EP1208255B1 - High-strength polyester threads and method for producing the same - Google Patents

High-strength polyester threads and method for producing the same Download PDF

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Publication number
EP1208255B1
EP1208255B1 EP00958291A EP00958291A EP1208255B1 EP 1208255 B1 EP1208255 B1 EP 1208255B1 EP 00958291 A EP00958291 A EP 00958291A EP 00958291 A EP00958291 A EP 00958291A EP 1208255 B1 EP1208255 B1 EP 1208255B1
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EP
European Patent Office
Prior art keywords
weight
strength polyester
copolymer
sum
filaments according
Prior art date
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EP00958291A
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German (de)
French (fr)
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EP1208255A1 (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
    • 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
    • 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
    • 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 high-strength polyester yarns with a Tear strength of> 70 cN / tex and a method for producing these Threads.
  • WO 99-07927A1 discloses that the elongation at break of preoriented polyester filaments (POY) spun at take-off speeds of at least 2500 m / min, preferably 3000 to 6000 m / min, by adding amorphous, thermoplastically processable copolymers based on styrene, Acrylic acid and / or maleic acid or derivatives thereof with respect to the elongation at break of spun under the same conditions polyester filaments can be increased without addition.
  • POY preoriented polyester filaments
  • the process is, however, not transferable to take-up speeds of less than 2500 m / min, since these fibers are less crystalline ( ⁇ 12%) than POY fibers, have a low orientation (birefringence ⁇ 25 - 10 -3 ) and a high Elongation at break (> 225%). Information on the production of high-strength yarns in the integrated spin-draw process is not included.
  • 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 is the combination of three properties - the chemical additive structure, which hardly allows any stretching of the additive molecules, the low mobility and the compatibility of polyester
  • 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 does not follow easily; in the In general, the achieved strengths are low, which is a considerable disadvantage for this product is.
  • the expert is also known that in the same spinning and Stretching conditions by changing the relax ratio the tear strength can be influenced dramatically.
  • the relaxation ratio is in the Practice of thermal shrinkage of such high-strength threads depending on set in industrial application. It is with increasing Relaxation ratio of the thermal shrinkage reduced, but also the Tear resistance and the LASE 5, whereas the elongation at break increases.
  • the present invention is based on the object, high-strength Polyester threads with a tear strength> 70 cN / tex are available too and to provide a method of making the same, in which Spinning withdrawal speeds and Aufspul yorken applied can be significantly higher than those of the prior art.
  • a relax ratio RR ⁇ 0.97 tear strengths > 80 cN / tex with a relaxation ratio of 0.95 ⁇ RR ⁇ 0.97 Tear strengths> 77 cN / tex and with a relaxation ratio RR ⁇ 0.95 Tear strengths> 70 cN / tex can be achieved.
  • Polyesters here are poly (C 2-4 -alkylene) terephthalates which contain 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.
  • 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
  • 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 may be added to the polyester or polyester-additive mixture in amounts of 0 to 5.0% by weight without any disadvantage.
  • the polyester is a copolymer in an amount of 0.1 added to 2.0 wt .-%, wherein the copolymer is amorphous and in the Polyester matrix must be largely insoluble. They are essentially the two polymers incompatible with each other and form two Phases that can be distinguished microscopically. Furthermore must the copolymer has a glass transition temperature (determined by DSC with 10 ° C / min heating rate) from 90 to 170 ° C and thermoplastic be processable.
  • 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. is the melt viscosity of the copolymer at least equal to or preferably higher than that of the polyester.
  • 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 high strength yarns above the Range, which in the literature for the mixing of two polymers is shown as cheap.
  • Polymer blends with high molecular weight copolymers to spin were Polymer blends with high molecular weight copolymers 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.
  • Component H is an optional component. Although the advantages to be achieved according to the invention already by Copolymers 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 Copolymer 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 having used copolymer.
  • the component H can u. a. therefore be used to the properties of the copolymer to desired Way to modify, for example, by increases or Improvements in flow properties when the copolymer is applied to the Melting temperature is heated, or to reduce a residual color in Copolymer or by using a polyfunctional monomer to in this way a certain degree of crosslinking in the copolymer 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.
  • Suitable monomers for this purpose include 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, ⁇ -methylstyrene and the various halogen-substituted styrenes, vinyl and Isopropenyl ethers, dienes such as 1,3-butadiene and Divinylbenzene.
  • the color reduction of the copolymer 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.
  • copolymers to be used according to the invention are 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 copolymers 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 copolymer types 2 and 3 can be made from both the monomers be prepared using a monomeric imide as well by subsequent complete or preferably partial imidization a copolymer containing the corresponding maleic acid derivative.
  • These additive polymers are obtained for example by complete or preferably partial reaction of the corresponding copolymer 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 Copolymers and, as far as given, their non-imidized Starting copolymers are commercially available or according to one of the Produce expert familiar process.
  • the amount of the copolymer to be added to the polyester is from 0.1 to 2.0% by weight, usually with addition amounts of less than 1.5%.
  • the concentration of the polymeric additive in the range from 0.1 to 2.0% by weight, depending on the desired spin-off speed (> 700-1500 m / min), is preferably chosen such that the birefringence of the spun yarn is ⁇ 3.5 ⁇ 10 . 3 is.
  • Such birefringence in the spun yarn allow draw ratios of 1: 5 and ensure the desired high thread strengths regardless of the spinning take-off speed of up to 1500 m / min at Aufspul yorken also well above 3800 m / min.
  • the mixing of the additive polymer (copolymer) with the matrix polymer takes place by adding as a solid to the matrix polymer chips in Extruder inlet with chip mixer or gravimetric dosing or alternatively by melting the additive polymer, dosage by means of Gear pump and feed into the melt stream of the matrix polymer. Also so-called masterbatch techniques are possible, with the additive as a concentrate in polyester chips, later in solid or molten state are added to the matrix polyester is present. Also, the addition of a partial stream of the matrix polymer, which then the Mainstream of the matrix polymer is mixed, 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 (sec.sup.- 1 ) and the power of 0.8 of the residence time (in seconds) should be at least 250, preferably 350 to 1250. Values over 2500 are generally avoided to keep the pressure drop in the piping limited.
  • 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 ° C.
  • Matrix polymer in the range of 220 to 320 ° C, preferably at (Melting temperature of the matrix polymer + 34) ⁇ 25 ° C.
  • PET preferably temperatures of 265 to 315 ° C set.
  • 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.
  • Typical of high-strength 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.
  • 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 to a high thermal in such systems Load at residence times up to 35 min.
  • the effectiveness of Polymer additive according to the invention leads due to the high thermal stability of the additive to no appreciable Limitations of its effect, so that a small addition amount of Additives ⁇ 2.0% and in many cases ⁇ 1.5% despite high thermal Load is sufficient.
  • an improvement of the stretchability characterized by an equally high draw ratio at higher Spinning take-off speed achieved.
  • the spinning deduction speed at the Spinneret set at least 200 m / min higher than the Spinning polyester without additive additive.
  • 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 copolymers of at least 80 kJ / mol, ie 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 high-strength filaments according to the invention have at least the same properties Quality values, like conventional threads 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 (I.V.) was measured on a solution of 0.5 g 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 fibers was determined by means of Polarizing microscope with tilt compensator and green filter (540 nm) determined using wedges. was measured the Gap difference between tidy and extraordinary beam when 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.
  • Polyethylene terephthalate chips with an intrinsic viscosity of 0.98 dl / g and a moisture content of 20 ppm were melted in a 7E extruder from. Barmag, DE, at a temperature of 295 ° C and with a pressure of 160 bar through Pressed a product line with installed static mixers and fed to a 2 x 15 cm 3 spin pump.
  • the polymer melt was subjected to a shear rate of 29 sec -1 .
  • the product of shear rate and the 0.8th power of the residence time in seconds was 532.
  • the spin pump conveyed the tempered to 298 ° C melt in two spin packs with rectangular nozzle plate (200 holes, 0.4 mm nozzle hole diameter).
  • the melt throughput per spin pack was 385 g / min at all settings. This corresponds to a titer of 1100 dtex at 3500 m / min winding speed.
  • the nozzle pressure was 330 bar.
  • the spun multifilament yarn passed through a 330 mm long reheater (330 ° C.) following the spinneret, was then cooled in a cross-impingement system, subjected to spin finish by means of a slot lubricator and fed to an unheated pair of inlet rollers. The speed of this inlet roller pair is conventionally referred to as spin-off speed. Only for sampling for the determination of the birefringence of the spun yarn was fed to a Aufspulaggregat already after this inlet roller pair.
  • the thread was passed through 4 heated godet duo rolls after the pair of infeed rolls and finally wound up.
  • the stretching took place between the 1st and 3rd duo, the heat setting on the 3rd duo and the relaxation on the 3rd duo and the winder (the relaxation ratio being the ratio of the winding speed to the speed of the fixing duo).
  • the 4 heated duos had the following temperatures: Duo 1 95 ° C Duo 2 120 ° C Duo 3 240 ° C Duo 4 150 ° C
  • the pretension ratio between duo 1 and inlet roller pair was in all cases 1.02.
  • the partial relaxation ratio between Duo 4 and Duo 3 was 0.995 in all cases.
  • Execution and polyethylene terephthalate correspond to the Comparative examples.
  • an additive by means of a metering device Type KCLKQX2 from K-Tron Soda, DE, into the filler piece of the extruder dosed.
  • the additive used was a copolymer of 90% by weight.
  • Methyl methacrylate and 10 wt .-% of styrene which selected a Glass transition point of 118.7 ° C and a melt viscosity ratio, based on PET, of 2.8.
  • the specified in the table Dosing was according to a gravimetric working Dosing flow control set.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

High strength polyester fibers comprising from 0.1 to 2.0 by weight of an incompatible, thermoplastic amorphous, polymeric additive.

Description

Die Erfindung betrifft hochfeste Polyesterfäden mit einer Reißfestigkeit von > 70 cN/tex und ein Verfahren zur Herstellung dieser Fäden.The invention relates to high-strength polyester yarns with a Tear strength of> 70 cN / tex and a method for producing these Threads.

Hochfeste Fäden aus Polyethylenterephthalat und Verfahren zu deren Herstellung sind seit langem bekannt (F. Fourné, Synthetische Fasern, Hanser Verlag München [1995] 584-586; US-Patente Nr. 3 758 658, 4 374 797 und 4 461 740).High strength polyethylene terephthalate filaments and processes for their use Production has long been known (F. Fourné, Synthetic fibers, Hanser Verlag Munich [1995] 584-586; U.S. Patent Nos. 3,758,658, 4,374,797 and 4,461,740).

Bei diesen hochfesten Fäden werden besondere Eigenschaften, vor allem eine hohe Reißfestigkeit, eine niedrige Reißdehnung und eine geringe Anzahl von Fadenfehlern gefordert. Diese Forderungen sind technologisch an die Anwendung hoher Verstreckverhältnisse von mindestens 1 : 5 bei der Rohgarnherstellung geknüpft. Höhere Verstreckverhältnisse haben jedoch ihre Grenze, wenn der Faden durch das Verstrecken bereits beschädigt wird und Fadenbrüche auftreten. Je höher die Produktionsgeschwindigkeit, desto niedriger liegt diese Grenze. Der technische und wirtschaftliche Wert des Spinnstreckprozesses bei Anwendung hoher Produktionsgeschwindigkeiten ist aber erst dann positiv zu bewerten, wenn gleichzeitig die texilen Fadenqualitäten nicht verschlechtert, sondern sogar noch verbessert werden. So ist die Spinnabzugsgeschwindigkeit bei kommerziellen Verfahren auf maximal 700 m/min, allgemein 500 bis 600 m/min begrenzt. Die Aufwickelgeschwindigkeit liegt dabei, dem Verstreckverhältnis entsprechend, bei über 2500 m/min bis unter 3800 m/min.These high-strength threads are special properties, especially a high tear strength, a low elongation at break and a low one Number of thread errors required. These demands are technological to the application of high draw ratios of at least 1: 5 at the Rohgarnherstellung knotted. Have higher stretch ratios however, its limit when the thread is already stretched is damaged and thread breaks occur. The higher the Production speed, the lower this limit. Of the technical and economic value of the spin-draw process However, using high production speeds is only then positive to evaluate, if at the same time the texile thread qualities not worsened, but even improved. That's how it is Spin-off speed in commercial processes to a maximum 700 m / min, generally limited to 500 to 600 m / min. The Winding speed is the draw ratio accordingly, at over 2500 m / min to below 3800 m / min.

Des weiteren ist aus WO 99-07927A1 bekannt, daß die Reißdehnung von bei Abzugsgeschwindigkeiten von mindestens 2500 m/min, bevorzugt 3000 bis 6000 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. Der Prozeß ist aber auf bei Abzugsgeschwindigkeiten von unter 2500 m/min hergestellte Spinnfäden nicht übertragbar, da diese im Gegensatz zu POY-Fasern wenig kristallin (< 12 %) sind, eine geringe Orientierung (Doppelbrechung < 25 - 10-3) und eine hohe Reißdehnung (> 225 %) aufweisen. Angaben zur Herstellung hochfester Garne im integrierten Spinnstreckprozeß sind nicht enthalten.Furthermore, WO 99-07927A1 discloses that the elongation at break of preoriented polyester filaments (POY) spun at take-off speeds of at least 2500 m / min, preferably 3000 to 6000 m / min, by adding amorphous, thermoplastically processable copolymers based on styrene, Acrylic acid and / or maleic acid or derivatives thereof with respect to the elongation at break of spun under the same conditions polyester filaments can be increased without addition. The process is, however, not transferable to take-up speeds of less than 2500 m / min, since these fibers are less crystalline (<12%) than POY fibers, have a low orientation (birefringence <25 - 10 -3 ) and a high Elongation at break (> 225%). Information on the production of high-strength yarns in the integrated spin-draw process is 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 das Zusammenwirken dreier Eigenschaften sein - die chemische Additivstruktur, die ein Verdehnen der Additivmoleküle kaum zuläßt, die geringe Mobilität und die Kompabilität von Polyester und Additiv.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 is the combination of three properties - the chemical additive structure, which hardly allows any stretching of the additive molecules, the low mobility and the compatibility of polyester and additive.

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 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 does not follow easily; in the In general, the achieved strengths are low, which is a considerable disadvantage for this product is.

Dem Fachmann ist auch bekannt, daß bei gleichen Spinn- und Streckbedingungen durch Veränderung des Relaxanteils die Reißfestigkeit dramatisch beeinflußt werden kann. Mit dem Relaxverhältnis wird in der Praxis der Thermoschrumpf solcher hochfester Fäden je nach industriellem Einsatzgebiet eingestellt. Dabei wird mit steigendem Relaxverhältnis der Thermoschrumpf reduziert, aber auch die Reißfestigkeit und der LASE 5, wogegen die Reißdehnung ansteigt.The expert is also known that in the same spinning and Stretching conditions by changing the relax ratio the tear strength can be influenced dramatically. With the relaxation ratio is in the Practice of thermal shrinkage of such high-strength threads depending on set in industrial application. It is with increasing Relaxation ratio of the thermal shrinkage reduced, but also the Tear resistance and the LASE 5, whereas the elongation at break increases.

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, hochfeste Polyesterfäden mit einer Reißfestigkeit > 70 cN/tex zur Verfügung zu stellen sowie ein Verfahren zu deren Herstellung zu schaffen, bei dem Spinnabzugsgeschwindigkeiten und Aufspulgeschwindigkeiten angewandt werden können, die deutlich über denen des Standes der Technik liegen. Insbesondere sollen bei einem Relaxverhältnis RR ≥ 0,97 Reißfestigkeiten > 80 cN/tex, bei einem Relaxverhältnis 0,95 < RR < 0,97 Reißfestigkeiten > 77 cN/tex und bei einem Relaxverhältnis RR < 0,95 Reißfestigkeiten > 70 cN/tex erreicht werden. The present invention is based on the object, high-strength Polyester threads with a tear strength> 70 cN / tex are available too and to provide a method of making the same, in which Spinning withdrawal speeds and Aufspulgeschwindigkeiten applied can be significantly higher than those of the prior art. In particular, with a relax ratio RR ≥ 0.97 tear strengths > 80 cN / tex, with a relaxation ratio of 0.95 <RR <0.97 Tear strengths> 77 cN / tex and with a relaxation ratio RR <0.95 Tear strengths> 70 cN / tex can be achieved.

Die Lösung dieser Aufgabe erfolgt erfindungsgemäß durch hochfeste Polyesterfäden sowie durch ein Verfahren zu dessen Herstellung gemäß den Angaben der Patentansprüche.The solution of this object is achieved by high-strength Polyester threads and by a process for its preparation according to the details of the claims.

Unter Polyester sind hierbei Poly(C2-4-alkylen)-terephthalate, welche bis zu 15 Mol-% anderer 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 Polyesteroder dem Polyester-Additiv-Gemisch in Mengen von 0 bis 5,0 Gew.-% ohne Nachteil zugesetzt werden.Polyesters here are poly (C 2-4 -alkylene) terephthalates which contain 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 may be added to the polyester or polyester-additive mixture in amounts of 0 to 5.0% by weight without any disadvantage.

Erfindungsgemäß wird dem Polyester ein Copolymer in einer Menge von 0,1 bis 2,0 Gew.-% zugesetzt, wobei das Copolymer amorph und in der Polyester-Matrix weitgehend unlöslich sein muß. Im wesentlichen sind die beiden Polymere miteinander nicht kompatibel und bilden 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.According to the invention, the polyester is a copolymer in an amount of 0.1 added to 2.0 wt .-%, wherein the copolymer is amorphous and in the Polyester matrix must be largely insoluble. They are essentially the two polymers incompatible with each other and form two Phases that can be distinguished microscopically. Furthermore must the copolymer has a glass transition temperature (determined by DSC with 10 ° C / min heating rate) from 90 to 170 ° C and thermoplastic be processable.

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 Copolymeren 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 hochfesten Garnen 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 Copolymeren 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. is the melt viscosity of the copolymer at least equal to or preferably higher than that of the polyester. First by choosing a specific viscosity ratio of additive and polyester, the optimum efficiency is achieved. In such a way 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 high strength yarns 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 copolymers 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 eine 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 one 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 erfindungsgemäß dem Polyester zuzusetzenden Additivpolymere können, sofern sie vorstehend genannte Eigenschaften besitzen, eine unterschiedliche chemische Zusammensetzung aufweisen. Bevorzugt werden drei verschiedene Copolymertypen, nämlich

  • 1. Ein Copolymer, welches folgende Monomereinheiten enthält:
    A =
    Acrylsäure, Methacrylsäure oder CH2 = CR - C00R', 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 Copolymer aus 60 bis 98 Gew.-% A und 2 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 Copolymer, welches folgende Monomereinheiten enthält:
    C =
    Styrol oder C1-3-alkylsubstituierte Styrole,
    D =
    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,
    wobei das Copolymer aus 15 bis 95 Gew.-% C und 5 bis 85 Gew.-% D, vorzugsweise aus 50 bis 90 Gew.-% C und 10 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 Copolymer, 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 00080001
    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 Copolymer 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 according to the invention may, if they possess the abovementioned properties, have a different chemical composition. Three different types of copolymers are preferred, namely
  • 1. A copolymer containing the following monomer units:
    A =
    Acrylic acid, methacrylic acid or CH 2 = CR - C00R ', where R is H or CH 3 and R' is C 1-15 alkyl or C 5-12 cycloalkyl or C 6-14 aryl is
    B =
    Styrene or C 1-3 alkyl-substituted styrenes,
    wherein the copolymer of 60 to 98 wt .-% A and 2 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. A copolymer containing 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 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,
    wherein the copolymer of 15 to 95 wt .-% C and 5 to 85 wt .-% D, preferably from 50 to 90 wt .-% C and 10 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. A copolymer containing the following monomer units:
    E =
    Acrylic acid, methacrylic acid or CH 2 = CR - COOR ', where R is H or CH 3 and R' is C 1-15 alkyl or C 5-12 cycloalkyl or C 6-14 aryl is
    F =
    Styrene or C 1-3 alkyl-substituted styrenes,
    G =
    one or more monomers of the formula I, II or III
    Figure 00080001
    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 diening, wherein the copolymer 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% by weight of G and 0 to 20% by weight of H, the sum of E, F, G and H together giving 100%.

    • Es handelt sich bei der Komponente H um eine optionale Komponente. Obwohl die erfindungsgemäß zu erzielenden Vorteile bereits durch Copolymere, 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 Copolymeren 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 Copolymers 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 Copolymer 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 Copolymers hat. Die Komponente H kann u. a. deswegen eingesetzt werden, um die Eigenschaften des Copolymeren auf erwünschte Weise zu modifizieren, beispielsweise durch Steigerungen oder Verbesserungen der Fließeigenschaften, wenn das Copolymer auf die Schmelztemperatur erhitzt wird, oder zur Reduzierung einer Restfarbe im Copolymer oder durch Verwendung eines polyfunktionellen Monomeren, um auf diese Art und Weise ein gewisses Maß an Vernetzung in das Copolymer 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 having used copolymer. The component H can u. a. therefore be used to the properties of the copolymer to desired Way to modify, for example, by increases or Improvements in flow properties when the copolymer is applied to the Melting temperature is heated, or to reduce a residual color in Copolymer or by using a polyfunctional monomer to in this way a certain degree of crosslinking in the copolymer 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 geeignete 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 Copolymeren 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 suitable monomers for this purpose include 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 copolymer 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 Copolymere 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 copolymers 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 Copolymere 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 copolymers 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 Copolymertypen 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 Copolymers. Erhalten werden diese Additivpolymere beispielsweise durch vollständige oder bevorzugt partielle Umsetzung des entsprechenden Copolymers 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 Copolymere als auch, soweit gegeben, deren nicht imidisierte Ausgangscopolymere sind im Handel erhältlich oder nach einem für den Fachmann geläufigen Verfahren herstellbar.The imidized copolymer types 2 and 3 can be made from both the monomers be prepared using a monomeric imide as well by subsequent complete or preferably partial imidization a copolymer containing the corresponding maleic acid derivative. These additive polymers are obtained for example by complete or preferably partial reaction of the corresponding copolymer 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 Copolymers and, as far as given, their non-imidized Starting copolymers are commercially available or according to one of the Produce expert familiar process.

    Die dem Polyester zuzusetzende Menge des Copolymers beträgt 0,1 bis 2,0 Gew.-%, wobei meist Zugabemengen von weniger als 1,5 % genügen. Bevorzugt wird die Konzentration des polymeren Additivs im Bereich 0,1 bis 2,0 Gew.-% in Abhängigkeit von der gewünschten Spinnabzugsgeschwindigkeit (> 700 - 1500 m/min) so gewählt, daß die Doppelbrechung des Spinnfaden < 3,5 · 10-3 ist. Solche Doppelbrechungen im Spinnfaden erlauben Verstreckverhältnisse von 1 : 5 und sichern die gewünschten hohen Fadenfestigkeiten unabhängig von der Spinnabzugsgeschwindigkeit von bis zu 1500 m/min bei Aufspulgeschwindigkeiten auch deutlich über 3800 m/min.The amount of the copolymer to be added to the polyester is from 0.1 to 2.0% by weight, usually with addition amounts of less than 1.5%. The concentration of the polymeric additive in the range from 0.1 to 2.0% by weight, depending on the desired spin-off speed (> 700-1500 m / min), is preferably chosen such that the birefringence of the spun yarn is <3.5 × 10 . 3 is. Such birefringence in the spun yarn allow draw ratios of 1: 5 and ensure the desired high thread strengths regardless of the spinning take-off speed of up to 1500 m / min at Aufspulgeschwindigkeiten also well above 3800 m / min.

    Die Bestimmung der Konzentration des Additivs erfolgt in diesem Fall experimentell in Vorversuchen unter Betriebsbedingungen, wie folgt:The determination of the concentration of the additive takes place in this case experimentally in preliminary tests under operating conditions, as follows:

    Dem Fachmann ist für ein bestimmtes Polymer ohne erfindungsgemäßes Additiv, unter den konkreten Spinn- und Streckbedingungen bei einer Spinnabzugsgeschwindigkeit vo das zur Erreichung hoher Reißfestigkeiten notwendige Streckverhältnis bekannt. Er kennt auch die Doppelbrechung des Spinnfadens bei diesem Prozeß bzw. kann diese ermitteln. Möchte er nun den Prozeß entsprechend der Erfindung bei höheren Geschwindigkeiten fahren, so muß er lediglich die Konzentration an Additiv mit der der Spinnfaden die gleiche Doppelbrechung aufweist, wie der Spinnfaden bei vo ohne Additiv ermitteln. Dazu wird die Doppelbrechung bei der höheren Spinngeschwindigkeit für etwa 4 verschiedene Additivkonzentrationen im Bereich 0,1 % bis 1,5 % ermittelt und aus der grafischen Darstellung dieses Zusammenhanges die notwendige Konzentration durch Interpolation bestimmt.The person skilled in the art is aware of the draw ratio necessary for achieving high tear strengths for a particular polymer without an additive according to the invention, under the specific spinning and stretching conditions at a spinning take-off speed v o . He also knows the birefringence of the filament in this process or can determine this. If he now wants to drive the process according to the invention at higher speeds, he must only the concentration of additive with the spun yarn has the same birefringence, as the spun yarn determine at v o without additive. For this purpose, the birefringence at the higher spinning speed for about 4 different additive concentrations in the range 0.1% to 1.5% is determined and determined from the graphical representation of this relationship, the necessary concentration by interpolation.

    Die Vermischung des Additivpolymers (Copolymer) 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 (copolymer) with the matrix polymer takes place by adding as a solid to the matrix polymer chips in Extruder inlet with chip mixer or gravimetric dosing or alternatively by melting the additive polymer, dosage by means of Gear pump and feed into the melt stream of the matrix polymer. Also so-called masterbatch techniques are possible, with the additive as a concentrate in polyester chips, later in solid or molten state are added to the matrix polyester is present. Also, the addition of a partial stream of the matrix polymer, which then the Mainstream of the matrix polymer is mixed, 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 (sec-1) und der 0,8ten Potenz der Verweilzeit (in sec) mindestens 250, vorzugsweise 350 bis 1250 betragen. Werte über 2500 werden im allgemeinen 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. The product of shear rate (sec.sup.- 1 ) and the power of 0.8 of the residence time (in seconds) should be at least 250, preferably 350 to 1250. Values over 2500 are generally avoided to keep the pressure drop in the piping limited.

    Hierbei ist die Scherrate definiert durch die Scherrate im Leerrohr (sec-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 (sec) gemäß t = V2 · ε · δ · 60F 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 (sec -1 ) times the mixer factor, wherein the mixer factor is 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 (sec) 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 °C. Für PET werden vorzugsweise Temperaturen von 265 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 ° C. For being PET preferably temperatures of 265 to 315 ° C set.

    Die Herstellung der hochfesten Fäden aus den erfindungsgemäßen Polymermischungen durch Spinnen mit Abzugsgeschwindigkeiten von > 700 m/min, vorzugsweise 750 bis 1000 m/min, Verstrecken mit einem Verstreckverhältnis von mindestens 1 : 5, Themofixieren und Aufwickeln mit einer entsprechenden Geschwindigkeit von > 3800 m/min, geschieht unter Verwendung an sich bekannter Spinneinrichtungen. Hierbei wird das Filterpaket nach dem bekannten Stand der Technik mit Filtereinrichtungen und/oder losen Filtermedien bestückt.The preparation of high-strength threads of the invention Polymer blends by spinning at withdrawal speeds of> 700 m / min, preferably 750 to 1000 m / min, drawing with a Draft ratio of at least 1: 5, theme fixing and winding with a corresponding speed of> 3800 m / min, happens using per se known spinning devices. Here is the Filter package according to the prior art with Filtering devices and / or loose filter media equipped.

    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.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.

    Typisch für hochfeste 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.Typical of high-strength 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.

    Die Schmelze unterliegt in derartigen Systemen einer hohen thermischen Belastung bei Verweilzeiten bis 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 ≤ 2,0 % und in vielen Fällen ≤ 1,5 % trotz hoher thermischer Belastung ausreicht.The melt is subject to a high thermal in such systems Load at residence times up to 35 min. The effectiveness of Polymer additive according to the invention leads due to the high thermal stability of the additive to no appreciable Limitations of its effect, so that a small addition amount of Additives ≤ 2.0% and in many cases ≤ 1.5% despite high thermal Load is sufficient.

    Erfindungsgemäß wird eine Verbesserung der Verstreckbarkeit, gekennzeichnet durch ein gleich hohes Verstreckverhältnis bei höherer Spinnabzugsgeschwindigkeit erzielt. Im besonderen kann durch geeignete Wahl der Additivkonzentration C die Spinnabzugsgeschwindigkeit an der Spinndüse um mindestens 200 m/min höher eingestellt werden als beim Verspinnen von Polyester ohne Additivzusatz.According to the invention, an improvement of the stretchability, characterized by an equally high draw ratio at higher Spinning take-off speed achieved. In particular, by suitable Choice of additive concentration C, the spinning deduction speed at the Spinneret set at least 200 m / min higher than the Spinning polyester without additive additive.

    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 nach der Verstreckung wurde mit ca. 40 nm und das Längen-/Durchmesserverhältnis der Fibrillen zu > 50 abgeschätzt. 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 mean diameter of the fibrils after stretching was with about 40 nm and the length / diameter ratio of the fibrils to> 50 estimated. Are these fibrils not formed or are the Additive particle after exiting the spinneret in diameter too large or is the size distribution too uneven, resulting in insufficient Viscosity ratio is the case, so does the effect effect lost.

    Ferner ist für die Wirksamkeit der Additive gemäß dieser Erfindung eine Glasumwandlungstemperatur von 90 bis 170 °C, sowie vorzugsweise eine Fließaktivierungsenergie der Copolymere 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.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 copolymers of at least 80 kJ / mol, ie 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.

    Die erfindungsgemäßen hochfesten Fäden besitzen zumindest die gleichen Qualitätswerte, wie herkömmliche Fäden ohne polymeres Additiv.The high-strength filaments according to the invention have at least the same properties Quality values, like conventional threads 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 (I.V.) 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 (I.V.) was measured on a solution of 0.5 g 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 der Fasern (Δη) wurde mittels Polarisationsmikroskop mit Kippkompensator und Grünfilter (540 nm) unter Verwendung von Keilschnitten bestimmt. Gemessen wurde der Gangunterschied zwischen ordentlichem und außerordentlichem Strahl beim 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 fibers (Δη) was determined by means of Polarizing microscope with tilt compensator and green filter (540 nm) determined using wedges. Was measured the Gap difference between tidy and extraordinary beam when 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.

    Vergleichsbeispiele 1 und 2:Comparative Examples 1 and 2:

    Polyethylenterephthalat-Chips mit einer Intrinsic-Viskosität von 0,98 dl/g und einem Feuchtegehalt von 20 ppm wurden in einem 7E-Extruder der Fa. Barmag, DE, bei einer Temperatur von 295 °C aufgeschmolzen und mit einem Druck von 160 bar durch eine Produktleitung mit installierten statischen Mischern gedrückt und einer 2 x 15 cm3-Spinnpumpe zugeführt. Die Polymerschmelze wurde dabei einer Scherrate von 29 sec-1 unterworfen. Das Produkt aus Scherrate und der 0,8ten Potenz der Verweilzeit in Sekunden betrug 532. Die Spinnpumpe förderte die auf 298 °C temperierte Schmelze in 2 Spinnpacks mit rechteckiger Düsenplatte (200 Loch, 0,4 mm Düsenloch-Durchmesser). Der Schmelzedurchsatz pro Spinnpaket betrug bei allen Einstellungen 385 g/min. Das entspricht einem Titer von 1100 dtex bei 3500 m/min Aufspulgeschwindigkeit. Der Düsendruck betrug 330 bar. Der ersponnene multifile Faden durchlief im Anschluß an die Spinndüse einen 330 mm langen Nacherhitzer (330 °C), wurde danach in einem Queranblaßsystem abgekühlt, mittels Breitschlitzöler mit Spinnpräparation beaufschlagt und einem unbeheizten Einlaufrollenpaar zugeführt. Die Geschwindigkeit dieses Einlaufrollenpaars wird vereinbarungsgemäß als Spinnabzugsgeschwindigkeit bezeichnet. Nur zur Probenahme für die Bestimmung der Doppelbrechung wurde der Spinnfaden bereits nach diesem Einlaufrollenpaar einem Aufspulaggregat zugeführt. Zur Herstellung des hochfesten Fadens wurde der Faden nach dem Einlaufrollenpaar über 4 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 (wobei das Relaxverhältnis das Verhältnis der Aufspulgeschwindigkeit zur Geschwindigkeit des Fixierduos darstellt).Polyethylene terephthalate chips with an intrinsic viscosity of 0.98 dl / g and a moisture content of 20 ppm were melted in a 7E extruder from. Barmag, DE, at a temperature of 295 ° C and with a pressure of 160 bar through Pressed a product line with installed static mixers and fed to a 2 x 15 cm 3 spin pump. The polymer melt was subjected to a shear rate of 29 sec -1 . The product of shear rate and the 0.8th power of the residence time in seconds was 532. The spin pump conveyed the tempered to 298 ° C melt in two spin packs with rectangular nozzle plate (200 holes, 0.4 mm nozzle hole diameter). The melt throughput per spin pack was 385 g / min at all settings. This corresponds to a titer of 1100 dtex at 3500 m / min winding speed. The nozzle pressure was 330 bar. The spun multifilament yarn passed through a 330 mm long reheater (330 ° C.) following the spinneret, was then cooled in a cross-impingement system, subjected to spin finish by means of a slot lubricator and fed to an unheated pair of inlet rollers. The speed of this inlet roller pair is conventionally referred to as spin-off speed. Only for sampling for the determination of the birefringence of the spun yarn was fed to a Aufspulaggregat already after this inlet roller pair. To make the high-strength thread, the thread was passed through 4 heated godet duo rolls after the pair of infeed rolls and finally wound up. The stretching took place between the 1st and 3rd duo, the heat setting on the 3rd duo and the relaxation on the 3rd duo and the winder (the relaxation ratio being the ratio of the winding speed to the speed of the fixing duo).

    Die 4 beheizten Duos hatten folgende Temperaturen: Duo 1 95 °C Duo 2 120 °C Duo 3 240 °C Duo 4 150 °C The 4 heated duos had the following temperatures: Duo 1 95 ° C Duo 2 120 ° C Duo 3 240 ° C Duo 4 150 ° C

    Das Vorspannungsverhältnis zwischen Duo 1 und Einlaufrollenpaar betrug in allen Fällen 1,02. Das Teilrelaxverhältnis zwischen Duo 4 und Duo 3 war in allen Fällen 0,995.The pretension ratio between duo 1 and inlet roller pair was in all cases 1.02. The partial relaxation ratio between Duo 4 and Duo 3 was 0.995 in all cases.

    Die weiteren Versuchsparameter und die Ergebnisse sind in der Tabelle zusammengestellt.The other experimental parameters and the results are in the table compiled.

    Beispiele 3 bis 7:Examples 3 to 7:

    Ausführung und Polyethylenterephthalat (PET) entsprechen den Vergleichsbeispielen. Jedoch wurde zur Herstellung der polymeren Mischung gemäß der Erfindung ein Additiv mittels eines Dosiergerätes Typ KCLKQX2 der Firma K-Tron Soda, DE, in das Füllstück des Extruders dosiert. Als Additiv wurde ein Copolymer aus 90 Gew.-% Methylmethacrylat und 10 Gew.-% Styrol gewählt, welches einen Glasumwandlungspunkt von 118,7 °C und ein Schmelzviskositätsverhältnis, bezogen auf PET, von 2,8 aufwies. Die in der Tabelle angegebene Dosiermenge wurde entsprechend einer gravimetrisch arbeitenden Dosiermengenregelung eingestellt.Execution and polyethylene terephthalate (PET) correspond to the Comparative examples. However, for the preparation of the polymeric Mixture according to the invention, an additive by means of a metering device Type KCLKQX2 from K-Tron Soda, DE, into the filler piece of the extruder dosed. The additive used was a copolymer of 90% by weight. Methyl methacrylate and 10 wt .-% of styrene, which selected a Glass transition point of 118.7 ° C and a melt viscosity ratio, based on PET, of 2.8. The specified in the table Dosing was according to a gravimetric working Dosing flow control set.

    Die weiteren Versuchsparameter und die Ergebnisse sind in der Tabelle zusammengestellt. In allen Fällen lag der mittlere Durchmesser der Fibrillen in den Fäden unter 80 nm. Beispiele Nr. 1 2 3 4 5 6 Vergl. Vergl. Erfdg. Erfdg. Erfdg. Erfdg. Spinnabzugsgeschindigkeit m/min 550 750 700 800 920 980 Additivkonzentration Gew.-% 0 0 0,6 0,95 1,5 1,8 Doppelbrechung x 10-3 1,9 3,9 1,8 1,9 2,2 2,8 1. Verstreckung 1 : 4 3,5 4 4 4 4 Gesamtverstreckung 1 : 5,8 5,35 5,82 5,78 5,7 5,5 Gesamtrelaxverhältnis 1 : 0,975 0,976 0,978 0,979 0,98 0,98 Aufspulgeschwindigkeit m/min 3170 3980 4060 4600 5240 5380 Garnviskosität (I.V.) dl/g 0,88 0,88 0,88 0,88 0,88 0,88 Reißfestigkeit cN/tex 85,7 78,2 84,3 82,9 81,3 80,4 Reißdehnung % 13,2 13,6 13,5 13,9 13,2 14 Lase 5 cN/tex 39,1 38,6 38,5 38,1 39,1 36,3 Schrumpf (160 °C) % 5,9 5,8 5,8 5,6 5,6 5,5 The other test parameters and the results are summarized in the table. In all cases, the mean diameter of the fibrils in the filaments was below 80 nm. Examples no. 1 2 3 4 5 6 Comp. Comp. Erfdg. Erfdg. Erfdg. Erfdg. Spinnabzugsgeschindigkeit m / min 550 750 700 800 920 980 additive concentration Wt .-% 0 0 0.6 0.95 1.5 1.8 birefringence x 10 -3 1.9 3.9 1.8 1.9 2.2 2.8 1. stretching 1 : 4 3.5 4 4 4 4 total stretch 1 : 5.8 5.35 5.82 5.78 5.7 5.5 Total relaxation ratio 1 : 0,975 0,976 0.978 0.979 0.98 0.98 winding speed m / min 3170 3980 4060 4600 5240 5380 Yarn viscosity (IV) dl / g 0.88 0.88 0.88 0.88 0.88 0.88 tear strength CN / tex 85.7 78.2 84.3 82.9 81.3 80.4 elongation at break % 13.2 13.6 13.5 13.9 13.2 14 Lase 5 CN / tex 39.1 38.6 38.5 38.1 39.1 36.3 Shrinkage (160 ° C) % 5.9 5.8 5.8 5.6 5.6 5.5

    Claims (14)

    1. High-strength polyester filaments having a tear strength of > 70 cN/tex, characterised in that they consist of
      α) a polyester containing at least 85 mole % of poly(C2-4-alkylene) terephthalate,
      β) from 0.1 to 2.0% by weight of an incompatible, thermoplastic, amorphous, polymeric additive having a glass transition temperature in the range from 90 to 170°C, and
      γ) from 0 to 5.0% by weight of conventional additives,
      where the sum 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 component α) is from 1:1 to 7:1, and the polymeric additive β) is present in the yam in the form of fibrils having a mean diameter of ≤ 80 nm which are distributed in the polyester component α).
    2. High-strength polyester filaments according to Claim 1, characterised in that the ratio of the melt viscosities is from 1.5:1 to 5:1.
    3. High-strength polyester filaments according to Claim 1 or 2, characterised in that the polymeric additive β) is a copolymer which comprises the following monomer units:
      A =
      acrylic acid, methacrylic acid or CH2=CR-COOR', where R is an H atom or a CH3 group, and R' is a C1-15-alkyl radical or a C5-12-cycloalkyl radical or a C6-14-aryl radical,
      B =
      styrene or C1-3-alkyl-substituted styrenes,
      the copolymer consisting of from 60 to 98% by weight of A and from 2 to 40% by weight of B (sum = 100% by weight).
    4. High-strength polyester filaments according to Claim 3, characterised in that the copolymer consists of from 83 to 98% by weight of A and from 2 to 17% by weight of B (sum = 100% by weight).
    5. High-strength polyester filaments according to Claim 3 or 4, characterised in that the copolymer consists of from 90 to 98% by weight of A and from 2 to 10% by weight of B (sum = 100% by weight).
    6. High-strength polyester filaments according to Claim 1 or 2, characterised in that the polymeric additive β) is a copolymer 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 00280001
      where 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 where the copolymer consists of from 15 to 95% by weight of C and from 5 to 85% by weight of D, the sum of C and D together giving 100%.
    7. High-strength polyester filaments according to Claim 6, characterised in that the copolymer consists of from 50 to 90% by weight of C and from 10 to 50% by weight of D, the sum of C and D together giving 100%.
    8. High-strength polyester filaments according to Claim 6 or 7, characterised in that the copolymer consists of from 70 to 85% by weight of C and from 30 to 15% by weight of D, the sum of C and D together giving 100%.
    9. High-strength polyester filaments according to Claim 1 or 2, characterised in that the polymeric additive β) is a copolymer which comprises the following monomer units:
      E =
      acrylic acid, methacrylic acid or CH2=CR-COOR', where R is an H atom or a CH3 group, and R' is a C1-15-alkyl radical or a 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 00290001
      where 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 which can be copolymerised with E and/or with F and/or G, from the group consisting of α-methylstyrene, vinyl acetate, acrylates and methacrylates which are different from E, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, vinyl ethers, isopropenyl ethers and dienes,
      where the copolymer consists of from 30 to 99% by weight of E, from 0 to 50% by weight of F, from > 0 to 50% by weight of G and from 0 to 50% by weight of H, the sum of E, F, G and H together giving 100%.
    10. High-strength polyester filaments according to Claim 9, characterised in that the copolymer consists of from 45 to 97% by weight of E, from 0 to 30% by weight of F, from 3 to 40% by weight of G and from 0 to 30% by weight of H, the sum of E, F, G and H together giving 100%.
    11. High-strength polyester filaments according to Claim 9 or 10, characterised in that the copolymer consists of from 60 to 94% by weight of E, from 0 to 20% by weight of F, from 6 to 30% by weight of G and from 0 to 20% by weight of H, the sum of E, F, G and H together giving 100%.
    12. Process for the production of the high-strength polyester filaments according to one of Claims 1 to 11, characterised in that
      a) a polyester α) which contains at least 85 Mole % of poly-(C2-4-alkylene) terephthalate and
      from 0.1 to 2.0% by weight of an incompatible, thermoplastic, amorphous, polymeric additive β) having a glass transition temperature in the range from 90 to 170°C, the ratio of the melt viscosity of the polymeric additive β) to the melt viscosity of the polyester component α) being from 1:1 to 7:1,
      where these may contain from 0 to 5.0% by weight of conventional additives γ),
      are mixed in the molten state at 220 - 320°C in a static mixer with shearing, where the shear rate is from 16 to 128 sec-1, and the product of the shear rate and the residence time in the mixer in seconds to the power 0.8 is set to a value of at least 250;
      b) the melt mixture from step a) is spun to give spun filaments at 220 - 320°C, the spinning take-off speed being from > 700 to 1500 m/min; and
      c) the spun filaments from step b) are stretched, heat-set and wound up, the stretching ratio being at least 1:5.
    13. Process for the production of high-strength polyester filaments according to Claim 12, characterised in that the spinning take-off speed is from 750 to 1000 m/min.
    14. Process for the production of high-strength polyester filaments according to one of Claims 12 and 13, characterised in that the concentration C of the polymeric additive is selected in the range from 0.1 to 2.0% by weight in such a way that the birefringence of the spun filaments is < 3.5x10-3.
    EP00958291A 1999-08-10 2000-07-25 High-strength polyester threads and method for producing the same Expired - Lifetime EP1208255B1 (en)

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    DE19937729A DE19937729A1 (en) 1999-08-10 1999-08-10 High tenacity polyester threads and process for their manufacture
    DE19937729 1999-08-10
    PCT/EP2000/007086 WO2001011123A1 (en) 1999-08-10 2000-07-25 High-strength polyester threads and method for producing the same

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    DE10319761A1 (en) * 2003-04-30 2004-11-18 Röhm GmbH & Co. KG Stretching agent for the production of synthetic filaments of melt-spinnable fiber-forming matrix polymers
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    CN100383341C (en) * 2005-07-12 2008-04-23 上海市第二市政工程有限公司 Large scale concrete box girder hoisting method
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    JP5924623B2 (en) * 2011-03-25 2016-05-25 国立大学法人 東京大学 Biodegradable polyester fiber excellent in thermal stability and strength and method for producing the same
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    CN102797063A (en) * 2012-07-04 2012-11-28 江南大学 Preparation method of low-melting-point high-strength dacron composite monofilament
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    JP2003506588A (en) 2003-02-18
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    KR20020036840A (en) 2002-05-16
    EP1208255A1 (en) 2002-05-29
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