs- oder Spinntemperatur des jeweiligen Polyesters. Die Probenmenge wurde so gewählt, daß der Rheometerspalt vollständig ausgefüllt war. Die Messung wurde in Oszillation mit der Frequenz 2,4 Hz (entsprechend einer Scherrate von 15 sec-1) und einer Deformations-Amplitude von 0,3 durchgeführt, und der Betrag der komplexen Viskosität als Funktion der Meßzeit bestimmt. Danach wurde die Anfangsviskosität durch lineare Regression auf die Meßzeit Null umgerechnet.To determine the melt viscosity (initial viscosity), the polymer was dried in vacuo to a water content of ≦ 1000 ppm (polyester ≦ 50 ppm). Subsequently, the granules were placed in a cone-plate rheometer, type UM100, Physica Meßtechnik GmbH, Stuttgart / DE, with aeration with nitrogen on the temperature-controlled measuring plate. The measuring cone (MK210) was positioned on the measuring plate after the sample had melted, ie after about 30 seconds. The measurement was started after a further heating-up period of 60 seconds (measuring time = 0 seconds). The measurement temperature was 290 ° C for polyethylene terephthalate and additive polymers, which are added to polyethylene terephthalate, or was equal to the melting temperature of the polyester concerned plus 34.0 ° C. The measuring temperature thus determined corresponds to the typical processing or spinning temperature of the respective polyester. The amount of sample was chosen so that the rheometer gap was completely filled. The measurement was carried out in oscillation with the frequency 2.4 Hz (corresponding to a shear rate of 15 sec -1 ) and a deformation amplitude of 0.3, and determines the amount of the complex viscosity as a function of the measuring time. Thereafter, the initial viscosity was converted to the zero measurement time by linear regression.

    Für die Bestimmung der Glasumwandlungstemperatur und der Schmelztemperatur des Polyesters wurde die Polyesterprobe zunächst bei 310 °C während 1 min aufgeschmolzen und unmittelbar danach auf Raumtemperatur abgeschreckt. Anschließend wurden die Glasumwandlungstemperatur und die Schmelztemperatur durch DSC-Messung (Differential Scanning Calorimetrie) bei einer Aufheizrate von 10 °C/min bestimmt. Vorbehandlung und Messung erfolgten unter Stickstoffbeschleierung. For the determination of the glass transition temperature and the Melting temperature of the polyester, the polyester sample was initially at Melted 310 ° C for 1 min and immediately afterwards Room temperature quenched. Subsequently, the Glass transition temperature and melting temperature by DSC measurement (Differential scanning calorimetry) at a heating rate of 10 ° C / min determined. Pretreatment and measurement were carried out under Nitrogen flow.

    Die Doppelbrechung des Spinnfadens (Δn) wurde mittels Polarisationsmikroskop mit Kippkompensator und Grünfilter (540 nm) unter Verwendung von Keilschnitten bestimmt. Gemessen wurde der Gangunterschied zwischen ordentlichem und außerordentlichem Strahl bei Durchtritt von linear polarisiertem Licht durch die Filamente. Die Doppelbrechung ist der Quotient aus dem Gangunterschied und dem Filament-Durchmesser. Beim Spinnstreckprozeß wurde der Spinnfaden nach der Abzugsgalette entnommen.The birefringence of the spun yarn (Δn) was determined by means of Polarizing microscope with tilt compensator and green filter (540 nm) determined using wedges. Was measured the Path difference between proper and extraordinary beam Passage of linearly polarized light through the filaments. The Birefringence is the quotient of the gait difference and the Filament diameter. In the spin draw process, the filament was after taken from the withdrawal godet.

    Die Bestimmung der Festigkeitseigenschaften der Fasern erfolgte an Fäden, denen ein Drall von 50 T/m aufgebracht wurde, an einer Prüflänge von 250 mm mit einer Abzugsgeschwindigkeit von 200 mm/min. Hierbei wird die Kraft, die im Kraft-Dehnungdiagramm einer Dehnung von 5 % entspricht, dividiert durch den Titer, als LASE-5 bezeichnet.The determination of the strength properties of the fibers was carried out on Threads to which a twist of 50 T / m was applied, on one test length of 250 mm with a withdrawal speed of 200 mm / min. This is the force in the force-elongation diagram of a strain of 5% equals, divided by the titer, referred to as LASE-5.

    Der Heißluftschrumpf wurde mit dem Shrinkage-Tester der Firma Testrite/USA bei 160 °C, einer Vorspannkraft von 0,05 cN/dtex und einer Behandlungsdauer von 2 min ermittelt.The hot air shrink was using the shrinkage tester of the company Testrite / USA at 160 ° C, a preload force of 0.05 cN / dtex and a Treatment duration of 2 min determined.

    Die Erfindung wird nachfolgend anhand von Beispielen näher erläutert:The invention is explained in more detail below with reference to examples:

    Vergleichsbeispiele 1 bis 3 und Beispiele 4 bis 8:Comparative Examples 1 to 3 and Examples 4 to 8:

    Zur Herstellung des HMLS-Garnes wurde ein Polyethylenterephthalat mit einer Intrinsic-Viskosität von 0,98 dl/g eingesetzt. Als Additiv wurde für die Beispiele 4 bis 7 ein Copolymer aus 90 Gew.-% Methylmethacrylat und 10 Gew.-% Styrol gewählt, welches eine Glasumwandlungstemperatur von 118,7 °C aufwies. Im Beispiel 8 wurde ein Copolymer aus 78 Gew.-% Styrol, und 22 Gew.-% imidisiertem Maleinsäureanhydrid mit einer Glasumwandlungstemperatur von 168 °C als Additiv verwendet. Die Polyesterchips und das Additiv-Polymer wurden in einem 7E-Extruder der Firma Barmag, DE, aufgeschmolzen. Das Additiv wurde in das Einfüllstück des Extruders dosiert. Verwendet wurde dazu das Dosiersystem, Typ KCLKQX2, der Firma K-Tron Soda, DE, mit gravimetrisch arbeitender Dosierregelung. Die im Extruder geschmolzene und vorgemischte Polymermischung wurde mit 160 bar durch statische Mischer gedrückt und einer 40-cm3-Schmelzedosierpumpe zugeführt. Die Mischung wurde dabei einer Scherrate von 23 sec-1 unterworfen. Das Produkt aus Scherrate und der 0,8ten Potenz der Verweilzeit in Sekunden betrug 475. Die Spinnpumpe förderte die auf 298 °C temperierte Schmelze in das Lurgi Zimmer Spinnsystem BN 110 mit rundem Spinndüsenpaket und Ringdüse (300 Löcher mit 0,4 mm Durchmesser). Der Schmelzedurchsatz betrug bei allen Einstellungen 660 g/min. Das entspricht einem Titer von 1100 dtex bei 6000 m/min Aufspulgeschwindigkeit. Der Düsendruck betrug 420 bar. Der ersponnene multifile Faden wurde in einem Radialanblassystem (außen nach innen) abgekühlt, mittels eines Ringölers mit Spinnpräparation beaufschlagt und einem 1. unbeheizten Galettenduo zugeführt. Die Geschwindigkeit dieses 1. Duos ist vereinbarungsgemäß gleich der Spinnabzugsgeschwindigkeit. Nur zur Probenahme für die Bestimmung der Doppelbrechung wurde der Spinnfaden bereits nach diesem 1. Duo einem Aufspulaggregat zugeführt. Zur Herstellung des HMLS-Fadens wurde der Faden nach dem 1. Duo über 3 weitere nun beheizte Galettenduos geführt und schließlich aufgespult. Zwischen dem 1. und dem 3. Duo erfolgte die Verstreckung, auf dem 3. Duo die Thermofixierung und zwischen dem 3. Duo und dem Spuler die Relaxation. Die drei beheizten Duos hatten folgende Temperaturen:

  • Duo 2: 85 °C
  • Duo 3: 240 °C
  • Duo 4: 150 °C
    • To prepare the HMLS yarn, a polyethylene terephthalate having an intrinsic viscosity of 0.98 dl / g was used. As an additive, a copolymer of 90% by weight of methyl methacrylate and 10% by weight of styrene was selected for Examples 4 to 7, which had a glass transition temperature of 118.7 ° C. In Example 8, a copolymer of 78% by weight of styrene and 22% by weight of imidized maleic anhydride having a glass transition temperature of 168 ° C was used as an additive. The polyester chips and the additive polymer were melted in a 7E extruder from Barmag, DE. The additive was metered into the filler of the extruder. For this purpose, the dosing system, type KCLKQX2, from K-Tron Soda, DE, with gravimetric dosing control was used. The polymer mixture melted and premixed in the extruder was forced through static mixers at 160 bar and fed to a 40 cm 3 melt metering pump. The mixture was subjected to a shear rate of 23 sec -1 . The product of shear rate and the 0.8th power of the residence time in seconds was 475. The spin pump conveyed the tempered to 298 ° C melt in the Lurgi Zimmer Spinning System BN 110 with round spinneret package and ring nozzle (300 holes with 0.4 mm diameter). The melt throughput was 660 g / min at all settings. This corresponds to a titer of 1100 dtex at 6000 m / min winding speed. The nozzle pressure was 420 bar. The spun multifilament yarn was cooled in a Radialanblassystem (outside to inside), applied by means of a ring oiler with spin finish and fed to a first unheated Galettendo duo. The speed of this 1st duo is the same as the spin-off speed. Only for sampling for the determination of the birefringence of the spun yarn was supplied after this first Duo a Aufspulaggregat. For the production of the HMLS thread, the thread was led after the first duo on 3 more now heated godet duo and finally wound up. The stretching took place between the 1st and the 3rd duo, the thermofixing on the 3rd duo and the relaxation between the 3rd duo and the winder. The three heated duos had the following temperatures:
  • Duo 2: 85 ° C
  • Duo 3: 240 ° C
  • Duo 4: 150 ° C

    • Das Teilrelaxverhältnis zwischen Duo 4 und Duo 3 war in allen Fällen 0,995. Die anderen Einstellungen sind der Tabelle zu entnehmen. Die Verfahrensparameter für den Spinnprozeß waren bei allen Beispielen identisch. Ausgehend von der vorgegebenen Spinngeschwindigkeit und einer gewünschten Doppelbrechung wurde der anzuwendende Bereich der Additiv-Polymerkonzentration gemäß Gleichung 1 errechnet, wobei der Faktor x additivspezifisch gleich 1 für die Beispiele 3 bis 7 und gleich 2,8 für Beispiel 8 eingesetzt wurde. Die tatsächliche Konzentration wurde innerhalb des berechneten Bereiches gewählt.The partial relaxation ratio between Duo 4 and Duo 3 was in all cases 0.995. The other settings are shown in the table. The Process parameters for the spinning process were in all examples identical. Starting from the given spinning speed and a desired birefringence was the applicable range of Additive polymer concentration calculated according to equation 1, wherein the Factor x additive-specific equal to 1 for Examples 3 to 7 and equal to 2.8 for example 8 was used. The actual Concentration was chosen within the calculated range.

    Der jeweilige bevorzugte Bereich für das Verstreckverhältnis wurde nach Gleichung 4 berechnet und das tatsächliche Streckverhältnis innerhalb des berechneten Bereiches gewählt. Die Verstreckung der Spinnfäden konnte in allen erfindungsgemäßen Beispielen erfolgreich durchgeführt werden. Kapillarbrüche wurden nur selten beobachtet. Die einzelnen Werte sind in der nachstehenden Tabelle zusammengestellt.The respective preferred range for the draw ratio became after Equation 4 calculates and the actual draw ratio within of the calculated range. The stretching of the filaments could be successfully carried out in all examples according to the invention become. Capillary fractures were rarely observed. The single ones Values are listed in the table below.

    Die Beispiele machen deutlich, daß die Konzentration des Additiv-Polymers nach der erfindungsgemäßen Gleichung (1) so bestimmt werden kann, daß bei vorgegebener Spinngeschwindigkeit die gewünschte Doppelbrechung realisiert werden kann. Insbesondere wird durch die erfindungsgemäße Wahl der Additiv-Konzentration der Maximalwert der gewünschten Doppelbrechung nicht überschritten. Dadurch können relativ hohe Spinngeschwindigkeiten eingestellt werden, ohne daß dies zu einer Verringerung der Festigkeit oder zu übermäßig vielen Faserdefekten führt, wie dies bei den bekannten Verfahren in nachteiliger Weise der Fall ist.The examples make it clear that the concentration of the Additive polymer according to the equation (1) according to the invention as determined be that at a given spinning speed the desired Birefringence can be realized. In particular, by the inventive choice of additive concentration of the maximum value of desired birefringence not exceeded. This can be relative high spinning speeds can be set without this to a Reduction in strength or too many fiber defects leads, as in the known methods disadvantageously the Case is.

    Bei allen erfindungsgemäßen Beispielen lag der mittlere Durchmesser der Fibrillen in den Fäden unter 80 nm.

    Figure 00230001
    In all the examples according to the invention, the mean diameter of the fibrils in the threads was less than 80 nm.
    Figure 00230001

    Claims (14)

    1. HMLS threads composed of polyester and having a breaking strength of > 70 cN/tex, an LASE 5 of > 35 cN/tex and a hot air shrinkage at 160°C of 1.5 - 3.5%, characterized in that they consist of
      α) a polyester which contains at least 85 mol% of poly(C2-4-alkylene) terephthalate,
      β) 0.1% to 2.5% by weight of an incompatible, thermoplastically processible, amorphous, polymeric additive which has a glass transition temperature in the range from 90 to 170°C, and
      γ) 0% to 5.0% by weight of customary additives,
      wherein the sum total of α), β) and γ) is equal to 100%, the ratio of the melt viscosity of the polymeric additive β) to the melt viscosity of the polyester α) is in the range from 1:1 to 7:1 and the polymeric additive β) is present in the HMLS threads in the form of fibrils distributed in the polyester α) which have an average diameter of ≤ 80 nm.
    2. HMLS threads according to Claim 1, characterized in that the ratio of the melt viscosities is in the range from 1.5:1 to 5:1.
    3. HMLS threads according to Claims 1 or 2, characterized in that the polymeric additive β) is the polymer which contains the following monomer units:
      A = acrylic acid, methacrylic acid or CH2 = CR - COOR', wherein R is an H atom or a CH3 group and R' is a C1-15-alkyl radical or C5-12-cycloalkyl radical or a C6-14-alkyl radical,
      B = styrene or C1-3-alkyl-substituted styrenes,
      wherein the polymer consists of 60% to 100% by weight of A and 0% to 40% by weight of B (sum total = 100% by weight).
    4. HMLS threads according to Claim 3, characterized in that the polymer consists of 83% to 98% by weight of A and 2% to 17% by weight of B (sum total = 100% by weight).
    5. HMLS threads according to Claim 3 or 4, characterized in that the polymer consists of 90% to 98% by weight of A and 2% to 10% by weight of B (sum total = 100% by weight).
    6. HMLS threads according to Claims 1 or 2, characterized in that the polymeric additive β) is a polymer which contains the following monomer units:
      C = styrene or C1-3-alkyl-substituted styrenes,
      D = one or more monomers of the formula I, II or III
      Figure 00330001
      wherein R1, R2 and R3 are each an H atom or a C1-15-alkyl radical or a C5-12-cycloalkyl radical or a C6-14-aryl radical and wherein the polymer consists of 15% to 100% by weight of C and 0% to 85% by weight of D, the sum of C and D together being 100%.
    7. HMLS threads according to Claim 6, characterized in that the polymer consists of 50% to 95% by weight of C and 5% to 50% by weight of D, the sum of C and D together being 100%.
    8. HMLS threads according to Claims 6 or 7, characterized in that the polymer consists of 70% to 85% by weight of C and 30% to 15% by weight of D, the sum of C and D together being 100%.
    9. HMLS threads according to Claims 1 or 2, characterized in that the polymeric additive β) is a polymer which contains the following monomer units:
      E = acrylic acid, methacrylic acid or CH2 = CR - COOR', wherein R is an H atom or a CH3 group and R' is a C1-15-alkyl radical or C5-12-cycloalkyl radical or a C6-14-aryl radical,
      F = styrene or C1-3-alkyl-substituted styrenes,
      G = one or more monomers of the formula I, II or III
      Figure 00340001
      wherein R1, R2 and R3 are each an H atom or a C1-15-alkyl radical or a C5-12-cycloalkyl radical or a C6-14-aryl radical,
      H = one or more ethylenically unsaturated monomers copolymerizable with E and/or with F and/or G from the group consisting of α-methylstyrene, vinyl acetate, acrylic esters, methacrylic esters other than E, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, vinyl ethers, isopropenyl ethers and dienes,
      wherein the polymer consists of 30% to 99% by weight of E, 0% to 50% by weight of F, > 0% to 50% by weight of G and 0% to 50% by weight of H, the sum of E, F, G and H together being 100%.
    10. HMLS threads according to Claim 9, characterized in that the polymer consists of 45% to 97% by weight of E, 0% to 30% by weight of F, 3% to 40% by weight of G and 0% to 30% by weight of H, the sum of E, F, G and H together being 100%.
    11. HMLS threads according to Claim 9 or 10, characterized in that the polymer consists of 60% to 94% by weight of E, 0% to 20% by weight of F, 6% to 30% by weight of G and 0% to 20% by weight of H, the sum of E, F, G and H together being 100%.
    12. A spin-draw process for producing the HMLS threads as per any one of Claims 1 - 11, characterized in that
      a) a polyester α) which contains at least 85 mol% of poly(C2-4-alkylene) terephthalate and
      an incompatible, thermoplastically processible, amorphous, polymeric additive β) which has a glass transition temperature in the range from 90 to 170°C, wherein the ratio of the melt viscosity of the polymeric additive β) to the melt viscosity of the polyester component α) is in the range from 1:1 to 7:1,
      wherein these may contain 0% to 5.0% by weight of customary additives γ),
      are mixed in the molten state in a static mixer by shearing, wherein the shear rate is 16 to 128 sec-1, and the product of shear rate and the 0.8th power of the residence time in seconds in the mixer is adjusted to a value of at least 250;
      b) the melt mixture from stage a) is spun into filaments at a spinning take-off speed in the range from 2500 to 4000 m/min; and
      c) the filaments from stage b) are spin finished, drawn, heat set and wound up,
      wherein the concentration c of the polymeric additive β in % by weight in the polyester is determined as a function of the predetermined take-off speed v in m/min and the desired birefringence Δn of the filaments as per the following formulae: x · f1 ≤ c ≤ x · f2 where f1 = 100 · (Δno - Δn)Δno (7,2589 · 10-6 · v2 - 7,7932 · 10-2 · v + 236,0755) f2 = 100 · (Δno - Δn)Δno (5,9391 · 10-6 · v2 - 6,3763 · 10-2 · v + 193,1527) where Δn < Δn0
      Δn = birefringence of inventive filament from polyester with additive addition,
      Δn0 = birefringence of filament from polyester without additive addition which has been produced using the same spinning conditions as the inventive filament,
      x = 1 for additive polymers of type 1 or 3,
      x = 2.8 for additive polymers of type 2 (without acrylic compound).
    13. A spin-draw process according to Claim 12, characterized in that in stage c) the draw ratio DR is determined as a function of the spinning speed v in m/min and the concentration c of the additive in % by weight as per the following formulae: f3 ≤ DR ≤ f4 f3 = -5 · 10-4 · v - 1,6 · 10-4 · v · c/x + 0,98 · c/x + 3,55 f4 = -5 · 10-4 · v - 2,4 · 10-4 · v · c/x + 1,46 · c/x + 3,55
    14. A spin-draw process according to Claim 13, characterized in that in stage c) the winding speed is equal to the product of the spinning speed v, the draw ratio DR and the relax ratio.
    EP00951438A 1999-08-10 2000-07-25 Hmls-fibers made of polyester and a spin-stretch process for its production Expired - Lifetime EP1208253B1 (en)

    Applications Claiming Priority (3)

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    DE19937728 1999-08-10
    DE19937728A DE19937728A1 (en) 1999-08-10 1999-08-10 HMLS threads made of polyester and spin stretching process for their production
    PCT/EP2000/007085 WO2001011122A1 (en) 1999-08-10 2000-07-25 Hmls-fibers made of polyester and a spin-stretch process for its production

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    DE10022889B4 (en) * 2000-05-25 2007-12-20 Lurgi Zimmer Gmbh Process for producing synthetic threads from a polyester-based polymer blend
    US6667003B2 (en) * 2000-05-25 2003-12-23 Zimmer A.G. Method for the manufacture of synthetic fibers from a melt mixture based on fiber forming polymers
    US6777496B2 (en) 2000-11-28 2004-08-17 Honeywell International Inc. Polymeric additives and polymeric articles comprising said additive
    KR100695613B1 (en) * 2005-10-27 2007-03-14 현대산업개발 주식회사 Floor structure of building for insulation and noise interruption
    CN101089266B (en) * 2007-07-04 2010-12-15 双双集团有限公司 Manufacturing method of antithermal shrink polyster high strength yarn
    DE102009052935A1 (en) 2009-11-12 2011-05-19 Teijin Monofilament Germany Gmbh Spun-dyed HMLS monofilaments, their preparation and use

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    US5234764A (en) 1988-07-05 1993-08-10 Allied-Signal Inc. Dimensionally stable polyester yarn for high tenacity treaty cords
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