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WO2005080660A1 - Procede de production de non-tisses, non-tisse correspondant et son utilisation - Google Patents

Procede de production de non-tisses, non-tisse correspondant et son utilisation Download PDF

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Publication number
WO2005080660A1
WO2005080660A1 PCT/EP2005/001632 EP2005001632W WO2005080660A1 WO 2005080660 A1 WO2005080660 A1 WO 2005080660A1 EP 2005001632 W EP2005001632 W EP 2005001632W WO 2005080660 A1 WO2005080660 A1 WO 2005080660A1
Authority
WO
WIPO (PCT)
Prior art keywords
nonwoven fabric
nonwovens
cellulose
continuous filaments
cellulose carbamate
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.)
Ceased
Application number
PCT/EP2005/001632
Other languages
German (de)
English (en)
Inventor
Peter Weigel
Hans-Peter Fink
Michael Doss
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.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Priority to JP2006553533A priority Critical patent/JP2007522359A/ja
Priority to US10/588,835 priority patent/US20070298670A1/en
Priority to EP05707469A priority patent/EP1716278B1/fr
Priority to DE502005010129T priority patent/DE502005010129D1/de
Publication of WO2005080660A1 publication Critical patent/WO2005080660A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/013Regenerated cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/03Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • D04H3/11Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically by fluid jet
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion

Definitions

  • the invention relates to a process for the production of nonwovens, in which a cellulose carbamate solution is spun by means of extrusion through a nozzle block containing a plurality of openings into a coagulation bath to form a plurality of continuous filaments which are subsequently intermingled with gaseous medium and / or fluid.
  • the invention also relates to such a nonwoven fabric and to the use thereof.
  • Nonwovens are textile fabrics in which the cohesion of the fibers is ensured not by weaving or knitting, but by interlocking and sometimes also gluing after the fibers have been swirled. Because of the wide range of possible uses and the low production costs, nonwovens production continues to show high annual rates Growth rates. The advantages of these nonwoven materials lie in particular in the high moisture absorption, the high variability of density and thickness as well as the extensive surface anisotropy, which results in the numerous possible uses, e.g.
  • Nonwovens made from continuous filaments are preferably made from synthetic fibers such as polyester, polyacrylonitrile or polypropylene. Viscose fibers are preferably used as short or staple fibers for the manufacture of nonwovens.
  • a process which has been known for a long time for the production of molded articles from regenerated cellulose consists in the precipitation of a solution of cellulose carbamate (EP-A-57 105, EP-A 178 292) which is obtained by reacting cellulose with urea with thermal splitting of the urea into isocyanic acid and Ammonia and reaction of the isocyanic acid with the OH groups of the cellulose is formed.
  • Cellulose carbamate is soluble in cold, dilute sodium hydroxide solution and can be regenerated back to cellulose in heated sodium hydroxide solution.
  • the object of the present invention was therefore to provide a process for producing nonwovens from cellulose carbamate in a continuous process with good product properties. Another task was that the process meets the requirements in terms of low investment and production costs and low environmental impact.
  • a process for producing nonwovens in which a cellulose carbamate solution is extruded through at least 20 openings, i.e. Nozzles containing the nozzle block is spun into a coagulation bath to form a plurality of continuous filaments, which are then swirled by flow with gaseous medium and / or fluid to form the nonwoven.
  • the number of on the nozzle block i.e. A rectangular area, the length of which is large compared to the width, arranged openings depends on the width and thickness of the desired product and is preferably at least 10,000.
  • the openings of the nozzle block are particularly preferably arranged in an array. However, it is also possible that the openings of the nozzle bar are arranged linearly.
  • the ratio of length to diameter (L / D ratio) of the nozzles is preferably between 1 and 20.
  • the continuous filaments are spun vertically from the bottom up into the precipitation bath.
  • the continuous filaments are spun in the wet state. After spinning, the continuous filaments are preferably guided downwards in a slit-shaped funnel, the intermingling with the gaseous medium and / or fluid taking place at the outlet of the funnel. In order to improve the intermingling of the continuous filaments, it is further preferred to carry out a vibrating movement of the funnel.
  • Air and / or water are preferably used as the gaseous medium and / or fluid.
  • the continuous threads are deposited on a conveyor belt after the intermingling.
  • a further intermingling of the continuous threads is preferably realized by shaking the conveyor belt.
  • a cellulose carbamate solution is preferably used which contains a cellulose carbamate content of at least 6 to 12, preferably 7 to 9% by weight, based on the solution.
  • the precipitation bath preferably contains sulfuric acid with a concentration of 50 to 200 g / 1, particularly preferably 70 to 100 g / 1 and 100 to 300 g / 1, particularly preferably 150 to 200 g / 1 sodium sulfate.
  • the nonwoven fabric is washed, pressed and dried following the steps described above.
  • the washing can preferably be carried out by a high pressure water jet.
  • the cellulose carbamate is preferably regenerated to cellulose in a regeneration bath. It is particularly preferred that the cellulose carbamate is regenerated to cellulose in a regeneration bath from 0.3 to 1% by weight sodium hydroxide in water at a temperature of 60 to 95 ° C. This makes it possible to produce nonwovens from regenerated cellulose. In a first advantageous variant, it is possible to carry out the regeneration between extrusion and swirling. Another preferred variant provides that the regeneration is carried out after the swirling.
  • a nonwoven fabric is also provided from a random scrim made of continuous filaments made of cellulose carbamate. It is preferred that the nonwoven fabric according to the invention can be produced by the method according to one of claims 1 to 16.
  • a nonwoven fabric is also made from a
  • Tangled scrim made of continuous filaments made of regenerated cellulose.
  • the regenerated cellulose preferably has a residual nitrogen content (residual N content) of 0.3 to 0.5, particularly preferably 0.1 to 1.2.
  • the nonwoven fabric has a pore structure with a preferred porosity of 1 to 10%.
  • the nonwoven fabric has a specific inner surface between 20 and 50 m 2 / cm 3 , measured by means of small angle x-ray scattering (SAXS).
  • SAXS small angle x-ray scattering
  • the invented Nonwoven according to the invention can be produced by the method according to one of claims 17 to 20.
  • the nonwovens according to the invention are preferably used in medicine, in particular as surgical drapes, bed sheets, wound coverings, gauze or cotton pads.
  • the nonwovens can also be used as hygiene materials or as wipes in the household.
  • a further field of application of the nonwovens according to the invention is decorative nonwovens, in particular tablecloths, napkins or curtains, and insert nonwovens in the clothing industry.
  • Another use relates to insulating mats and reinforcement fleeces, e.g. as a replacement for glass fiber fleeces, in the construction industry.
  • FIG. 1 shows a schematic representation of the process sequence according to the invention.
  • Fig. 2 shows a slot-shaped funnel according to the invention, at the exit of which the swirling takes place.
  • the basic sequence of the method is shown in FIG. 1.
  • the spinning solution 1 is extruded into a precipitation bath 4 by means of a spinning pump 2 by means of a nozzle bar 3, which contains a large number of nozzles.
  • Spinning is carried out vertically from the bottom upwards into the precipitation bath. Be about 5 pulleys the fibers are drawn off in a horizontal direction.
  • a first wash bath and a stretching section can optionally be located on this route.
  • Another deflection roller 6 then leads the fiber bundle down into a slit-shaped funnel 7, at the exit of which the fiber bundle is flown by air or water on both sides.
  • the fibers which are swirled in this way are deposited on the conveyor belt 8 located underneath, with further swirling being effected transversely to the running direction by shaking the depositing device or the conveyor belt.
  • the belt runs through a washing bath with a washing nozzle 9, which can also be realized by a water jet under high pressure, and thus leads to a further solidification of the material in the sense of spun lacing.
  • the conveyor belt consists of a wide-meshed network, preferably made of metal, which ensures that the washing liquid runs off quickly.
  • the material can then be dried in appropriate drying devices. However, the water can also be squeezed out by a pair of rollers, which at the same time enables the nonwoven to be compressed.
  • Figure 2 shows the structure of a slot-shaped funnel according to the invention.
  • the fiber can be introduced into said funnel via the fiber inlet 1.
  • the transport of the fiber through the funnel is made possible by a Venturi nozzle, which implements the water jet principle.
  • a Venturi nozzle which implements the water jet principle.
  • the fiber exit is located at the lower end 5 of the funnel, from where the continuous filaments then continue. can be transported.
  • 800 g of pulp with a DP (uo ⁇ am) of 520 become intensive in a kneader with 3200 g of a solution consisting of 12% by weight NaOh, 30% by weight urea and 58% by weight water at 25 ° C. for 1 hour mixed and then matured at 23 ° C for 48 h to a DP (C uoxam) of 300.
  • the moist alkali cellulose is at room temperature in a 5 1 kneader with 1200 g of solid crystalline urea for 30 min. kneaded. The temperature of the kneader is then raised to 140 ° C. and the water present is drawn off.
  • the mass After reaching a product temperature of 140 ° C, the mass is kneaded for a further 120 min and then discharged from the kneader. To obtain the pure cellulose carbamate, the dry crumbly mass is washed 3 times with deionized water at a liquor ratio of 1:16, suctioned off over a frit and then at
  • 800 g of pulp with a DP ( Cu oxam) of 520 are mixed in a kneader with 3200 g of a solution consisting of 12% by weight NaOh, 30% by weight urea and 58% by weight water at 25 ° C. for 1 hour mixed intensively and then matured at 23 ° C for 48h on a DP ( u oxam).
  • the moist alkali cellulose is kneaded at room temperature in a 5 l kneader with 1200 g of solid crystalline urea for 30 minutes. The temperature of the kneader is then raised to 140 ° C. and the water present is drawn off.
  • the mass After reaching a product temperature of 140 ° C, the mass is kneaded for a further 120 min and then discharged from the kneader. To obtain the pure cellulose carbamate, the dry crumbly mass is washed 3 times with deionized water at a liquor ratio of 1:16, suction filtered over a frit and then dried at room temperature. This loosened and crumbly product had a nitrogen content of 3.0% and a DP (cuo m) of 290.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé permettant de produire des non-tissés, selon lequel une solution de carbamate de cellulose est filée, par extrusion à travers un bloc de tuyères comprenant plusieurs ouvertures, dans un bain de précipitation pour former plusieurs fils continus. Ladite solution de carbamate de cellulose est ensuite mise en tourbillonnement par action d'un milieu et/ou d'un fluide gazeux. L'invention concerne également un non-tissé de ce type, ainsi que son utilisation.
PCT/EP2005/001632 2004-02-17 2005-02-17 Procede de production de non-tisses, non-tisse correspondant et son utilisation Ceased WO2005080660A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2006553533A JP2007522359A (ja) 2004-02-17 2005-02-17 不織布の製造方法、不織布およびその使用
US10/588,835 US20070298670A1 (en) 2004-02-17 2005-02-17 Method for Producing Non-Wovens, a Corresponding Non-Woven and the Production Thereof
EP05707469A EP1716278B1 (fr) 2004-02-17 2005-02-17 Procede de production de non-tisses, non-tisse correspondant et son utilisation
DE502005010129T DE502005010129D1 (de) 2004-02-17 2005-02-17 Verfahren zur herstellung von vliesstoffen, vliesstoff und dessen verwendung

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004007618.9 2004-02-17
DE200410007618 DE102004007618A1 (de) 2004-02-17 2004-02-17 Verfahren zur Herstellung von Vliesstoffen, Vliesstoff und dessen Verwendung

Publications (1)

Publication Number Publication Date
WO2005080660A1 true WO2005080660A1 (fr) 2005-09-01

Family

ID=34877029

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/001632 Ceased WO2005080660A1 (fr) 2004-02-17 2005-02-17 Procede de production de non-tisses, non-tisse correspondant et son utilisation

Country Status (4)

Country Link
EP (1) EP1716278B1 (fr)
JP (1) JP2007522359A (fr)
DE (2) DE102004007618A1 (fr)
WO (1) WO2005080660A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114787440A (zh) * 2019-12-17 2022-07-22 兰精股份公司 用于制造纺粘型无纺织物的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004007617B4 (de) * 2004-02-17 2007-02-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines Vliesstoffes, Vliesstoff und dessen Verwendung
JP5579870B2 (ja) * 2010-09-14 2014-08-27 テューリンギッシェス・インスティトゥート・フューア・テクスティル−ウント・クンストストッフ−フォルシュング・エー・ファウ 粒子含有繊維から作製される高機能スパンボンド布帛およびその製造方法
EP2629663B1 (fr) * 2010-10-23 2018-01-10 Pop Test LLC Dispositifs et formulations pour détecter, sélectionner et contrôler des niveaux de certains constituants dans liquides organiques, et procédé

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB955128A (en) * 1961-09-28 1964-04-15 Onderzoekings Inst Res Gas treatment of a moving artificial multi-filament thread
DE2539725A1 (de) * 1974-09-13 1976-03-25 Asahi Chemical Ind Als traegermaterial fuer kunstleder geeignete faservliese, ihre herstellung und verwendung
WO1983003433A1 (fr) * 1982-03-30 1983-10-13 Turunen, Olli, T. Procede de traitement de fibres de derives de cellulose
WO1988005090A1 (fr) * 1986-12-31 1988-07-14 Neste Oy Produit en fibres non-tissees
EP0879906A2 (fr) * 1997-05-23 1998-11-25 Zimmer Aktiengesellschaft Procédé et dispositif pour filer des solutions de carbamate de cellulose

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2399258A (en) * 1943-03-20 1946-04-30 American Viscose Corp Novel filamentous product and method of making it
JPS5132704A (en) * 1974-09-13 1976-03-19 Asahi Chemical Ind Hikakujobutsu oyobi sonoseizohoho
JPS5230632B2 (fr) * 1974-12-11 1977-08-09
JPS5188714A (ja) * 1975-01-28 1976-08-03 Seruroosuzanteetochosenitonokaisenhoho
DD223740A1 (de) * 1984-03-08 1985-06-19 Groebzig Spinnduesenfab Grossspinnduese
US5312500A (en) * 1989-01-27 1994-05-17 Nippon Petrochemicals Co., Ltd. Non-woven fabric and method and apparatus for making the same
DE4409609A1 (de) * 1994-03-21 1994-10-13 Thueringisches Inst Textil Verfahren zum Erspinnen von Cellulosefasern und -filamentgarnen
US20030003830A1 (en) * 2001-06-29 2003-01-02 Mabrouk Ouederni Air-laid web with high modulus fibers
JP4001783B2 (ja) * 2002-06-18 2007-10-31 旭化成せんい株式会社 セルロース極細長繊維不織布の製造方法
DE102004007617B4 (de) * 2004-02-17 2007-02-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines Vliesstoffes, Vliesstoff und dessen Verwendung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB955128A (en) * 1961-09-28 1964-04-15 Onderzoekings Inst Res Gas treatment of a moving artificial multi-filament thread
DE2539725A1 (de) * 1974-09-13 1976-03-25 Asahi Chemical Ind Als traegermaterial fuer kunstleder geeignete faservliese, ihre herstellung und verwendung
WO1983003433A1 (fr) * 1982-03-30 1983-10-13 Turunen, Olli, T. Procede de traitement de fibres de derives de cellulose
WO1988005090A1 (fr) * 1986-12-31 1988-07-14 Neste Oy Produit en fibres non-tissees
EP0879906A2 (fr) * 1997-05-23 1998-11-25 Zimmer Aktiengesellschaft Procédé et dispositif pour filer des solutions de carbamate de cellulose

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114787440A (zh) * 2019-12-17 2022-07-22 兰精股份公司 用于制造纺粘型无纺织物的方法
CN114787440B (zh) * 2019-12-17 2023-09-12 兰精股份公司 用于制造纺粘型无纺织物的方法

Also Published As

Publication number Publication date
DE502005010129D1 (de) 2010-10-07
JP2007522359A (ja) 2007-08-09
DE102004007618A1 (de) 2005-09-22
EP1716278A1 (fr) 2006-11-02
EP1716278B1 (fr) 2010-08-25

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