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EP1208255B1 - Fils en polyester a resistance elevee et procede de fabrication desdites fibres - Google Patents

Fils en polyester a resistance elevee et procede de fabrication desdites fibres 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
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Prior art keywords
weight
strength polyester
copolymer
sum
filaments according
Prior art date
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EP00958291A
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German (de)
English (en)
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EP1208255A1 (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
    • 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)
  • Processing Of Meat And Fish (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Claims (14)

  1. Fils en polyester de grande résistance ayant une résistance à la rupture supérieure à 70 cN/tex, caractérisés en ce qu'ils sont constitués,
    α) d'un polyester qui contient au moins 85 % en mole de poly(téréphtalate d'alcoylène) ayant de 2 à 4 atomes de carbone dans la partie alcoylène,
    β) de 0,1 à 2,0 % en poids d'un additif polymère, amorphe, incompatible, pouvant être transformé thermoplastiquement et qui a un point de transition à l'état vitreux de l'ordre de 90 à 170°C, et
    γ) de 0 à 5,0 % en poids d'additifs habituels,
    la somme de α), β) et γ) étant égale à 100 %, le rapport de la viscosité à l'état fondu de l'additif β) polymère à la viscosité à l'état fondu du constituant α) de polyester étant compris en 1:1 et 7:1, et l'additif β) polymère se présentant dans le fil sous la forme de fibrilles réparties dans le constituant α) de polyester et d'un diamètre moyen inférieur ou égal à 80 nm.
  2. Fils en polyester de grande résistance suivant la revendication 1, caractérisés en ce que le rapport des viscosités à l'état fondu est compris entre 1,5:1 et 5:1.
  3. Fils en polyester de grande résistance suivant les revendications 1 ou 2, caractérisés en ce que l'additif β) polymère est un copolymère qui contient des motifs monomères suivants :
    A = acide acrylique, acide méthacrylique ou CH2 = CR-COOR1, dans laquelle R est un atome de H ou un groupe CH3 et R1 est un radical alcoyle ayant de 1 à 15 atomes de carbone ou un radical cycloalcoyle ayant de 5 à 12 atomes de carbone ou un radical aryle ayant de 6 à 14 atomes de carbone,
    B = styrène ou styrène substitué par un alcoyle ayant de 1 à 3 atomes de carbone,
       le copolymère étant constitué de 60 à 98 % en poids de A et de 2 à 40 % en poids de B (la somme étant égale à 100 % en poids).
  4. Fils en polyester de grande résistance suivant la revendication 3, caractérisés en ce que le copolymère est constitué de 83 à 98 % en poids de A et de 2 à 17 % en poids de B (la somme étant égale à 100 % en poids).
  5. Fils en polyester de grande résistance suivant la revendication 3 ou 4, caractérisés en ce que le copolymère est constitué de 90 à 98 % en poids de A et de 2 à 10 % en poids de B (la somme étant égale à 100 % en poids).
  6. Fils en polyester de grande résistance suivant les revendications 1 ou 2, caractérisés en ce que l'additif β) polymère est un copolymère qui contient les motifs monomères suivants :
    C = styrène ou styrène substitué par un alcoyle ayant de 1 à 3 atomes de carbone,
    D = un ou plusieurs monomères de formule I, II ou III,
    Figure 00330001
    dans lesquelles R1, R2 et R3 sont respectivement un atome de H ou un radical alcoyle ayant de 1 à 15 atomes de carbone ou un radical cycloalcoyle ayant de 5 à 12 atomes de carbone ou un radical aryle ayant de 6 à 14 atomes de carbone et le copolymère est constitué de 15 à 95 % en poids de C et 5 à 85 % en poids de D, la somme de C et de D représentant ensemble 100 %.
  7. Fils en polyester de grande résistance suivant la revendication 6, caractérisés en ce que le copolymère est constitué de 50 à 90 % en poids de C et de 10 à 50 % en poids de D, la somme de C et de D représentant ensemble 100 %.
  8. Fils en polyester de grande résistance suivant les revendications 6 ou 7, caractérisés en ce que le copolymère est constitué de 70 à 85 % en poids de C et de 30 à 15 % en poids de D, la somme de C et de D représentant ensemble 100 %.
  9. Fils en polyester de grande résistance suivant les revendications 1 ou 2, caractérisés en ce que l'additif β) polymère est un copolymère qui contient les motifs monomères suivants :
    E = acide acrylique, acide méthacrylique ou CH2 = CR-COOR1, dans laquelle R est un atome de H ou un groupe CH3 et R1 est un radical alcoyle ayant de 1 à 15 atomes de carbone ou un radical cycloalcoyle ayant de 5 à 12 atomes de carbone ou un radical aryle ayant de 6 à 14 atomes de carbone,
    F = styrène ou styrène substitué par un alcoyle ayant de 1 à 3 atomes de carbone,
    G = un ou plusieurs monomères de formule I, II, III
    Figure 00340001
    dans lesquelles R1, R2 et R3 sont respectivement un atome de H ou un radical alcoyle ayant de 1 à 15 atomes de carbone ou un radical cycloalcoyle ayant de 5 à 12 atomes de carbone ou un radical aryle ayant de 6 à 14 atomes de carbone,
    H = un ou plusieurs monomères à insaturation éthylénique pouvant être copolymérisé avec E et/ou avec F et/ou avec G choisis dans le groupe constitué de l'α-méthylstyrène, de l'acétate de vinyle, des esters de l'acide acrylique, des esters de l'acide méthacrylique qui sont différents de E, du chlorure de vinyle, du chlorure de vinylidène, des styrènes à substitution halogène, des étheroxydes de vinyle, des étheroxydes d'isopropényle et des diènes,
       le copolymère étant constitué de 30 à 99 % en poids de E, de 0 à 50 % en poids de F, de plus de 0 à 50 % en poids de G et de 0 à 50 % en poids de H, la somme de E, F, G et H représentant ensemble 100 %.
  10. Fils en polyester de grande résistance suivant la revendication 9, caractérisés en ce que le copolymère est constitué de 45 à 97 % en poids de E, de 0 à 30 % en poids de F, de 3 à 40 % en poids de G et de 0 à 30 % en poids de H, la somme de E, F, G et H représentant ensemble 100 %.
  11. Fils en polyester de grande résistance suivant la revendication 9 ou 10, caractérisés en ce que le copolymère est constitué de 60 à 94 % en poids de E, de 0 à 20 % en poids de F, de 6 à 30 % en poids de G et de 0 à 20 % en poids de H, la somme de E, F, G et H représentant ensemble 100 %.
  12. Procédé de fabrication de fils en polyester de grande résistance suivant l'une des revendications 1 à 11, caractérisé en ce que
    a) on mélange à l'état fondu dans un mélangeur statique sous agitation entre 220 et 320°C un polyester α) qui contient au moins 85 % en mole de poly(téréphtalate d'alcoylène) ayant de 2 à 4 atomes de carbone dans la partie alcoylène, et
       de 0,1 à 2,0 % en poids d'un additif β) polymère amorphe incompatible, pouvant être transformé thermoplastiquement, et qui a une température de transition à l'état vitreux de l'ordre de 90 à 170°C, le rapport de la viscosité à l'état fondu de l'additif β) polymère à la viscosité à l'état fondu du constituant α) en polyester étant compris entre 1:1 et 7:1,
       ceux-ci pouvant contenir de 0 à 5,0 % en poids d'additifs γ) habituels,
       le taux de cisaillement étant compris entre 16 et 128 sec-1 et le produit du taux de cisaillement et de la 0,8ème puissance de la durée de séjour en secondes dans le mélangeur étant réglé à une valeur d'au moins 250 ;
    b) on file le mélange fondu du stade a) entre 220 et 320°C en des fils de filature, la vitesse de sortie de filature étant supérieure à 700 à 1500 m/min, et
    c) on étire, fixe thermiquement et enroule les fils filés du stade b), le rapport d'étirage étant d'au moins 1:5.
  13. Procédé de fabrication de fils en polyester de grande résistance suivant la revendication 12, caractérisé en ce que la vitesse de sortie de filature est comprise entre 750 à 1000 m/min.
  14. Procédé de fabrication de fils en polyester de grande résistance suivant l'une des revendications 12 à 13, caractérisé en ce que la concentration C de l'additif polymère est choisie de l'ordre de 0,1 à 2,0 % en poids, de sorte que la biréfringence des fils de filature soit inférieure à 3,5 x 10-3.
EP00958291A 1999-08-10 2000-07-25 Fils en polyester a resistance elevee et procede de fabrication desdites fibres Expired - Lifetime EP1208255B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19937729A DE19937729A1 (de) 1999-08-10 1999-08-10 Hochfeste Polyesterfäden und Verfahren zu deren Herstellung
DE19937729 1999-08-10
PCT/EP2000/007086 WO2001011123A1 (fr) 1999-08-10 2000-07-25 Fils en polyester a resistance elevee et procede de fabrication desdites fibres

Publications (2)

Publication Number Publication Date
EP1208255A1 EP1208255A1 (fr) 2002-05-29
EP1208255B1 true EP1208255B1 (fr) 2003-09-03

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EP00958291A Expired - Lifetime EP1208255B1 (fr) 1999-08-10 2000-07-25 Fils en polyester a resistance elevee et procede de fabrication desdites fibres

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EP (1) EP1208255B1 (fr)
JP (1) JP2003506588A (fr)
KR (1) KR20020036840A (fr)
CN (1) CN1166825C (fr)
AT (1) ATE248939T1 (fr)
AU (1) AU6986200A (fr)
DE (2) DE19937729A1 (fr)
EA (1) EA004441B1 (fr)
WO (1) WO2001011123A1 (fr)

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DE19937728A1 (de) * 1999-08-10 2001-02-15 Lurgi Zimmer Ag HMLS-Fäden aus Polyester und Spinnstreckverfahren zu deren Herstellung
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
DE10319761A1 (de) * 2003-04-30 2004-11-18 Röhm GmbH & Co. KG Dehnungserhöhungsmittel für die Herstellung von synthetischen Fäden aus schmelzspinnbaren faserbildenden Matrix-Polymeren
US20050147784A1 (en) * 2004-01-06 2005-07-07 Chang Jing C. Process for preparing poly(trimethylene terephthalate) fiber
CN100383341C (zh) * 2005-07-12 2008-04-23 上海市第二市政工程有限公司 一种大型混凝土箱梁的起吊方法
DE102009052935A1 (de) * 2009-11-12 2011-05-19 Teijin Monofilament Germany Gmbh Spinngefärbte HMLS-Monofilamente, deren Herstellung und Anwendung
CN102534849A (zh) 2010-12-22 2012-07-04 杜邦公司 由聚对苯二甲酸丙二醇酯组合物制备的单丝刷丝以及包含该单丝刷丝的刷子
WO2012133231A1 (fr) * 2011-03-25 2012-10-04 国立大学法人 東京大学 Fibre polyester biodégradable ayant d'excellentes stabilité thermique et résistance, et procédé pour la production de ladite fibre
CH705306B1 (de) * 2011-07-25 2015-06-30 Trützschler Switzerland AG Verfahren und Vorrichtung zur Herstellung eines HMLS-Garnes aus einer Polyesterschmelze.
CH705305B1 (de) * 2011-07-25 2015-06-30 Trützschler Switzerland AG Vorrichtung und Verfahren zur Herstellung eines endlosen Fadens aus einer synthetischen Polymerschmelze.
EP2660372A1 (fr) 2012-05-04 2013-11-06 LANXESS Deutschland GmbH Fibres thermoplastiques avec une tension de surface réduite
CN102797063A (zh) * 2012-07-04 2012-11-28 江南大学 一种低熔点高强度涤纶复合单丝的制备方法
US10094355B2 (en) * 2012-10-03 2018-10-09 Kyowa Engineering Consultants Co., Ltd. Water turbine generator
US10119214B2 (en) * 2013-07-17 2018-11-06 Sabic Global Technologies B.V. Force spun sub-micron fiber and applications
CN105452547B (zh) 2013-08-15 2018-03-20 沙特基础全球技术有限公司 剪切纺丝亚微米纤维
CN107663665B (zh) * 2017-10-19 2019-06-25 浙江恒逸高新材料有限公司 一种高强低收缩特亮绣花线聚酯牵伸丝的制备方法
US20220275536A1 (en) * 2019-12-02 2022-09-01 Kao Corporation Melt spinning resin composition, manufacturing method for same, and fiber manufacturing method

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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
DE4208916A1 (de) 1992-03-20 1993-09-23 Akzo Nv Polyesterfaser und verfahren zu deren herstellung
ATE219171T1 (de) * 1997-08-05 2002-06-15 Roehm Gmbh Verfahren zur verarbeitung von polymermischungen zu filamenten
EP1062928A1 (fr) * 1999-06-25 2000-12-27 The Procter & Gamble Company Procédé de fabrication des articles absorbants jetable, et appareil pour réaliser ledit procédé

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JP2003506588A (ja) 2003-02-18
EA004441B1 (ru) 2004-04-29
WO2001011123A1 (fr) 2001-02-15
CN1370247A (zh) 2002-09-18
AU6986200A (en) 2001-03-05
DE19937729A1 (de) 2001-02-15
CN1166825C (zh) 2004-09-15
EP1208255A1 (fr) 2002-05-29
US6656583B1 (en) 2003-12-02
DE50003569D1 (de) 2003-10-09
EA200200173A1 (ru) 2002-10-31
ATE248939T1 (de) 2003-09-15
KR20020036840A (ko) 2002-05-16

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