EP0987353B1 - Fibres et filaments en polyester et procédé pour les produire - Google Patents

Fibres et filaments en polyester et procédé pour les produire Download PDF

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Publication number
EP0987353B1
EP0987353B1 EP99117671A EP99117671A EP0987353B1 EP 0987353 B1 EP0987353 B1 EP 0987353B1 EP 99117671 A EP99117671 A EP 99117671A EP 99117671 A EP99117671 A EP 99117671A EP 0987353 B1 EP0987353 B1 EP 0987353B1
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EP
European Patent Office
Prior art keywords
polymethyl methacrylate
melt
thread
filaments
fibres
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP99117671A
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German (de)
English (en)
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EP0987353A1 (fr
Inventor
Raimund Schwarz
Werner Stibal
Gustav Schütze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Priority claimed from DE19935145A external-priority patent/DE19935145C2/de
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP0987353A1 publication Critical patent/EP0987353A1/fr
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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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • Y10T428/2933—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 present invention relates to polyester fibers and filaments, which in have small additional additives and a process for their preparation.
  • fibers or filaments containing small amounts of additives depending on the composition of the mixture can be processed via melt spinning and partially at the same take-off speed, an increase in the elongation at break in can produce undrawn yarn.
  • EP 0 047 464 B1 discloses that polymethyl methacrylate (hereinafter abbreviated to Called PMMA) in principle to increase the elongation at break at higher spinning speeds can be used.
  • EP 0 631 638 B1 like EP 0 047 464 B1, describes that polymethyl methacrylate has a having limited spinnability.
  • EP 0 631 638 B1 describes a fiber polymer, which at 0.1 to 5 wt .-%, based on the fiber polymer, of a 50 to 90% imidized Polymethacryl73realkylesters, essentially in the form of inclusions contains.
  • a major disadvantage of imidized Polymethacrylklarealkylester additives but is the relatively high price of the additive.
  • the cost of the imidated polymethacrylic acid alkyl ester show that the economy of a process, which is the said Additive needed, not given.
  • the additive described is not in available on a large scale, and it is also a dependency on a few manufacturers given.
  • Another disadvantage, as described above, is that the spinning security is limited. It increasingly comes with the use of this material as an additive Thread breaks.
  • the object of the present invention is therefore polymer blends for the production of polyester fibers and filaments which are readily spinnable and not contain more than 4 wt .-% additive, wherein the manufacturing process by the low Addition, a wide availability of the additive and a strong increase in Elongation at break should have a high economy.
  • polyester i. in particular Polyethylene terephthalate (PET) and small amounts of polymethyl methacrylate (PMMA) produced fibers or filaments very high elongation at break, before especially at high spinning speeds, can produce and at the same time show excellent spinning behavior.
  • PET Polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • Blends of polyester, i. especially PET and Polymethylmethacrylate and the elongation-enhancing effect of the polymethylmethacrylate Although known, but also known is the tendency to break yarn in spinning the Mixture, which is all the more evident when very high polymethyl methacrylate molecular weights be used.
  • EP 0 047 464 B1 describes, as already mentioned above, that the increase in the Although polymethyl methacrylate molecular weight, a gain of the strain-increasing Effect, but also that spinning problems occur simultaneously, i. the reinforced one elongation-enhancing effect at very high molecular weights of the polymethylmethacrylate can due to the associated tendency to increased thread breaks not come into play at all.
  • the economy of an industrial process on the basis of the product described in EP 0 047 464 B1 is thus limited.
  • the lateral diameter of the novel rod-shaped Structures are very small.
  • the rod-like deposits shown in the example have For example, a lateral diameter of about 300 to 400 nm, measured in the extruded from the spinneret, still unoriented melt filaments, the so-called Gewölle.
  • the diameter is smaller than 800 nm. Preferred is a size of less than 600 nm, more preferably less than 400 nm.
  • the PMMA-containing polymer mixture used according to the invention can also be used at high temperatures Spinning speeds easily by means of a conventional cross-flow blowing be spun.
  • cooling devices such as e.g. devices for passive cooling by air suction of the high-speed threads or blowing devices, which are arranged in the center of the thread bundle.
  • the present invention is suitable both for the production of partially oriented yarns (POY) (as illustrated in the example) and for the production of fibers (ie staple fibers), at which much slower spun (stripped), then much more stretched thereafter (as is known to one skilled in the art from Ullmann's Encyclopedia of Industrial Chemistry, 5 th Ed., Vol. A10, Fibers, 3rd General Production Technology, pages 550-561).
  • POY partially oriented yarns
  • fibers ie staple fibers
  • the economic gain in the present invention manifests itself in the case of fiber production, especially in a significantly increased draw ratio on the fiber, in addition to the correspondingly higher throughput in melt spinning.
  • Fibers with the present invention is preferably a Withdrawal speed selected in the range of 800 to 2,400 m / min, during manufacture of partially oriented filament yarns (POY), a take-off speed of 3,000 to 8,000 m / min.
  • a Withdrawal speed selected in the range of 800 to 2,400 m / min, during manufacture of partially oriented filament yarns (POY), a take-off speed of 3,000 to 8,000 m / min.
  • polymethyl methacrylate is in comparison to that in EP 0 631 638 B1 described additive component (polymethylmethacrylimide) significantly cheaper and readily available.
  • polymethyl methacrylate molecular weights (Weight average) between 20,000 and 200,000 g / mol suitable.
  • suitable are molecular weights between 50,000 and 160,000 g / mol.
  • All Particularly suitable are molecular weights between 80,000 and 140,000 g / mol.
  • the molecular weight data for the PMMA refer to the following method of measurement (internal analysis specification No. LC 012 of EMS-CHEMIE AG):
  • the molecular weight distribution and the weight-average molecular weight (M w ) of PMMA are determined by gel permeation chromatography (GPC), ie with a GPC instrument with the basic apparatus components pump, chromatography column and detector known for liquid chromatography.
  • GPC gel permeation chromatography
  • a device from WATERS, type GPC 150A with IR detector is used.
  • As a column four individual columns of dimension 250 mm x 7 mm (diameter) are connected in series to form a total column length of 1 m.
  • the columns are filled with MERCK LiChrogel® 10 ⁇ m, in the combination PS4000, PS400, PS20 and PS4 (characteristic for the pore size) for the four individual sections, so that each molecular weight fraction of the PMMA is optimally separated.
  • Chloroform containing 0.1% 1,2-dichlorobenzene as a flowmarker, serves as the stock solution for the PMMA samples.
  • the eluent used is chloroform at a flow rate of 1 ml / min.
  • 50 mg PMMA are weighed into a sealable 20 ml glass, filled up to the mark with stock solution and shaken until complete dissolution.
  • the standards are used to calibrate the molecular weight measurement.
  • the injection volume of the sample solutions is 200 ⁇ l each. All temperature settings are at 30 ° C.
  • the evaluation of the measurements (chromatograms) is carried out with the aid of the GPC software MILLENIUM (by WATERS) according to the method of the Narrow Standard.
  • the amount of PMMA mixed is in the range of 0.1 to 4 wt .-%, based on the Polyester as a thread-forming polymer.
  • the range is from 0.2 to 3% by weight;
  • Particularly preferred is a PMMA amount in the range of 0.3 to 2 wt .-%.
  • the admixture of polymethyl methacrylate as an additive to PET can, for example, about the so-called "Melt Conditioning" method for the continuous modification of Polymer melts are carried out (DE 40 39 857 C2).
  • Melt There will be a part of Melt that come directly from a polycondensation or from a reflow can, diverted from the main melt stream.
  • This partial flow is in one Side stream extruder fed and there with the additive, which in granules, powder or is preferably bead form, applied and then dispersed.
  • the dispersed and mixed melt concentrate is then returned to the main melt line and diluted there to the final concentration.
  • melt conditioning it is also possible to use a melt extruder to produce a pure additive melt and into the main melt stream to inject.
  • An appropriate arrangement of mixing elements ensures thereafter for homogenization and dispersion of the additive in the filament-forming matrix polymer (Polyethylene terephthalate).
  • the PMMA as an additive (in granules, powder or Pearl form) directly to the PET granules in the Spinnextruder metered, there the To disperse additive in polyethylene terephthalate and then the melt mixture to spin.
  • the starting form of the PMMA is preferred as beads because this is a fine distribution in the PET melt favors and also the PMMA commercial products in general anyway available in this form.
  • These beads can be considered small beads imagine with a diameter of about 0.3 mm; They are occasionally also called semolina designated.
  • the additive can be added both as a pure substance and in masterbatch form. In addition, other additives or additives can be incorporated and spun become.
  • the polyethylene terephthalate itself can also already the usual additives such as Matting agents (titanium dioxide), stabilizers, catalysts, etc. included.
  • PET polyethylene terephthalate
  • Polyyester means the polyester containing at least 80% polyethylene terephthalate units and contain a maximum of 20% units, derived from a diol other than ethylene glycol as e.g. Diethylene glycol, tetramethylene glycol or a dicarboxylic acid other than terephthalic acid, for example, isophthalic acid, hexahydroterephthalic acid, dibenzoic acid.
  • Polyethylene terephthalate may optionally be mixed with small molar amounts of Branching agent having from 3 to 4 functional alcohol or acid groups, trimethylpropane, Trimethyloletane, pentaerythritol, glycerol, trimesic acid, trimellitic acid or pyromellitic acid, modify.
  • Branching agent having from 3 to 4 functional alcohol or acid groups, trimethylpropane, Trimethyloletane, pentaerythritol, glycerol, trimesic acid, trimellitic acid or pyromellitic acid, modify.
  • the starting polyester may also contain known additives to enhance the ability of the To modify coloration, e.g. Sodium 3,5-dicarboxybenzenesulfonate.
  • the ready to use dispersed Melt mixture obtained by any of the described admixture variants can be prepared, not initially spun into threads, but granulated.
  • This High-performance granules can later on conventional spinning machines with Aufschmelzextruder further processed, i. spun into fibers or filaments.
  • the processor for example, a customer of the granule manufacturer, has all the advantages of According to the invention modified polyester, without his conventional Retrofit spinning machine with expensive dosing and mixing equipment and a separate Must buy additive. The whole handling is thus in this way for a processor as easy as with normal PET granules.
  • Figures 1, 2 and 3 show SEM cross-sectional photographs of an inventive Melt filament in the matrix polymer (PET), which under the nozzle plate in the unoriented Condition was taken.
  • PTA matrix polymer
  • Figures 1, 2 and 3 show SEM cross-sectional photographs of an inventive Melt filament in the matrix polymer (PET), which under the nozzle plate in the unoriented Condition was taken.
  • Fig. 3 ("sticks", laterally cut) the axial storage of PMMA additive visible (extension in thread axis).
  • Table 1 shows results from spinning experiments at a winding speed (Vwick) of 4.950 m / min.
  • the spinning temperature was 285 ° C, with the range of 280 ° C to 295 ° C being preferred.
  • a passive cooling was used, as described for example in DE 197 16 394 C1. After passing through the cooling section, the yarn was passed over a cold godet duo and then wound up.
  • the godet speed amounted to 3,225 m / min.
  • the "melt conditioning" process (DE 40 39 857 C2) was used, which is usually used for melt modification in continuous polyester-polycondensation plants with directly connected spinning.
  • a common, for textile applications common, frosted polyethylene terephthalate from EMS-CHEMIE AG with the type designation Grilene® M764 was used.
  • the additive used was a polymethyl methacrylate from DEGUSSA with the type designation DEGALAN® G8E having a molecular weight of 126,580 g / mol (weight average). The concentration was 0.65 to 0.90 weight percent.
  • the mean lateral diameters of the polymethyl methacrylate inclusions (see Figures 1, 2, 3) were less than 400 nm. The spinning behavior was very good. Only full bobbins were produced.
  • Table 2 shows textile data of the textured yarn.
  • the quality data obtained with the modified polyester correspond to that of good, conventionally produced Texturgam.
  • the gain lies in the enormous productivity increase in spinning, considering that normal POY yarn is spun only at about 3,200 m / min. 6-thread position of a production plant Add.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Claims (18)

  1. Fibres et filaments constitués principalement de polytéréphtalate d'éthylène comme polymère qui forme les fils,
    caractérisés en ce qu'
    ils contiennent de 0,1 à 4 % en poids rapporté au polymère qui forme les fils, de polyméthacrylate de méthyle ayant un poids moléculaire moyen en poids, compris entre 20.000 et 200.000 g/mol comme autre polymère, principalement sous la forme d'insertions en forme de bâtonnets, mesuré dans les fils de fusion extrudés de la buse de filage non encore orientés, dans lesquels la taille de particules latérale des insertions en forme de bâtonnets de l'autre polymère est plus petite que 800 nm et dans lesquels la vitesse d'écoulement des fils de filage lors de la production s'élève jusqu'à 8000 m/min. Avec la précision que le polyméthacrylate de méthyle est exclus avec une température de stabilité de forme dans la plage de 105 à 130°C.
  2. Fibres ou filaments conformément à la revendication 1,
    caractérisés en ce que
    les insertions de polyméthacrylate de méthyle en forme de bâtonnets, possèdent un diamètre latéral moyen inférieur à 600 nm.
  3. Fibres ou filaments conformément à la revendication 1,
    caractérisés en ce que
    les insertions de polyméthacrylate de méthyle en forme de bâtonnets, possèdent un diamètre latéral moyen inférieur à 400 nm.
  4. Fibres ou filaments conformément à l'une quelconque des revendications 1 à 3,
    caractérisés en ce que
    le polyméthacrylate de méthyle possède un poids moléculaire moyen en poids, compris entre 50.000 et 160.000 g/mol.
  5. Fibres ou filaments conformément à l'une quelconque des revendications 1 à 4,
    caractérisés en ce que
    le polyméthacrylate de méthyle possède un poids moléculaire moyen en poids compris entre 80.000 et 140.000 g/mol.
  6. Fibres ou filaments conformément à l'une quelconque des revendications 1 à 5,
    caractérisés en ce qu'
    ils renferment de 0,2 à 3 % en poids de polyméthacrylate de méthyle.
  7. Fibres ou filaments conformément à l'une quelconque des revendications 1 à 6,
    caractérisés en ce qu'
    ils renferment de 0,3 à 2 % en poids de polyméthacrylate de méthyle.
  8. Procédé de production de fibres et de filaments consistant essentiellement en du polytéréphalate d'éthylène, filés par fusion, par polycondensation ou mise en fusion du polymère qui forme les fibres et filage par fusion, consécutif,
    caractérisé en ce qu'
    on mélange au polymère qui forme les fibres de 0,1 à 4 % en poids, rapporté au polymère qui forme les fibres, d'un polymère à base essentiellement de polyméthacrylate de méthyle ayant un poids moléculaire moyen en poids compris entre 20.000 et 200.000 g/mol avant le filage par fusion et on l'y met en dispersion et en ce qu'on règle lors du filage par fusion une vitesse d'écoulement des fils de jusqu'à 8.000 m/min, grâce à quoi, par la mise en dispersion dans les fibres de fusion extrudés de la buse de filage encore non orientées, on obtient des insertions en forme de bâtonnets de PMMA ayant une taille latérale de particules inférieure à 800 nm, avec la précision que le polyméthacrylate de méthyle est éliminé avec une température de stabilité de forme dans la plage de 105 à 130°C.
  9. Procédé selon la revendication 8,
    caractérisé en ce qu'
    on mélange au polymère qui forme les fils de 0,2 à 3 % en poids rapporté au polymère qui forme les fils, de polyméthacrylate de méthyle.
  10. Procédé selon l'une quelconque des revendications 8 ou 9,
    caractérisé en ce qu'
    on mélange au polymère qui forme les fils, de 0,3 à 2 % en poids, rapporté au polymère qui forme les fils de polyméthacrylate de méthyle.
  11. Procédé selon l'une quelconque des revendications 8 à 10,
    caractérisé en ce qu'
    on branche en vue de la modification continue du produit de fusion de polytéréphtalate d'éthylène, une partie du produit de fusion provenant du courant de fusion principal, on injecte ce courant partiel dans une extrudeuse à courant latéral, on y met en contact avec le polyméthacrylate de méthyle et on y met en dispersion celui-ci, on ramène le concentré de produit de fusion mis en dispersion et mélangé provenant du courant latéral dans la conduite de fusion principale, où on le dilue à la concentration finale et ensuite on file le mélange de fusion.
  12. Procédé selon l'une quelconque des revendications 8 à 10,
    caractérisé en ce qu'
    on obtient à l'aide d'une extrudeuse de mise en fusion, un produit de fusion de PMMA et on injecte celui-ci dans le courant de fusion principal à base de polytéréphtalate d'éthylène, ensuite on homogénéise à l'aide d'un dispositif de mélange et on met en dispersion dans le polymère de matrice et ensuite on file le mélange de produits de fusion.
  13. Procédé selon l'une quelconque des revendications 8 à 10,
    caractérisé en ce qu'
    on part du granulé de polytéréphtalate d'éthylène et on met en fusion celui-ci dans une extrudeuse de filage, on ajoute par doses le PMMA directement au granulé de polytéréphtalate d'éthylène dans l'extrudeuse de filage où on le met en dispersion dans le polytéréphtalate d'éthylène, et on file ensuite le mélange de produits de fusion.
  14. Procédé selon l'une quelconque des revendications 11 ou 13,
    caractérisé en ce que
    le polyméthacrylate de méthyle est ajouté par doses sous forme de perles.
  15. Procédé selon l'une quelconque des revendications 8 à 14,
    caractérisé en ce qu'
    on ajoute par dose en même temps que le polyméthacrylate de méthyle encore d'autres produits additionnels ou additifs, et on les mélange au polymère qui forme les fils.
  16. Procédé selon l'une quelconque des revendications 8 à 15,
    caractérisé en ce que
    le mélange de produits de fusion mis en dispersion, prêt à l'emploi n'est pas filé directement ensuite en fils, mais est en premier lieu granulé et ensuite transformé sur une machine de filage, avec une extrudeuse de mise en fusion.
  17. Procédé selon l'une quelconque des revendications 8 à 16,
    caractérisé en ce que
    lors de la production des fibres, la vitesse d'écoulement s'élève de 800 à 2400 m/min.
  18. Procédé selon l'une quelconque des revendications 8 à 16,
    caractérisé en ce que
    lors de la production de fils de filament partiellement orientés, la vitesse d'écoulement s'élève de 3000 à 8000 m/min.
EP99117671A 1998-09-16 1999-09-07 Fibres et filaments en polyester et procédé pour les produire Expired - Lifetime EP0987353B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19842463 1998-09-16
DE19842463 1998-09-16
DE19935145A DE19935145C2 (de) 1998-09-16 1999-07-27 Polyesterfasern und -filamente sowie Verfahren zu deren Herstellung
DE19935145 1999-07-27

Publications (2)

Publication Number Publication Date
EP0987353A1 EP0987353A1 (fr) 2000-03-22
EP0987353B1 true EP0987353B1 (fr) 2003-11-05

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EP99117671A Expired - Lifetime EP0987353B1 (fr) 1998-09-16 1999-09-07 Fibres et filaments en polyester et procédé pour les produire

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US (2) US6235389B1 (fr)
EP (1) EP0987353B1 (fr)
KR (1) KR20000023034A (fr)
CN (1) CN1159475C (fr)
BR (1) BR9904204A (fr)
ES (1) ES2210929T3 (fr)
ID (1) ID23998A (fr)
MX (1) MXPA99008258A (fr)
TR (1) TR199902159A3 (fr)
TW (1) TW490513B (fr)

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CN102828278A (zh) * 2012-09-20 2012-12-19 苏州大学 一种聚酯全拉伸竹节丝及其方法制备
CN107663686B (zh) * 2017-08-31 2019-08-30 安徽省德邦瓷业有限公司 一种日用陶瓷制坯用棒状泥料切割线的加工方法

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KR100392965B1 (ko) * 1995-03-02 2003-10-30 도레이 가부시끼가이샤 폴리에스테르고배향미연신섬유및그제조방법
JP3769379B2 (ja) * 1998-03-19 2006-04-26 帝人ファイバー株式会社 捲取性の改善された高伸度ポリエステルフィラメント糸およびその製造方法

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MXPA99008258A (es) 2004-11-26
TW490513B (en) 2002-06-11
CN1159475C (zh) 2004-07-28
BR9904204A (pt) 2000-09-05
US6544456B1 (en) 2003-04-08
US6235389B1 (en) 2001-05-22
EP0987353A1 (fr) 2000-03-22
ES2210929T3 (es) 2004-07-01
KR20000023034A (ko) 2000-04-25
TR199902159A2 (xx) 2000-08-21
TR199902159A3 (tr) 2000-08-21
ID23998A (id) 2000-06-14

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