EP1670418A2 - Chitosan spinning method, device therefor, and resulting chitosan yarn, and uses thereof - Google Patents

Chitosan spinning method, device therefor, and resulting chitosan yarn, and uses thereof

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Publication number
EP1670418A2
EP1670418A2 EP04816135A EP04816135A EP1670418A2 EP 1670418 A2 EP1670418 A2 EP 1670418A2 EP 04816135 A EP04816135 A EP 04816135A EP 04816135 A EP04816135 A EP 04816135A EP 1670418 A2 EP1670418 A2 EP 1670418A2
Authority
EP
European Patent Office
Prior art keywords
chitosan
manufacture
gas
collodion
wire
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Withdrawn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
EP04816135A
Other languages
German (de)
French (fr)
Inventor
Laure Notin
Alain Domard
Christophe Viton
Richard Cancel
Richard Wallace
Gérard Sassi
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.)
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Europlak SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
Europlak SAS
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 Centre National de la Recherche Scientifique CNRS, Universite Claude Bernard Lyon 1 UCBL, Europlak SAS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1670418A2 publication Critical patent/EP1670418A2/en
Withdrawn legal-status Critical Current

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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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P9/00—Drugs for disorders of the cardiovascular system
    • A61P9/14—Vasoprotectives; Antihaemorrhoidals; Drugs for varicose therapy; Capillary stabilisers

Definitions

  • the present invention relates to a new process for spinning chitosan or its derivatives.
  • spinning is an operation for producing fibers or filaments capable of leading to a thread after elongation and / or twisting.
  • Chitosan a deacetylated derivative of chitin
  • Chitosan and chitin are both copolymers with the same overall chemical structure and are distinguished only by the relative proportion of the N-acetyl glucosamine and glucosamine units constituting them, that is to say their degree of acetylation.
  • the viscosity of chitosan depends on its degree of acetylation: the more it is deacetylated, the more free amino groups there are, the more the chitosan is soluble in the dilute acids which protonate its amino groups, and therefore the higher its viscosity. ; viscosity of chitosan also depends on its concentration, on its temperature since the viscosity drops when the temperature increases and on the pH conditions in which it is placed. It can also depend on the deacetylation process used to obtain it. As with any polymer, it also depends on its molecular distribution, characterized in particular by its weight-average molecular weight M w .
  • extrusion unit is then used on a laboratory scale, namely an experimental spinning bench which consists of a reservoir, a metering pump and an extrusion die with 20 holes of 80 ⁇ m in diameter.
  • the filaments are coagulated in a dilute sodium hydroxide (NaOH) bath, about 100 cm long, then they are drawn with rollers in hot water at 80-85 ° C, then washed and dried on rollers in chrome under radiant heat.
  • NaOH sodium hydroxide
  • Chitosan has many properties, and is used in a large number of industries, however its price, which remains high, has been a limiting factor for its development.
  • the wiring of chitosan requires significant installations, and the quality control of the various stages is particularly important when the chitosan is intended in particular for medical applications.
  • the inventors have therefore sought to simplify the processes of the prior art, so as to allow easier industrial implementation, and to reduce the manufacturing costs of chitosan fibers by reducing the amount of chitosan used and the treatment of waste. .
  • the method according to the invention provides the advantage of avoiding the use of a soda bath and eliminates a bath in the spinning bench.
  • the proposed method plays an important role in the mechanical properties of the resulting materials.
  • the subject of the invention is therefore a new process for spinning chitosan according to which a solution of chitosan is prepared at a certain concentration by weight of polymer called collodion, by dissolving chitosan in an aqueous solution of weak acid at stoichiometry with respect to the free amine functions on the chitosan, we filter, we degass, we extrude this collodion and we submit it to the coagulating action of a gas which is capable of deprotonating the ine functions and making them insoluble in water and thus make the collodion coagulate.
  • the collodion is a solution concentrated in chitosan.
  • the method according to the invention uses chitosan whose molar mass is high, which makes it possible to have a high collodion viscosity for a low concentration of chitosan, and at the end of the method, to obtain yarns having good mechanical properties superior to those obtained with lower molar masses.
  • the concentrated chitosan solution must have an apparent viscosity sufficient to allow the solution to be extruded.
  • the chitosan used for implementing the process according to the invention has a degree of acetylation preferably less than 5%, determined according to the technique described by the US Pharmacopoeia, ie, by NMR spectroscopy of the proton " ""H
  • the DA is then calculated by the Hirai et al method (Hirai A, Odani H, Nakajima A. Determination of degree of deacetylation of chitosan by 1 H NMR spectroscopy. Polym. Bull. 1991, 26, 87).
  • Chitosan used can also be selected on the fact that it has a high molar mass average, preferably greater than 500,000 g / mol.
  • the mass average molar mass is determined according to the technique recommended by the American Pharmacopoeia, ie, by static light scattering coupled with size exclusion chromatography, taking into account the increment of refractive index of the polymer, dn / dc for the solvent used.
  • the concentration of the chitosan solution is between 1 and 3% by weight, preferably 2% by weight.
  • the viscosity is preferably between 100 and 1500 poises and preferably around 600 poises.
  • the high molecular weight chitosan is dissolved in an aqueous weak acid solution, the acid being added in stoichiometric amount in relation to the amino functions.
  • the weak acid used to dissolve the chitosan and prepare the collodion is acetic acid.
  • the collodion is then extruded, and the filament leaving the extrusion die is brought into contact with a coagulating gas.
  • this gas is ammonia.
  • filament is defined within the meaning of the present invention as a very long fiber, the fiber being the element of material which constitutes the basic element of a textile material, woven or nonwoven.
  • a stretching is carried out during the coagulation step, that is to say while the collodion filament leaving the extrusion die, is subjected to a coagulating gas action .
  • the drawing can be carried out hot or cold and aims to lengthen the continuous filaments and to orient the crystal structure of the polymer fibers constituting the filaments, in order to improve the mechanical properties of the resulting wire or filament.
  • the drawing speed of the extruded chitosan is between 1 and 20 times the speed of extrusion.
  • the drawing is carried out by means of reels and the drawing speed must be greater than or equal to the extrusion speed, namely the ratio of the flow rate over the section of the extruded chitosan.
  • the step of bringing the extruded collodion filament into contact with the gas is followed by a washing step, prior to drying.
  • the objective of washing is to eliminate the weak acid salts used to dissolve the chitosan and prepare the collodion, these salts forming in the extruded chitosan during contact with the coagulating gas.
  • the washing step consists in passing the extruded, coagulated and at least partially drawn chitosan through a bath of demineralized water which is agitated and replaced continuously to ensure a treatment flow rate of approximately 25 ml of water per mm 3 of chitosan fiber.
  • the weak acid for solubilization of chitosan in the first step, is acetic acid and the gas coagulating the filament at the outlet of extrusion is ammonia: the ammonium acetate salts formed inside the still partially drawn wire during coagulation, in the presence of ammonia gas, are known to be easily hydrolyzed to generate both ammonia and acetic acid. These molecules are relatively poorly soluble in water and are easily extracted in the form of gas by evaporation of the solution.
  • the method does not include a step of washing the extruded and drawn chitosan: the drying step is chained directly after the coagulation step.
  • the invention also relates to a chitosan spinning device characterized in that it comprises an extrusion die placed in a gaseous atmosphere.
  • the gas can flow from bottom to top in a closed circuit, with a controlled flow.
  • the device according to the invention comprises a continuous air heating system regulated in temperature, preferably between 40 and 110 ° C, and ventilated.
  • the device according to the invention also comprises at least one system for drawing the extruded chitosan which can operate simultaneously with the heating system.
  • the device comprises: a reactor vessel provided with a stirring assembly and with a complete vacuum generator group a positive displacement volumetric pump "titration" ensuring a constant flow of a value given in chitosan - an assembly carrying the spinning head a coagulation chamber allowing the application of gas on the extrusion outlet two winding systems for drawing the fibers - a washing tub a drying assembly
  • the extrusion die is of variable dimensions, preferably of diameter less than or equal to 0.8 mm and of length less than or equal to 25 mm.
  • the extrusion die can be monofilament or multifilament.
  • the extrusion die is directly immersed in the coagulation chamber.
  • the stretching system consists of two rewinder systems, the first placed at the outlet of the coagulation chamber and the second placed at the outlet. of the drying system.
  • the linear drawing speeds are between 0.005 m / s and 0.15 m / s.
  • the device contains a washing bath, it preferably consists of demineralized water regenerated with permanent stirring.
  • the drying of the extruded and drawn chitosan is carried out at a temperature between 40 and 110 ° C.
  • the subject of the invention is also a chitosan wire, characterized in that it is obtained by the process described above.
  • a thread is one or more continuous strands of fibers, filaments or materials suitable for knitting or weaving or for any intertwining producing a woven or nonwoven material.
  • a yarn can consist of a single filament with or without twist, a set of fibers or filaments twisted together, a set of fibers or filaments held together without twist, a narrow ribbon formed with or without torsion.
  • Another object of the invention is the use of this chitosan yarn in all applications where it is of industrial interest, and in particular for the manufacture of textiles comprising woven or nonwoven chitosan, for the manufacture of woven medical devices or non-woven, for the manufacture of a reinforcing plate intended in particular for traumatic, visceral or muscular surgery, for the repair of soft tissues, for the manufacture of artificial skin, for the manufacture of a medicament intended for the treatment of ulcers varicose and sluggish wounds.
  • the invention also relates to the use of the chitosan wire obtained by the above process in periodontology, to fight against the formation of caries and dental plaque, stomatitis and gingivitis.
  • Another object of the invention is the use of chitosan yarn obtained by the above process in cosmetics for the manufacture of moisturizing, regenerating and protective skin products, or even for the manufacture of hair products.
  • the invention also relates to the use of the chitosan wire obtained by the above process for the treatment of waste water, for fixing heavy metals, for agglomerating and then separating dispersed colloidal particles, for immobilizing industrial enzymes, for seed coating, for spreading in agriculture.
  • the invention will be better understood on reading the examples which follow, which illustrate, without limitation, the invention.
  • Example 1 Raw Material: Chitosan 114 (Mahtani Chitosan)
  • chitosan degree of acetylation (DA): 2 ⁇ DA ⁇ 3% 500,000 ⁇ average molar mass by mass ⁇ 600,000 g / mol
  • DA degree of acetylation
  • the chitosan is dissolved in an aqueous solution of acetic acid, added in stoichiometric amount relative to the amino functions of the chitosan .
  • the resulting solution is 2% by weight of chitosan and has an apparent viscosity greater than 620 poises.
  • the solution is left in the ambient air for a few hours to ensure better degassing.
  • This solution is then introduced into a 20 ml syringe, which is itself placed on a syringe pump maintained in vertical position.
  • the needle at the end of the syringe having the function of die is not bevelled and has no structural defect which could lead to spinning problems. Cleaning the die is therefore an important step in the spinning process.
  • the die has a diameter of 0.8 mm and a length of 22 mm.
  • the extrusion speed used varies between 0.1 and 35 mL / hour.
  • a piece of glassware, hereinafter called the coagulation chamber consisting of two coaxial glass tubes and sliding joints, was manufactured to create an ammonia atmosphere of variable volume and thus obtain a circulation of gas from bottom to top in circuit closed .
  • the extrusion die is directly immersed in the coagulation chamber. The solution is coagulated at the outlet of the die in the presence of ammonia gas.
  • the extruded chitosan will have a more or less coagulated appearance at this stage of the spinning process.
  • the extruded chitosan is stretched: a drawing ratio is then applied to the extruded chitosan (drawing speed greater than the extrusion speed, the latter being directly related to the flow rate).
  • the extruded and drawn chitosan is immersed in two washing baths containing distilled water with continuous stirring for respective times of one minute. Stretch again, and dry in ambient air while continuing the stretch.
  • Example 2 The chitosan, acetic acid and distilled water are introduced into a 316L stainless steel reactor provided with a stirring system provided with an electronic speed variator. The chitosan is thus dissolved in a way homogeneous. The air bubbles present in the solution are removed by a degassing system. After complete dissolution of the chitosan, the resulting solution, called collodion, is filtered through a 200 ⁇ m poral filter, then extruded through a die of variable diameter, using a titration pump which can control a flow rate between 0.1 and 300 ml / hour .
  • the monofilament die is a non-bevelled needle with a diameter less than or equal to 1 mm and a length less than or equal to 50 mm.
  • the extrusion die is then directly immersed in a gaseous atmosphere so that, as soon as it leaves, the solution coagulates in the presence of ammonia.
  • the coagulation time can vary from a few seconds to several minutes depending on the diameter of the die, the flow rate and the length of the chamber.
  • the fiber then continues its course by being stretched by means of winders of variable speeds which generate a rate of drawing relative to the speed of extrusion.
  • the fiber is then drawn to the washing bath, with a volume of 15 L, where the distilled water is stirred there and replaced continuously thanks to an overflow circulation.
  • Example 3 Safety of the Wire Obtained by the Process According to the Invention Animal experiments were carried out on New Zealand rabbits in order to verify the safety of the chitosan material.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Organic Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Vascular Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Cardiology (AREA)
  • Textile Engineering (AREA)
  • Dermatology (AREA)
  • Artificial Filaments (AREA)
  • Materials For Medical Uses (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention concerns a chitosan spinning method characterized in that it consists in subjecting the chitosan collodion to the coagulating action of a gas, preferably ammonia. The invention also concerns a device for implementing said method, which consists in placing the extrusion die output in a coagulating gas atmosphere. The invention further concerns the yarn obtained by said method and uses thereof in various types of industries.

Description

PROCEDE DE FILAGE DU CHITOSANE, DISPOSITIF DE MISE EN ŒUVRE DE CE PROCEDE, FIL DE CHITOSANE OBTENU, ET UTILISATIONS DUDIT FIL PROCESS FOR SPINNING CHITOSAN, DEVICE FOR CARRYING OUT SAID PROCESS, CHITOSAN THREAD OBTAINED, AND USES THEREOF
La présente invention a pour objet un nouveau procédé de filage du chitosane ou de ses dérivés . Au sens de la présente invention, le filage est une opération de production de fibres ou de filaments susceptibles de conduire à un fil après allongement et/ou torsion.The present invention relates to a new process for spinning chitosan or its derivatives. Within the meaning of the present invention, spinning is an operation for producing fibers or filaments capable of leading to a thread after elongation and / or twisting.
Domaine technique Le chitosane, dérivé désacétylé de la chitine, est un copolymère linéaire de N-acétyl-D-glucosamine et de D- glucosamine liés par une liaison de type β, (1—>4) . Il se trouve rarement dans la nature : il n'est présent que dans la paroi cellulaire d'une classe particulière de champignons, les zygomycètes, et chez quelques insectes. La chitine, présente dans les carapaces de crustacés, est ainsi la source la plus fréquemment utilisée pour l'obtention de chitosane. Le chitosane et la chitine sont tous les deux des copolymères de même structure chimique globale et ne se distinguent que par la proportion relative des unités N-acétyl glucosamine et glucosamine les constituant, c'est-à-dire leur degré d'acétylation.Technical field Chitosan, a deacetylated derivative of chitin, is a linear copolymer of N-acetyl-D-glucosamine and D-glucosamine linked by a β-type bond, (1—> 4). It is rarely found in nature: it is only present in the cell wall of a particular class of fungi, the zygomycetes, and in some insects. Chitin, present in the shell of crustaceans, is thus the most frequently used source for obtaining chitosan. Chitosan and chitin are both copolymers with the same overall chemical structure and are distinguished only by the relative proportion of the N-acetyl glucosamine and glucosamine units constituting them, that is to say their degree of acetylation.
Ce paramètre influe sur leurs propriétés physicochimiques, notamment sur leur viscosité et leur solubilité. La viscosité du chitosane dépend en effet de son degré d'acétylation : plus il est désacétylé, plus il y a de groupements aminé libre, plus le chitosane est soluble dans les acides dilués qui protonent ses groupes aminé, et donc plus sa viscosité est élevée ; la viscosité du chitosane dépend aussi de sa concentration, de sa température puisque la viscosité chute lorsque la température augmente et des conditions de pH dans lesquelles il est placé. Elle peut aussi dépendre du procédé de désacétylation mis en œuvre pour l'obtenir. Comme pour tout polymère, elle dépend aussi de sa distribution moléculaire caractérisée notamment par sa masse molaire moyenne en poids Mw.This parameter influences their physicochemical properties, in particular their viscosity and their solubility. The viscosity of chitosan depends on its degree of acetylation: the more it is deacetylated, the more free amino groups there are, the more the chitosan is soluble in the dilute acids which protonate its amino groups, and therefore the higher its viscosity. ; viscosity of chitosan also depends on its concentration, on its temperature since the viscosity drops when the temperature increases and on the pH conditions in which it is placed. It can also depend on the deacetylation process used to obtain it. As with any polymer, it also depends on its molecular distribution, characterized in particular by its weight-average molecular weight M w .
Etat de la technique Différents procédés de filage du chitosane sont connus dans l'état de la technique : Georges C. East et Yimin Qin (Wet spinning of chitosan and the acetylation of chitosan fibers , Journal of Applied Polymer Science 1993, 50(10), 1773-9) décrivent un procédé de filage au mouillé qui consiste à dissoudre 50 g de chitosane dans 950 mL d'une solution d'acide acétique à 2 % (v/v) . La solution d'acétate de chitosane est ensuite filtrée et dégazée sous vide avant de l'introduire dans le réservoir du système de filage. On utilise alors une unité d'extrusion à l'échelle d'un laboratoire, à savoir un banc de filage expérimental qui est constitué d'un réservoir, d'une pompe de dosage et d'une filière d'extrusion de 20 trous de 80 μm de diamètre. Les filaments sont coagulés dans un bain de soude (NaOH) diluée, d'une longueur de 100 cm environ, puis ils sont étirés avec des rouleaux dans de l'eau chaude à 80-85°C, puis lavés et séchés sur des rouleaux en chrome sous chaleur rayonnante. Problème technique Le chitosane présente de nombreuses propriétés, et est utilisé dans un grand nombre d'industries, toutefois son prix, qui reste élevé, a été un facteur limitant pour son développement. Au niveau industriel, le filage du chitosane nécessite des installations importantes, et le contrôle de la qualité des différentes étapes est particulièrement important quand le chitosane est destiné notamment à des applications médicales . Les Inventeurs ont donc cherché à simplifier les procédés de l'art antérieur, de manière à permettre une mise en œuvre industrielle plus aisée, et à amoindrir les coûts de fabrication des fibres de chitosane en réduisant la quantité de chitosane utilisée et le traitement des déchets. Le procédé selon l'invention apporte l'avantage d'éviter la mise en œuvre d'un bain de soude et permet de supprimer un bain dans le banc de filage. De plus, la méthode proposée joue un rôle important sur les propriétés mécaniques des matériaux qui en résultent.State of the art Different processes for spinning chitosan are known in the state of the art: Georges C. East and Yimin Qin (Wet spinning of chitosan and the acetylation of chitosan fibers, Journal of Applied Polymer Science 1993, 50 (10) , 1773-9) describe a wet spinning process which consists in dissolving 50 g of chitosan in 950 ml of a 2% (v / v) acetic acid solution. The chitosan acetate solution is then filtered and degassed under vacuum before introducing it into the tank of the spinning system. An extrusion unit is then used on a laboratory scale, namely an experimental spinning bench which consists of a reservoir, a metering pump and an extrusion die with 20 holes of 80 μm in diameter. The filaments are coagulated in a dilute sodium hydroxide (NaOH) bath, about 100 cm long, then they are drawn with rollers in hot water at 80-85 ° C, then washed and dried on rollers in chrome under radiant heat. Technical problem Chitosan has many properties, and is used in a large number of industries, however its price, which remains high, has been a limiting factor for its development. At the industrial level, the wiring of chitosan requires significant installations, and the quality control of the various stages is particularly important when the chitosan is intended in particular for medical applications. The inventors have therefore sought to simplify the processes of the prior art, so as to allow easier industrial implementation, and to reduce the manufacturing costs of chitosan fibers by reducing the amount of chitosan used and the treatment of waste. . The method according to the invention provides the advantage of avoiding the use of a soda bath and eliminates a bath in the spinning bench. In addition, the proposed method plays an important role in the mechanical properties of the resulting materials.
Solution apportée L'invention a donc pour objet un nouveau procédé de filage de chitosane selon lequel on prépare une solution de chitosane à une certaine concentration en poids de polymère appelée collodion, en dissolvant du chitosane dans une solution aqueuse d'acide faible à la stœchiométrie par rapport aux fonctions aminé libre sur le chitosane, on filtre, on dégaze, on extrude ce collodion et on le soumet à l'action coagulante d'un gaz qui est capable de déprotoner les fonctions a iné et de les rendre insolubles dans l'eau et de faire ainsi coaguler le collodion. Cette coagulation intervient après que le collodion a été extrudé ou mis en forme ou étiré, par exemple en étant passé au travers d'une filière d'extrusion. Suivant un premier mode de réalisation préféré de l'invention, le collodion est une solution concentrée en chitosane. Suivant une variante avantageuse de l'invention, le procédé selon l'invention met en œuvre du chitosane dont la masse molaire est élevée, ce qui permet d'avoir une viscosité du collodion élevée pour une faible concentration en chitosane, et à l'issue du procédé, d'obtenir des fils ayant de bonnes propriétés mécaniques supérieures à celles obtenues avec des masses molaires plus faibles. La solution concentrée de chitosane doit présenter une viscosité apparente suffisante pour permettre 1' extrusion de la solution. De préférence, le chitosane utilisé pour la mise en œuvre du procédé selon l'invention présente un degré d' acétylation préférentiellement inférieur à 5 %, déterminé selon la technique décrite par la Pharmacopée US, soit, par spectroscopie RMN du proton """H. Le DA est alors calculé par la méthode d'Hirai et col (Hirai A, Odani H, Nakajima A. Détermination of degree of deacetylation of chitosan by 1H RMN spectroscopy. Polym. Bull. 1991, 26, 87). Le chitosane utilisé peut également être sélectionné sur le fait qu'il présente une masse molaire moyenne en masse élevée, de préférence supérieure à 500 000 g/mol. La masse molaire moyenne en masse est déterminée selon la technique préconisée par la Pharmacopée américaine, soit, par la diffusion statique de la lumière couplée à la chromatographie d'exclusion stérique, en tenant compte de l'incrément d'indice de réfraction du polymère, dn/dc pour le solvant utilisé. Suivant un mode de réalisation particulier de l'invention, la concentration de la solution de chitosane est comprise entre 1 et 3 % en poids, de préférence de 2 % en poids. Dans ce mode de réalisation, la viscosité est de préférence comprise entre 100 et 1500 poises et de préférence d'environ 600 poises. Le chitosane de masse molaire élevée est solubilisé dans une solution aqueuse d'acide faible, l'acide étant ajouté en quantité stœchiométrique par rapport aux fonctions aminés . Suivant un mode de réalisation préféré de l'invention, l'acide faible utilisé pour solubiliser le chitosane et préparer le collodion est l'acide acétique. Le collodion est ensuite extrudé, et le filament en sortie de filière d' extrusion, est mis en contact avec un gaz coagulant. Avantageusement, ce gaz est de l'ammoniac. Le terme filament est défini au sens de la présente invention comme une fibre de très grande longueur, la fibre étant l'élément de matière qui constitue l'élément de base d'un matériau textile, tissé ou non tissé. Suivant un mode de réalisation préféré de l'invention, un étirage est effectué pendant l'étape de coagulation, c'est-à-dire pendant que le filament de collodion en sortie de filière d'extrusion, est soumis à une action gazeuse coagulante. Cet étirage peut être poursuivi pendant toutes les étapes du procédé suivant la coagulation, ou pendant certaines de ces étapes seulement. L' étirage peut être réalisé à chaud ou à froid et a pour buts d'allonger les filaments continus et d'orienter la structure cristalline des fibres polymère constituant les filaments, pour améliorer les propriétés mécaniques du fil ou du filament résultant. De préférence, la vitesse d'étirage du chitosane extrudé est comprise entre 1 et 20 fois la vitesse d'extrusion. L'étirage s'effectue au moyen d'enrouleurs et la vitesse d'étirage doit être supérieure ou égale à la vitesse d'extrusion, à savoir au rapport du débit sur la section du chitosane extrudé. Suivant un mode de réalisation de l'invention l'étape de mise en contact du filament de collodion extrudé avec le gaz est suivie d'une étape de lavage, préalable au séchage. L'objectif du lavage est d'éliminer les sels d'acide faible utilisés pour solubiliser le chitosane et préparer le collodion, ces sels se formant dans le chitosane extrudé pendant le contact avec le gaz coagulant. Avantageusement, l'étape de lavage consiste à faire passer le chitosane extrudé, coagulé et au moins partiellement étiré dans un bain d'eau déminéralisée agitée et remplacée en continu pour assurer un débit de traitement d'environ 25 mL d'eau par mm3 de fibre de chitosane. Suivant un mode de réalisation avantageux, l'acide faible de solubilisation du chitosane, dans la première étape, est l'acide acétique et le gaz coagulant le filament en sortie d'extrusion est l'ammoniac : les sels d'acétate d'ammonium formés à l'intérieur du fil encore partiellement étiré lors de la coagulation, en présence du gaz ammoniac, sont connus pour être facilement hydrolyses pour générer à la fois de l'ammoniaque et de l'acide acétique. Ces molécules sont relativement peu solubles dans l'eau et sont facilement extraites sous forme de gaz par évaporation de la solution. Suivant un mode de réalisation avantageux, le procédé ne comprend pas d' étape de lavage du chitosane extrudé et étiré : l'étape de séchage est enchaînée directement après l'étape de coagulation. Ce mode de réalisation est particulièrement avantageux car il permet de supprimer un deuxième bain dans le dispositif, et allège ainsi considérablement le dispositif. L'invention a également pour objet un dispositif de filage de chitosane caractérisé en ce qu' il comprend une filière d'extrusion placée dans une atmosphère gazeuse. Suivant un mode de réalisation particulier, dans le dispositif de l'invention, le gaz peut circuler de bas en haut en circuit fermé, avec un débit contrôlé. Avantageusement, le dispositif selon l'invention comprend un système de chauffage à air en continu régulé en température, de préférence entre 40 et 110 °C, et ventilé. Le dispositif selon l'invention comprend également au moins un système d' étirage du chitosane extrudé qui peut fonctionner simultanément avec le système de chauffage. Suivant un mode de réalisation particulier, le dispositif selon l'invention comprend : une cuve réacteur munie d'un ensemble d' agitation et d'un groupe générateur de vide complet une pompe volumétrique à engrenage « titrage » assurant un débit constant d'une valeur donnée en chitosane - un ensemble porte tête de filage une chambre de coagulation permettant l'application du gaz sur la sortie d'extrusion deux systèmes d' enrouleurs pour l'étirage des fibres - un bac de lavage un ensemble de séchage Suivant un mode de réalisation préféré de l'invention, la filière d'extrusion est de dimensions variables, de préférence de diamètre inférieur ou égal à 0.8 mm et de longueur inférieure ou égale à 25 mm. La filière d'extrusion peut être monofilament ou multifilament . Avantageusement, la filière d'extrusion est directement plongée dans la chambre de coagulation. Avantageusement, le système d'étirage est constitué de deux systèmes d'enrouleurs, le premier placé en sortie de la chambre de coagulation et le second placé en sortie du système de séchage. Les vitesses linéaires d'étirage sont comprises entre 0.005 m/s et 0.15 m/s. Lorsque le dispositif contient un bain de lavage, il est constitué de préférence d'eau déminéralisée régénérée sous agitation permanente Le séchage du chitosane extrudé et étiré est effectué à une température comprise entre 40 et 110°C. L'invention a encore pour objet un fil de chitosane caractérisé en ce qu'il est obtenu par le procédé décrit ci-dessus. Au sens de la présente invention, un fil est un ou plusieurs brins continus de fibres, filaments ou matières appropriées au tricotage ou au tissage ou à tout entrelacement produisant un matériau tissé ou non tissé. Un fil peut être constitué d'un seul filament avec ou sans torsion, d'un ensemble de fibres ou de filaments tordus ensemble, d'un ensemble de fibres ou de filaments maintenus ensemble sans torsion, d'un ruban étroit formé avec ou sans torsion. Un autre objet de l'invention est l'utilisation de ce fil de chitosane dans toutes les applications où il présente un intérêt industriel, et notamment pour la fabrication de textile comprenant du chitosane tissé ou non tissé, pour la fabrication de dispositifs médicaux tissés ou non tissés, pour la fabrication d'une plaque de renfort destinée en particulier à la chirurgie traumatique, viscérale ou musculaire, pour la réparation des tissus mous, pour la fabrication de peau artificielle, pour la fabrication d'un médicament destiné au traitement des ulcères variqueux et des plaies atones . L'invention concerne aussi l'utilisation du fil de chitosane obtenu par le procédé ci-dessus en parodontologie, pour lutter contre la formation des caries et de la plaque dentaire, les stomatites et les gingivites. Un autre objet de l'invention est l'utilisation du fil de chitosane obtenu par le procédé ci-dessus en cosmétique pour la fabrication de produits hydratants, régénérants, et protecteurs de la peau, ou encore pour fabrication de produits capillaires . L'invention concerne encore l'utilisation du fil de chitosane obtenu par le procédé ci-dessus pour le traitement des eaux usées, pour fixer les métaux lourds, pour agglomérer puis séparer des particules colloïdales dispersées, pour immobiliser des enzymes industriels, pour l'enrobage de semences, pour l'épandage en agriculture. L'invention se comprendra mieux à la lecture des exemples qui suivent, qui illustrent non limitativement l'invention.Solution provided The subject of the invention is therefore a new process for spinning chitosan according to which a solution of chitosan is prepared at a certain concentration by weight of polymer called collodion, by dissolving chitosan in an aqueous solution of weak acid at stoichiometry with respect to the free amine functions on the chitosan, we filter, we degass, we extrude this collodion and we submit it to the coagulating action of a gas which is capable of deprotonating the ine functions and making them insoluble in water and thus make the collodion coagulate. This coagulation occurs after the collodion has been extruded or shaped or stretched, for example by being passed through an extrusion die. According to a first preferred embodiment of the invention, the collodion is a solution concentrated in chitosan. According to an advantageous variant of the invention, the method according to the invention uses chitosan whose molar mass is high, which makes it possible to have a high collodion viscosity for a low concentration of chitosan, and at the end of the method, to obtain yarns having good mechanical properties superior to those obtained with lower molar masses. The concentrated chitosan solution must have an apparent viscosity sufficient to allow the solution to be extruded. Preferably, the chitosan used for implementing the process according to the invention has a degree of acetylation preferably less than 5%, determined according to the technique described by the US Pharmacopoeia, ie, by NMR spectroscopy of the proton " ""H The DA is then calculated by the Hirai et al method (Hirai A, Odani H, Nakajima A. Determination of degree of deacetylation of chitosan by 1 H NMR spectroscopy. Polym. Bull. 1991, 26, 87). Chitosan used can also be selected on the fact that it has a high molar mass average, preferably greater than 500,000 g / mol. The mass average molar mass is determined according to the technique recommended by the American Pharmacopoeia, ie, by static light scattering coupled with size exclusion chromatography, taking into account the increment of refractive index of the polymer, dn / dc for the solvent used. particular of the invention, the concentration of the chitosan solution is between 1 and 3% by weight, preferably 2% by weight. In this embodiment, the viscosity is preferably between 100 and 1500 poises and preferably around 600 poises. The high molecular weight chitosan is dissolved in an aqueous weak acid solution, the acid being added in stoichiometric amount in relation to the amino functions. According to a preferred embodiment of the invention, the weak acid used to dissolve the chitosan and prepare the collodion is acetic acid. The collodion is then extruded, and the filament leaving the extrusion die is brought into contact with a coagulating gas. Advantageously, this gas is ammonia. The term filament is defined within the meaning of the present invention as a very long fiber, the fiber being the element of material which constitutes the basic element of a textile material, woven or nonwoven. According to a preferred embodiment of the invention, a stretching is carried out during the coagulation step, that is to say while the collodion filament leaving the extrusion die, is subjected to a coagulating gas action . This stretching can be continued during all the stages of the process following coagulation, or during some of these stages only. The drawing can be carried out hot or cold and aims to lengthen the continuous filaments and to orient the crystal structure of the polymer fibers constituting the filaments, in order to improve the mechanical properties of the resulting wire or filament. Preferably, the drawing speed of the extruded chitosan is between 1 and 20 times the speed of extrusion. The drawing is carried out by means of reels and the drawing speed must be greater than or equal to the extrusion speed, namely the ratio of the flow rate over the section of the extruded chitosan. According to one embodiment of the invention, the step of bringing the extruded collodion filament into contact with the gas is followed by a washing step, prior to drying. The objective of washing is to eliminate the weak acid salts used to dissolve the chitosan and prepare the collodion, these salts forming in the extruded chitosan during contact with the coagulating gas. Advantageously, the washing step consists in passing the extruded, coagulated and at least partially drawn chitosan through a bath of demineralized water which is agitated and replaced continuously to ensure a treatment flow rate of approximately 25 ml of water per mm 3 of chitosan fiber. According to an advantageous embodiment, the weak acid for solubilization of chitosan, in the first step, is acetic acid and the gas coagulating the filament at the outlet of extrusion is ammonia: the ammonium acetate salts formed inside the still partially drawn wire during coagulation, in the presence of ammonia gas, are known to be easily hydrolyzed to generate both ammonia and acetic acid. These molecules are relatively poorly soluble in water and are easily extracted in the form of gas by evaporation of the solution. According to an advantageous embodiment, the method does not include a step of washing the extruded and drawn chitosan: the drying step is chained directly after the coagulation step. This embodiment is particularly advantageous because it makes it possible to eliminate a second bath in the device, and thus considerably lightens the device. The invention also relates to a chitosan spinning device characterized in that it comprises an extrusion die placed in a gaseous atmosphere. According to a particular embodiment, in the device of the invention, the gas can flow from bottom to top in a closed circuit, with a controlled flow. Advantageously, the device according to the invention comprises a continuous air heating system regulated in temperature, preferably between 40 and 110 ° C, and ventilated. The device according to the invention also comprises at least one system for drawing the extruded chitosan which can operate simultaneously with the heating system. According to a particular embodiment, the device according to the invention comprises: a reactor vessel provided with a stirring assembly and with a complete vacuum generator group a positive displacement volumetric pump "titration" ensuring a constant flow of a value given in chitosan - an assembly carrying the spinning head a coagulation chamber allowing the application of gas on the extrusion outlet two winding systems for drawing the fibers - a washing tub a drying assembly According to a mode preferred embodiment of the invention, the extrusion die is of variable dimensions, preferably of diameter less than or equal to 0.8 mm and of length less than or equal to 25 mm. The extrusion die can be monofilament or multifilament. Advantageously, the extrusion die is directly immersed in the coagulation chamber. Advantageously, the stretching system consists of two rewinder systems, the first placed at the outlet of the coagulation chamber and the second placed at the outlet. of the drying system. The linear drawing speeds are between 0.005 m / s and 0.15 m / s. When the device contains a washing bath, it preferably consists of demineralized water regenerated with permanent stirring. The drying of the extruded and drawn chitosan is carried out at a temperature between 40 and 110 ° C. The subject of the invention is also a chitosan wire, characterized in that it is obtained by the process described above. For the purposes of the present invention, a thread is one or more continuous strands of fibers, filaments or materials suitable for knitting or weaving or for any intertwining producing a woven or nonwoven material. A yarn can consist of a single filament with or without twist, a set of fibers or filaments twisted together, a set of fibers or filaments held together without twist, a narrow ribbon formed with or without torsion. Another object of the invention is the use of this chitosan yarn in all applications where it is of industrial interest, and in particular for the manufacture of textiles comprising woven or nonwoven chitosan, for the manufacture of woven medical devices or non-woven, for the manufacture of a reinforcing plate intended in particular for traumatic, visceral or muscular surgery, for the repair of soft tissues, for the manufacture of artificial skin, for the manufacture of a medicament intended for the treatment of ulcers varicose and sluggish wounds. The invention also relates to the use of the chitosan wire obtained by the above process in periodontology, to fight against the formation of caries and dental plaque, stomatitis and gingivitis. Another object of the invention is the use of chitosan yarn obtained by the above process in cosmetics for the manufacture of moisturizing, regenerating and protective skin products, or even for the manufacture of hair products. The invention also relates to the use of the chitosan wire obtained by the above process for the treatment of waste water, for fixing heavy metals, for agglomerating and then separating dispersed colloidal particles, for immobilizing industrial enzymes, for seed coating, for spreading in agriculture. The invention will be better understood on reading the examples which follow, which illustrate, without limitation, the invention.
Exemple 1 : Matière Première : Chitosane 114 (Mahtani Chitosan)Example 1: Raw Material: Chitosan 114 (Mahtani Chitosan)
; degré d' acétylation (DA) : 2 < DA < 3 % 500000 < masse molaire moyenne en masse < 600000 g/mol Le chitosane est solubilisé dans une solution aqueuse d'acide acétique, ajoutée en quantité stœchiométrique par rapport aux fonctions aminé du chitosane. La solution résultante est à 2 % en poids de chitosane et présente une viscosité apparente supérieure à 620 poises. La solution est laissée à l'air ambiant pendant quelques heures pour assurer un meilleur dégazage. Cette solution est ensuite introduite dans une seringue de 20 mL, qui est elle-même placée sur un pousse-seringue maintenu en position verticale. L'aiguille en bout de seringue ayant fonction de filière, est non biseautée et ne présente aucun défaut de structure qui pourrait entraîner des problèmes de filage . Le nettoyage de la filière constitue donc une étape importante dans le procédé de filage. La filière a un diamètre de 0.8 mm et une longueur de 22 mm. La vitesse d'extrusion utilisée varie entre 0.1 et 35 mL/heure. Une pièce en verrerie, appelée ci-après chambre de coagulation, constituée de deux tubes de verre coaxiaux et jointifs coulissants, a été fabriquée pour créer une atmosphère d'ammoniac de volume variable et ainsi obtenir une circulation du gaz de bas en haut en circuit fermé . La filière d' extrusion est directement plongée dans la chambre de coagulation. La coagulation de la solution est assurée en sortie de filière en présence du gaz ammoniac. Ainsi, selon la longueur du tube et le débit contrôlé par le pousse-seringue, le chitosane extrudé va avoir un aspect plus ou moins coagulé à ce stade du procédé de filage. Durant l'étape de coagulation, le chitosane extrudé est étiré : un rapport d'étirage est alors appliqué au chitosane extrudé (vitesse d'étirage supérieure à la vitesse d'extrusion, cette dernière étant directement reliée au débit) . A la sortie du tube, le chitosane extrudé et étiré est plongé dans deux bains de lavage contenant de l'eau distillée sous agitation permanente pendant des temps respectifs d'une minute. On étire à nouveau, et on sèche à l'air ambiant en poursuivant l'étirage. Exemple 2 Le chitosane, l'acide acétique et l'eau distillée sont introduits dans un réacteur en inox 316L pourvu d'un système d'agitation muni d'un variateur à vitesse électronique. Le chitosane est ainsi dissous de façon homogène. L'élimination des bulles d'air présentes dans la solution est assurée par un système de dégazage. Après dissolution complète du chitosane, la solution résultante, dite collodion, est filtrée sur un filtre poral 200 μm, puis extrudée à travers une filière de diamètre variable, grâce à une pompe de titrage pouvant contrôler un débit compris entre 0.1 et 300 mL/heure. La filière monofilament est une aiguille non biseautée de diamètre inférieur ou égal à 1 mm et de longueur inférieure ou égale à 50 mm. La filière d' extrusion est alors directement plongée dans une atmosphère gazeuse pour que, dès sa sortie, la solution coagule en présence d'ammoniac. Le temps de coagulation peut varier de quelques secondes à plusieurs minutes selon le diamètre de la filière, le débit et la longueur de la chambre . La fibre poursuit alors son parcours en étant étirée grâce à des enrouleurs de vitesses variables qui engendrent un taux d'étirage par rapport à la vitesse d'extrusion. La fibre est alors entraînée jusqu'au bain de lavage, d'un volume de 15 L, où l'eau distillée y est agitée et remplacée en continu grâce à une circulation par débordement. Le séchage de la fibre est enfin assuré par un système de chauffage à air en continu constitué d'une chambre (tunnel en verre borosilicaté) régulée en température et d'une turbine assurant la ventilation. Lors du séchage, la fibre est à nouveau étirée grâce à d'autres enrouleurs ayant des vitesses de rotation supérieures à la vitesse d'extrusion et à celle des premiers enrouleurs : on peut ainsi établir un taux d'étirage contrôlé en fin de filière. Exemple 3 : innocuité du fil obtenu par le procédé selon l' invention Des expérimentations animales ont été menées sur des lapins néo-zélandais afin de vérifier l'innocuité du matériau chitosane. Pour cette étude in vivo, on utilise des brins constitués de 5 fibres (fibre d'un diamètre de l'ordre de 30 μm) torsadées et nouées entre elles à trois endroits différents (extrémités et milieu) pour éviter toute dispersion d'une fibre à l'intérieur du site. Les brins de chitosane sont implantés dans la cavité abdominale; degree of acetylation (DA): 2 <DA <3% 500,000 <average molar mass by mass <600,000 g / mol The chitosan is dissolved in an aqueous solution of acetic acid, added in stoichiometric amount relative to the amino functions of the chitosan . The resulting solution is 2% by weight of chitosan and has an apparent viscosity greater than 620 poises. The solution is left in the ambient air for a few hours to ensure better degassing. This solution is then introduced into a 20 ml syringe, which is itself placed on a syringe pump maintained in vertical position. The needle at the end of the syringe having the function of die, is not bevelled and has no structural defect which could lead to spinning problems. Cleaning the die is therefore an important step in the spinning process. The die has a diameter of 0.8 mm and a length of 22 mm. The extrusion speed used varies between 0.1 and 35 mL / hour. A piece of glassware, hereinafter called the coagulation chamber, consisting of two coaxial glass tubes and sliding joints, was manufactured to create an ammonia atmosphere of variable volume and thus obtain a circulation of gas from bottom to top in circuit closed . The extrusion die is directly immersed in the coagulation chamber. The solution is coagulated at the outlet of the die in the presence of ammonia gas. Thus, depending on the length of the tube and the flow rate controlled by the syringe pump, the extruded chitosan will have a more or less coagulated appearance at this stage of the spinning process. During the coagulation step, the extruded chitosan is stretched: a drawing ratio is then applied to the extruded chitosan (drawing speed greater than the extrusion speed, the latter being directly related to the flow rate). At the outlet of the tube, the extruded and drawn chitosan is immersed in two washing baths containing distilled water with continuous stirring for respective times of one minute. Stretch again, and dry in ambient air while continuing the stretch. Example 2 The chitosan, acetic acid and distilled water are introduced into a 316L stainless steel reactor provided with a stirring system provided with an electronic speed variator. The chitosan is thus dissolved in a way homogeneous. The air bubbles present in the solution are removed by a degassing system. After complete dissolution of the chitosan, the resulting solution, called collodion, is filtered through a 200 μm poral filter, then extruded through a die of variable diameter, using a titration pump which can control a flow rate between 0.1 and 300 ml / hour . The monofilament die is a non-bevelled needle with a diameter less than or equal to 1 mm and a length less than or equal to 50 mm. The extrusion die is then directly immersed in a gaseous atmosphere so that, as soon as it leaves, the solution coagulates in the presence of ammonia. The coagulation time can vary from a few seconds to several minutes depending on the diameter of the die, the flow rate and the length of the chamber. The fiber then continues its course by being stretched by means of winders of variable speeds which generate a rate of drawing relative to the speed of extrusion. The fiber is then drawn to the washing bath, with a volume of 15 L, where the distilled water is stirred there and replaced continuously thanks to an overflow circulation. The drying of the fiber is finally ensured by a continuous air heating system consisting of a chamber (borosilicate glass tunnel) regulated in temperature and a turbine ensuring ventilation. During drying, the fiber is again drawn thanks to other reels having rotational speeds higher than the extrusion speed and that of the first reels: it is thus possible to establish a controlled drawing rate at the end of the die. Example 3: Safety of the Wire Obtained by the Process According to the Invention Animal experiments were carried out on New Zealand rabbits in order to verify the safety of the chitosan material. For this in vivo study, we use strands made up of 5 fibers (fiber with a diameter of around 30 μm) twisted and knotted together in three different places (ends and middle) to avoid any dispersion of a fiber inside the site. The strands of chitosan are implanted in the abdominal cavity
(implantation intra-cavitaire) , dans la cuisse(intra-cavitary implantation), in the thigh
(implantation intra musculaire) , et sur le site para vertébral (implantation sous-cutanée) . Les brins sont fixés à chacune de leur extrémité à l'aide de fil non résorbable bleu repérable facilement lors de la dissection ex-vivo, après euthanasie de l'animal. L'observation de la réponse a eu lieu sur trois périodes : une semaine, quatre semaines et douze semaines. Après une, quatre et douze semaines d'implantation, les résultats sont positifs, puisque aucune réponse inflammatoire ni immunitaire néfaste n'est relevée en vue des quantités de chitosane implantées localement. (intramuscular implantation), and on the para vertebral site (subcutaneous implantation). The strands are fixed at each of their ends using blue non-absorbable wire that can be easily identified during ex-vivo dissection, after euthanasia of the animal. The observation of the response took place over three periods: one week, four weeks and twelve weeks. After one, four and twelve weeks of implantation, the results are positive, since no inflammatory or harmful immune response is noted in view of the quantities of chitosan implanted locally.

Claims

REVENDICATIONS
1. Procédé de filage de chitosane caractérisé en ce que l'on soumet le collodion de chitosane à l'action coagulante d' un gaz . 1. Process for spinning chitosan, characterized in that the collodion of chitosan is subjected to the coagulating action of a gas.
2. Procédé selon la revendication 1, caractérisé en ce que ledit gaz est appliqué sur un filament de collodion de chitosane à la sortie d'une filière d'extrusion. 2. Method according to claim 1, characterized in that said gas is applied to a chitosan collodion filament at the outlet of an extrusion die.
3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que pendant ladite étape de coagulation, ledit filament est soumis à un étirage. 3. Method according to any one of claims 1 or 2, characterized in that during said coagulation step, said filament is subjected to drawing.
4. Procédé selon la revendication 3, caractérisé en ce que la vitesse d'étirage est comprise entre 1 et 20 fois la vitesse d'extrusion. 4. Method according to claim 3, characterized in that the drawing speed is between 1 and 20 times the extrusion speed.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ladite étape d' application du gaz est suivie des étapes de séchage et d'étirage simultanées. 5. Method according to any one of claims 1 to 4, characterized in that said step of applying the gas is followed by simultaneous drying and stretching steps.
6. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'étape d'application dudit gaz est suivie d'une étape de lavage préalable au séchage. 6. Method according to any one of claims 1 to 4, characterized in that the step of applying said gas is followed by a washing step prior to drying.
7. Procédé selon la revendication 6, caractérisé en ce que ladite étape de lavage est un bain d' eau déminéralisée agitée et remplacée en continu pour assurer un débit d'environ 25mL d'eau par mm3 de filament ou fil de chitosane, ledit filament ou fil étant éventuellement étiré pendant le lavage. 7. Method according to claim 6, characterized in that said washing step is a bath of demineralized water stirred and replaced continuously to ensure a flow rate of about 25mL of water per mm 3 of filament or chitosan wire, said filament or yarn possibly being drawn during washing.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que ledit gaz est de l' ammoniac. 8. Method according to any one of claims 1 to 7, characterized in that said gas is ammonia.
9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que ledit collodion est préparé à partir de chitosane présentant de préférence un degré d' acétylation inférieur à 5%, en solubilisant ledit chitosane dans une solution d' acide acétique pour l'obtention d'un collodion dont la viscosité apparente est suffisante pour permettre le filage de la solution, et de préférence comprise entre 500 et 800 poises, et en dégazant ledit collodion notamment au moyen d'une pompe à vide. 9. Method according to any one of claims 1 to 8, characterized in that said collodion is prepared from chitosan preferably having a degree of acetylation less than 5%, by dissolving said chitosan in a solution of acetic acid to obtain a collodion whose apparent viscosity is sufficient to allow spinning of the solution, and preferably between 500 and 800 poises, and by degassing said collodion in particular by means of a vacuum pump.
10. Procédé selon la revendication 9, caractérisé en ce que la masse molaire moyenne dudit chitosane est supérieure à 500 000 g/mol. 10. Method according to claim 9, characterized in that the average molar mass of said chitosan is greater than 500,000 g / mol.
11. Dispositif de filage de chitosane caractérisé en ce qu'il comprend au moins une filière d'extrusion placée dans une atmosphère gazeuse. 11. A chitosan spinning device characterized in that it comprises at least one extrusion die placed in a gaseous atmosphere.
12. Dispositif selon la revendication 12, caractérisé en ce que le gaz peut circuler de bas en haut en circuit fermé, avec un débit contrôlé. 12. Device according to claim 12, characterized in that the gas can circulate from bottom to top in a closed circuit, with a controlled flow rate.
13. Dispositif selon l'une quelconque des revendications 11 ou 12, caractérisé en ce qu'il comprend un système de chauffage à air en continu régulé en température, de préférence entre 40 et 110 °C, et ventilé. 13. Device according to any one of claims 11 or 12, characterized in that it comprises a continuous air heating system regulated in temperature, preferably between 40 and 110 ° C, and ventilated.
14. Dispositif selon la revendication 13, caractérisé en ce qu'il comprend un système d'étirage du chitosane extrudé qui peut fonctionner simultanément avec le système de chauffage. 14. Device according to claim 13, characterized in that it comprises a system for drawing the extruded chitosan which can operate simultaneously with the heating system.
15. Fil de chitosane caractérisé en ce qu'il est obtenu par le procédé selon l'une quelconque des revendications 1 à 10. 15. Chitosan wire, characterized in that it is obtained by the process according to any one of claims 1 to 10.
16. Utilisation du fil de chitosane selon la revendication 15 pour la fabrication de textile de chitosane, tissés ou non tissés. 16. Use of the chitosan yarn according to claim 15 for the manufacture of chitosan textile, woven or nonwoven.
17. Utilisation du fil de chitosane selon la revendication 15 pour la fabrication de dispositifs médicaux tissés ou non tissés. 17. Use of the chitosan wire according to claim 15 for the manufacture of woven or nonwoven medical devices.
18. Utilisation du fil de chitosane selon la revendication 15 pour la fabrication d'une plaque de renfort destinée en particulier à la chirurgie traumatique, viscérale ou musculaire. 18. Use of the chitosan wire according to claim 15 for the manufacture of a reinforcing plate intended in particular for traumatic, visceral or muscular surgery.
19. Utilisation du fil de chitosane selon la revendication 15 pour la fabrication de peau artificielle. 19. Use of the chitosan thread according to claim 15 for the manufacture of artificial skin.
20. Utilisation du fil de chitosane selon la revendication 15 pour la fabrication d'un médicament destiné au traitement des ulcères variqueux et des plaies atones . 20. Use of the chitosan wire according to claim 15 for the manufacture of a medicament intended for the treatment of varicose ulcers and atonic wounds.
21. Utilisation du fil de chitosane selon la revendication 15 pour la fabrication d'une composition en parodontologie destinée à lutter contre la formation des caries et de la plaque dentaire, les stomatites et les gingivites . 21. Use of the chitosan wire according to claim 15 for the manufacture of a periodontology composition intended to combat the formation of caries and dental plaque, stomatitis and gingivitis.
22. Utilisation du fil de chitosane selon la revendication 15 en cosmétique pour la fabrication de produits hydratants, régénérants, et protecteurs de la peau, ou encore pour fabrication de produits capillaires. 22. Use of the chitosan wire according to claim 15 in cosmetics for the manufacture of moisturizing, regenerating and protective skin products, or also for the manufacture of hair products.
23. Utilisation du fil de chitosane selon la revendication 15 pour le traitement des eaux usées, pour fixer les métaux lourds, pour agglomérer puis séparer des particules colloïdales dispersées, pour immobiliser des enzymes industriels, pour l'enrobage de semences, pour l'épandage en agriculture. 23. Use of the chitosan wire according to claim 15 for the treatment of waste water, for fixing heavy metals, for agglomerating and then separating dispersed colloidal particles, for immobilizing industrial enzymes, for coating seeds, for spreading in agriculture.
EP04816135A 2003-09-18 2004-09-17 Chitosan spinning method, device therefor, and resulting chitosan yarn, and uses thereof Withdrawn EP1670418A2 (en)

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FR0350571A FR2860007A1 (en) 2003-09-18 2003-09-18 Spinning chitosan to produce chitosan yarn, e.g. for medical, cosmetic or agricultural applications, comprises subjecting a chitosan solution to the coagulating action of a gas
PCT/FR2004/050441 WO2005025520A2 (en) 2003-09-18 2004-09-17 Chitosan spinning method, device therefor, and resulting chitosan yarn, and uses thereof

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WO2009035413A1 (en) * 2007-09-10 2009-03-19 National University Of Singapore A chitosan solution and method of preparing the same
FR2942242B1 (en) 2009-02-17 2011-06-03 Laboratoire Tetra Medical PROCESS FOR OBTAINING A LONGIFORM ELEMENT OF POLYSACCHARIDE, IN PARTICULAR A CHITOSAN YARN AND POLYSACCHARIDE YARN OBTAINED
WO2011095203A1 (en) 2010-02-02 2011-08-11 Medovent Gmbh Chitosan fiber
FR2957091B1 (en) 2010-03-05 2012-04-27 Tetra Medical Lab PROCESS FOR OBTAINING A LONGIFORM ELEMENT OF POLYSACCHARIDE, IN PARTICULAR A CHITOSAN WIRE

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IT1144925B (en) * 1981-10-08 1986-10-29 Anic Spa CHITOSAN QUARRY FIBERS AND PROCEDURE FOR THEIR OBTAINING
JPS6040224A (en) * 1983-08-16 1985-03-02 Dainichi Seika Kogyo Kk Manufacture of formed article of chitosan

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WO2005025520A3 (en) 2005-05-19
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