EP0779382B1 - Fibres et filaments de polyester ayant une stabilité à l'hydrolyse, mélanges maítres et procédé de fabrication de fibres et filaments de polyester - Google Patents

Fibres et filaments de polyester ayant une stabilité à l'hydrolyse, mélanges maítres et procédé de fabrication de fibres et filaments de polyester Download PDF

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Publication number
EP0779382B1
EP0779382B1 EP96119409A EP96119409A EP0779382B1 EP 0779382 B1 EP0779382 B1 EP 0779382B1 EP 96119409 A EP96119409 A EP 96119409A EP 96119409 A EP96119409 A EP 96119409A EP 0779382 B1 EP0779382 B1 EP 0779382B1
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EP
European Patent Office
Prior art keywords
filaments
end group
polyester fibres
polyester
masterbatch
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Expired - Lifetime
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EP96119409A
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German (de)
English (en)
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EP0779382A1 (fr
Inventor
Herbert Dl. Zeitler
Reimund Brecheler
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Teijin Monofilament Germany GmbH
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Teijin Monofilament Germany GmbH
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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • the invention relates to polyester fibers and filaments, preferably Monofilaments made of polyester, in which the end groups of the polyester are added by Mono, bis and Polycarbodiimides as end group capping agents against the thermal and in particular the hydrolytic degradation have been stabilized, concentrates (masterbatches) containing these end group capping agents and inert polymeric carriers, and Process for the production of the fibers.
  • polyester molecules split under thermal stress become.
  • a polyethylene terephthalate for example Splitting of the ester bond to form a carboxyl end group and of a vinyl ester, the vinyl ester then with elimination of acetaldehyde reacts further.
  • Such thermal decomposition is mainly due to the Amount of the reaction temperature, the residence time and possibly by the The nature of the polycondensation catalyst is affected.
  • EP-A-0 506 983 and DE 43 07 394 include monofilaments dirt-repellent properties and with improved Resistance to hydrolysis is known.
  • the described monofilaments consist of Polyester based on polyethylene terephthalate or poly-1,4-cyclohexanedimethylene terephthalate with additions of fluorine-containing polymers.
  • DE 43 07 392 also describes hydrolysis-resistant monofilaments made of polyester.
  • carbodiimides are mixed in as a concentrate (masterbatch) in the extruder.
  • the carrier material for the carbodiimide concentrate consists of polyethylene terephthalate.
  • ketenimines are also used as polyester stabilizers.
  • the monofilaments described, which contain fluorine-containing polymers, have dirt-repellent properties. This property is attributed to the migration effect in which the fluorine component migrates to the surface of the monofilament.
  • this object is achieved by a method in which the usually as a carrier in the concentrate for the end group closing agent (Masterbatch) material used by a related to the End group sealing agent inert material is replaced.
  • the carrier materials contain used carrier materials such as polyethylene terephthalate practically no reactive end groups, so that actual effect of the end group closure agent is not already in Masterbatch previously produced but only after addition during production the fibers can be done.
  • the carrier materials are from halogenated ethylenically unsaturated hydrocarbon derived polymers.
  • Polymers or copolymers are preferably used as carrier materials Based on ethylenically unsaturated fluorinated hydrocarbons, in particular copolymers based on tetrafluoroethylene, ethylene and optionally at least one further ⁇ -olefin copolymerizable therewith used, provided they have a melting point which is a softening or Liquefaction of the copolymers in the manufacturing plant used for the Permits polyester fibers.
  • Fluorinated copolymers are particularly preferred preferably a crystallite melting point in the range from 160 ° C to 270 ° C exhibit. Examples of suitable tetrafluoroethylene copolymers are in DE-OS 41 31 756 described in detail.
  • PVDF fluorinated polyvinylidene
  • a particularly preferred carrier material in the masterbatch is Polytetrafluoroethylene copolymer (trade name ® HOSTAFLON ET 6060 from Hoechst AG) used.
  • Polymers and copolymers based on tetrafluoroethylene are characterized by a number of advantages, such as good UV transmission and thus good UV resistance, due to good weather resistance, good dielectric Properties and high chemical resistance, especially good ones Hydrolysis resistance.
  • the highly hydrophobic surface of molded parts made from these Polymers and copolymers lead to a correspondingly low Adhesion behavior, which can be found, for example, in a pronounced Repels dirt.
  • Examples of means for sealing the end groups in the polyester are Mono-, bis- or polycarbodiimides, and glycidyl ethers such as N-glycidyl phthalimide (Trade name ® DENACOL EX 731 from Nagase).
  • the end group capping agents can preferably also be in mixtures be used.
  • polyester as the spinning material that already due to their production only a small amount of carboxyl end groups exhibit. This can be done, for example, by using the so-called Solid condensation process take place. It was found that Polyesters to be used less than 20, preferably even less than 10 mVal should have carboxyl end groups per kg. Is already in these values the increase by melting, preferably in the extruder, with been taken into account.
  • thread-forming polyester i.e. aliphatic / aromatic polyester such as e.g. Polyethylene terephthalate or polybutylene terephthalate, but also Completely aromatic and, for example, halogenated polyesters are in can be used in the same way.
  • Building blocks of thread-forming polyesters are preferably diols and dicarboxylic acids, or correspondingly constructed Oxycarboxylic acids.
  • the preferred acid component of the polyesters used according to the invention is the terephthalic acid.
  • terephthalic acid preferably para- or trans-standing aromatic compounds, e.g. 2,6-naphthalene but also p-hydroxybenzoic acid.
  • Typical suitable dihydric alcohols are, for example, ethylene glycol, Propanediol, 1,4-butanediol but also hydroquinone.
  • Preferred aliphatic diols have two to four carbon atoms.
  • Ethylene glycol is particularly preferred.
  • Longer-chain diols can, however, be used in proportions of up to approximately 20 mol%, preferably less than 10 mol% are used to modify the properties.
  • polyester fibers and - filaments consisting predominantly or wholly of polyethylene terephthalate exist and especially those that have a molecular weight corresponding to one Intrinsic viscosity (intrinsic viscosity) of at least 0.64, preferably have at least 0.70 [dl / g].
  • the intrinsic viscosities are in Dichloroacetic acid determined at 25 ° C.
  • the Carboxyl end groups in that the carboxyl end groups predominantly with Mono- and / or biscarbodiimides are implemented and the fibers and Filaments only very little or no amounts of these carbodiimides in free Form included.
  • the polyester fibers and filaments contain preferably 0.05% by weight of at least one polycarbodiimide, where this polycarbodiimide in free form or with at least some more reactive carbodiimide groups should be present. Preferably should less than 3 meq / kg carboxyl end groups in the fibers or filament dents be included. Fibers and filaments in which the Number of carboxyl end groups to less than 2, in particular even less than 1.5 mVal / kg polyester was reduced.
  • the content of free mono- and / or Bis-carbodiimides in the fiber or filament should preferably be less than 500 ppm, in particular less than 200 ppm (weight) of polyester.
  • these end group capping agents are less than 50, especially less than 20, very particularly preferably even less than 10 ppm (weight) polyester Cheap.
  • monocarbodiimides which are particularly preferred preferably as such, ie not as a batch of material.
  • This Connections are particularly characterized by a high Reaction speed in the reaction with the polyester.
  • these are partially or completely by appropriate amounts of biscarbodiimides to replace those in these Compounds to use noticeable lower volatility.
  • care must be taken to ensure that the contact time is sufficiently long is chosen to also when using biscarbodiimides in mixing and Melt in the melt extruder to ensure a sufficient reaction.
  • Polyesters and many common end group capping agents such as carbodiimides should not be stored indefinitely at high temperatures. Already above was pointed out that when melting polyesters additional Carboxyl end groups arise. Many of the used End group sealing agents can become at the high temperatures Decompose polyester melts. It is therefore desirable that the contact or Reaction time of the end group capping agent with the molten polyesters limit as much as possible. When using melt extruders, it is possible to use them Residence time in the molten state to less than 5 minutes, preferably less than 3 minutes. A limitation of Melting time in the extruder is only given by the fact that for a perfect Reaction between end group capping agent and carboxyl end groups or sufficient hydroxyl end groups to mix the reactants must be done. This can be done by appropriate design of the extruder or for example by using static mixers.
  • Those remaining in the polyesters after the polycondensation End groups are according to the preferred Embodiment predominantly carboxyl end groups and are said to be by reaction preferably closed with a mono- or biscarbodiimide. A smaller proportion of the carboxyl end groups is preferred among them Conditions also with carbodiimide groups in addition as a master batch supplied polycarbodiimide react.
  • the polyester fibers and filaments therefore contain instead of Carboxyl end groups essentially their reaction products with the carbodiimides used.
  • Mono- or bis-carbodiimides which only if in general, to a very small extent in free form in the fibers and filaments should occur are the known, aryl, alkyl and cycloalkyl carbodiimides.
  • the diarylcarbodiimides which are preferably used, the aryl nuclei may be unsubstituted. However, in 2- or 2,6-position substituted and thus sterically hindered aromatic Carbodiimide used.
  • DE-AS 1 494 009 already describes a large number of Monocarbodiimides with steric hindrance to the carbodiimide group enumerated.
  • Monocarbodiimides for example, are particularly suitable the N, N '- (di-o-tolyl) carbodiimide and the N, N' - (2,6,2 ', 6'-tetraisopropyl) diphenyl carbodiimide.
  • Biscarbodiimides useful in the invention are described for example in DE-OS 20 20 330.
  • arylene nuclei being phenylene, naphthylene, Diphenylene and the divalent radicals derived from diphenylmethane in Come into consideration and the substituents by type and place of substitution Substituents of the mono-diarylcarbodiimides substituted in the aryl nucleus correspond.
  • the one fed in with the masterbatch in concentrated form End group capping agent is preferably a polycarbodiimide with a average molecular weight of 2000 to 15000, but especially of 5000 to 10000.
  • These polycarbodiimides react with significantly less Speed with the carboxyl end groups and are therefore either bound or in free form. If there is such a reaction, will preferably first react only one group of the carbodiimide.
  • further groups present in the polymeric carbodiimide lead to the desired depot effect and are the cause of the essential improved stability of the fibers and filaments obtained.
  • the in them existing polymeric carbodiimides have not yet been fully implemented, but still free carbodiimide groups to trap more Have carboxyl end groups.
  • a particularly preferred polycarbodiimide is the commercially available aromatic Polycarbodiimide which is in the o-position to the carbodiimide groups, i.e. in 2,6- or 2,4,6-position on the benzene nucleus is substituted with isopropyl groups.
  • Such polycarbodiimide is available from Rhein-Chemie, Rheinhausen under Trade name ® Stabaxol P100.
  • this polycarbodiimide will only as a masterbatch with a polymeric, non-inert carrier, such as, for example Polyethylene terephthalate offered.
  • polyester fibers and filaments produced according to the invention can usual additives such as Titanium dioxide as matting agent or additives for example to improve the dyeability or to reduce electrostatic charges included.
  • additives such as Titanium dioxide as matting agent or additives for example to improve the dyeability or to reduce electrostatic charges included.
  • Additives or comonomers are suitable to reduce the flammability of the fibers produced and can reduce filaments in a known manner.
  • Polyester melt Colored pigments, soot or soluble dyes in the Polyester melt are incorporated or already included.
  • Admixing other polymers e.g. Polyolefins, polyesters or polyamides it is possible to achieve desired technical textile effects.
  • the addition of known crosslinking substances and Similar additives can bring advantages for selected areas of application.
  • Polyester fibers and filaments require mixing and melting. This melting can preferably take place in the melt extruder directly before actual spinning process take place.
  • the addition of end group capping agents takes place either via the previous production of master batches, so-called masterbatches or at least partially directly through admixture in liquid or solid form. With masterbatches as concentrates, this can be done treating polyester material directly before the extruder or, when used for example a twin screw extruder, also in the extruder with the End group sealing agents are mixed.
  • a suitable end group sealing agent is first worked, preferably a mono- and / or biscarbodiimide, without a masterbatch especially in liquid form, added to the polyester.
  • the Amount of the additive usually according to the end group content of the Starting polyester, preferably according to the carboxyl end group content, under Consideration of the expected melting process emerging additional end groups of the polyester.
  • To one if possible To achieve low pollution of the environment and the operating personnel, it is also possible, preferably with substoichiometric amounts and mono- or biscarbodiimides to work.
  • the amount should added mono- or biscarbodiimides less than 90% of stoichiometrically calculated amount, particularly preferably 50 to 85% of the Carboxyl end group content corresponding stoichiometric amount of Mono- or biscarbodiimides can be added. It is important to ensure that no losses due to premature evaporation of the mono- or Bisdicarbodiimide occur.
  • At least one end group capping agent is used as Concentrate in the form of master batches from a carrier material and a higher percentage, e.g. 15% of polycarbodiimide added.
  • end group sealing agents added as a master batch Polycarbodiimides.
  • End group sealing agent still unreacted or as a reaction product with the reactive groups.
  • Concentrations of 0.02 to 2 are preferred. in particular from 0.1 to 0.6% by weight of end group sealing agent in the Polyester fibers and filaments.
  • a content of is very particularly preferred 0.3 to 0.5% by weight.
  • the residence time of the End group sealing agent in the melt preferably less than 5 min, in particular be less than 3 minutes.
  • the resistance to hydrolysis is determined analogously to that in EP-A-0 486 916 method described about the decrease in strength of the filament treatment in an environment damaging the filament. That too testing monofilament is made of an atmosphere of steam with a 80 hours Exposed to temperature of 135 ° C. The monofilament is then dried and the tensile strength is determined by conventional methods. The comparison of the Tear resistance with the untreated monofilament is a measure of that Hydrolysis resistance.
  • the percentage residual tensile strength of the Fibers according to the invention are preferably above 50%, in particular above 75%. A residual tensile strength of more than is particularly preferred 80%. Values above 90% are very particularly preferred.
  • Evidence of the inhomogeneous distribution of the introduced closure over the cross-section of the monofilament can, for example, by severing the outer layer of the monofilament and determination of the proportion Closure means in the remaining core and by subsequent comparison this value with the proportion of closure agent in the original fiber respectively.
  • the carrier in the Fibers produced according to the invention have a kind of core-sheath structure over the Create cross-section of the fiber with respect to the end-capping agent. This enriches the means of end group closure in the area of Coat of the fiber so that the proportion of the added as a masterbatch End group sealing means increases continuously towards the cladding of the fiber.
  • polyester fibers preferably monofilaments, compared to conventional homogeneous fibers at the same concentration of End group capping agent on the surface due to the inhomogeneous Distribution of a lower total amount of occluding agent within the Have monofilaments.
  • the fineness-related maximum tensile force ( Tensile strength) on the monofilaments obtained once directly after the Generation and a second time after storing the monofilaments at 135 ° C in one Water vapor atmosphere checked after 80 hours and the quotient off Residual tear strength and original tear strength are calculated. It is a measure of the stabilizing effect achieved by the additives and is in%, based on the value before storage.
  • the invention preferably provides fibers which, according to the Treatment in steam has a residual tensile strength of more than 50% in particular have more than 70%. Monofilaments with are particularly preferred Residual tear strengths greater than 80%, in particular greater than 90%.
  • the nitrogen content of the fibers according to the invention is self-evident depending on the amount of end group capping agent added, if the end group capping agent contains nitrogen. With exclusive Use of nitrogen-containing end group capping agents, such as for example carbodiimides, the nitrogen content can be used as a measure of the content be used on end group closure means.
  • Such Fibers according to the invention preferably contain less than 0.5% by weight Nitrogen, in particular less than 0.2% by weight, particularly preferably less than 0.12% by weight of nitrogen, based on the total weight.
  • polyester fibers according to the invention are especially for use under aggressive conditions, such as in a Prevail paper machine, suitable. Thereby the pollution of the environment and in particular the burden on the operating personnel due to the reduced End-capping agent content less than known Polyester fibers or filaments of comparable structure.
  • Polyester filaments with a round or profiled cross-section are preferred, the one - possibly equivalent - diameter of preferably 0.1 up to 2.0 mm.
  • These filaments are preferably used for the production of Paper machine screens used.
  • the masterbatch was a mixture from 15% by weight polycarbodiimide (commercial product ®Stabaxol P100 from Rhein-Chemie, Rheinhausen, Germany) and 85% by weight of a PTFE copolymer with ethylene as a comonomer (commercial product ®HOSTAFLON ET 6060 der Hoechst AG, Frankfurt).
  • polycarbodiimide commercial product ®Stabaxol P100 from Rhein-Chemie, Rheinhausen, Germany
  • a PTFE copolymer with ethylene as a comonomer commercial product ®HOSTAFLON ET 6060 der Hoechst AG, Frankfurt.
  • the temperature during the drawing in the first stage was 80 ° C. and in the second stage 90 ° C, the running speed of the spun threads after leaving the quench bath was 32 m / min. Subsequently, one Heat setting in a fixing channel at a temperature of 275 ° C carried out. All spun monofilaments had one Final diameter of 0.5 mm.
  • Example 2 A monofilament was again used under the same conditions as in Example 1 prepared, with 0.25 or 0.45 wt .-% of the N, N '- (2,6,2', 6'-tetraisopropyldiphenyl) carbodiimide used as a closing agent for the carboxyl groups has been.
  • the amount of 0.45% by weight in Example 2 corresponded to a value of 0.029 wt .-% nitrogen based on the total weight.
  • PTFE copolymer ®HOSTAFLON ET was also used Polycarbodiimide, added in different amounts.
  • a monofilament was produced, according to the invention
  • a polycarbodiimide is also used, which as Masterbatch with ®HOSTAFLON ET as carrier was supplied.
  • This example was also carried out according to the invention.
  • This monofilament was manufactured exclusively as polycarbodiimide Masterbatch added.
  • the polymeric carrier consisted again ®HOSTAFLON ET.
  • a masterbatch based on 85% by weight Polyethylene terephthalate and 15% by weight polycarbodiimide commercial product ®Stabaxol KE 7646 from Rhein-Chemie, Rheinhausen, Germany.
  • Example 9a shows that an example corresponds to 7a Residual tensile strength after hydrolysis of about 83% can only be achieved if a significantly larger amount of polycarbodiimides than in Example 7a is added.
  • the last two columns show the tensile strength values and the residual tensile strengths of monofilaments that were previously fixed at 200 ° C for 10 minutes (the steam-treated fibers were fixed before the steam treatment).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Claims (13)

  1. Procédé de fabrication de fibres et filaments de polyester résistant à l'hydrolyse, comprenant un procédé dans lequel on ajoute en premier directement des mono- et/ou bis-carbodiimides et ensuite on introduit en plus des polycarbodiimides en tant que mélanges maítres, les mélanges maítres contenant un substrat polymère qui ne contient pratiquement pas de groupes terminaux réagissant avec les agents de coiffage des groupes terminaux, dans lesquels on amène le matériau polyester formant des fils ensemble avec les additifs à une buse de filage et dans lequel on utilise comme substrat polymère des polymères obtenus à partir d'hydrocarbures halogénés éthyléniquement insaturés, de préférence des copolymères fluorés à base de tétrafluoroéthylène, d'éthylène et le cas échéant d'une autre α-oléfine copolymérisable avec ces derniers ou bien des polymères ou copolymères à base d'éthylène, propylène et α-oléfines supérieures.
  2. Mélanges maítres pour la fabrication de fibres et filaments de polyester avec une résistance à l'hydrolyse élevée, contenant un substrat polymère et un agent de coiffage des groupes terminaux, caractérisés en ce que le substrat polymère ne contient pratiquement pas de groupes terminaux pouvant réagir avec les agents de coiffage des groupes terminaux dans les conditions de fabrication des fibres et filaments de polyester, en ce que le substrat polymère contient des polymères obtenus à partir d'hydrocarbures halogénés éthyléniquement insaturés, à savoir des copolymères fluorés à base de tétrafluoroéthylène, d'éthylène et le cas échéant d'une autre α-oléfine copolymérisable liée à ces derniers, et en ce que les agents de coiffage des groupes terminaux sont des polycarbodiimides.
  3. Mélanges maítres selon la revendication 1, caractérisés en ce que la proportion de l'agent de coiffage des groupes terminaux dans les mélanges maítres est de 5 à 30% en poids.
  4. Fibres ou filaments de polyester avec une résistance à l'hydrolyse élevée, pouvant être obtenu(e)s par un procédé selon la revendication 1.
  5. Fibres ou filaments de polyester avec une résistance à l'hydrolyse élevée selon la revendication 4, contenant un agent de coiffage des groupes terminaux, caractérisé(e)s en ce qu'ils (elles) contiennent des polymères obtenus à partir d'hydrocarbures halogénés éthyléniquement insaturés, de préférence des copolymères fluorés à base de tétrafluoroéthylène, d'éthylène et le cas échéant d'une autre α-oléfine copolymérisable liée à ces derniers, et en ce que les agents de coiffage des groupes terminaux sont répartis de manière inhomogène sur la section du monofilament, l'inhomogénéité consistant de préférence en ce que la proportion d'agent de coiffage des groupes terminaux augmente de manière continue depuis l'âme jusqu'à l'enveloppe de la fibre.
  6. Fibres ou filaments de polyester selon la revendication 4 ou la revendication 5, caractérisé(e)s en ce que le polyester possède une masse moléculaire moyenne correspondant à une viscosité intrinsèque au moins égale à 0,64 (dl/g), mesurée dans l'acide dichloroacétique à 25°C.
  7. Fibres ou filaments de polyester selon l'une des revendications 4 à 6, caractérisé(e)s en ce que la majeure partie des groupes terminaux est coiffée par du mono- ou bis-carbodiimide et en ce que du polycarbodiimide est également encore présent.
  8. Fibres ou filaments de polyester avec une résistance à l'hydrolyse élevée selon l'une des revendications 4 à 7, caractérisé(e)s en ce qu'ils (elles) contiennent des polymères obtenus à partir d'hydrocarbures halogénés éthyléniquement insaturés, de préférence des copolymères fluorés à base de tétrafluoroéthylène, d'éthylène et le cas échéant d'une autre α-oléfine copolymérisable liée à ces derniers, et en ce que la résistance à l'hydrolyse, exprimée par la résistance résiduelle à la rupture en pourcentage, est supérieure à 50%, de préférence 70%, et la teneur en agents de coiffage des groupes terminaux contenant de l'azote est inférieure à 0,5% en poids.
  9. Fibres ou filaments de polyester selon la revendication 8, caractérisé(e)s en ce que la résistance à l'hydrolyse, exprimée par la résistance résiduelle à la rupture en pourcentage, est supérieure à 80%.
  10. Fibres ou filaments de polyester selon la revendication 8, caractérisé(e)s en ce que la teneur en agents de coiffage des groupes terminaux contenant de l'azote est inférieure à 0,2% en poids.
  11. Fibres ou filaments de polyester selon l'une au moins des revendications 4 à 10, caractérisé(e)s en ce qu'il s'agit de monofilaments de section ronde ou profilée présentant un diamètre - le cas échéant un diamètre équivalent - de 0,1 à 2,0 mm.
  12. Utilisation de mélanges maítres selon l'une des revendications 2 ou 3 pour la fabrication de fibres ou filaments en polyester.
  13. Utilisation du filament selon l'une des revendications 4 à 11 pour la fabrication de tamis de machines à papier.
EP96119409A 1995-12-15 1996-12-04 Fibres et filaments de polyester ayant une stabilité à l'hydrolyse, mélanges maítres et procédé de fabrication de fibres et filaments de polyester Expired - Lifetime EP0779382B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19547028A DE19547028A1 (de) 1995-12-15 1995-12-15 Hydrolysebeständige Polyesterfasern und -filamente, Masterbatches und Verfahren zur Hestellung von Polyesterfasern und -filamenten
DE19547028 1995-12-15

Publications (2)

Publication Number Publication Date
EP0779382A1 EP0779382A1 (fr) 1997-06-18
EP0779382B1 true EP0779382B1 (fr) 2002-03-20

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EP96119409A Expired - Lifetime EP0779382B1 (fr) 1995-12-15 1996-12-04 Fibres et filaments de polyester ayant une stabilité à l'hydrolyse, mélanges maítres et procédé de fabrication de fibres et filaments de polyester

Country Status (5)

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US (1) US5811508A (fr)
EP (1) EP0779382B1 (fr)
JP (1) JPH09195123A (fr)
BR (1) BR9605999A (fr)
DE (2) DE19547028A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6082760A (en) * 1997-04-18 2000-07-04 Toyota Jidosha Kabushiki Kaisha Air bag apparatus for passenger seat
US20050203258A1 (en) * 2002-08-30 2005-09-15 Toray Industriies, Inc. Polylactic acid fiber, yarn package, and textile product
US7014914B2 (en) * 2004-01-09 2006-03-21 Milliken & Company Polyester yarn and airbags employing certain polyester yarn
DE102005033350A1 (de) * 2005-07-16 2007-01-18 Teijin Monofilament Germany Gmbh Polyesterfasern, Verfahren zu deren Herstellung und deren Verwendung
DE102007056631A1 (de) * 2007-11-24 2009-05-28 Teijin Monofilament Germany Gmbh Hydrolysebeständig ausgerüstete Fäden, Verfahren zu deren Herstellung und deren Verwendung
BR112012005904A2 (pt) 2009-09-16 2019-09-24 Teijin Ltd fibra, e, estrutura de fibra
JP5694092B2 (ja) * 2011-08-31 2015-04-01 富士フイルム株式会社 ポリエステルフィルムとその製造方法、太陽電池用バックシートおよび太陽電池モジュール
CN105177743B (zh) * 2015-09-30 2017-12-08 海盐海利环保纤维有限公司 一种利用再生聚酯瓶片生产细旦及微细旦扁平再生聚酯长丝的方法
CN112725931B (zh) * 2019-10-14 2022-11-25 中国石油化工股份有限公司 一种亲/疏水双组份聚酯纤维及其制备方法和应用

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL273087A (fr) 1960-12-31
DE2020330A1 (de) 1970-04-25 1971-11-11 Glanzstoff Ag Verfahren zur Verbesserung der Stabilitaet von Polyestern
EP0072917B1 (fr) * 1981-08-17 1986-10-22 BASF Aktiengesellschaft Polyéthylène téréphtalate à résistance à l'hydrolyse et son utilisation
IT1148619B (it) * 1981-10-09 1986-12-03 Jwi Ltd Monofilamento a basso contenuto carbossilico per l'impiego nella fabbricazione di un telo per macchine essiccatrici della carta
CH645658A5 (en) * 1981-12-29 1984-10-15 Inventa Ag Thermoplastic, polyester-containing moulding compositions which contain macromolecular, highly fluorinated hydrocarbon
DE3930845A1 (de) * 1989-09-15 1991-03-28 Hoechst Ag Mit carbodiimiden modifizierte polyesterfasern und verfahren zu ihrer herstellung
DE69131343T2 (de) 1990-10-19 2000-01-13 Toray Industries, Inc. Polyester monofilament
JP3228977B2 (ja) * 1991-03-14 2001-11-12 ジョーンズ・マンヴィル・インターナショナル・インコーポレーテッド カルボジイミド変性ポリエステル繊維およびその製造方法
DE4131756A1 (de) 1991-09-24 1993-04-01 Plibrico Gmbh Gasspuelstein
JPH05302212A (ja) * 1992-04-27 1993-11-16 Toray Ind Inc ポリエステルモノフィラメントおよびその製造方法
DE4307392C2 (de) 1993-03-10 2001-03-29 Klaus Bloch Monofil mit erhöhter Hydrolysebeständigkeit auf Basis Polyester für die Verwendung in technischen Geweben und Verfahren zu dessen Herstellung
DE4307394C1 (de) 1993-03-10 1994-06-16 Klaus Bloch Monofil mit erhöhter Hydrolysebeständigkeit auf Basis Polyester und Verfahren zu dessen Herstellung
JPH07145511A (ja) * 1993-11-24 1995-06-06 Nippon Ester Co Ltd ポリエステルモノフィラメント
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

Also Published As

Publication number Publication date
BR9605999A (pt) 1999-06-15
DE19547028A1 (de) 1997-07-17
JPH09195123A (ja) 1997-07-29
US5811508A (en) 1998-09-22
EP0779382A1 (fr) 1997-06-18
DE59608917D1 (de) 2002-04-25

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