EP1869232A1 - Textiles containing at least one layer of polymeric nanofibres and method of production of the layer of polymeric nanofibres from the polymer solution through electrostatic spinning - Google Patents

Textiles containing at least one layer of polymeric nanofibres and method of production of the layer of polymeric nanofibres from the polymer solution through electrostatic spinning

Info

Publication number
EP1869232A1
EP1869232A1 EP20060722445 EP06722445A EP1869232A1 EP 1869232 A1 EP1869232 A1 EP 1869232A1 EP 20060722445 EP20060722445 EP 20060722445 EP 06722445 A EP06722445 A EP 06722445A EP 1869232 A1 EP1869232 A1 EP 1869232A1
Authority
EP
European Patent Office
Prior art keywords
nanofibres
polymer
spinning
low molecular
created
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.)
Withdrawn
Application number
EP20060722445
Other languages
German (de)
English (en)
French (fr)
Inventor
Oldrich Jirsak
Filip Sanetrnik
Ladislav Mares
David Petras
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.)
Elmarco sro
Original Assignee
Elmarco sro
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 Elmarco sro filed Critical Elmarco sro
Publication of EP1869232A1 publication Critical patent/EP1869232A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • 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
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/603—Including strand or fiber material precoated with other than free metal or alloy
    • Y10T442/607—Strand or fiber material is synthetic polymer
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608—Including strand or fiber material which is of specific structural definition
    • Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/654—Including a free metal or alloy constituent
    • Y10T442/658—Particulate free metal or alloy constituent

Definitions

  • the invention relates to the textile containing at least one layer of polymeric nanofibres having diameter to 600 nanometres produced through electrostatic spinning of the polymer solution.
  • the invention also relates to the production method of the layer of nanofibres from the polymer solution through electrostatic spinning in electric field created by difference of potentials between the charged electrode and the counterelectrode, at which the solution of polymer is brought into the electric field for spinning through the surface of the rotating charged electrode, at the same time the nanofibres created in this electric field are carried to the counterelectrode and they deposit on the surface designated to it.
  • the textiles containing at least one layer of polymeric nanofibres are used, next to others, in health practice, e.g. to cover the wounds because thanks to the small dimensions of poruses they prevent the bacteria to penetrate into the wound, and simultaneously enable the liquid products of the healing process to go away and the access of air to the wound.
  • Other known textiles used in health practice sometimes contain physiologic active substances which are released from them in a controlled speed and support the healing process. On the finished textile these substances are deposited through dipping the textile into the solution of the respective substance and through its consequent drying, when the quantity of the substance that gets stuck on the textile is very difficult to control, respectively it is difficult to deposit very small quantity of the active substance which restricts usage of such textiles.
  • silver is present in the form of metallic particles, whose magnitude is in micrometers as to numerical order.
  • a similar form of silver is used also in textile materials, e.g. in socks, to prevent creation of odour due to bacteria.
  • chemical or catalytic acting of solid matters is being increased with specific surface of active substances.
  • the necessary proportion of effect of this substance may be achieved through a lower quantity of active substance in the carrier or through a lower concentration of active substance in the carrier.
  • the objective of invention is to propose a suitable carrier, respectively a carrying substrate for nanoparticles of low-molecular substances, as e.g. silver and other metals of suitable properties, salts, physiological active substances, etc.
  • the objective of invention is also to create a method for production of such carrier.
  • the principle of invention The objective of invention has been reached through a textile containing at least one layer of polymeric nanofibres, whereas the principle of the invention consists in that the dimensions are smaller than the diameter of nanofibres, at the same time the particles of low molecular substance are deposited in polymer of nanofibre.
  • the polymeric nanofibres contain particles of low-molecular substance dissolved or dispersed in electrostatic spinning solution of polymer before spinning. Or they contain the polymeric nanofibres of particle of low molecular substance which was created after fibration through a consequent chemical reaction of the original low molecular substance dissolved in electrostatic spinning solution of polymer before spinning.
  • the low molecular substance is deposited directly in polymeric nanofibres of the layer and its concentration is close to the concentration of the low molecular substance in the solution of polymer during spinning process.
  • the resulting concentration of active substance in nanofibres of the layer may be controlled exactly.
  • the particles of low molecular substance are created by at least one substance from the group of metals, salts, dyes, physiological active substances, odours, indicators and catalyzers.
  • the nanofibres then contain mostly very small quantity of corresponding substance that they are able to release in long-term period, thus creating the required effect.
  • the dimensions of particles of low molecular substance are smaller than the diameter of nanofibres, whereas according to the claim 3 it is advantageous if these particles are of dimensions from 5 to 100 nanometers, which enables their depositing in the nanofibres.
  • the nanofibres in the layer of textile may be created by a polymer which undergoes the electrostatic spinning from the water solution and subsequently is reticulated, in which the particles of low molecular substance were dissolved or dispersed before the spinning.
  • the nanofibres of this textile usually contain low-molecular substances soluble in water, which may be after netting treated by a way of chemical reaction in other water solution.
  • the nanofibres may, according to the claim 5, contain particles of metal created through a following chemical reaction of salt particles of metal contained in nanofibres before the netting process.
  • Salt particles of metal deposited in nanofibres may consist of the silver nitrate from which through a following reduction the silver particles are created, at the same time the reduction takes place though the particles of silver nitrate are deposited in nanofibres.
  • the nanofibres are in the textile layer created by a polymer which is subject to the electrostatic spinning from the non-water solution.
  • the fine particles of the low molecular substance may be dispersed in the non-water solution.
  • the nanofibres contain the metal particles dispersed in the non-water solution being subject to electrostatic spinning before the spinning or during its course.
  • the metallic particles are the particles of silver.
  • the principle of production method of layer of nanofibres from the polymer solution through electrostatic spinning consists in that, the polymer solution for spinning contains the particles of low-molecular substance having dimensions smaller than the diameter of nanofibres, which are at spinning seized together with polymer to the nanofibres being created.
  • the particles of low molecular substance are created by at least one substance from the group of metals, salts, dyes, physiological active substance, odours, indicators, e.g. reacting to pH and the catalysts.
  • the polymer solution for spinning is water solution in which, together with polymer and a substance causing polymer netting, the low molecular substance is dissolved, that the nanofibres should contain after spinning, or the low molecular substance containing a substance, that the nanofibres should contain after spinning, and which will be created through a following chemical reaction of the original low molecular substance dissolved in polymer solution being subject to electrostatic spinning.
  • the low molecular substance may be as well dispersed in the water solution.
  • the low molecular substance dissolved in water solution of polymer is, with advantage, the metallic salt which, after completion of netting, is treated with solution of a suitable substance and through a consequent chemical reaction the required low molecular substance is created in nanofibres.
  • the low molecular substance dissolved in the water solution of polymer is the silver nitrate, from which by acting of an reduction agent after completion of netting the metallic silver is created in nanofibres.
  • the polymer solution for spinning is the non-water solution in which the low molecular substance is dispersed together with polymer, that the nanofibres should contain after spinning, or the low molecular substance containing the substance which the nanofibres should contain after spinning, and which will be created through consequent chemical reaction of the original low molecular substance dispersed in polymer solution being subject to electrostatic spinning.
  • the low molecular substance may be also dissolved in the non-water solution.
  • the low molecular substance may be, with advantage, the silver which will be obtained through reduction of the silver nitrate contained in non-water solution of polymer.
  • nanofibres from the polymer solution through electrostatic spinning in electric field created by a difference of potentials between the charged electrode positioned in rotational manner and the counterelectrode
  • the charged electrode is with a part of its perimeter dipped in polymer solution and through its surface it brings the polymer solution into the electric field for spinning.
  • the charged electrode is, with advantage, created with a cylinder according to CZ 294274 and to it analogical international application WO 2005/024101 Al
  • the mentioned textiles are made of various polymers soluble in water or non-water solution.
  • the diameter of nanofibres is less than 600 nanometers, usually in the range from 100 to 600 nanometers.
  • the particles of low molecular substance are created at least of one substance from the group of metals, salts, dyes, physiological active substances, odours, indicators and catalyzers.
  • the manner of production of layer of nanofibres according to the invention shall be described for the low molecular substance created by metallic particles, e.g. silver and the water solution of polymer.
  • metallic particles e.g. silver and the water solution of polymer.
  • the water solution of polyvinyl alcohol is prepared, which further contains a netting agent and soluble silver salt, with advantage the silver nitrate.
  • the particles of silver nitrate are seized together with polymer into the nanofibres being created.
  • the polymer is transferred to the three-dimensional insoluble form through activating the netting agent using heat.
  • the silver nitrate is reduced through a known manner upon acting of solution of a known reductant, e.g.
  • the non-water solution of dimethylformamide is subject to electrostatic spinning, at the same time the silver nitrate is dissolved in this solution, which is reduced out of it still in this solution using suitable reductant and the silver created is dispersed in the spinning solution. During the electrostatic spinning these particles of silver are seized together with polymer and deposited in nanofibres.
  • a low concentration of metallic ions in the basic polymer and the restricted moveability of reacting agents prevents agglomeration of atoms of reduced metal into larger particles, and so the nanoparticles are created.
  • the final product - textile containing at least one layer of nanofibres does not have the black colour, but a colour which is brown up to yellow. Finally the layer of nanofibres is deprived of the soluble products of chemical reactions using water and after then is dried and sterilised.
  • Such layer of nanofibres of polyvinyl alcohol or polyurethane with particles of silver anchored in nanofibres features a high and long-term antimicrobial efficiency and prevents bacteria, fimbria and fungus to grow.
  • the surface weight of textiles is only 0,5 to 2 gm "2 , at the same time they contain 0,01 to 0,2 gm '2 metallic silver. This quantity is significantly lower than at the up to now used products, hence adequately lower is also loading of human organism with side toxic effects.
  • the water solution of black-and- white photographic developer sold in the CR under the METOL designation is acting on the layer of nanofibres, through which the silver nitrate reduces and particles of silver having dimensions from 10 to 100 nanometers are created inside the polymeric nanofibres.
  • Example 2 The layer of nanofibres is produced in the same manner as in example 1 from mixture of the same substances in the ratio 5 : 1 : 0,2. After reduction of silver nitrate deposited in nanofibres during spinning, the particles of silver having dimensions from 5 to 50 nanometers are created in nanofibres.
  • the layer of nanofibres is being produced in the same manner as in example 1 while the reductant of silver nitrate deposited in nanofibres during spinning shall be the two percent water solution of ascorbic acid.
  • the bacteriological test were performed on the final product and according to the tests the product completely prevents bacteria, yeast and fungus to grow.
  • dimethylformamide solution which contains eighteen percent of polyurethane of average molecular mass 120000 and one percent of silver nitrate, through equivalent of acetaldehyde, if standing during 4 hours at the temperature of 20 0 C, the metallic silver shall be reduced.
  • the solution will be mixed after then, homogenized, and the fine suspension created will be subject to spinning through the process of electrostatic spinning according to CZ 294274 to the layer of nanofibres with surface weight approximately 10 gm "2 with diameter of nanofibres in the range from 100 to 500 nanometers.
  • the silver nitrate may be in the polymer solution superseded with another metallic salt, e.g. of copper or with another low-molecular substance from the group of metals, salts, dyes, physiologically active substances, odours, indicators and catalysts, at the same time the nanofibres of the layer produced through the electrostatic spinning contain the corresponding low molecular substance, mostly in a very small quantity, and they are able, as the need may be, to release it in a controlled way. From the dyes it is possible to use the two percent water solution of Saturn red upon spinning of the water solution of polymer

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Woven Fabrics (AREA)
EP20060722445 2005-04-11 2006-04-10 Textiles containing at least one layer of polymeric nanofibres and method of production of the layer of polymeric nanofibres from the polymer solution through electrostatic spinning Withdrawn EP1869232A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZ20050225A CZ300797B6 (cs) 2005-04-11 2005-04-11 Textilie obsahující alespon jednu vrstvu polymerních nanovláken a zpusob výroby vrstvy polymerních nanovláken z roztoku polymeru elektrostatickým zvláknováním
PCT/CZ2006/000018 WO2006108364A1 (en) 2005-04-11 2006-04-10 Textiles containing at least one layer of polymeric nanofibres and method of production of the layer of polymeric nanofibres from the polymer solution through electrostatic spinning

Publications (1)

Publication Number Publication Date
EP1869232A1 true EP1869232A1 (en) 2007-12-26

Family

ID=36676579

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20060722445 Withdrawn EP1869232A1 (en) 2005-04-11 2006-04-10 Textiles containing at least one layer of polymeric nanofibres and method of production of the layer of polymeric nanofibres from the polymer solution through electrostatic spinning

Country Status (11)

Country Link
US (1) US20080207076A1 (cs)
EP (1) EP1869232A1 (cs)
JP (1) JP2008536022A (cs)
KR (1) KR20080005549A (cs)
CN (1) CN101198728B (cs)
AU (1) AU2006233443A1 (cs)
CA (1) CA2602450A1 (cs)
CZ (1) CZ300797B6 (cs)
EA (1) EA012635B1 (cs)
TW (1) TW200702502A (cs)
WO (1) WO2006108364A1 (cs)

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KR20210115050A (ko) 2014-06-26 2021-09-24 이엠디 밀리포어 코포레이션 개선된 먼지 포집 능력을 갖는 필터 구조
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CA2602450A1 (en) 2006-10-19
US20080207076A1 (en) 2008-08-28
TW200702502A (en) 2007-01-16
HK1118872A1 (en) 2009-02-20
CZ2005225A3 (cs) 2006-11-15
EA200702132A1 (ru) 2008-08-29
JP2008536022A (ja) 2008-09-04
CN101198728A (zh) 2008-06-11
EA012635B1 (ru) 2009-12-30
AU2006233443A1 (en) 2006-10-19
CN101198728B (zh) 2010-09-08
WO2006108364A1 (en) 2006-10-19
KR20080005549A (ko) 2008-01-14
CZ300797B6 (cs) 2009-08-12

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