EP1637633A1 - Fibres de polyester, leur procédé de fabrication et leur utilisation. - Google Patents

Fibres de polyester, leur procédé de fabrication et leur utilisation. Download PDF

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Publication number
EP1637633A1
EP1637633A1 EP05016263A EP05016263A EP1637633A1 EP 1637633 A1 EP1637633 A1 EP 1637633A1 EP 05016263 A EP05016263 A EP 05016263A EP 05016263 A EP05016263 A EP 05016263A EP 1637633 A1 EP1637633 A1 EP 1637633A1
Authority
EP
European Patent Office
Prior art keywords
polyester
fiber
equal
spherical particles
silicon
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Withdrawn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
EP05016263A
Other languages
German (de)
English (en)
Inventor
Rex Dr. Delker
Hans-Joachim Brüning
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.)
Teijin Monofilament Germany GmbH
Original Assignee
Teijin Monofilament Germany GmbH
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 Teijin Monofilament Germany GmbH filed Critical Teijin Monofilament Germany GmbH
Publication of EP1637633A1 publication Critical patent/EP1637633A1/fr
Withdrawn legal-status Critical Current

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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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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

Definitions

  • the present invention relates to polyester fibers with high flexural resistance, in particular monofilaments, which can be used for example in screens or in conveyor belts.
  • polyester fibers in particular monofilaments for technical applications, are in most cases subjected to high mechanical and / or thermal stresses during use.
  • the material must have good dimensional stability and constancy of force-elongation properties over as long as possible usage periods.
  • Molding compositions with high chemical and physical resistance and their use for fiber production are known. Widely used Materials are polyester. It is also known to combine these polymers with other materials, for example, to set the abrasion resistance targeted.
  • polyester-based manmade fibers have proven successful in such environments, when used in humid-hot environments, polyesters are prone to mechanical abrasion in addition to hydrolytic degradation.
  • abrasion can have a variety of causes.
  • the sheet forming screen is pulled in paper machines for dewatering suction boxes with the result of increased Siebverschl constituentes.
  • screen wear occurs due to differences in speed between the paper web and the screen surface or between the screen surface and the surface of the drying drums.
  • Tissue wear also occurs in other technical fabrics due to abrasion; e.g. in conveyor belts by grinding over fixed surfaces, in filter fabrics by mechanical cleaning and in screen printing fabrics by passing a squeegee over the screen surface.
  • GB-A-759,374 describes the production of synthetic fibers and films with improved mechanical properties.
  • the claimed process is characterized by the use of very finely divided metal oxides in the form of aerosols. Particle sizes are up to 150 nm specified.
  • polymers are called viscose, polyacrylonitrile and polyamides.
  • polyester raw material containing finely dispersed silica gels is known.
  • the individual particles have diameters of up to 60 nm and aggregates, if present, are not larger than 5 ⁇ m.
  • the filler is said to result in polyester fibers having improved mechanical properties, improved color and improved handleability. Notes on applications for these polyester fibers are not apparent from the document.
  • EP-A-1,199,389 describes an ethylene glycol dispersion containing aggregates of ceramic nanoparticles, which are suitable for the production of high-strength and transparent polyester moldings.
  • JP-A-02 / 099,606 discloses a fiber having improved antimicrobial properties containing finely divided zinc oxide / silica particles.
  • selected hydrolysis-stabilized polyester raw materials comprising certain nanoscale fillers have a significantly improved abrasion resistance compared to unmodified polyester raw materials without their dynamic load capacity, expressed by the bending resistance is appreciably reduced or even increased by the filler. This property profile was found on selected polyester raw materials.
  • the present invention the object of the invention to provide filled polyester fibers, which in addition to excellent abrasion resistance compared with the unfilled polyester fibers have comparable or even improved dynamic loads.
  • Another object of the present invention was to provide transparent fibers having high abrasion resistance and excellent dynamic loadability.
  • the invention relates to fibers containing aliphatic-aromatic polyester, at least one hydrolysis stabilizer and spherical particles of oxides of silicon, aluminum and / or titanium having an average diameter of less than or equal to 100 nm.
  • polyester fibers having a content of free carboxyl groups of less than or equal to 3 meq / kg.
  • Such equipped polyester fibers are stabilized against hydrolytic degradation and are particularly suitable for use in humid-hot environments, especially in paper machines or as a filter.
  • the fiber-forming polyesters may be of any nature as long as they have aliphatic and aromatic groups and are melt-deformable. Within the scope of this description, aliphatic groups are also to be understood as meaning cycloaliphatic groups.
  • thermoplastic polyesters are known per se. Examples of these are polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or, in particular, polyethylene terephthalate. Building blocks of thread-forming polyesters are preferably diols and dicarboxylic acids, or appropriately constructed oxycarboxylic acids.
  • the main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para- or trans-aromatic compounds, e.g.
  • Aliphatic dicarboxylic acids e.g. Adipic acid or sebacic acid, are preferably used in combination with aromatic dicarboxylic acids.
  • Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol or mixtures thereof. Preference is given to aliphatic diols having from two to four carbon atoms, in particular ethylene glycol; furthermore preferred are cycloaliphatic diols, such as 1,4-cyclohexanedimethanol.
  • polyesters which have repeating structural units which are derived from an aromatic dicarboxylic acid and a aliphatic and / or cycloaliphatic diol.
  • thermoplastic polyesters are in particular selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethanol terephthalate or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
  • the polyesters used according to the invention usually have solution viscosities (IV values) of at least 0.60 dl / g, preferably from 0.60 to 1.05 dl / g, particularly preferably from 0.62 to 0.93 dl / g ( measured at 25 ° C in dichloroacetic acid (DCE)).
  • IV values solution viscosities
  • nanoscale spherical oxides of silicon, aluminum and / or titanium used according to the invention impart excellent abrasion resistance to the polyester fibers without adversely affecting the dynamic properties, expressed by the bending resistance.
  • spherical silica is used.
  • the nanoscale spherical oxides of silicon, aluminum and / or titanium used according to the invention typically have average particle diameters (D 50 values) of less than or equal to 50 nm, preferably less than or equal to 30 nm and particularly preferably from 10 to 25 nm.
  • polyester raw materials required and filled to produce the fibers according to the invention can be produced in different ways.
  • polyester, hydrolysis stabilizer and filler and optionally further additives can be melted with the polyester in one Mixing unit, for example in an extruder, mix and the composition is then fed directly to the spinneret or the composition is granulated and spun in a separate step. If appropriate, the resulting granules can also be spun as a masterbatch together with additional polyester. It is also possible to add the nanoscale fillers before or during the polycondensation of the polyester.
  • Suitable nanoscale fillers are commercially available.
  • the Nyacol® products of Nano Technologies, Inc., Ashland, MA, U.S.A. may be used.
  • the content of nanoscale spherical filler of the fiber according to the invention can vary within wide ranges, but is typically not more than 5 wt.%, Based on the mass of the fiber.
  • the content of nanoscale spherical filler in the range of 0.1 to 2.5 wt.%, In particular from 0.5 to 2.0 wt.%.
  • the type and amount of components a) and b) are preferably chosen so that transparent products are obtained.
  • the polyesters used according to the invention are distinguished by transparency. Surprisingly, it has been found that the nanoscale spherical fillers do not adversely affect the transparency. The addition of already about 0.3 wt.% Non-nanoscale titanium dioxide (matting agent), however, causes a complete whitening of the fiber.
  • the abrasion resistance of the fibers according to the invention can be further increased by the addition of polycarbonate.
  • the amount of polycarbonate is up to 5 wt.%, Preferably 0.1 to 5.0 wt.%, Particularly preferably 0.5 to 2.0 wt.%, Based on the total mass of the polymers.
  • fibers are to be understood as meaning any fibers.
  • filaments or staple fibers which consist of several individual fibers, but in particular monofilaments.
  • polyester fibers according to the invention can be prepared by processes known per se.
  • the hydrolysis stabilizer may already be contained in the polyester raw material, or added before and / or after spinning.
  • the polyester fibers according to the invention are drawn one or more times in the preparation.
  • a polyester produced by solid phase condensation is used in the production of the polyester fibers.
  • polyester fibers according to the invention can be present in any desired form, for example as multifilaments, as staple fibers or in particular as monofilaments.
  • the titer of the polyester fibers according to the invention can likewise vary within wide limits. Examples are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
  • polyester raw material can be used. This typically has levels of free carboxyl groups of 15 to 50 meq / kg of polyester. Preference is given to using polyester raw materials produced by solid phase condensation; in these, the content of free carboxyl groups is typically 5 to 20 meq / kg, preferably less than 8 meq / kg of polyester.
  • polyester raw material which already contains the nanoscale, spherical filler.
  • the filler is added during the polycondensation and / or at least one of the monomers.
  • the hot polymer filament is cooled, e.g. in a cooling bath, preferably in a water bath, and then wound up or peeled off.
  • the removal speed is greater than the injection rate of the polymer melt.
  • polyester fiber produced in this way is then preferably subjected to a post-drawing, more preferably in several stages, in particular a two- or three-stage post-drawing, with a total draw ratio of 1: 3 to 1: 8, preferably 1: 4 to 1: 6.
  • the take-off speed is usually 10 - 80 m per minute.
  • polyester fibers according to the invention can be used in addition to nanoscale, spherical filler still contain other auxiliaries.
  • auxiliaries include processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
  • processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
  • antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
  • pigments or matting agents examples include organic dye pigments or titanium dioxide.
  • viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
  • the fibers of the invention can be used in all industrial fields. They are preferably used in applications in which increased wear due to mechanical stress is to be expected. Examples include the use in screens or in conveyor belts. These uses are also the subject of the present invention.
  • polyester fibers according to the invention are preferably used for the production of fabrics, in particular fabrics, which are used in fabrics.
  • polyester fibers in the form of monofilaments according to the invention relates to their use as conveyor belts or as components of conveyor belts.
  • Another object of the present invention is the use of spherical particles of inorganic oxides having an average diameter of less than or equal to 100 nm for the production of fibers, in particular monofilaments, with high bending resistance.
  • PET polyethylene terephthalate
  • optionally hydrolysis stabilizer were mixed in the extruder, melted and spun through a 20 hole spinneret with a hole diameter of 1.0 mm at a flow rate of 488 g / min and a take-off speed of 31 m / min to monofilaments , stretched three times with degrees of stretching 1: 4,95; 1: 1.13; and 1: 0.79; and heat-set in the hot air duct at 255 ° C under heat shrinkage.
  • the total draw was 1: 4.52.
  • Monofilaments with a diameter of 0.40 mm were obtained.
  • the PET used was a type to which different amounts of nanoscale spherical silica had been added during the polycondensation.
  • the mean diameter (D 50 value) of the nanoscale filler was 50 nm.
  • hydrolysis stabilizer used was a carbodiimide (Stabaxol® 1, Rheinchemie).
  • Monofilaments were prepared as described in the working instructions of Examples 1, V1 and V2. Different nanoscale fillers were used and a hydrolysis stabilizer was used.
  • the monofilaments of Example 7 was a Ketttype with (in comparison to the monofilaments of Example 4) comparatively steep course of the force-strain diagram and comparatively low elongation at break. This property profile was adjusted by appropriately stretching and relaxing the monofilaments.
  • Monofilament according to Example 4 Threefold orientation with draw ratios of 1: 5.0, 1: 1.1 and 1: 0.9 (total draw ratio: 1: 4.8) and heat setting at 185 ° C. with shrinkage admission
  • Monofilament according to Example 7 Threefold orientation with draw ratios of 1: 4.8, 1: 1.2 and 1: 1.04 (total draw ratio: 1: 5.7) and heat setting in the third draw step at 250.degree
  • the fiber properties were determined as follows:
  • Dynamic bending test (bending strength): In a rotary head, the test specimen was bent between two metal jaws with a defined bending edge by a rotary movement (double strokes 146 / min) at an angle of 60 ° to the right and left until breakage. A fineness-related preload force of 0.675 cN / dtex was applied to the test sample. The metal baking stood in a distance corresponding to the diameter of the sample, to each other. The bending edge of the metal jaws was exactly predetermined by a fixed radius. The number of bending cycles (number of turns) to break was determined.
  • Knife scouring test In a double-stroke movement (60 double strokes / min), the test sample was scrubbed over a length of 70 mm over a ceramic capillary tube. A fineness-related preload force of 0.135 cN / dtex was applied to the test sample. The number of double strokes to break was determined.
  • Tables 1 and 2 below show the composition and properties of the monofilaments. ⁇ u> Table 2 ⁇ / u> Example no. filler Amount of filler [wt. %] Dynamic bending test (cycles) Knife scouring test (cycles) 3 spherical silica 20 nm 0.4 66736 140233 4 Spherical silica 50 nm 0.4 114989 181223 5 spherical silica 100 nm 0.4 90985 142343 6 Spherical alumina 50 nm 0.04 16238 65822 7 Spherical silica 50 nm 0.4 49673 102986 V3 Nanoton (not sparse) 0.1 272 19929
EP05016263A 2004-08-28 2005-07-27 Fibres de polyester, leur procédé de fabrication et leur utilisation. Withdrawn EP1637633A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102004041755A DE102004041755A1 (de) 2004-08-28 2004-08-28 Polyesterfasern, Verfahren zu deren Herstellung und deren Verwendung

Publications (1)

Publication Number Publication Date
EP1637633A1 true EP1637633A1 (fr) 2006-03-22

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Family Applications (1)

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EP05016263A Withdrawn EP1637633A1 (fr) 2004-08-28 2005-07-27 Fibres de polyester, leur procédé de fabrication et leur utilisation.

Country Status (6)

Country Link
US (1) US20060058441A1 (fr)
EP (1) EP1637633A1 (fr)
JP (1) JP2006063511A (fr)
BR (1) BRPI0503561A (fr)
DE (1) DE102004041755A1 (fr)
TW (1) TW200617225A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008065571A1 (fr) * 2006-11-30 2008-06-05 The Procter & Gamble Company Voiles non-tissés extensibles contenant des fibres de nanocomposite monocomposant
WO2008065572A1 (fr) * 2006-11-30 2008-06-05 The Procter & Gamble Company Voiles non-tissés extensibles contenant des fibres de nanocomposite multicomposant
WO2010043603A1 (fr) * 2008-10-13 2010-04-22 Basf Se Procédé de fabrication d'un monofilament et utilisation dudit monofilament

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070232174A1 (en) * 2006-03-31 2007-10-04 Arvind Karandlkar Polybutylene naphthalate filtration media
JP2011058121A (ja) * 2009-09-10 2011-03-24 Teijin Fibers Ltd ポリ乳酸繊維
DE102009053588A1 (de) 2009-11-17 2011-05-19 Teijin Monofilament Germany Gmbh Abriebbeständige Monofilamente
DE202012001985U1 (de) 2012-02-25 2012-03-30 Nextrusion Gmbh Abriebbeständige Monofilamente für Papiermaschinenbespannungen
DE102014009238A1 (de) 2014-06-20 2015-12-24 Perlon Nextrusion Monofil GmbH Monofilamente mit hoher Abrieb- und Formbeständigkeit, textile Flächengebilde daraus und deren Verwendung
PL3359597T3 (pl) 2015-10-05 2020-07-27 Albany International Corp. Kompozycje i sposoby do uzyskania ulepszonej odporności na ścieranie komponentów polimerowych
CN111118662A (zh) * 2019-12-18 2020-05-08 晋江市远祥服装织造有限公司 一种可生物降解环保面料及其制备方法和制品

Citations (6)

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Publication number Priority date Publication date Assignee Title
GB954024A (en) * 1959-05-26 1964-04-02 Du Pont Production of improved polyester filaments
US5207959A (en) * 1989-12-20 1993-05-04 Rhone Poulenc Fibres Process for obtaining pet yarns with an improved production efficiency
EP0761847A2 (fr) * 1995-07-17 1997-03-12 Hoechst Trevira GmbH & Co. KG Toiles pour machine à papier, filtres et structures de renforcement pour élastomères contenant des monofilaments de copolyesters
US5851668A (en) * 1992-11-24 1998-12-22 Hoechst Celanese Corp Cut-resistant fiber containing a hard filler
US6254987B1 (en) * 1998-07-29 2001-07-03 Johns Manville International, Inc. Monofil bicomponent fibres of the sheath/core type
US20030143396A1 (en) * 1999-07-06 2003-07-31 Franck Bouquerel Abrasion-resistant spun articles

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JPH0299606A (ja) * 1988-09-29 1990-04-11 Kuraray Co Ltd 消臭性能と抗菌性能を有する繊維及びその製造方法
JPH02210020A (ja) * 1989-02-03 1990-08-21 Kuraray Co Ltd 耐光性ポリエステル繊維
DE3930845A1 (de) * 1989-09-15 1991-03-28 Hoechst Ag Mit carbodiimiden modifizierte polyesterfasern und verfahren zu ihrer herstellung
JP3110633B2 (ja) * 1994-02-02 2000-11-20 東レ株式会社 ポリエステル組成物、モノフィラメントおよび工業用織物
JP2002121270A (ja) * 2000-10-16 2002-04-23 Nippon Aerosil Co Ltd 高強度および高透明性を有するポリエステル成形体の製造を可能とする超微粒セラミック粉末凝集体分散含有のグリコール類原料材
DE102005033350A1 (de) * 2005-07-16 2007-01-18 Teijin Monofilament Germany Gmbh Polyesterfasern, Verfahren zu deren Herstellung und deren Verwendung

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB954024A (en) * 1959-05-26 1964-04-02 Du Pont Production of improved polyester filaments
US5207959A (en) * 1989-12-20 1993-05-04 Rhone Poulenc Fibres Process for obtaining pet yarns with an improved production efficiency
US5851668A (en) * 1992-11-24 1998-12-22 Hoechst Celanese Corp Cut-resistant fiber containing a hard filler
EP0761847A2 (fr) * 1995-07-17 1997-03-12 Hoechst Trevira GmbH & Co. KG Toiles pour machine à papier, filtres et structures de renforcement pour élastomères contenant des monofilaments de copolyesters
US6254987B1 (en) * 1998-07-29 2001-07-03 Johns Manville International, Inc. Monofil bicomponent fibres of the sheath/core type
US20030143396A1 (en) * 1999-07-06 2003-07-31 Franck Bouquerel Abrasion-resistant spun articles

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008065571A1 (fr) * 2006-11-30 2008-06-05 The Procter & Gamble Company Voiles non-tissés extensibles contenant des fibres de nanocomposite monocomposant
WO2008065572A1 (fr) * 2006-11-30 2008-06-05 The Procter & Gamble Company Voiles non-tissés extensibles contenant des fibres de nanocomposite multicomposant
WO2010043603A1 (fr) * 2008-10-13 2010-04-22 Basf Se Procédé de fabrication d'un monofilament et utilisation dudit monofilament
US8691906B2 (en) 2008-10-13 2014-04-08 Basf Se Method for producing an monofilament and use of the monofilament

Also Published As

Publication number Publication date
DE102004041755A1 (de) 2006-03-02
TW200617225A (en) 2006-06-01
US20060058441A1 (en) 2006-03-16
JP2006063511A (ja) 2006-03-09
BRPI0503561A (pt) 2007-07-10

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