EP0407960B1 - Filament âme-gaine antistatique - Google Patents

Filament âme-gaine antistatique Download PDF

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Publication number
EP0407960B1
EP0407960B1 EP90113145A EP90113145A EP0407960B1 EP 0407960 B1 EP0407960 B1 EP 0407960B1 EP 90113145 A EP90113145 A EP 90113145A EP 90113145 A EP90113145 A EP 90113145A EP 0407960 B1 EP0407960 B1 EP 0407960B1
Authority
EP
European Patent Office
Prior art keywords
core
sheath
polymer
bicomponent filament
filaments
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
Application number
EP90113145A
Other languages
German (de)
English (en)
Other versions
EP0407960A3 (en
EP0407960A2 (fr
Inventor
Werner Bruckner
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.)
Hoechst AG
Original Assignee
Hoechst 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 Hoechst AG filed Critical Hoechst AG
Publication of EP0407960A2 publication Critical patent/EP0407960A2/fr
Publication of EP0407960A3 publication Critical patent/EP0407960A3/de
Application granted granted Critical
Publication of EP0407960B1 publication Critical patent/EP0407960B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]

Definitions

  • the present invention relates to antistatic, synthetic two-component filaments of the core-shell type, in which both the core and the shell have an increased electrical conductivity.
  • Core-sheath filaments with an electrically conductive core are already known from DEC-23 37 103.
  • the conductive core of these filaments contains finely divided, electrically conductive carbon black in amounts of 15 to 50%.
  • the sheath of these filaments is free from dispersed carbon black and other additives that increase conductivity and is therefore electrically non-conductive.
  • sufficient electrical conductivity only arises when a relatively high electrical voltage is applied to them. Therefore, the antistatic effect of these known filaments does not meet higher requirements, such as those e.g. when used in clean room clothing.
  • Filaments that contain carbon black dispersed over their entire cross-section are not only unsightly, but because of their low strength they are difficult to process further and also show poor wearing properties.
  • GB-A-2,077,182 discloses core-sheath filaments.
  • the addition of metal salts of long-chain aliphatic radicals acting sulfonic or carboxylic acids to the coat is not known from this document.
  • the antistatic, synthetic two-component filaments according to the invention have a considerably improved property profile compared to the known antistatic filaments of the core-sheath type.
  • the antistatic, synthetic two-component filaments according to the invention are those of the core-shell type, with a core of increased electrical conductivity; However, they are distinguished from the known ones in that their sheath also has an increased electrical conductivity.
  • the core and sheath of the filaments according to the invention contain different conductivity additives. While the core consists of a synthetic polymer in which solid, electrically conductive particles are dispersed, the sheath consists of a thread-forming polymer, which contains an addition of known antistatic agents based on sulfonate or carboxylate groups, organic compounds with low diffusivity in the Contains polymer; these are metal salts of a long aliphatic radical having sulfonic or carboxylic acid.
  • the solid, electrically conductive particles of the core material consist of conductive carbon modifications or of semiconductor materials known per se.
  • Conductive carbon black or graphite can be considered as conductive carbon modifications.
  • furnace black, oil furnace black or gas black, acetylene black, in particular their special, electrically highly conductive types can be used as conductive carbon black.
  • high-conductivity carbon blacks such as e.g. the commercially available high conductivity carbon black (R) Printex XE2 from Degussa, Frankfurt (M).
  • Semiconductor materials which are suitable in fine distribution to impart the desired conductivity to the core material of the filaments according to the invention are, for example, n- or p-doped metal oxides.
  • Electrically conductive materials based on metal oxides consist of mixed oxides in which an oxide component of a metal which is present in a smaller or smaller amount with a different valence or with a different ion radius is built into the crystal lattice of the main component.
  • Examples of such mixed oxides are nickel oxide, cobalt oxide, iron oxide or manganese oxide, doped with lithium oxide; Zinc oxide doped with aluminum oxide; Titanium oxide doped with tantalum oxide; Bismuth oxide doped with barium oxide; Iron oxide (Fe2O3) doped with titanium oxide; Titanium barium oxide (BaTiO3) doped with lanthanum or tantalum oxide; Chromium-lanthanum oxide (LaCrO3) or manganese-lanthanum oxide (LaHnO3) doped with strontium oxide or chromium oxide doped with magnesium oxide.
  • the above list is by no means exhaustive. Numerous other known mixed oxides are suitable, but also other known compounds with electrical semiconductor properties, e.g. those based on metal sulfides.
  • a preferred solid semiconductor material that can impart the desired electrical conductivity to the core material of the filaments according to the invention in finely divided form is e.g. antimony or iodine-doped tin oxide.
  • the electrically conductive particles dispersed in the core of the electrically conductive filaments according to the invention have an average particle size, which is expediently below 5 »m for" textile "filament titers.
  • the conductive particles preferably have an average particle size below 1 »m, in particular below 0.3» m.
  • the amount of conductive particles contained in the core polymer depends on the requirements placed on the conductivity of the filament and on the nature of the conductivity additive.
  • Conductive carbon modifications are dispersed in a fine distribution in the core of the filaments according to the invention in an amount of 5-60% by weight, preferably 5 to 30% by weight, in particular 8-15% by weight.
  • Semiconductor materials e.g. the above-mentioned, based on doped metal oxides, are contained in the core in an amount of 60-80% by weight, preferably 65-75% by weight.
  • the antistatic contained in the sheath of the filaments according to the invention has sulfonate or carboxylate groups, ie salts of sulfonic or carboxylic acids.
  • the nature of the salt-forming metal is of minor importance in principle. However, preference is given to sulfonates or carboxylates which have a mono- or divalent metal, preferably an alkali metal or an alkaline earth metal. Of the two salt-forming groups mentioned, the sulfonic acid group and thus the sulfonates are particularly preferred.
  • the organic compounds containing the sulfonate or carboxylate groups should diffuse as little as possible in the sheath polymer of the filaments according to the invention.
  • One way of keeping the diffusion of these antistatic additives low is to use compounds which have a long-chain polyether or alkyl radical which has 8 to 30 C atoms in its chain.
  • compositions which contain an alkyl chain having 8 to 30, preferably 12 to 18, carbon atoms are particularly preferred.
  • Particularly preferred as antistatic agents for the shell polymer of the filaments according to the invention are alkanesulfonates with the chain lengths mentioned above, in particular their sodium or potassium salts.
  • the polymers used for the core and the sheath of the two-component filaments according to the invention can be the same or different. With regard to the functions of the core and the sheath, it has proven to be advantageous to use different materials that can be optimally adapted to the desired function.
  • the sheath is expediently made of a polymer which conveys the desired textile properties, in particular strength and further processability, to the two-component filament according to the invention, while the core must guarantee the permanent electrical conductivity of the material, ie that it maintains its continuity in all further processing steps of the filament must maintain and have an optimal carrying capacity for the dispersed solid semiconductor material. It is not essential for the core that the polymer can be spun into threads on its own and therefore no thread-forming polymer has to be used for this. On the other hand, the use of thread-forming polymers for the core material is generally advisable.
  • a polymer for the core of the two-component filaments according to the invention which has a lower melting point than the polymer of the sheath.
  • the melting point difference should be at least 20 ° C, preferably at least 40 ° C.
  • the polymer of the core consists of polyethylene or polyamide 6 or of a copolyamide or a copolyester, the co-components of which are selected in a manner known per se so that the desired melting point difference is obtained.
  • suitable polymers for the core of the filaments according to the invention are block copolymers with hard and soft segments, e.g. Block polyether esters or other polyalkylenes such as e.g. rel. low molecular weight polypropylene.
  • High-molecular polymers in particular polyesters or polyamides, are particularly suitable as the material for the sheath of the two-component filaments according to the invention, which preferably determines the textile properties of the filament material.
  • Particularly advantageous properties have two-component filaments according to the invention, the sheath of which consists of polyesters, preferably of polyethylene terephthalate.
  • the volume fraction of the core in the total filament according to the invention is 2 to 50, preferably 5 to 20%.
  • the sheath of the antistatic filaments according to the invention can also contain other additives customary in synthetic fibers, such as e.g. Matting agents or pigments, contained in the usual amounts.
  • the sheath of the filaments according to the invention contains a matting agent which prevents or reduces the shining through of the core, which may be colored due to its added conductivity.
  • the amount of matting agent is chosen so that the desired effect is achieved.
  • a preferred matting agent is titanium dioxide, which can usually be present in the filament sheath in proportions of 0.5 to 3% by weight.
  • the electrically conductive two-component filaments according to the invention are produced by first producing a core material by homogeneously mixing in a finely divided form or preparation, e.g. a powder or a user-friendly powder preparation in granular or pearl form, one of the above-mentioned electrically conductive materials made of conductive carbon or of semiconductor materials in a first polymer material that a jacket material is produced by homogeneously mixing in one of the above-mentioned antistatic agents based on a metal salt of a long-chain aliphatic residue having carbon or sulfonic acid and optionally other conventional additives in a second polymer material, wherein the first and second polymer material can also be identical in that the prepared core and sheath materials are spun out of a known spinning arrangement to core-sheath filaments, the volume shares of core and cladding material spun out in the time unit are in a ratio of 2:98 to 1: 1.
  • a core material by homogeneously mixing in a finely divided form or preparation
  • filaments with different degrees of orientation and thus different mechanical properties e.g. Tear resistance, extensibility, initial modulus, preserved.
  • the filaments, as they are spun already have a high degree of orientation and therefore good mechanical and textile technology quality.
  • This stretching takes place in the range from 5% above the natural stretching ratio to 95% of the maximum stretching ratio, preferably in a ratio of 1: 3 to 1: 5, in particular from 1: 3 to 1: 4.
  • the filaments can, if desired, also be subjected to a conventional fixing treatment, a shrinkage of 0 to 8%, preferably 0 to 4%, being generally permitted during the fixing or immediately thereafter.
  • the drawing and fixing temperatures are adapted to the processed fiber material in a known manner.
  • the stretching temperature is usually in the range from 40 to 200 ° C., preferably from 40 to 160 ° C., while the fixing treatment is carried out in the temperature range from 100 to 240 ° C.
  • the filaments thus produced can then be further processed into textile products in any known manner.
  • the filaments can be combined to form continuous yarns and, if necessary, textured in the usual way, for example by blast texturing, by a false twist process or by further stretch texturing, or the spun filaments can be subjected to compression crimping before or after texturing, cut into staple fibers and secondary spun.
  • Preference is given to further processing the electrically conductive filaments according to the invention into continuous yarns, which are then converted into the desired textile products in a manner known per se.
  • the textile products produced from the electrically conductive two-component filaments according to the invention such as continuous yarn in textured or non-textured form, staple fiber yarn, but also intermediate forms such as cables or filament tapes, and those made from the filamentary materials sheet-like textile products are the subject of this invention.
  • the electrically conductive filaments according to the invention surprisingly have good electrical conductivity even at low voltages, which means that only significantly lower electrical charges can result than with conventional filaments with an electrically conductive core.
  • the electrical conductivity of the filaments according to the invention has a significantly better wash resistance than known filaments which are modified in a conventional manner with antistatic agents.
  • the particularly advantageous conductivity behavior of the filaments according to the invention is supplemented by excellent textile technology properties.
  • a core-sheath thread was spun from these two components using a bicomponent melt spinning unit at 265 ° C. from a 32-hole nozzle and spooled at 700 m / min.
  • the volume fraction of the core was 10%.
  • a core-sheath thread was produced from these two components as described in Example 1.
  • Example 1 The antistatic jacket material from Example 1 was spun on the same bicomponent system, but no core material was added, so that a One-component thread was obtained, which was drawn as in Examples 1 and 2.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Multicomponent Fibers (AREA)
  • Artificial Filaments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (10)

  1. Filaments à deux composants, synthétiques, antistatiques, de type âme-gaine, avec une âme ayant une conductibilité électrique élevée, à base d'un polymère synthétique, dans lequels sont dispersées des particules solides, conductrices de l'électricité, les particules conductrices solides de l'âme étant formées de carbone conducteur ou de matériaux semi-conducteurs connus, caractérisés en ce que la gaine a de même une conductibilité élevée et est formée d'un polymère formant des fils, qui contient un sel métallique d'un acide sulfonique ou carboxylique présentant un reste aliphatique à longue chaîne, la quantité de carbone conducteur dans l'âme étant de 3 à 60% en poids et la quantité en matériau semi-conducteur dans l'âme étant de 60 à 80% en poids.
  2. Filaments à deux composants selon la revendication 1, caractérisés en ce que les particules conductrices solides du matériau de l'âme sont formées de noir de fumée hautement conducteur ou d'oxyde d'étain dopé par de l'antimoine ou de l'iode.
  3. Filaments à deux composants selon une des revendications 1 à 2, caractérisés en ce que, dans l'âme, 5 à 30% en poids de carbone conducteur ou 65 à 75% en poids de matériau semi-conducteur sont dispersés en fines particules.
  4. Filaments à deux composants selon au moins une des revendications 1 à 3, caractérisés en ce que l'agent antistatique de la gaine est un sel métallique d'un acide alkylsulfonique ayant de 8 à 30 atomes de carbone, de préférence de 12 à 18 atomes de carbone.
  5. Filaments à deux composants selon au moins une des revendications 1 à 4, caractérisés en ce que le sel métallique, utilisé en tant qu'agent antistatique, de la gaine est un sel de sodium ou de potassium.
  6. Filaments à deux composants selon au moins une des revendications 1 à 5, caractérisés en ce que le polymère de l'âme a un point de fusion inférieur à celui de la gaine.
  7. Filaments à deux composants selon au moins une des revendications 1 à 6, caractérisés en ce que le polymère de l'âme est un polyéthylène ou un polyéther-ester séquencé.
  8. Filaments à deux composants selon au moins une des revendications 1 à 8, caractérisés en ce que le polymère de la gaine est un polyamide ou un polyester, de préférence le polyéthylènetéréphtalate.
  9. Filaments à deux composants synthétiques, antistatiques, selon la revendication 1, se présentant sous la forme d'un matériau textile de forme plane ou à base de fils.
  10. Procédé de préparation d'un filament à deux composants synthétique, antistatique, de type âme-gaine, caractérisé en ce que un matériau de l'âme est préparé par mélange homogène d'un matériau conducteur de l'électricité, solide, finement divisé, à base de carbone conducteur ou à base de matériau semi-conducteur dans un premier matériau polymère, un matériau de gaine est préparé par mélange homogène d'un sel métallique d'un acide sulfonique ou carboxylique présentant un reste aliphatique à longue chaîne dans un deuxième matériau polymère, le matériau de l'âme et le matériau de la gaine sont filés en filaments âme-gaine à partir d'un dispositif de filage connu en soi, les parties en volume filées du matériau de l'âme et du matériau de la gaine dans l'unité de temps se trouvant dans un rapport compris entre 2:98 et 1:1, les filaments obtenus sont étirés dans un domaine allant de 5% au dessus du rapport d'étirage naturel jusqu'à 95% du rapport d'étirage maximum à une température d'étirage comprise entre 90 et 200°C et ensuite sont fixés à une température comprise entre 100 et 240°C en autorisant un changement de longueur de 0 à 8%, de préférence de 0 à 4%.
EP90113145A 1989-07-13 1990-07-10 Filament âme-gaine antistatique Expired - Lifetime EP0407960B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3923086A DE3923086A1 (de) 1989-07-13 1989-07-13 Antistatisches kern-mantel-filament
DE3923086 1989-07-13

Publications (3)

Publication Number Publication Date
EP0407960A2 EP0407960A2 (fr) 1991-01-16
EP0407960A3 EP0407960A3 (en) 1991-09-11
EP0407960B1 true EP0407960B1 (fr) 1995-06-28

Family

ID=6384904

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90113145A Expired - Lifetime EP0407960B1 (fr) 1989-07-13 1990-07-10 Filament âme-gaine antistatique

Country Status (8)

Country Link
US (1) US5213892A (fr)
EP (1) EP0407960B1 (fr)
JP (1) JPH0345705A (fr)
AT (1) ATE124473T1 (fr)
BR (1) BR9003334A (fr)
CA (1) CA2021011A1 (fr)
DE (2) DE3923086A1 (fr)
ES (1) ES2076267T3 (fr)

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DE19646519A1 (de) * 1996-11-12 1998-05-14 Pedex & Co Gmbh Zahnpflegegerät und Verfahren zur Herstellung von Reinigungselementen für Zahnpflegegeräte
US6589392B1 (en) * 2001-10-18 2003-07-08 Shakespeare Company Llc Multicomponent monofilament for papermaking forming fabric
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US7238415B2 (en) * 2004-07-23 2007-07-03 Catalytic Materials, Llc Multi-component conductive polymer structures and a method for producing same
FR2933426B1 (fr) * 2008-07-03 2010-07-30 Arkema France Procede de fabrication de fibres conductrices composites, fibres obtenues par le procede et utilisation de telles fibres
EP3199673B1 (fr) * 2014-09-24 2020-08-05 Kai-Li Huang Fibre de contrôle environnemental à énergie verte, procédé de fabrication de celle-ci et tissu fabriqué à partir de celle-ci
WO2017176604A1 (fr) * 2016-04-06 2017-10-12 Ascend Performance Materials Operations Llc Fibre antistatique de couleur claire/résistance faible et textiles incorporant la fibre
CA3039312A1 (fr) * 2016-11-01 2018-05-11 Teijin Limited Tissu, son procede de fabrication et produit fibreux
US10760186B2 (en) * 2017-03-29 2020-09-01 Welspun Flooring Limited Manufacture of bi-component continuous filaments and articles made therefrom
JP7394439B2 (ja) * 2019-09-25 2023-12-08 日本エステル株式会社 導電性マルチフィラメント、導電性マルチフィラメントの製造方法、織編物およびブラシ
DE102020120303A1 (de) 2020-07-31 2022-02-03 Rheinisch-Westfälische Technische Hochschule (Rwth) Aachen Elektrisch leitfähiges Monofilament

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Also Published As

Publication number Publication date
ES2076267T3 (es) 1995-11-01
DE59009318D1 (de) 1995-08-03
EP0407960A3 (en) 1991-09-11
DE3923086A1 (de) 1991-01-24
US5213892A (en) 1993-05-25
JPH0345705A (ja) 1991-02-27
EP0407960A2 (fr) 1991-01-16
BR9003334A (pt) 1991-08-27
ATE124473T1 (de) 1995-07-15
CA2021011A1 (fr) 1991-01-14

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