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EP1283283B1 - Procédé pour la fabrication d'un produit fibreux - Google Patents

Procédé pour la fabrication d'un produit fibreux Download PDF

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Publication number
EP1283283B1
EP1283283B1 EP02016474A EP02016474A EP1283283B1 EP 1283283 B1 EP1283283 B1 EP 1283283B1 EP 02016474 A EP02016474 A EP 02016474A EP 02016474 A EP02016474 A EP 02016474A EP 1283283 B1 EP1283283 B1 EP 1283283B1
Authority
EP
European Patent Office
Prior art keywords
process according
polymer
spun
polymers
group
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
EP02016474A
Other languages
German (de)
English (en)
Other versions
EP1283283A1 (fr
Inventor
Wolfgang Dr. 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
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 Helsa Automotive GmbH and Co KG filed Critical Helsa Automotive GmbH and Co KG
Publication of EP1283283A1 publication Critical patent/EP1283283A1/fr
Application granted granted Critical
Publication of EP1283283B1 publication Critical patent/EP1283283B1/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
    • 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
    • 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

Definitions

  • the present invention relates to a process for producing a fiber product and in particular a process for producing a fiber product in one electrostatic spinning process in which at least two polymers each made at least one polymer solution and / or at least one polymer melt is spun out.
  • Such methods are basically known from the prior art, wherein In general, an electrode usually a receiving device for the spun fibers forms, while the counter electrode as Absprühelektrode or Spray nozzle is designed. It is also known that in such a Nano- and microfibers not isolated, but e.g. as fleece be filed. Such a method finds e.g. in the production of Filter materials application. Electrostatic spinning processes and apparatus for carrying out such spinning processes, e.g. from US Pat. No. 4,144,553, DE 20 32,072, EP 1 059 106, US 3,994,258, US 4,323,525 and US 4,287,139.
  • the object of the present invention is therefore at least one further process for producing a fiber product in an electrostatic spinning process so as to enrich the state of the art. It is still a task the present invention, a method for producing a fiber product in specify an electrostatic spinning process, the technically simple as possible feasible and economical and to products with improved Product properties leads.
  • the present object is achieved by a method with the Characteristics of the attached claim 1 solved.
  • the method according to the invention are at least two polymers different electrical charge at the same time to form a product of Fibers of different polarity by the action of one of two as Absprühelektroden formed electrode pair generated electric field spun.
  • two Absprühelektroden arranged opposite each other and formed as an electrode and counter electrode. This will cause simultaneous spinning of negatively and positively charged fibers, i.e. Fibers of opposite polarity possible.
  • the method according to the invention meet those of the spray-off electrodes spun fibers of different polarity in the space between the Absprühelektroden together and form a loose, cotton-like Fabric of fibers of opposite polarity.
  • This directly by the Spinning process formed product can be by rewinding, vacuuming, blowing away or brought out of the formation zone in other ways familiar to the person skilled in the art become.
  • This material has excellent properties due to the in the Fibers preserved charge and is particularly suitable for the production of nonwovens, the e.g. can be used as filter materials. Because of the Fibers "stored" charges, as well as the low air resistance, the so produced nonwovens when used as a filter are the products of the inventive method particularly advantageous as filter materials with low air resistance and high dust absorbency suitable.
  • the electrostatically spun fibers directly onto a substrate be applied.
  • This carrier material is preferably a pile, scrim, knitted fabric, Knitted or net of natural or artificial material, in particular Cotton, polypropylene, upholstery, nylon or mixtures of these.
  • this carrier material between the two passed as electrode and counter electrode trained Absprühelektroden becomes. It is particularly advantageous that the freshly spun fibers in in general, due to a residual content of solvent or due to a sufficiently high temperature readily adhere to the fiber material.
  • the binding of the fibers or the fiber material to the Carrier material can also be subsequently improved, e.g. through needles or Calendering. It is alternatively also possible for the carrier material below the zone along, in which the differently charged fibers meet and form a cotton-like product. This is advantageously a material obtained in which fibers of different polarity on one side of the Carrier material are arranged side by side.
  • the fillers and / or holding agents and / or adsorbents after spinning the at least two polymers are incorporated into the fiber product.
  • This can e.g. on simple manner by mixing in the electrostatic spinning process produced fibers with commercial fibers in fiber mixers and subsequent nonwoven production happen.
  • others can Substances and substances, such as e.g. Absorbents later in the fiber material be introduced and fixed.
  • the procedure here is obvious to the person skilled in the art the field of filter and / or nonwoven manufacturing generally known and includes the Fixing such additives e.g. through the use of binders or by calendering.
  • the inventive electrostatic spinning process at a formed between the Absprühelektroden electric field with a Potential difference is carried out in the range of 5 kV to 1000 kV, stronger preferably at a potential difference in the range of 10 to 100 kV and the strongest preferably at a potential difference in the range of 10 kV to 50 kV.
  • polymer in the polymer solution is obtained with the Processes of the invention generally include microfibers having a major Fiber diameter in the range between 1 and 5 microns. At polymer concentrations > 13 wt .-% gives very coarse and particularly griffeste fibers, the one Have diameter of> 5 microns. According to the invention thus also the Production of fibers with different fiber diameters on special easy way allows. It is even conceivable that the polymer concentration during spinning, thereby varying e.g. a product with one certain gradients in terms of fiber diameter. Here is e.g. possible first to deposit thicker fibers and in the further course of the Process the concentration of the polymer solution for the production of fibers with lower diameter. As a result, e.g. made a fleece be used as a filter, this filter then advantageously initially has fibers of a smaller diameter on its upstream side and the fiber diameter increases toward the downstream side.
  • the polymer solution or the Polymer melt before spinning preferably adjuvants and / or additives added, in particular those which act charge stabilizing or a charge can pick up or transport.
  • auxiliary substances and / or additives are in particular in a concentration of 0.001 to 20 wt .-% in Added to the mass of the polymer solution or polymer melt.
  • auxiliary substances and / or additives are in particular metal or Carbon or graphite powder in question, dyes, metallocenes, amines and phosphines.
  • powders are others, electric conductive materials such as electrically conductive polymers and ceramics as well Mixtures of these substances as an additive in the preparation of the Fiber product according to the invention substances which are preferably used.
  • the method according to the invention is an easy in the Gas phase convertible substance with an electronegativity> 2 or higher molar mass of at least one polymer solution or polymer melt added or introduced into the space between the Absprühelektroden, as a result positively influence the shape of the fibers produced. They let themselves In particular, produce very evenly in the desired strengths.
  • the abovementioned substance of the polymer solution or polymer melt or of the process air is added in a comparatively small amount. It is therefore preferred that the at least one easily convertible into the gas phase substance of the polymer solution or polymer melt in an amount of 0.5 to 50 g / l is added or so dosed into the process air in the area between the Absprühelektroden that an operating or Working concentration in the range of 0.5 to 500 g / m 3 results.
  • the process according to the invention is suitable for spinning polymers Solution as well as from the melt. It is preferred if at least one Polymer of the polyvinyl alcohol, polyvinyl pyrrolidole, polyethylene oxide and its Copolymers, cellulose derivatives, starch and mixtures of these polymers comprehensive group of aqueous solution is spun.
  • polystyrene When spinning from an organic solvent, it is preferably at least a polymer of polystyrene, polycarbonate, polyvinyl chloride, polyacrylate, Polymethacrylate, polyvinyl acetate, polyvinyl acetal, polyvinyl ether, polyurethane, Polyamide, polysulfone, polyethersulfone, polyacrylonitrile, cellulose derivatives and Spinning mixtures of these polymers comprehensive group, this in particular from a solution in a solvent of aldehydes, Alcohols, chlorides, hydrocarbons and aromatics, esters, ethers, ketones, Hydrocarbons and aromatics, acetone, formic acid, benzyl alcohol, butanol, Chloroform, cyclohexane, dichloroethane, dichloromethane, dichloropropane, DMF, DMSO, Dioxane, acetic acid ester, ethanol, ether, propanol, tetrahydr
  • From the melt is preferably at least one Polymer of polyolefins, polyesters, polyoxymethylene, polychlorotrifluoroethylene, Polyphenylene sulfide, polyaryletherketone, polyvinylidene fluoride and mixtures spun into this group of polymers.
  • a 20% polystyrene solution in 2-butanone is added with 0.5 g / l rhodamine G6 and spun at a flow rate of 0.3 ml of polymer solution per minute per nozzle.
  • the nozzles face each other directly at a distance of 25 cm.
  • the forming fleece is wound up by a spool. At the nozzles there is a high voltage of + or - 15 kV.
  • the thus-prepared material is processed into a sheet having a basis weight of 50 g / m 2 , and then has a deposition rate of 80% of the 0.3 to 0.5 ⁇ m fraction. Measured at a flow rate of 50 l / min. and an inflow area of 100 cm 2 with NaCl as test dust. The air resistance of the nonwoven under these conditions was 30 Pa.
  • a 15% polycarbonate solution in dichloromethane is added with 0.5 g / l rhodamine G6 and spun at a flow rate of 0.3 ml of polymer solution per minute per nozzle.
  • the nozzles face each other directly at a distance of 25 cm.
  • the forming fleece is wound up by a spool.
  • the material thus prepared is processed into a sheet having a basis weight of 60 g / m 2 and then has a deposition rate of 68% of the 0.3 to 0.5 micron fraction. Measured at a flow rate of 50 l / min. and an inflow area of 100 cm 2 with NaCl as test dust.
  • the air resistance of the nonwoven under these conditions was 15 Pa.
  • a 15% polystyrene solution in dichloromethane is added with 5 g of chlorine and spun at a flow rate of 0.3 ml of polymer solution per minute per nozzle.
  • the nozzles face each other directly at a distance of 25 cm.
  • the forming fleece is sucked off.
  • the material thus produced is processed into a sheet having a basis weight of 68 g / m 2 and then has a deposition rate of 72% of the 0.3 to 0.5 micron fraction. Measured at a flow rate of 50 l / min. and an inflow area of 100 cm 2 with NaCl as test dust. The air resistance of the nonwoven under these conditions was 21 Pa.

Landscapes

  • 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)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)

Claims (17)

  1. Procédé de production d'un produit fibreux dans un procédé de filage électrostatique, dans lequel au moins deux polymères sont filés à partir d'au moins une solution de polymère et/ou à partir d'au moins une fusion de polymère, caractérisé en ce que lesdits au moins deux polymères sont de charge électrique différente et sont filés simultanément afin de former un produit de fibres de polarité différente sous l'action d'un champ électrostatique généré par une paire d'électrodes configurée sous la forme de deux électrodes de pulvérisation.
  2. Procédé selon la revendication 1, caractérisé en ce que, pendant le filage desdits au moins deux polymères, des matières de charge et/ou de rétention et/ou des adsorbants sont introduits dans le champ électrostatique généré entre les électrodes de pulvérisation.
  3. Procédé selon la revendication 2, caractérisé en ce que les matières de charge et/ou de rétention et/ou les adsorbants sont choisis parmi un ou plusieurs membres du groupe comprenant les fibres de coton, les fibres de polyester, les fibres de nylon, le charbon actif, la silice ou l'oxyde d'aluminium.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que les fibres sont déposées directement sur un matériau support.
  5. Procédé selon la revendication 4, caractérisé en ce que le matériau support est un voile de carde, un non-tissé, un tissu, un tricot ou un réseau fait d'un matériau naturel ou artificiel, en particulier de coton, de polypropylène, de polyester, de nylon ou de mélanges de ceux-ci.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que des matières de charge et/ou de rétention et/ou des adsorbants sont introduits dans le produit fibreux après le filage desdits au moins deux polymères.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que le procédé de filage électrostatique se fait en appliquant entre les électrodes configurées sous forme d'électrodes de pulvérisation une différence de potentiel dans la plage de 5 kV à 1 000 kV, en particulier une différence de potentiel dans la plage de 10 à 100 kV et de la façon la plus préférentielle une différence de potentiel dans la plage de 10 kV à 50 kV.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que le filage de l'un au moins des polymères à filer se fait à partir d'une solution de polymère et en ce que la solution présente une concentration en polymère inférieure à 8% en poids, de 8 à 13% en poids ou supérieure 13% en poids.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on ajoute à la solution de polymère ou à la fusion de polymère, avant le filage, des adjuvants et/ou des additifs, en particulier des substances ou des additifs qui ont un effet de stabilisation de la charge ou qui sont capables d'absorber ou de transporter une charge, ces adjuvants et/ou additifs étant ajoutés notamment à une concentration de 0,001 à 20% en poids, ramenée à la masse de la solution de polymère ou fusion de polymère.
  10. Procédé selon la revendication 9, caractérisé en ce que les adjuvants et/ou additifs sont choisis dans le groupe comprenant des poudres de métaux, des poudres de carbone ou de graphite, des colorants, des métallocènes, des amines, des phosphines, ainsi que des poudres d'autres matériaux électriquement conducteurs tels que des polymères électriquement conducteurs et des céramiques, ainsi que des mélanges de ces substances.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins une substance facile à convertir en phase gazeuse ayant une électronégativité supérieure à 2 ou une masse molaire élevée est ajoutée à au moins une solution de polymère ou fusion de polymère ou introduite dans l'espace entre les électrodes de pulvérisation.
  12. Procédé selon la revendication 11, caractérisé en ce que ladite au moins une substance facile à convertir en phase gazeuse est choisie dans le groupe comprenant des halogènes, des oxydes d'halogènes, des hydrohalogènes, des halogénures de gaz nobles, des oxydes nitriques, des oxydes de soufre et l'hexafluorure de soufre.
  13. Procédé selon la revendication 11 ou la revendication 12, caractérisé en ce que ladite au moins une substance facile à convertir en phase gazeuse est ajoutée à la solution de polymère ou fusion de polymère en une quantité de 0,5 à 50 g/l ou bien introduite de manière dosée dans l'air de processus, dans la zone entre les électrodes de pulvérisation, de façon à obtenir une concentration de fonctionnement ou de travail dans la plage de 0,5 à 500 g/cm3.
  14. Procédé selon l'une des revendications 11 à 13, caractérisé en ce que ladite au moins une substance facile à convertir en phase gazeuse est récupérée à partir de l'air de processus et recyclée dans le procédé.
  15. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins un polymère du groupe comprenant l'alcool polyvinylique, la polyvinylpyrrolidone, le polyoxyde d'éthylène et leurs copolymères, des dérivés de la cellulose, des amidons et des mélanges de ces polymères, est filé à partir d'une solution aqueuse.
  16. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins un polymère choisi dans le groupe comprenant le polystyrène, le polycarbonate, le polychlorure de vinyle, le polyacrylate, le polyméthacrylate, le polyacétate de vinyle, le polyvinylacétal, le polyvinyléther, le polyuréthane, le polyamide, la polysulfone, la polyéthersulfone, le polyacrylonitrile, des dérivés de la cellulose, ainsi que des mélanges de ces polymères, est filé à partir d'un solvant, en particulier à partir d'un solvant choisi dans le groupe comprenant des aldéhydes, des alcools, des chlorures, des hydrocarbures et des aromatiques, des esters, des éthers, des cétones, des hydrocarbures et des aromatiques, l'acétone, l'acide formique, l'alcool benzylique, le butanol, le chloroforme, le cyclohexane, le dichloroéthane, le dichlorométhane, le dichloropropane, le DMF, le DMSO, le dioxane, l'acétate d'éthyle, l'éthanol, l'éther, le propanol, le tétrahydrofurane et le toluène.
  17. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins un polymère choisi dans le groupe comprenant des polyoléfines, des polyesters, le polyoxyméthylène, le polychlorotrifluoroéthylène, le polysulfure de phénylène, la polyaryléthercétone, le polyfluorure de vinylidène ainsi que des mélanges de ces polymères est filé à partir d'une fusion.
EP02016474A 2001-07-30 2002-07-23 Procédé pour la fabrication d'un produit fibreux Expired - Lifetime EP1283283B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10137153A DE10137153A1 (de) 2001-07-30 2001-07-30 Verfahren zur Herstellung eines Faserprodukts
DE10137153 2001-07-30

Publications (2)

Publication Number Publication Date
EP1283283A1 EP1283283A1 (fr) 2003-02-12
EP1283283B1 true EP1283283B1 (fr) 2005-06-01

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Family Applications (1)

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EP02016474A Expired - Lifetime EP1283283B1 (fr) 2001-07-30 2002-07-23 Procédé pour la fabrication d'un produit fibreux

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EP (1) EP1283283B1 (fr)
DE (2) DE10137153A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100526524C (zh) * 2007-02-02 2009-08-12 吉林大学 微纳米纤维的无溶剂电纺丝法制备方法
US8512431B2 (en) 2000-09-05 2013-08-20 Donaldson Company, Inc. Fine fiber media layer

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004069378A2 (fr) * 2003-02-05 2004-08-19 Helsa-Werke Helmut Sandler Gmbh & Co. Kg Element filtrant et procede de realisation
US7390760B1 (en) 2004-11-02 2008-06-24 Kimberly-Clark Worldwide, Inc. Composite nanofiber materials and methods for making same
DE102005063038A1 (de) * 2005-12-29 2007-07-05 Basf Ag Nano Thermoelektrika
CN105040123A (zh) * 2015-09-11 2015-11-11 中国人民解放军军事医学科学院卫生装备研究所 一种静电纺丝制备水性聚氨酯纳米纤维的方法
CN109467965A (zh) * 2018-09-30 2019-03-15 江苏斯沃得环保科技有限公司 一种活性炭吸附涂料的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5311844A (en) * 1992-03-27 1994-05-17 Foster Wheeler Energy Corporation Internested superheater and reheater tube arrangement for heat recovery steam generator
DE4402857C2 (de) * 1994-01-31 1996-11-28 Freudenberg Carl Fa Verfahren zum Herstellen eines Mikrofaser-Vliesstoffs, Mikrofaser-Vliesstoff und dessen Verwendung
IL132945A0 (en) * 1999-06-07 2001-03-19 Nicast Ltd Filtering material and device and method of its manufacture
US6753454B1 (en) * 1999-10-08 2004-06-22 The University Of Akron Electrospun fibers and an apparatus therefor
WO2001051690A1 (fr) * 2000-01-06 2001-07-19 Drexel University Electrofilage de fibres de polymeres conductrices ultrafines

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8512431B2 (en) 2000-09-05 2013-08-20 Donaldson Company, Inc. Fine fiber media layer
US8709118B2 (en) 2000-09-05 2014-04-29 Donaldson Company, Inc. Fine fiber media layer
CN100526524C (zh) * 2007-02-02 2009-08-12 吉林大学 微纳米纤维的无溶剂电纺丝法制备方法

Also Published As

Publication number Publication date
DE10137153A1 (de) 2003-02-27
EP1283283A1 (fr) 2003-02-12
DE50203245D1 (de) 2005-07-07

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