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EP1417360B1 - Procede de production de fibres ou d'un produit fibreux dans un processus de filage electrostatique - Google Patents

Procede de production de fibres ou d'un produit fibreux dans un processus de filage electrostatique Download PDF

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Publication number
EP1417360B1
EP1417360B1 EP02754415A EP02754415A EP1417360B1 EP 1417360 B1 EP1417360 B1 EP 1417360B1 EP 02754415 A EP02754415 A EP 02754415A EP 02754415 A EP02754415 A EP 02754415A EP 1417360 B1 EP1417360 B1 EP 1417360B1
Authority
EP
European Patent Office
Prior art keywords
substance
added
process according
electron system
solution
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
EP02754415A
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German (de)
English (en)
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EP1417360A1 (fr
Inventor
Wolfgang Czado
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.)
Mann and Hummel Innenraumfilter GmbH and Co KG
Original Assignee
Helsa Automotive GmbH and Co KG
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Publication date
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Priority claimed from DE10155448A external-priority patent/DE10155448A1/de
Application filed by Helsa Automotive GmbH and Co KG filed Critical Helsa Automotive GmbH and Co KG
Publication of EP1417360A1 publication Critical patent/EP1417360A1/fr
Application granted granted Critical
Publication of EP1417360B1 publication Critical patent/EP1417360B1/fr
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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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • 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

Definitions

  • the present invention relates to a process for producing fibers or a fiber product in an electrostatic spinning process.
  • the production of fibers or fiber products, e.g. of nonwovens, in an electrostatic spinning process has been known in principle from the prior art for some time.
  • a polymer solution or a polymer melt is applied to an electrode and charged by a high electrical voltage. If you now bring a counter electrode in the vicinity, then electrical forces act on the polymer solution or on the polymer melt and pull the finest fibers from this electrode.
  • Various electrode and applicator devices have already been described for carrying out these methods. Representative here are e.g. DE 20 32 072, EP 1 059 106, US 3,994,258, US 4,144,553, US 4,323,525 and US 4,287,139.
  • DE 20 32 072 discloses the fiber diameter of the fiber produced during spinning of a polymer solution in an electrostatic spinning process. In this case, with an improved conductivity of the polymer solution to be spun fibers with a smaller fiber diameter can be obtained.
  • DE 20 32 072 discloses the addition of ionizable organic salts.
  • EP 1 059 106 likewise discloses additives for controlling the charge, viscosity, surface tension and the conductivity of a polymer solution or polymer melt to be spun in an electrostatic spinning process.
  • these additives are expressly used to improve the spinning of the polymer solution or the polymer melt, without a remaining charge or To charge the generated fibers.
  • a permanent electrical charging of the fibers or fiber products produced is to be avoided according to the teaching of EP 1 059 106.
  • this is disadvantageous for the use of these materials for the filtering of air, since it is only possible to mechanically deposit dust particles without electrically charged fibers.
  • the method mentioned in the introduction is inventively further developed in that polymers are spun from solution and / or from the melt and the solution and / or the melt before spinning one or more oxidizable substances or substances are added with a ⁇ -electron system, whereby the charge advantageously increased in the solution to be spun and preserved in the fibers. That the process according to the invention makes it possible to produce electrically charged fibers or a fiber product consisting of such fibers in an electrostatic spinning process.
  • the products of the process according to the invention are preferably used in the production of filter materials.
  • the added substance or the added substances preferably at least stabilize a positive charge or these Have substances in the corresponding solvent over one or more oxidation potentials, which can be determined by cyclic voltammetry.
  • the present invention is based on the finding that a significant procedural improvement is possible when in the to be spun polymer solution or polymer melt a real excess charge is generated, acts on the electric field.
  • Bromothymol blue, methyl red, rhodamine B and crystal violet in dichloromethane as solvent and ferrocene as reference were measured cyclovoltammetrically to investigate this phenomenon.
  • Bromthymolblau has no oxidation potential in the measuring range, which is accessible in dichloromethane.
  • Bromthymolblau has also shown to be completely ineffective as an additive in dichloromethane in the context of the present invention.
  • methyl red, rhodamine B and crystal violet have oxidation potentials in the range from 0.9 to 1.14 V and are extremely effective representatives of the additives according to the invention.
  • Ferrocene itself with an oxidation potential of 0.38 V is also an effective additive.
  • solvents with comparatively high dielectric constants as particularly preferred e.g. Butanone, acetonitrile, dimethyl sulfoxide, water, dimethylformamide, n-methylformamide, acetone, ethanol and ethylene glycol
  • solvents with comparatively high dielectric constants as particularly preferred e.g. Butanone, acetonitrile, dimethyl sulfoxide, water, dimethylformamide, n-methylformamide, acetone, ethanol and ethylene glycol
  • the content of polymer in the same can vary accordingly, in particular also increase.
  • the polarity of the solvent can be further increased or increased by adding a substance with a very high dielectric constant.
  • the solvent having a comparatively large dielectric constant has a relative dielectric constant of at least 15.0 at a temperature of 20 ° C.
  • the substance used to increase the polarity of the solvent having a very high dielectric constant or substances having very high dielectric constants respectively has or has a relative dielectric constant of at least 20.0, more preferably of at least 30.0 at 20 ° C. . exhibit.
  • diazonium dyes preferably diazo salts, e.g. Echtblausalz B or BB, Echtviolettsalz B or Echtrotsalz GG suitable.
  • charge transfer complexes such as e.g. crystal violet and iodine, or quinone and hydroquinone, have been found to be effective in the present invention.
  • much of the cited dyes are attributed to the basic or acid dyes, i. they are salts of negatively or positively charged dye molecules. It can be concluded that dye molecules charged from the outset represent a particularly suitable additive in the process according to the invention.
  • substances with an extended ⁇ -electron system which is preferably resonance-stabilized, are particularly well suited as an additive in the process according to the invention if they contain functional groups such as amino, amido, imino, azo, nitro , Carboxy, diazonium, hydroxy, thio, sulfo or halogen groups.
  • functional groups such as amino, amido, imino, azo, nitro , Carboxy, diazonium, hydroxy, thio, sulfo or halogen groups.
  • the addition of the one or more substances to the polymer solution or polymer melt can take place according to the invention over a relatively broad range.
  • the person skilled in the art will easily determine the required proportion by weight based on the desired and desired product properties in the end product. In principle, however, it is preferred if the addition of one or more substances takes place in an amount of from 0.1 to 50% by weight of the polymer solution or polymer melt, more preferably in an amount of from 0.5 to 5% by weight.
  • halogens preferably with chlorine, or strong acids or bases, nitrogen oxides or sulfur oxides.
  • hydrogen halides e.g. Hydrochloric acid gas
  • bases e.g. Ammonia
  • polymers can be spun with the process according to the invention, which can be spun from a solution or from the melt.
  • polymers soluble in organic solvents are mentioned here, such as polystyrene, polycarbonate, polyvinyl chloride, polyacrylate, polymethacrylate, polyvinyl acetate, polyvinyl acetal, polyvinyl ether, polyurethane, polyamide, polysulfone, polyethersulfone, polyacrylonitrile, cellulose derivatives, and the like Mixtures and copolymers of these polymers.
  • thermoplastics here are, for example, polyolefins, polyesters, polyoxymethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyaryletherketone, polyvinylidene fluoride and mixtures and copolymers of these polymers mentioned.
  • copolymers of polystyrene such as styrene / acrylonitrile copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer have been found to be particularly suitable.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (8)

  1. Procédé pour la fabrication de fibres ou d'un produit fibreux, dans un processus de filage électrostatique, dans lequel des polymères sont filés à partir de leur solution ou de leur état de fusion, et, à la solution et/ou à la fusion est, ou sont ajoutée(s), avant le filage, une ou plusieurs substances oxydables ou une ou plusieurs substances comportant un système électronique π et un solvant polaire et/ou une substance destinée à augmenter la polarité de l'agent dissolvant, et dans lequel la solution de polymère ou le polymère en fusion est pulvérisé à partir de l'anode, et la, ou les substance(s) oxydable(s) ajoutée(s), ou la, ou les substances comportant un système électronique π est (sont) stabilisée(s) par au moins une charge positive, de telle sorte que les fibres ou le produit fibreux porte(nt), après le filage, une charge électrique.
  2. Procédé selon la revendication 1, caractérisé en ce que la, ou les substance(s) oxydable(s) ajoutée(s), et la, ou les substance(s) comportant un système électronique π ajoutée(s) est (sont) choisie(s) dans le groupe constitué par les matières colorantes organiques, de préférence les matières colorantes basiques ou acides, leurs précurseurs ou leur dérivés, les complexes de transfert de charge, les métallocènes, et les phtalocyanines, ainsi que les éclaircisseurs optiques.
  3. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la, ou les substance(s) oxydable(s) ou la, ou les substance(s) comportant un système électronique π ajoutée(s) présente(nt) des propriétés de stabilisation de charge apportées par un groupe fonctionnel, plus particulièrement un groupe amino-, amido- imino-, azo-, diazonium, nitro-, carboxy-, hydroxy-, thio-, sulfo- ou halogèno-.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le filage est exécuté à partir d'une solution, et comme agent dissolvant est utilisé, en particulier la butanone, l'acétonitrile, le diméthylsulfoxyde, l'eau, la diméthylformamide, un ester acétique, l'acétone, l'éthanol ou l'éthylène-glycol.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'addition de la (ou des) substance(s) oxydable(s) ou de la (ou des) substance(s) comportant un système électronique π est pratiquée à raison d'une quantité de 0,1 à 50 % en poids de la solution de polymère ou du polymère en fusion, et de préférence de 0,5 à 5 % en poids.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le (ou les) substance(s) oxydable(s), ou la (ou les) substance(s) comportant un système électronique π est (sont) incolore(s).
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la (ou les) substance(s) oxydable(s), ou la (ou les) substance(s) comportant un système électronique π est (sont) décolorée(s), avant addition à la solution de polymère ou au polymère en fusion, par transformation chimique, en particulier par alkylation, acylation, estérification, silylation, diazotation, ou oxydation, ou par réaction avec des halogènes, plus particulièrement le chlore, ou avec des acides ou bases forts, des oxydes d'azote ou des oxydes de soufre.
  8. Utilisation des fibres ou des produits fibreux fabriqués conformément à un procédé selon l'une quelconque des revendications précédentes, en vue de la fabrication d'agents de filtration de l'air, et plus particulièrement de filtres d'air de cabine, de filtres pour air recyclé, de filtres d'air évacué, de filtres pour habitation, ou de filtres pour aspirateurs de poussière.
EP02754415A 2001-07-30 2002-07-23 Procede de production de fibres ou d'un produit fibreux dans un processus de filage electrostatique Expired - Lifetime EP1417360B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10137160 2001-07-30
DE10137160 2001-07-30
DE10155448 2001-11-12
DE10155448A DE10155448A1 (de) 2001-07-30 2001-11-12 Verfahren zur Herstellung von Fasern oder eines Faserprodukts in einem elektrostatischen Spinnverfahren
PCT/DE2002/002704 WO2003014430A1 (fr) 2001-07-30 2002-07-23 Procede de production de fibres ou d'un produit fibreux dans un processus de filage electrostatique

Publications (2)

Publication Number Publication Date
EP1417360A1 EP1417360A1 (fr) 2004-05-12
EP1417360B1 true EP1417360B1 (fr) 2004-12-22

Family

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EP02754415A Expired - Lifetime EP1417360B1 (fr) 2001-07-30 2002-07-23 Procede de production de fibres ou d'un produit fibreux dans un processus de filage electrostatique

Country Status (3)

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US (1) US20040207126A1 (fr)
EP (1) EP1417360B1 (fr)
WO (1) WO2003014430A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6743273B2 (en) 2000-09-05 2004-06-01 Donaldson Company, Inc. Polymer, polymer microfiber, polymer nanofiber and applications including filter structures
WO2004069378A2 (fr) * 2003-02-05 2004-08-19 Helsa-Werke Helmut Sandler Gmbh & Co. Kg Element filtrant et procede de realisation
DE102008022759B4 (de) * 2007-05-17 2019-03-07 Sumitomo Chemical Co. Ltd. Verfahren zur Herstellung einer Polyethersulfonfaser, Polyethersulfonfaser und deren Verwendung
WO2010107503A1 (fr) 2009-03-19 2010-09-23 Millipore Corporation Élimination de micro-organismes dans des échantillons de fluide en utilisant des milieux de filtration à nanofibres
SG185659A1 (en) 2010-08-10 2012-12-28 Emd Millipore Corp Method for retrovirus removal
US11154821B2 (en) 2011-04-01 2021-10-26 Emd Millipore Corporation Nanofiber containing composite membrane structures
US9365951B2 (en) 2014-01-30 2016-06-14 Kimberly-Clark Worldwide, Inc. Negative polarity on the nanofiber line
KR20160134792A (ko) 2014-06-26 2016-11-23 이엠디 밀리포어 코포레이션 개선된 먼지 포집 능력을 갖는 필터 구조
EP3283202A1 (fr) 2015-04-17 2018-02-21 EMD Millipore Corporation Procédé de purification d'une matière biologique d'intérêt dans un échantillon au moyen de membranes d'ultrafiltration à nanofibres mises en oeuvre en mode de filtration de flux tangentiel
US9951443B2 (en) * 2015-12-31 2018-04-24 University Of Tartu Separators, electrodes, half-cells, and cells of electrical energy storage devices
WO2019016605A1 (fr) 2017-07-21 2019-01-24 Merck Millipore Ltd Membranes de fibres non tissées
US11180867B2 (en) 2019-03-20 2021-11-23 University Of Kentucky Research Foundation Continuous wet-spinning process for the fabrication of PEDOT:PSS fibers with high electrical conductivity, thermal conductivity and Young's modulus
CN116043339B (zh) * 2022-07-19 2024-05-31 国家粮食和物资储备局科学研究院 一种纳米纤维递送载体及其制备方法和应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US705691A (en) * 1900-02-20 1902-07-29 William James Morton Method of dispersing fluids.
US1935205A (en) * 1927-12-13 1933-11-14 Celanese Corp Manufacture of new dyestuffs and the application thereof
US2197896A (en) * 1937-02-15 1940-04-23 Du Pont Artificial wool
US3411903A (en) * 1964-11-23 1968-11-19 Xerox Corp Xerographic method and plate comprising photoconductive insulating fibers
US4657793A (en) * 1984-07-16 1987-04-14 Ethicon, Inc. Fibrous structures
DE3837345A1 (de) * 1988-11-03 1990-05-10 Hoechst Ag Verwendung farbloser hochgradig fluorierter ammonium- und immoniumverbindungen als ladungssteuermittel fuer elektrophotographische aufzeichnungsverfahren
DE59410352D1 (de) * 1993-03-09 2004-03-11 Trevira Gmbh Elektretfasern mit verbesserter Ladungsstabilität, Verfahren zu ihrer Herstellung, und Textilmaterial enthaltend diese Elektretfasern
US6800155B2 (en) * 2000-02-24 2004-10-05 The United States Of America As Represented By The Secretary Of The Army Conductive (electrical, ionic and photoelectric) membrane articlers, and method for producing same
DE10063518C2 (de) * 2000-12-20 2003-11-20 Sandler Helmut Helsa Werke Verfahren zum elektrostatischen Spinnen von Polymeren zum Erhalt von Nano- und Mikrofasern

Also Published As

Publication number Publication date
US20040207126A1 (en) 2004-10-21
EP1417360A1 (fr) 2004-05-12
WO2003014430A1 (fr) 2003-02-20

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