EP0439733A2 - Fibres de polyamide ou de polyester ayant des caractéristiques amÀ©liorées - Google Patents

Fibres de polyamide ou de polyester ayant des caractéristiques amÀ©liorées Download PDF

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Publication number
EP0439733A2
EP0439733A2 EP90123383A EP90123383A EP0439733A2 EP 0439733 A2 EP0439733 A2 EP 0439733A2 EP 90123383 A EP90123383 A EP 90123383A EP 90123383 A EP90123383 A EP 90123383A EP 0439733 A2 EP0439733 A2 EP 0439733A2
Authority
EP
European Patent Office
Prior art keywords
weight
fibers
polymer
polyamides
additives
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.)
Withdrawn
Application number
EP90123383A
Other languages
German (de)
English (en)
Other versions
EP0439733A3 (en
Inventor
Hans-Detlef Dr. Heinz
Siegfried Dr. Korte
Rolf-Volker Dr. Meyer
Hans-Georg Dr. Gelhaar
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.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0439733A2 publication Critical patent/EP0439733A2/fr
Publication of EP0439733A3 publication Critical patent/EP0439733A3/de
Withdrawn legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent 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
    • D01F6/90Monocomponent 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 polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D41/00Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/02Caps or cap-like covers without lines of weakness, tearing strips, tags, or like opening or removal devices
    • B65D41/04Threaded or like caps or cap-like covers secured by rotation
    • B65D41/0471Threaded or like caps or cap-like covers secured by rotation with means for positioning the cap on the container, or for limiting the movement of the cap, or for preventing accidental loosening of the cap
    • B65D41/0478Threaded or like caps or cap-like covers secured by rotation with means for positioning the cap on the container, or for limiting the movement of the cap, or for preventing accidental loosening of the cap the cap being formed by several elements connected together
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent 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
    • D01F6/92Monocomponent 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

Definitions

  • the invention relates to polyamide or polyester fibers with improved properties, obtained by adding polyarylene sulfides in amounts of 0.1 to 10% by weight, preferably 0.3 to 5% by weight and subsequent melt spinning and customary fiber post-treatment.
  • thermoplastic polyamides e.g. PA-6 and -66
  • polyesters e.g. polyethylene terephthalate
  • the fibers generally have the known good properties, such as high tensile strength / tear strength, elongation at break, comfort and good appearance.
  • the polymers 2) are arylene sulfide homo- and copolymers.
  • the poly-p-phenylene sulfide (PPS) (II) is preferred.
  • those polyarylene sulfides 2) are used which were directly condensed to high molecular weights in solution in one step without solution, but instead in oxidative molecular weight build-up. Methods for their production are known, see e.g. EP 0 171 021.
  • Corresponding polyarylene sulfides are commercially available, for example, under the trade names Tedur® and Fortron®.
  • Polymers 2 with melt viscosities (at 320 ° C and 100 s ⁇ 1) of approx. 5 to 500 Pa.s. are suitable.
  • the melt viscosity should be 10 to 200 Pa.s.
  • Suitable polyamides 1 are the polyamides (PA) usually used for the production of fibers by melt spinning, for example PA-6, 66, 610, 46, 1212, 6T6, 6T / 6, and various copolyamides or mixtures of the polyamides mentioned.
  • PA polyamides
  • PA.6, Pa.66 and mixtures thereof or copolyamides based on these are preferred.
  • PA6 or copolyamides based on PA.6 are particularly preferred.
  • polyesters based on terephthalic acid and aliphatic glycols, for example polyethylene terephthalate, polybutylene terephthalate and poly (1,4-cyclohexylene dimethylene terephthalate), are suitable as polyester 1).
  • Polyethylene terephthalate is preferred.
  • the polyesters 1) can optionally, in addition to terephthalic acid and the glycols, also modifying amounts of other monomers, e.g. Isophthalic acid, adipic acid and diethylene glycol.
  • Polyamides are preferred over polyesters.
  • Particularly preferred component 1) are PA6, 66 and mixtures or copolyamides based thereon.
  • polymer mixtures are used which can be produced in various ways, for example by compounding (for example using a kneader or extruder), by producing the polyamide or polyester in the presence of the polymers 2) or by mixing the granules and subsequent ones Spinning.
  • fiber production all types of fibers such as filaments, monofilaments, wires, staple fibers, "bulk continuous filament” and others are to be understood more under the term “fibers" is carried out as usual, preferably by melt spinning; all usual post-treatment methods such as stretching, fixing, crimping, dyeing etc. can be used.
  • drawn fibers are understood to mean those fibers which are produced, for example, by drawing twists, drawing winches in filament yarns, by roll or calender drawing in fiber cable processing or by spinning, e.g. also in the course of a rapid spinning process, stretched and thus oriented. All other stretching methods are also suitable in principle.
  • Such drawn fibers have an increased orientation and crystallinity compared to standard injection molded or extrusion molded articles.
  • additives 3 All substances commonly used in fiber production are suitable as additives 3), e.g. Matting agents (TiO2 and others), UV stabilizers, pigments, dyes, nucleating agents, antioxidants, optical brighteners, dyeing aids, sizing and others.
  • Matting agents TiO2 and others
  • UV stabilizers pigments, dyes, nucleating agents, antioxidants, optical brighteners, dyeing aids, sizing and others.
  • the polyamides or polyesters 1) may also contain monomers which increase the dyeability of the fibers; such monomers are known.
  • WO 86/03212 describes polymer alloys made of polyamide 46 and at least 5% by weight of polyarylene sulfides, which are said to have very good mechanical properties.
  • the cited application discloses that polyamide 6 and 66 are not sufficiently compatible with polyphenylene sulfide to achieve good mechanical properties.
  • Comparative Example 3 shows that an alloy of polyamide 6 and 15% PPS shows very poor extrusion behavior due to the insufficient compatibility and that the test specimens have a poor appearance and unusually low values for tensile strength and flexural modulus.
  • the application mentioned contains no reference to the use of the molding compositions for the production of fibers.
  • polyarylene sulfides are described as nucleating agents, ie additives which increase the degree of crystallization, for polyamides, this being shown only for a special polyamide made from terephthalic acid and a C10-diamine mixture.
  • the addition of the PPS generally lowers the tensile strength and flexural modulus; the elongation at break and the impact strength usually increase significantly.
  • This extremely unusual combination of effects is applied to all polyamides.
  • the application contains no indication that the stretchability or strength of fibers based on aliphatic polyamides (in particular PA6 or copolyamides based on PA6) can be significantly increased by adding PPS. In particular, a decrease in strength should be expected according to US 4,292,416.
  • the invention is based on the surprising finding that only a narrow range of the latter is suitable for significantly improving the properties (stretchability, strength) of the fibers by means of polyarylene sulfide additives. According to the invention, this is preferably 0.3 to 5.0%, particularly preferably 0.5 to 3.0, in particular 0.6 to 2.5%. According to the invention, the stretchability and the strengths of, for example, PA6 fibers are increased in this narrow quantity range; For example, the strength of PA6 fibers can be increased by 25 to 30%, whereby the rigidity and the heat resistance can also be improved. The elongation of the fibers is practically unchanged.
  • the effects mentioned, which form the basis of the present invention, are unexpected and cannot be derived from the prior art.
  • the fibers according to the invention can be produced by all customary processes, generally by means of the melt. All usual post-treatment methods can be used.
  • All usual post-treatment methods can be used.
  • For the production of fibers reference is made, for example, to Encyclopedia of Polymer Science and Engineering, 2nd Edition, Wiley Interscience, John Wiley and Sons, New York, and H. Klare, Technology and Chemistry of Synthetic Fibers from Polyamides, VEBtechnik, Berlin 1954 .
  • the melt spinning can take place both above and below the melting temperature of the polymers 2).
  • the fibers according to the invention are a valuable addition to the prior art. They can be used alone or, if appropriate, in combination with other natural or synthetic fibers. They are suitable for all applications of polyamide and polyester fibers, especially for those that require high strength.
  • a polyamide 6 ( ⁇ rel ⁇ 4.0; 1% in m-cresol, 25 ° C) was at 285 ° C and a throughput of 30 kg h ⁇ 1 with 1, 2 and 5 wt .-% PPS (39 Pas, 310 ° C, 1000 s ⁇ 1) or compounded without PPS via a twin-screw extruder (ZSK 53). Viscosities and work input values of the extruder can be found in Table 1.
  • Caprolactam and water (0.5 l without PPS; 0.6 l with PPS) as well as 100, 200 or 500 g PPS (the sum of the weights of caprolactam and PPS was always 10 kg) (melt viscosity: 31 Pas at 306 ° C and 1000 s ⁇ 1) were placed in a 25 l autoclave. After three nitrogen equalizations, the mixture was heated to 200 ° C. and held under autogenous pressure for 1 hour. The mixture was then depressurized to normal pressure, 40 l h ⁇ 1 of nitrogen passed over and simultaneously heated to 270 ° C (in the presence of 1 and 5% PPS 280 ° C). The reaction times were 4 to 7 hours until the desired melt viscosity was reached.
  • the polyamides of Examples 1 to 8 were melted and spun in multiple threads in an extrusion spinning apparatus. The spun material thus obtained was drawn.
  • the PPS-modified fibers have improved properties (degree of stretch, strength), these being most pronounced in the range from 1 to 2% addition.
  • the degree of stretching of the fibers should be> 1: 2, e.g. 1: 2-1: 10, preferably 1: 2.5 to 1: 7.5, in particular 1: 3 to 1: 6, up to the maximum degree of stretching at the stretching temperature used.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP19900123383 1990-01-30 1990-12-06 Improved polyamide- or polyester fibres with improved characteristics Withdrawn EP0439733A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904002607 DE4002607A1 (de) 1990-01-30 1990-01-30 Polyamid-bzw. polyesterfasern mit verbesserten eigenschaften
DE4002607 1990-01-30

Publications (2)

Publication Number Publication Date
EP0439733A2 true EP0439733A2 (fr) 1991-08-07
EP0439733A3 EP0439733A3 (en) 1992-06-17

Family

ID=6399027

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900123383 Withdrawn EP0439733A3 (en) 1990-01-30 1990-12-06 Improved polyamide- or polyester fibres with improved characteristics

Country Status (3)

Country Link
EP (1) EP0439733A3 (fr)
JP (1) JPH04352813A (fr)
DE (1) DE4002607A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005064049A3 (fr) * 2003-12-23 2005-09-22 Invista Tech Sarl Composition polyamide comprenant un azurant optique, fils fabriques a partir de celle-ci et procede pour chauffer lesdits fils
CN111826737A (zh) * 2020-06-23 2020-10-27 浙江恒澜科技有限公司 一种安全气囊用聚酰胺56工业丝的制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005064049A3 (fr) * 2003-12-23 2005-09-22 Invista Tech Sarl Composition polyamide comprenant un azurant optique, fils fabriques a partir de celle-ci et procede pour chauffer lesdits fils
EP1992722A3 (fr) * 2003-12-23 2009-12-09 Invista Technologies S.a.r.l. Composition polyamide comprenant un azurant optique, fils fabriques a partir de celle-ci et procede pour chauffer lesdits fils
CN111826737A (zh) * 2020-06-23 2020-10-27 浙江恒澜科技有限公司 一种安全气囊用聚酰胺56工业丝的制备方法

Also Published As

Publication number Publication date
JPH04352813A (ja) 1992-12-07
EP0439733A3 (en) 1992-06-17
DE4002607A1 (de) 1991-08-01

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