EP1417360A1 - 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

Info

Publication number
EP1417360A1
EP1417360A1 EP02754415A EP02754415A EP1417360A1 EP 1417360 A1 EP1417360 A1 EP 1417360A1 EP 02754415 A EP02754415 A EP 02754415A EP 02754415 A EP02754415 A EP 02754415A EP 1417360 A1 EP1417360 A1 EP 1417360A1
Authority
EP
European Patent Office
Prior art keywords
substance
added
electron system
solution
oxidizable
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.)
Granted
Application number
EP02754415A
Other languages
German (de)
English (en)
Other versions
EP1417360B1 (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+hummel Innenraumfilter & Co KG GmbH
Original Assignee
Helsa Werke Helmut Sandler GmbH and Co KG
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
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Priority claimed from DE10155448A external-priority patent/DE10155448A1/de
Application filed by Helsa Werke Helmut Sandler GmbH and Co KG filed Critical Helsa Werke Helmut Sandler GmbH and Co KG
Publication of EP1417360A1 publication Critical patent/EP1417360A1/fr
Application granted granted Critical
Publication of EP1417360B1 publication Critical patent/EP1417360B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 method for producing fibers or a fiber product in an electrostatic spinning process.
  • the manufacture of fibers or fiber products, e.g. of nonwovens, in an electrostatic spinning process has basically been known for some time from the prior art.
  • a polymer solution or a polymer melt is applied to an electrode and charged by a high electrical voltage. If a counterelectrode is brought close, electrical forces act on the polymer solution or on the polymer melt and pull the finest fibers from this electrode.
  • Various electrode and application 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 already discloses that the fiber diameter of the fiber produced when spinning a polymer solution in an electrostatic spinning process can be influenced by the conductivity of the solution. Fibers with a smaller fiber diameter can be obtained with an improved conductivity of the polymer solution to be spun. To achieve this, DE 20 32 072 discloses the addition of organic salts which can be converted into ions.
  • EP 1 059 106 also contains additives for controlling the charge, viscosity, surface tension and conductivity in an electrostatic
  • the above-mentioned process is further developed according to the invention in that polymers are spun from solution and / or from the melt and one or more oxidizable substances or substances with a ⁇ -electron system are added to the solution and / or the melt before spinning, whereby the charge is advantageously increased in the solution to be spun and can be preserved in the fibers. That the method according to the invention enables the production of electrically charged fibers or a fiber product consisting of such fibers in an electrostatic spinning process.
  • the products of the method according to the invention are preferably used in the manufacture of filter materials.
  • the present invention is based on the finding that a significant improvement in process engineering is possible if in the a real excess charge is generated on the polymer solution or polymer melt to be spun, on which the electric field acts.
  • bromothymol blue, methyl red, rhodamine B and crystal violet were measured in dichloromethane as a solvent and with ferrocene as a reference using cyclic voltammetry.
  • Bromthymol blue has no oxidation potential in the measuring range which is accessible in dichloromethane.
  • bromothymol blue as an additive in dichloromethane has been shown to be completely ineffective in the sense of the present invention.
  • Methyl red, rhodamine B and crystal violet have an oxidation potential 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 large dielectric constants such as particularly preferably e.g. Butanone, acetonitrile,
  • the fiber diameter of the fibers obtained in the process according to the invention can preferably be set by the suitable choice of the solvent and / or the added substances.
  • the polarity of the solvent can also be increased or increased by adding a substance with a very high dielectric constant. For a solution of polystyrene in dichloromethane or ethyl acetate this is e.g. possible by adding acetamide.
  • increasing the polarity of the solvent is not sufficient. It is therefore of crucial importance for the present invention that both a charge carrier and a polar solvent are present which presumably stabilize the charge carrier.
  • the solvent with a comparatively large dielectric constant has a relative dielectric constant of at least 15.0 at a temperature of 20 ° C. It is further preferred that the substance used to increase the polarity of the solvent with a very high dielectric constant or substances used with very high dielectric constants each have a relative dielectric constant of at least 20.0, more preferably of at least 30.0 at 20 ° C. . exhibit. In combination with the polar solvents listed above, a surprisingly large number of substances are suitable as charge carriers, which then do not necessarily have to have an oxidation potential.
  • diazonium dyes preferably diazo real salts, such as e.g. Real blue salt B or BB, real violet salt B or real red salt GG.
  • diazo real salts such as e.g. Real blue salt B or BB, real violet salt B or real red salt GG.
  • Charge transfer complexes e.g. from crystal violet and iodine or from quinone and hydroquinone, proven to be effective in the sense of the present invention.
  • a large part of the dyes listed can be assigned to the basic or acid dyes, i.e. they are salts of negatively or positively charged dye molecules. It can be concluded from this that dye molecules which have been charged from the outset represent a particularly suitable additive in the process according to the invention.
  • substances with an extensive ⁇ -electron system which is preferably resonance-stabilized, are particularly suitable as an additive in the process according to the invention if they contain functional groups such as amino, amido, imino, azo, nitro- Contain, carboxy, diazonium, hydroxy, thio, sulfo or halogen groups.
  • functional groups such as amino, amido, imino, azo, nitro- Contain, carboxy, diazonium, hydroxy, thio, sulfo or halogen groups.
  • the one or more substances can be added to the polymer solution or polymer melt over a relatively wide 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. Basically, however, it is preferred if one or more substances are added in an amount of 0.1 to 50% by weight of the polymer solution or polymer melt, more preferably in an amount of 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, or bases, e.g. Ammonia, especially proven.
  • polymers which can be spun from a solution or from the melt can be spun using the process according to the invention.
  • Polymers that are soluble in organic solvents such as polystyrene, polycarbonate, polyvinyl chloride, polyacrylate, polymethacrylate, polyvinyl acetate, polyvinyl acetal, polyvinyl ether, polyurethane, polyamide, polysulfone, polyethersulfone, polyacrylonitrile, cellulose derivatives and the like, are particularly worth mentioning here Mixtures and copolymers of these polymers.
  • thermoplastics examples are polyolefins, polyesters, polyoxymethylene, polychlorotrifluoroethylene, polyphenylene sulfide, polyaryl ether ketone, polyvinylidene fluoride and mixtures and copolymers of these polymers.
  • copolymers of polystyrene such as styrene / acrylonitrile copolymer, styrene / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, have proven to be particularly suitable.
  • Polymethyl methacrylate is possible, it being possible for these polymers to be spun in the solution even at concentrations below 10% by weight of polymer, in particular up to a concentration of about 3% by weight.

Abstract

L'invention concerne un procédé permettant de produire des fibres ou un produit fibreux dans un processus de filage électrostatique. Des polymères sont filés en solution et/ou en fusion et avant filage, une ou plusieurs substances oxydables ou des substances ayant un système d'électrons TT sont ajoutées à la solution et/ou à la matière en fusion.
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
DE10155448A DE10155448A1 (de) 2001-07-30 2001-11-12 Verfahren zur Herstellung von Fasern oder eines Faserprodukts in einem elektrostatischen Spinnverfahren
DE10155448 2001-11-12
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 true EP1417360A1 (fr) 2004-05-12
EP1417360B1 EP1417360B1 (fr) 2004-12-22

Family

ID=26009812

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

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

Families Citing this family (10)

* 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
EP2408482A1 (fr) 2009-03-19 2012-01-25 Millipore Corporation Élimination de micro-organismes dans des échantillons de fluide en utilisant des milieux de filtration à nanofibres
WO2012021308A2 (fr) 2010-08-10 2012-02-16 Millipore Corporation Procédé pour l'élimination de rétrovirus
JP6219811B2 (ja) 2011-04-01 2017-10-25 イー・エム・デイー・ミリポア・コーポレイシヨン ナノファイバー含有複合材構造体
US9365951B2 (en) 2014-01-30 2016-06-14 Kimberly-Clark Worldwide, Inc. Negative polarity on the nanofiber line
KR102206963B1 (ko) 2015-04-17 2021-01-25 이엠디 밀리포어 코포레이션 접선방향 유동 여과 모드에서 작동되는 나노섬유 한외여과막을 사용하여 샘플에서 목적하는 생물학적 물질을 정제하는 방법
US9951443B2 (en) * 2015-12-31 2018-04-24 University Of Tartu Separators, electrodes, half-cells, and cells of electrical energy storage devices
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

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
ATE259007T1 (de) * 1993-03-09 2004-02-15 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03014430A1 *

Also Published As

Publication number Publication date
WO2003014430A1 (fr) 2003-02-20
EP1417360B1 (fr) 2004-12-22
US20040207126A1 (en) 2004-10-21

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