EP1208253B1 - Fils a haut module et faible retrait en polyester et procede d'etirage de filaments pour leur production - Google Patents

Fils a haut module et faible retrait en polyester et procede d'etirage de filaments pour leur production Download PDF

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Publication number
EP1208253B1
EP1208253B1 EP00951438A EP00951438A EP1208253B1 EP 1208253 B1 EP1208253 B1 EP 1208253B1 EP 00951438 A EP00951438 A EP 00951438A EP 00951438 A EP00951438 A EP 00951438A EP 1208253 B1 EP1208253 B1 EP 1208253B1
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Prior art keywords
weight
hmls
polyester
additive
polymer
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German (de)
English (en)
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EP1208253A1 (fr
Inventor
Joachim Cziollek
Werner Mrose
Dietmar Wandel
Helmut Schwind
Wolfgang Janas
Werner Ude
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Roehm GmbH Darmstadt
LL Plant Engineering AG
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ZiAG Plant Engineering GmbH
Roehm GmbH Darmstadt
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

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

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

Claims (14)

  1. Fils à haut module et faible retrait (HMLS) en polyester présentant une résistance au déchirement > 70 cN/tex, une charge à l'élongation spécifique de 5% (LASE 5) > 35 cN/tex et un retrait à l'air chaud à 160°C de 1,5 à 3,5%, caractérisés en ce qu'ils sont constitués par
    α) un polyester qui contient au moins 85% en mole de poly(téréphtalate d'alkylène en C2 à C4)
    β) 0,1 à 2,5% en poids d'un additif incompatible, transformable par voie thermoplastique, amorphe, polymère, qui présente une température de transition vitreuse dans la plage de 90 à 170°C et
    γ) 0 à 5,0% en poids d'additifs usuels
    où la somme de α), β) et γ) est égale à 100%, le rapport de la viscosité de la masse fondue de l'additif polymère β) à la viscosité de la masse fondue du polyester α) est de 1:1 à 7:1 et l'additif polymère β) se trouve dans les fils HMLS sous forme de fibrilles réparties dans le polyester α) avec un diamètre moyen ≤ 80 nm.
  2. Fils HMLS selon la revendication 1, caractérisés en ce que le rapport des viscosités de masse fondue est de 1,5:1 à 5:1.
  3. Fils HMLS selon la revendication 1 ou 2,
    caractérisés en ce que l'additif polymère β) est un polymère contenant les unités monomères suivantes :
    A = acide acrylique, acide méthacrylique ou CH2=CR-COOR', où R est un atome d'hydrogène ou un groupe CH3 et R' représente un radical alkyle en C1 à C15 ou un radical cycloalkyle en C5 à C12 ou un radical alkyle en C6 à C14,
    B = styrène ou styrènes substitués par alkyle en C1 à C3,
    le polymère étant constitué par 60 à 100% en poids de A et 0 à 40% en poids de B (somme = 100% en poids).
  4. Fils HMLS selon la revendication 3, caractérisés en ce que le polymère est constitué par 83 à 98% en poids de A et 2 à 17% en poids de B (somme = 100% en poids).
  5. Fils HMLS selon la revendication 3 ou 4, caractérisés en ce que le polymère est constitué par 90 à 98% en poids de A et 2 à 10% en poids de B (somme = 100% en poids).
  6. Fils HMLS selon la revendication 1 ou 2,
    caractérisés en ce que l'additif polymère β) est un polymère qui contient les unités monomères suivantes :
    C = styrène ou styrènes substitués par alkyle en C1 à C3,
    D = un ou plusieurs monomères de formule I, II ou III
    Figure 00390001
    où R1, R2 et R3 représentent à chaque fois un atome d'hydrogène ou un radical alkyle en C1 à C15 ou un radical cycloalkyle en C5 à C12 ou un radical aryle en C6 à C14 et où le polymère est constitué par 15 à 100% en poids de C et 0 à 85% en poids de D, la somme de C et D étant égale à 100%.
  7. Fils HMLS selon la revendication 6, caractérisés en ce que le polymère est constitué par 50 à 95% en poids de C et 5 à 50% en poids de D, la somme de C et D étant égale à 100%.
  8. Fils HMLS selon la revendication 6 ou 7, caractérisés en ce que le polymère est constitué par 70 à 85% en poids de C et 30 à 15% en poids de D, la somme de C et D étant égale à 100%.
  9. Fils HMLS selon la revendication 1 ou 2, caractérisés en ce que l'additif polymère β) est un polymère qui contient les unités monomères suivantes :
    E = acide acrylique, acide méthacrylique ou CH2=CR-COOR', où R est un atome d'hydrogène ou un groupe CH3 et R' est un radical alkyle en C1 à C15 ou un radical cycloalkyle en C5 à C12 ou un radical aryle en C6 à C14,
    F = styrène ou styrènes substitués par alkyle en C1 à C3,
    G = un ou plusieurs monomères de formule I, II ou III
    Figure 00400001
    où R1, R2 et R3 représentent à chaque fois un atome d'hydrogène ou un radical alkyle en C1 à C15 ou un radical cycloalkyle en C5 à C12 ou un radical aryle en C6 à C14,
    H = un ou plusieurs monomères éthyléniquement insaturés copolymérisables avec E et/ou avec F et/ou G du groupe constitué par l'α-méthylstyrène, l'acétate de vinyle, les esters de l'acide acrylique, les esters de l'acide méthacrylique qui sont différents de E, le chlorure de vinyle, le chlorure de vinylidène, les styrènes substitués par halogène, les vinyléthers, les isopropényléthers et les diènes,
    le polymère étant constitué par 30 à 99% en poids de E, 0 à 50% en poids de F, > 0 à 50% en poids de G et 0 à 50% en poids de H, la somme de E, F, G et H étant égale à 100%.
  10. Fils HMLS selon la revendication 9, caractérisés en ce que le polymère est constitué par 45 à 97% en poids de E, 0 à 30% en poids de F, 3 à 40% en poids de G et 0 à 30% en poids de H, la somme de E, F, G et H étant égale à 100%.
  11. Fils HMLS selon la revendication 9 ou 10, caractérisés en ce que le polymère est constitué par 60 à 94% en poids de E, 0 à 20% en poids de F, 6 à 30% en poids de G et 0 à 20% en poids de H, la somme de E, F, G et H étant égale à 100%.
  12. Procédé de filage-étirage pour la fabrication des fils HMLS selon l'une quelconque des revendications 1 à 11, caractérisé en ce que
    a) un polyester α) qui contient au moins 85% en mole de poly(téréphtalate d'alkylène en C2 à C4) et un additif β) incompatible, transformable par voie thermoplastique, amorphe, polymère, qui présente une température de transition vitreuse dans la plage de 90 à 170°C, le rapport de la viscosité de la masse fondue de l'additif polymère β) à la viscosité de la masse fondue du composant polyester α) étant de 1:1 à 7:1,
    ceux-ci pouvant contenir 0 à 5,0% en poids d'additifs usuels γ),
    sont mélangés avec cisaillement à l'état fondu dans un mélangeur statique, la vitesse de cisaillement étant de 16 à 128 sec-1 et le produit de la vitesse de cisaillement et de 0,8 fois le potentiel de temps de séjour en secondes dans le mélangeur étant réglé à une valeur d'au moins 250,
    b) le mélange des masses fondues de l'étape a) est filé en fils, la vitesse de défilage étant de 2500 à 4000 m/min et
    c) on prépare, étire, thermofixe et bobine les fils filés de l'étape b),
    la concentration c en additif polymère β en % en poids dans le polyester, comme fonction de la vitesse de défilage prédéfinie ν en m/min et de la double réfraction Δn souhaitée des fils filés, étant déterminée selon les formules suivantes x. f1 ≤ c ≤ x . f2 où f1 = 100 · (Δno - Δn)Δno (7,2589 · 10-6 · v2 - 7,7932 · 10-2 · v + 236,0755) f2 = 100 · (Δno - Δn)Δno (5,9391 · 10-6 · v2 - 6,3763 · 10-2 · v + 193,1527)
    où Δn < Δn0
    Δn = double réfraction du fil filé selon l'invention en polyester avec addition d'additif,
    Δn0 = double réfraction de fils filés, fabriqués dans les mêmes conditions de filage que selon l'invention, en polyester sans addition d'additif
    x = 1 pour les polymères additifs du type 1 ou 3
    x = 2,8 pour les polymères additifs du type 2 (sans composé acryle).
  13. Procédé de filage-étirage selon la revendication 12, caractérisé en ce que dans l'étape c), le rapport d'étirage DR comme fonction de la vitesse de filage ν en m/min et de la concentration c en additif en % en poids est déterminé selon les formules suivantes : f3 ≤ DR ≤ f4 f3 = -5 · 10-4 . ν - 1,6 . 10-4 . ν . c/x + 0,98 . c/x + 3,55 f4 = -5 . 10-4 . ν - 2,4 . 10-4 . ν . c/x + 1,46 . c/x + 3,55
  14. Procédé de filage-étirage selon la revendication 13, caractérisé en ce que dans l'étape c), la vitesse de bobinage est égale au produit de la vitesse de filage ν, du rapport d'étirage DR et du rapport de relaxation.
EP00951438A 1999-08-10 2000-07-25 Fils a haut module et faible retrait en polyester et procede d'etirage de filaments pour leur production Expired - Lifetime EP1208253B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19937728 1999-08-10
DE19937728A DE19937728A1 (de) 1999-08-10 1999-08-10 HMLS-Fäden aus Polyester und Spinnstreckverfahren zu deren Herstellung
PCT/EP2000/007085 WO2001011122A1 (fr) 1999-08-10 2000-07-25 Fils a haut module et faible retrait en polyester et procede d'etirage de filaments pour leur production

Publications (2)

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EP1208253A1 EP1208253A1 (fr) 2002-05-29
EP1208253B1 true EP1208253B1 (fr) 2004-09-08

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US (1) US6740404B1 (fr)
EP (1) EP1208253B1 (fr)
JP (1) JP2003506587A (fr)
KR (1) KR20020036843A (fr)
CN (1) CN1168856C (fr)
AT (1) ATE275650T1 (fr)
AU (1) AU6437200A (fr)
DE (2) DE19937728A1 (fr)
EA (1) EA004429B1 (fr)
WO (1) WO2001011122A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10022889B4 (de) * 2000-05-25 2007-12-20 Lurgi Zimmer Gmbh Verfahren zum Herstellen von synthetischen Fäden aus einer Polymermischung auf Polyesterbasis
US6667003B2 (en) * 2000-05-25 2003-12-23 Zimmer A.G. Method for the manufacture of synthetic fibers from a melt mixture based on fiber forming polymers
US6777496B2 (en) 2000-11-28 2004-08-17 Honeywell International Inc. Polymeric additives and polymeric articles comprising said additive
KR100695613B1 (ko) * 2005-10-27 2007-03-14 현대산업개발 주식회사 층간의 소음방지를 위한 건축물의 바닥구조
CN101089266B (zh) * 2007-07-04 2010-12-15 双双集团有限公司 一种抗热缩涤纶高强丝的制造方法
DE102009052935A1 (de) 2009-11-12 2011-05-19 Teijin Monofilament Germany Gmbh Spinngefärbte HMLS-Monofilamente, deren Herstellung und Anwendung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN167096B (fr) 1985-04-04 1990-09-01 Akzo Nv
BR8907519A (pt) * 1988-07-05 1991-06-18 Allied Signal Inc Processo para a producao de um fio de tereftalato de polietileno estirado,fio e produtos resultantes
US5234764A (en) 1988-07-05 1993-08-10 Allied-Signal Inc. Dimensionally stable polyester yarn for high tenacity treaty cords
US5067538A (en) * 1988-10-28 1991-11-26 Allied-Signal Inc. Dimensionally stable polyester yarn for highly dimensionally stable treated cords and composite materials such as tires made therefrom
DE4208916A1 (de) 1992-03-20 1993-09-23 Akzo Nv Polyesterfaser und verfahren zu deren herstellung
EP1002146B1 (fr) 1997-08-05 2002-06-12 Röhm GmbH &amp; Co. KG Procede de traitement de melanges polymeres pour former des filaments
DE19937729A1 (de) * 1999-08-10 2001-02-15 Lurgi Zimmer Ag Hochfeste Polyesterfäden und Verfahren zu deren Herstellung

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WO2001011122A1 (fr) 2001-02-15
CN1168856C (zh) 2004-09-29
DE50007704D1 (de) 2004-10-14
EP1208253A1 (fr) 2002-05-29
DE19937728A1 (de) 2001-02-15
CN1370248A (zh) 2002-09-18
US6740404B1 (en) 2004-05-25
KR20020036843A (ko) 2002-05-16
ATE275650T1 (de) 2004-09-15
AU6437200A (en) 2001-03-05
EA200200196A1 (ru) 2002-10-31
JP2003506587A (ja) 2003-02-18
EA004429B1 (ru) 2004-04-29

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