EP1716278B1 - 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
EP1716278B1
EP1716278B1 EP05707469A EP05707469A EP1716278B1 EP 1716278 B1 EP1716278 B1 EP 1716278B1 EP 05707469 A EP05707469 A EP 05707469A EP 05707469 A EP05707469 A EP 05707469A EP 1716278 B1 EP1716278 B1 EP 1716278B1
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EP
European Patent Office
Prior art keywords
wovens
continuous filaments
woven
cellulose carbamate
cellulose
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 - Fee Related
Application number
EP05707469A
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German (de)
English (en)
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EP1716278A1 (fr
Inventor
Peter Weigel
Hans-Peter Fink
Michael Doss
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-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
    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/013—Regenerated cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-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
    • D04H3/03—Non-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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10—Non-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
    • D04H3/11—Non-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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-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 extrusion through a die block containing a plurality of openings in a precipitation bath to form a plurality of continuous filaments, which is subsequently fluidized by influx with gaseous medium and / or fluid.
  • the invention relates to such a nonwoven fabric and its use.
  • Nonwovens are textile fabrics in which the cohesion of the fibers is not ensured by weaving or knitting, but by entanglements and sometimes also adhesions after swirling of the fibers. Because of its versatility and low production costs, nonwovens production continues to be high annual Growth rates.
  • the advantages of these nonwoven materials are in particular the high moisture absorption, the high variability of density and thickness and the extensive surface anisotropy, resulting in the numerous possible uses, for example in medicine (surgical drapes, sheets, wound dressings, gauze, cotton wool pads, etc.) for hygiene products, as wipes in household and industry, as decorative nonwovens (tablecloths, napkins, curtains), nonwovens in the clothing industry and for numerous technical applications (eg insulating mats in the construction industry).
  • nonwoven fabrics are preferably produced from synthetic fibers such as polyester, polyacrylonitrile or polypropylene. Viscose fibers are preferably used as short or staple fibers for nonwoven production.
  • a long-known process for the production of shaped articles of regenerated cellulose consists in precipitating a solution of cellulose carbamate (EP-A-57 105 . EP-A 178 292 ), which is formed by reaction of cellulose with urea with thermal decomposition of the urea into isocyanic acid and ammonia and reaction of the isocyanic acid with the OH groups of the cellulose.
  • 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 the production of nonwovens from cellulose carbamate in a continuous process with good product properties. Another object was that the method meets the requirements in terms of low investment and production costs and low environmental impact.
  • a process for making nonwoven webs wherein a cellulose carbamate solution is extruded through at least 20 orifices, i. Nozzles containing nozzle block is spun in a precipitation bath to form a plurality of endless filaments, which are subsequently vortexed by influx with gaseous medium and / or fluid to form the nonwoven fabric.
  • filaments spun by the carbamate process can also be processed into nonwoven fabrics in a continuous process.
  • the number of times on the nozzle block i. A rectangular area whose length is large compared to the width, arranged openings is dependent 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 like an array. However, it is also possible that the openings of the nozzle beam 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 bottom to top in the precipitation bath.
  • the spinning of the continuous filaments takes place in the wet state.
  • the continuous filaments are preferably guided downwards in a slot-shaped funnel, wherein the turbulence with the gaseous medium and / or fluid takes place at the outlet of the funnel.
  • the gaseous medium and / or fluid used are preferably air and / or water.
  • the filaments are deposited after the turbulence on a conveyor belt.
  • a further turbulence of the endless threads is realized by shaking movement of the conveyor belt.
  • a cellulose carbamate solution which contains a cellulose carbamate content of at least 6 to 12, preferably 7 to 9 wt .-%, based on the solution.
  • the precipitation bath preferably contains sulfuric acid at a concentration of 50 to 200 g / l, more preferably 70 to 100 g / l and 100 to 300 g / l, particularly preferably 150 to 200 g / l of sodium sulfate.
  • the nonwoven fabric is washed, pressed and dried following the steps described above.
  • the washing can be carried out preferably by a high pressure water jet.
  • the cellulose carbamate is regenerated to cellulose in a regeneration bath.
  • the cellulose carbamate is regenerated in a regeneration from 0.3 to 1 wt .-% sodium hydroxide in water at a temperature of 60 to 95 ° C to cellulose. This makes it possible to produce nonwovens from regenerated cellulose.
  • a further preferred variant provides that the regeneration is carried out after the turbulence.
  • a nonwoven fabric is also provided from a random knit of cellulose carbamate continuous filaments. 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.
  • inventive Nonwoven fabric according to the method of any one of claims 17 to 20 can be produced.
  • the nonwoven fabrics according to the invention are preferably used in medicine, in particular as surgical drapes, bed sheets, wound coverings, gauze or cotton wool pads. Likewise, the nonwovens are also used as hygiene substances or as wipes in the home. Another field of application of the nonwovens according to the invention are decorative nonwovens, in particular tablecloths, napkins or curtains, as well as insertable nonwovens in the clothing industry.
  • Another use relates to insulating mats and reinforcing nonwovens, e.g. as a substitute for glass fiber fleeces, in the construction industry.
  • FIG. 1 The basic procedure of the method is in FIG. 1 shown.
  • the spinning solution 1 is extruded via a spin pump 2 by means of a nozzle bar 3, which contains a plurality of nozzles, in a precipitation 4.
  • the spinning takes place vertically from bottom to top in the precipitation bath.
  • About pulleys 5 are the fibers are pulled off in a horizontal direction.
  • a first wash bath and a stretch can be located on this route.
  • a further deflection roller 6 then leads the fiber bundle downwards into a slot-shaped funnel 7, at the exit of which the fiber bundle flows on both sides of air or water.
  • the so swirled fibers are deposited on the underlying conveyor belt 8, wherein by swirling movement of the depositing device or the conveyor belt transversely to the direction of further turbulence takes place.
  • the belt passes through a washing bath with a washing nozzle 9, which can also be realized by a high pressure water jet, and thus leads to a further solidification of the material in the sense of SpunLacing.
  • the conveyor belt consists of a wide-meshed, preferably made of metal, which ensures a rapid drainage of the washing liquid. Subsequently, the material can be dried in appropriate drying devices. But the water can also be squeezed out by a pair of rollers, which at the same time a compression of the nonwoven fabric can be achieved.
  • FIG. 2 shows the structure of a slot-shaped funnel according to the invention.
  • the fiber inlet 1 the fiber can be introduced into the said funnel.
  • the transport of the fiber through the funnel is made possible by a Venturi nozzle, which implements the water jet principle.
  • the opening 3 Through the opening 3, the supply of water, air or a mixture thereof, which flows due to the Venturi profile on the channel 4 so that a negative pressure is created, which transports the fiber through the channel 4.
  • the fiber exit from where the endless threads are then transported can be.
  • 800 g of pulp with a DP (Cuoxam) of 520 are in a kneader with 3200 g of a solution consisting of 12 wt .-% NaOh, 30 wt .-% urea and 58 wt .-% water for 1 h at 25 ° C intensive mixed and then at 23 ° C for 48 to a DP (cuoxam) of 300 h pre matures.
  • the wet alkali cellulose is at room temperature in a 5 1 kneader with 1200 g of solid crystalline urea for 30 min. kneaded. Subsequently, the temperature of the kneader is raised to 140 ° C and the water present withdrawn.
  • the mass After reaching a product temperature of 140 ° C, the mass is further kneaded for 120 minutes 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, filtered off with suction through a frit and then dried at room temperature. This loosened and crumbly product had a nitrogen content of 3.0% and a DP (Cuoxam) of 290.
  • 800 g of pulp with a DP (Cuoxam) of 520 are in a kneader with 3200 g of a solution consisting of 12 wt .-% NaOh, 30 wt .-% urea and 58 wt .-% water for 1 h at 25 ° C intensive mixed and nashlig at 23 ° C for 48 h to a DP (Cuoxam) of 300 pre- matured .
  • the wet 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 raised to 140 ° C and the water present withdrawn.
  • the mass is further kneaded for 120 minutes and then discharged from the kneader.
  • the dry crumbly mass is washed 3 times with deionized water at a liquor ratio of 1:16, filtered off with suction through a frit and then dried at room temperature. This loosened and crumbly product had a nitrogen content of 3.0% and a DP (Cuoxam) of 290.
  • 800 g pulp with a DP (Cuoxam) of 520 are intensively in a kneader with 3200 g of a solution consisting of 12 wt .-% NaOH, wt .-% urea and 30 wt .-% water 58 1 h at 25 ° C mixed and then pre- matured for 48 h at 23 ° C on a DP (Cuoxam) .
  • the wet alkali cellulose is kneaded at room temperature in a 5 1 kneader with 1200 g of solid crystalline urea for 30 min. Subsequently, the temperature of the kneader is raised to 140 ° C and the water present withdrawn.
  • the mass After reaching a product temperature of 140 ° C, the mass is further kneaded for 120 minutes 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, filtered off with suction through a frit and then dried at room temperature. This loosened and crumbly product had a nitrogen content of 3.0% and a DP (Cuoxam) 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.

Claims (27)

  1. Procédé de fabrication de tissus non tissés dans lequel une solution de carbamate de cellulose est filée par extrusion à travers un bloc de buses contenant au moins 20 ouvertures dans un bain de précipitation en plusieurs fils sans fin qui sont ensuite entrelacés par soufflage avec un milieu et/ou un fluide gazeux.
  2. Procédé selon la revendication 1, caractérisé en ce qu'un bloc de buses avec au moins 10000 ouvertures est utilisé.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que les ouvertures du bloc de buses sont disposées de manière linéaire ou matricielle.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le rapport entre la longueur et le diamètre des buses est de 1 à 20.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que les fils sans fin sont filés verticalement du bas vers le haut dans le bain de précipitation.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le filage des fils sans fin a lieu par voie humide.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que les fils sans fin sont guidés après le filage vers le bas dans une trémie en forme de fente, le tourbillonnement avec le milieu gazeux et/ou le fluide ayant lieu à la sortie de la trémie.
  8. Procédé selon la revendication précédente, caractérisé en ce qu'un tourbillonnement supplémentaire des fils sans fin est effectué grâce à un mouvement vibratoire de la trémie.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce que le milieu gazeux et/ou le fluide utilisé peut être de l'air et/ou de l'eau.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que les fils sans fin sont déposés sur une courroie de transport après le tourbillonnement.
  11. Procédé selon la revendication précédente, caractérisé en ce qu'un tourbillonnement supplémentaire des fils sans fin est obtenu grâce à un mouvement vibratoire de la courroie de transport.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que le carbamate de cellulose est dissous dans une solution de soude.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que la part de carbamate de cellulose dans la solution de carbamate de cellulose est d'au moins 6 à 12 %, plus particulièrement de 7 à 9 % en poids par rapport à la solution.
  14. Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain de précipitation est constitué d'acide sulfurique avec une concentration de 50 à 200 g/l, plus particulièrement de 70 à 100 g/l, ainsi que de 100 à 300 g/l, plus particulièrement de 150 à 200 g/l de sulfate de sodium.
  15. Procédé selon l'une des revendications précédentes, caractérisé en ce que le tissu non tissé est ensuite lavé, pressé et séché.
  16. Procédé selon la revendication précédente, caractérisé en ce que le lavage a lieu à l'aide d'un jet d'eau sous haute pression.
  17. Procédé selon l'une des revendications précédentes, caractérisé en ce que le carbamate de cellulose est régénéré en cellulose dans un bain de régénération.
  18. Procédé selon la revendication précédente, caractérisé en ce que le bain de régénération constitué de 0,3 à 1 % en poids d'hydroxyde de sodium dans l'eau et en ce que la régénération a lieu à une température comprise entre 60 et 95° C.
  19. Procédé selon la revendication précédente, caractérisé en ce que la régénération est effectuée entre l'extrusion et le tourbillonnement.
  20. Procédé selon la revendication 18, caractérisé en ce que la régénération est effectuée après la fabrication du tissu non tissé.
  21. Tissu non tissé constitué d'un entrelacs de fils sans fins en carbamate de cellulose.
  22. Tissu non tissé selon la revendication 21, caractérisé en ce que le tissu non tissé peut être fabriqué selon le procédé d'une des revendications 1 à 16.
  23. Utilisation des tissus non tissés en médecine, selon l'une des revendications 21 à 22, plus particulièrement en tant que draps de salles d'opération, draps de lits, recouvrement de blessures, gaze ou tampons de ouate.
  24. Utilisation des tissus non tissés selon l'une des revendications 21 ou 22 en tant que produits hygiéniques ou en tant que chiffons de ménage.
  25. Utilisation des tissus non tissés selon l'une des revendications 21 ou 22 en tant que tissus non tissés de décoration, plus particulièrement en tant que nappes, serviettes ou rideaux.
  26. Utilisation des tissus non tissés selon l'une des revendications 21 ou 22 en tant que tissus non tissés de doublure intérieure dans l'industrie de l'habillement.
  27. Utilisation des tissus non tissés selon l'une des revendications 21 ou 22 en tant que tissus non tissés de renforcement et en tant que tapis isolants dans le domaine du bâtiment.
EP05707469A 2004-02-17 2005-02-17 Procede de production de non-tisses, non-tisse correspondant et son utilisation Expired - Fee Related EP1716278B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410007618 DE102004007618A1 (de) 2004-02-17 2004-02-17 Verfahren zur Herstellung von Vliesstoffen, Vliesstoff und dessen Verwendung
PCT/EP2005/001632 WO2005080660A1 (fr) 2004-02-17 2005-02-17 Procede de production de non-tisses, non-tisse correspondant et son utilisation

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Publication Number Publication Date
EP1716278A1 EP1716278A1 (fr) 2006-11-02
EP1716278B1 true EP1716278B1 (fr) 2010-08-25

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

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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
WO2012034679A1 (fr) * 2010-09-14 2012-03-22 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Non-tissé par filature directe hautement fonctionnel, formé de fibres renfermant des particules, et procédé de production correspondant
CA2814350C (fr) * 2010-10-23 2018-05-22 Pop Test LLC Dispositifs et formulations pour detecter, selectionner et controler des niveaux de certains constituants dans liquides organiques, et procede
TW202140884A (zh) * 2019-12-17 2021-11-01 奧地利商蘭仁股份有限公司 製造紡黏非織物的方法

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DE502005010129D1 (de) 2010-10-07
DE102004007618A1 (de) 2005-09-22
WO2005080660A1 (fr) 2005-09-01
JP2007522359A (ja) 2007-08-09
EP1716278A1 (fr) 2006-11-02

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