EP0932709B1 - Wässrige koagulationsmittel für flüssigkristalllösungen aus cellulosematerialen - Google Patents

Wässrige koagulationsmittel für flüssigkristalllösungen aus cellulosematerialen Download PDF

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Publication number
EP0932709B1
EP0932709B1 EP97910443A EP97910443A EP0932709B1 EP 0932709 B1 EP0932709 B1 EP 0932709B1 EP 97910443 A EP97910443 A EP 97910443A EP 97910443 A EP97910443 A EP 97910443A EP 0932709 B1 EP0932709 B1 EP 0932709B1
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EP
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Prior art keywords
tex
coagulating agent
cellulose
spinning
fibers
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EP97910443A
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English (en)
French (fr)
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EP0932709A1 (de
Inventor
Jean-Paul Meraldi
Rima Huston
Vlastimil Cizek
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Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
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Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
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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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • 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
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T152/00—Resilient tires and wheels
    • Y10T152/10—Tires, resilient
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2965—Cellulosic

Definitions

  • the present invention relates to cellulosic materials, ie to cellulose or cellulose derivatives, to liquid-crystal solutions based on such cellulosic materials, in particular to spinnable solutions capable of giving after coagulation spun articles such as fibers or films, to these spun articles themselves, as well as to methods for obtaining such spun articles.
  • the invention relates more particularly to an aqueous coagulating agent capable of coagulating liquid-crystal solutions based on cellulosic materials, the use of such a coagulating agent for the coagulation of such solutions, in particular in a spinning process, as well as a new cellulosic fiber with an unexpected combination of mechanical characteristics.
  • liquid-crystal solutions are essential for obtaining fibers with high or very high mechanical properties by spinning, as shown in particular by the patents US-A-3,767,756 relating to fibers. aramids, and US-A-4,746,694 relating to the fibers of aromatic polyesters.
  • the spinning of liquid crystal solutions of cellulose also makes it possible to obtain fibers with high mechanical properties, in particular by the so-called "dry-jet-wet spinning" methods, as described for example in international patent applications PCT / CH85 / 00065 and PCT / CH95 / 00206 for liquid crystal solutions based on cellulose and at least one phosphoric acid.
  • Patent application PCT / CH85 / 00065 published under the number WO85 / 05115, or the equivalent patents EP-B-179 822 and US-A-4 839 113, describe the obtaining of spinning solutions based on formate of cellulose, by reaction of cellulose with formic acid and phosphoric acid, these solutions having a liquid crystal state. These documents also describe the spinning of these solutions, according to the so-called "dry-jet-wet spinning" technique, for obtaining cellulose formate fibers, as well as cellulose fibers regenerated from these formate fibers.
  • Patent application PCT / CH95 / 00206 published under the number WO96 / 09356, describes a means for directly dissolving, without formic acid, cellulose in a solvent agent in order to obtain a liquid crystal solution, this solvent agent containing more than 85% by weight of at least one phosphoric acid.
  • the fibers obtained after spinning this solution are fibers of non-regenerated cellulose.
  • the cellulose fibers described in these two applications WO85 / 0511 and WO96 / 09356 are characterized by a much more ordered or oriented structure, due to the crystal-liquid nature of the spinning solutions from which they come. They have very high mechanical properties in extension, in particular toughness of the order of 80 to 120 cN / tex, or even more, and initial modules which can exceed 2500 to 3000 cN / tex.
  • acetone is a relatively expensive, volatile product, which furthermore presents risks of explosion which require special safety measures.
  • Such drawbacks are moreover not specific to acetone, but in fact common to many organic solvents used in the spinning industry, in particular as coagulating agents.
  • Such values of 30 to 40 cN / tex are in all cases lower than the known tenacity of a conventional fiber of the rayon type (40-50 cN / tex), yet obtained from a non-liquid crystal liquid spinning solution. , ie optically isotropic.
  • water has proved to be a coagulating agent incapable of producing fibers having satisfactory mechanical properties, in particular a toughness at least equal to that of a fiber.
  • conventional rayon for technical applications, for example for the reinforcement of rubber articles or tires.
  • a first object of the present invention is to provide a new coagulating agent, based on water, more advantageous from the industrial point of view than acetone and more effective than water alone, capable of producing fibers whose properties of toughness and modulus are significantly improved compared to those of fibers coagulated simply with water.
  • the aqueous coagulating agent of the invention capable of coagulating a crystal-liquid solution based on cellulosic materials, is characterized in that it comprises at least one water-soluble additive chosen from the group consisting of ammonia , the amines or the salts of these compounds, the additive being such that the pH of the said coagulating agent is greater than 6.
  • the invention also relates to a process for spinning a liquid-crystal solution based on cellulosic materials, for obtaining a spun article, used with a coagulating agent according to the invention.
  • Another object of the invention is to propose a new cellulosic fiber which can be obtained by the process according to the invention; this new fiber, compared to a conventional rayon fiber, has a tenacity at least equal if not greater, a comparable resistance to fatigue, all combined with an initial module in extension significantly higher.
  • the degree of substitution (denoted DS) of the fibers regenerated from a cellulose derivative, for example from cellulose formate, is measured in known manner, as indicated below: approximately 400 mg of fiber are cut into pieces of 2 to 3 cm long, then weighed with precision and introduced into a 100 ml Erlenmeyer flask containing 50 ml of water. 1 ml of normal sodium hydroxide (1N NaOH) is added. The whole is mixed at room temperature for 15 minutes. The cellulose is thus completely regenerated by transforming the last substituent groups which had withstood the regeneration treatment on continuous fibers into hydroxyl groups. The excess soda is titrated with a solution of decinormal hydrochloric acid (0.1 N HCl), and the degree of substitution is therefore deduced therefrom.
  • decinormal hydrochloric acid 0.1 N HCl
  • the isotropy or the optical anisotropy of the solutions is determined by placing a drop of solution to be studied between crossed linear polarizer and analyzer of a polarization optical microscope, then observing this solution at rest, that is to say in the absence of dynamic stress, at room temperature.
  • an optically anisotropic solution also called liquid-crystal
  • a solution which depolarizes light that is to say which exhibits, thus placed between crossed linear polarizer and analyzer, a transmission of light (colored texture ).
  • An optically isotropic solution that is to say one which is not liquid-crystal, is a solution which, under the same observation conditions, does not have the above depolarization property, the field of the microscope remaining black.
  • fibers is meant here multifilament fibers (also called “spun"), constituted in known manner of a large number of elementary filaments of small diameter (small titer). All the mechanical properties below are measured on fibers which have been subjected to prior conditioning.
  • Pre-conditioning means storing the fibers for at least 24 hours, before measurement, in a standard atmosphere according to European standard DIN EN20139 (temperature of 20 ⁇ 2 ° C; hygrometry of 65 ⁇ 2%). For fibers made of cellulosic materials, such prior conditioning makes it possible to stabilize their moisture content at an equilibrium level of less than 15% by weight of dry fiber.
  • the fiber titer is determined on at least three samples, each corresponding to a length of 50 m, by weighing this length of fiber. The title is given in tex (weight in grams of 1000 m of fiber).
  • the mechanical properties in extension are measured in known manner using a ZWICK GmbH & Co (Germany) type 1435 or type 1445 traction machine.
  • the fibers after have received a small preliminary protective twist (helix angle of approximately 6 °), undergo traction over an initial length of 400 mm at a nominal speed of 200 mm / min, or at a speed of 50 mm / min if their elongation at break does not exceed 5%. All the results given are an average over 10 measurements.
  • the initial modulus Mi is defined as the slope of the linear part of the Force-Elongation curve, which occurs just after a standard pretension of 0.5 cN / tex.
  • bar test A simple test called "bar test” is used to determine the fatigue strength of the fibers studied.
  • a short section of fiber is used (length of at least 600 mm) which has been subjected to prior conditioning, the test being carried out at room temperature (approximately 20 ° C.).
  • This section subjected to a tension of 0.25 cN / tex thanks to a constant weight fixed to one of its free ends, is stretched on a polished steel bar, and bent around the latter according to a 90 degree angle of curvature about.
  • a mechanical device to which the other end of the fiber section is fixed ensures the forced and repeated sliding of the fiber on the polished steel bar, according to a linear reciprocating movement of frequency (100 cycles per minute) and amplitude (30 mm ) determined.
  • the vertical plane containing the axis of the fiber is always substantially perpendicular to the vertical plane containing the bar which is itself horizontal.
  • the diameter of the bar is chosen to cause a compression of 3.5% during each passage of the filaments of the fiber around the bar.
  • a rod with a diameter of 360 ⁇ m (micrometer) is used for a fiber whose average diameter of the filaments is 13 ⁇ m (or an average filament titer of 0.20 tex, for a cellulose density equal to 1 , 52).
  • ⁇ F 100 [F 0 - F 1 ] / F 0
  • F 0 being the breaking strength of the fiber before fatigue and F 1 its breaking strength after fatigue.
  • liquid-crystal solutions are prepared in a known manner, by dissolving the cellulosic materials in a suitable solvent or solvent mixture - called “spinning solvent” - as indicated for example in the aforementioned applications WO85 / 05115 and WO96 / 09356.
  • solution is meant here in a known manner a homogeneous liquid composition in which no solid particle is visible to the naked eye.
  • liquid-crystal solution we means an optically anisotropic solution at room temperature (around 20 ° C) and at rest, ie in the absence of any dynamic constraint.
  • the coagulating agent of the invention is used to coagulate liquid-crystal solutions containing at least one acid, this acid more preferably belonging to the group consisting of formic acid, acetic acid, phosphoric acids, or mixtures of these acids.
  • the starting cellulose can be in various known forms, in particular in the form of a powder, prepared for example by spraying a cellulose plate in the raw state.
  • its initial water content is less than 10% by weight
  • its DP (degree of polymerization) is between 500 and 1000.
  • the appropriate kneading means for obtaining a solution are known to those skilled in the art: they must be capable of kneading, kneading correctly, preferably at an adjustable speed, the cellulose and the acids until the obtaining of the solution.
  • the kneading can be carried out for example in a mixer comprising Z-shaped arms, or in a continuous screw mixer.
  • These kneading means are preferably equipped with a vacuum evacuation device and a heating and cooling device making it possible to adjust the temperature of the mixer and its contents, in order to accelerate for example the dissolution operations. , or to control the temperature of the solution being formed.
  • a suitable mixture of orthophosphoric acid is introduced into a double-jacket mixer, comprising Z arms and an extrusion screw. (99% crystalline) and formic acid.
  • Cellulose powder is then added (the humidity of which is in equilibrium with the ambient humidity of the air); the whole is mixed for a period of approximately 1 to 2 hours, for example, the temperature of the mixture being maintained between 10 and 20 ° C., up to obtaining a solution.
  • WO96 / 09356 it is possible to proceed in the same way, by replacing formic acid for example with a polyphosphoric acid.
  • the solutions thus obtained are ready to spin, they can be transferred directly, for example by means of an extrusion screw placed at the outlet of the mixer, to a spinning machine to be spun there, without any further processing than usual operations such as degassing or filtration steps for example.
  • the solution is transferred in a known manner to a spinning block where it feeds a spinning pump. From this spinning pump, the solution is extruded through at least one die, preceded by a filter. During the journey to the die, the solution is gradually brought to the desired spinning temperature.
  • Each die can include a variable number of extrusion capillaries, for example a single capillary in the form of a slot for spinning a film, or in the case of a fiber several hundred capillaries, for example of cylindrical shape (diameter from 50 to 80 micrometers for example).
  • a variable number of extrusion capillaries for example a single capillary in the form of a slot for spinning a film, or in the case of a fiber several hundred capillaries, for example of cylindrical shape (diameter from 50 to 80 micrometers for example).
  • a liquid solution extrudate is therefore obtained, consisting of a variable number of elementary liquid veins.
  • the solutions are spun according to the so-called “dry-jet-wet-spinning" technique using a non-coagulating fluid layer, generally air (“air-gap”), placed between the die and the means of coagulation.
  • air-gap a non-coagulating fluid layer
  • Each elementary liquid vein is stretched in this air gap, by a factor generally between 2 and 10 (stretching factor on spinning), before entering the coagulation zone, the thickness of the air gap being able to vary to a large extent, depending on the particular spinning conditions, for example from 10 mm to 100 mm.
  • the stretched liquid veins After crossing the above non-coagulating layer, the stretched liquid veins enter a coagulation device where they then come into contact with the coagulating agent. Under the action of the latter, they are transformed, by precipitation of cellulosic materials (cellulose or cellulose derivative) into solid filaments which thus form a fiber.
  • the coagulation devices to be used are known devices, composed for example of baths, pipes and / or cabins, containing the coagulating agent and in which the fiber circulates during formation. It is preferable to use a coagulation bath placed under the die, at the outlet of the non-coagulating layer. This bath is generally extended at its base by a vertical cylindrical tube, called “spinning tube", through which the coagulated fiber passes and circulates the coagulating agent.
  • coagulating agent means in known manner an agent capable of coagulating a solution, that is to say an agent capable of rapidly precipitating the polymer in solution, in other words to quickly separate it from its solvent; the coagulating agent must be both a non-solvent for the polymer and a good solvent for the solvent for the polymer.
  • the coagulating agent used is an aqueous coagulating agent comprising at least one water-soluble additive chosen from the group consisting of ammonia, the amines or the salts of these compounds, the additive being such that the pH of said coagulating agent is greater than 6.
  • ammonia aqueous ammonia
  • aliphatic or heterocyclic amines such as ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylamine, imidazole, 1-methyl imidazole, morpholine, piperazine, the preferred amines being primary or secondary amines having from 1 to 5 carbon atoms.
  • an organic or inorganic ammonium salt is used as an additive, and more preferably a salt chosen from the group consisting of formiates, acetates and ammonium phosphates, mixed salts of these compounds, or mixtures of these constituents, this ammonium salt possibly being in particular a salt of an acid present in the liquid-crystal solution, for example (NH4) 2 HPO4, (NH4) 3 PO4, NaNH 4 HPO 4 , CH 3 COONH 4 , HCOONH 4 .
  • ammonium salts which are not suitable (pH of the coagulating agent not greater than 6), there may be mentioned in particular (NH4) 2 SO4, (NH4) HSO 4 , (NH4) H 2 PO4, NH 4 NO 3 .
  • the coagulating agent of the invention is preferably used on liquid crystal solutions based on cellulose or cellulose formate dissolved in at least one phosphoric acid, as described for example in applications WO85 / 05115 and WO96 / 09356 mentioned above: diammonic orthophosphate (NH4) 2 HPO4 is then advantageously used.
  • diammonic orthophosphate (NH4) 2 HPO4 is then advantageously used.
  • the concentration of additive in the coagulating agent can vary to a large extent, for example from 2 to 25% (% by total weight of coagulating agent), or even more, depending on the particular conditions for producing the invention.
  • the temperature of the coagulating agent (noted Tc below), it has been observed that low temperatures, in particular close to 0 ° C., could in certain cases cause certain filaments to stick together during their formation (" married filaments "). This disrupts the spinning operations and is generally detrimental to the quality of the yarn obtained; thus, preferably, the coagulating agent of the invention is used at a temperature Tc greater than 10 ° C, more preferably close to room temperature (20 ° C) or higher. It has been found that adding a surfactant, for example isopropanol or phosphate-based soaps, is another possible solution for eliminating or at least reducing the above difficulties.
  • Tc temperature of the coagulating agent
  • the level of spinning solvent provided by the solution in the coagulating agent is preferably maintained at a level of less than 10%, so even more preferably less than 5% (% by total weight of coagulating agent), in any case controlled so that the pH of said coagulating agent is, according to the invention, greater than 6.
  • the total depth of coagulating agent traversed by the filaments being formed in the coagulation bath can vary to a large extent, for example by a few millimeters to several centimeters.
  • the depth of the coagulating agent is chosen to be greater than 20 mm.
  • the coagulating agent according to the invention is used in a so-called “dry-jet-wet-spinning” spinning process, as described above, but it could also be used in other spinning processes, for example.
  • a process called “wet-spinning” that is to say a spinning process in which the die is immersed in the coagulating agent.
  • the fiber is taken up on a drive device, for example on motorized cylinders, to be washed in a known manner, preferably with water, for example in baths or cabins.
  • a drive device for example on motorized cylinders
  • the fiber is dried by any suitable means, for example by continuous scrolling on heating rollers preferably maintained at a temperature below 200 ° C.
  • the percentages of the compositions of the solutions or of the coagulating agents are percentages by total weight of the solution or of the coagulating agent, respectively.
  • the pH values indicated are the values measured on the pH meter. even more preferably less than 5% (% by total weight of coagulating agent), in any case controlled so that the pH of said coagulating agent is, according to the invention, greater than 6.
  • the total depth of coagulating agent traversed by the filaments being formed in the coagulation bath can vary to a large extent, for example by a few millimeters to several centimeters.
  • the depth of the coagulating agent is chosen to be greater than 20 mm.
  • the coagulating agent according to the invention is used in a so-called “dry-jet-wet-spinning” spinning process, as described above, but it could also be used in other spinning processes, for example.
  • a process called “wet-spinning” that is to say a spinning process in which the die is immersed in the coagulating agent.
  • the fiber is taken up on a drive device, for example on motorized cylinders, to be washed in a known manner, preferably with water, for example in baths or cabins.
  • a drive device for example on motorized cylinders
  • the fiber is dried by any suitable means, for example by continuous scrolling on heating rollers preferably maintained at a temperature below 200 ° C.
  • the percentages of the compositions of the solutions or of the coagulating agents are percentages by total weight of the solution or of the coagulating agent, respectively.
  • the pH values indicated are the values measured on the pH meter.
  • a liquid crystal solution of cellulose formate is prepared from 22% of powdered cellulose (initial DP of 600), 61% of orthophosphoric acid (99% crystalline) and 17% of formic acid. After dissolving (1 h of mixing), the cellulose has a DS (degree of substitution) of 33% and a DP (degree of polymerization, measured in known manner) of approximately 480.
  • the solution is then spun, unless otherwise indicated, according to the general conditions described in ⁇ II-2. above, through a die made up of 250 holes (capillaries with a diameter of 65 ⁇ m), at a spinning temperature of around 50 ° C; the liquid veins thus formed are drawn (drawing stretching factor equal to 6) in an air-gap of 25 mm and then are coagulated in contact with various coagulating agents (depth crossed: 30 mm), whether or not in accordance with the invention , without using a surfactant.
  • the cellulose formate fibers thus obtained are washed with water (15 ° C), then sent continuously to a regeneration line, at a speed of 150 m / min, to be regenerated therein in an aqueous solution of sodium hydroxide. room temperature (sodium hydroxide concentration: 30% by weight), washed with water (15 ° C) and finally dried by passage over heating cylinders (180 ° C) to adjust their humidity to less than 15% .
  • a liquid crystal solution is prepared from cellulose (22%), orthophosphoric acid (66%) and formic acid (12%). After dissolving, the cellulose has a DS of 29% and a DP of approximately 490. This solution is then spun as indicated for test 1, unless otherwise indicated, using in all the examples a coagulating agent in accordance with l invention having the same additive: aqueous solutions of (NH 4 ) 2 HPO 4 , with concentrations of additive Ca and varying temperatures Tc.
  • a liquid crystal solution is prepared from cellulose (24%), orthophosphoric acid (70%) and formic acid (6%). After dissolution, the cellulose has a DS of 20% and a DP of around 480. This solution is then spun as indicated for test 1, unless otherwise indicated, using various coagulating agents, all in accordance with the invention , whose composition, concentration of Ca additive or temperature Tc vary.
  • a liquid crystal solution of cellulose is prepared in accordance with the description of the preceding chapter II and with the abovementioned application WO96 / 09356, from 18% of powdered cellulose (initial DP 540), 65.5% of orthophosphoric acid and 16.5% polyphosphoric acid (grading 85% by weight of P 2 O 5 ), that is to say that the cellulose is dissolved directly in the mixture of acids without going through a derivation.
  • the two acids are mixed beforehand, the acid mixture is cooled to 0 ° C and then introduced into an arm mixer Z itself previously cooled to -15 ° C; then the powdered cellulose, previously dried, is added and kneaded with the acid mixture while maintaining the temperature of the mixture at a value at most equal to 15 ° C. After dissolving (0.5 h of mixing), the cellulose has a DP of around 450. This solution is then spun, unless otherwise indicated, as indicated for test 1 above with the difference, in particular, that there is no regeneration step. The spinning temperature is 40 ° C and the drying temperature 90 ° C.
  • the coagulating agents in accordance with the invention make it possible to obtain cellulosic fibers, of regenerated cellulose or of non-regenerated cellulose, the initial modulus and the toughness of which are notably greater than those obtained by using water alone as a coagulating agent.
  • the toughness and the initial modulus are both increased by at least 20% compared to those obtained after a simple coagulation in water, the gain being able to reach 50% in certain cases; the initial modulus is very high, with values that can exceed 2000 cN / tex.
  • Cellulosic fibers of the invention were subjected to the bar test described in the preceding chapter I, and their performances were compared both with those of conventional rayon fibers, and with those of fibers with very high mechanical properties obtained by spinning of liquid crystal solutions identical to those used in the four preceding tests, but after coagulation in acetone (in accordance with the above-mentioned applications WO85 / 05115 and WO96 / 09356).
  • the cellulosic fibers according to the invention have a strength-breaking strength ⁇ F which is always less than 30%, generally between 5 and 25%, while the fibers coagulated in acetone, obtained from the same crystal-liquid solutions, show a lapse which is greater than 30%, generally between 35 and 45%.
  • the cellulosic fibers of the invention therefore have a resistance to fatigue markedly greater than that recorded on the fibers obtained from the same liquid-crystal solutions in cellulosic materials, but coagulated in a known manner in acetone. It was further observed that the fibrillation was reduced on the fibers of the invention, compared to these anterior fibers coagulated in acetone.
  • These fibers of the invention are characterized by a combination of properties which is new: toughness equal or greater, and fatigue resistance practically equivalent to that of a conventional rayon fiber, all combined with an initial modulus significantly greater than that of '' such a fiber radiates, up to 2000 cN / tex and more.
  • This fiber according to the invention is advantageously a cellulose fiber regenerated from cellulose formate, the degree of substitution of the cellulose for formate groups being between 0 and 2%.
  • constituents can be optionally added to the basic constituents previously described (cellulose, formic acid, phosphoric acids, coagulating agents), without the spirit of the invention being modified.
  • the additional constituents can be, for example, plasticizers, sizes, dyes. polymers other than cellulose which may possibly be esterified during the production of the solution; it may also be products making it possible, for example, to improve the spinability of spinning solutions, the use properties of the fibers obtained, the adhesiveness of these fibers to a gum matrix.
  • cellulose formate used in this document covers cases where the hydroxyl groups of the cellulose are substituted by groups other than the formate groups, in addition to the latter, for example ester groups, in particular acetate groups, the degree of substitution of cellulose for these other groups is preferably less than 10%.
  • the fibers of the invention are of industrial interest both in the field of technical fibers and in that of textile fibers.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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Claims (17)

  1. Wäßriges Koagulationsmittel für flüssigkristalline Lösungen auf der Basis von Cellulosematerial, dadurch gekennzeichnet, daß es mindestens einen in Wasser löslichen Zusatzstoff umfasst, der unter Ammoniak, den Aminen oder den Salzen dieser Verbindungen ausgewählt ist, wobei der Zusatzstoff so gewählt ist, daß der pH-Wert des Koagulationsmittels über 6 liegt.
  2. Koagulationsmittel nach Anspruch 1, dadurch gekennzeichnet, daß die flüssigkristalline Lösung mindestens eine Säure enthält.
  3. Koagulationsmittel nach Anspruch 2, dadurch gekennzeichnet, daß der Zusatzstoff ein Salz dieser Säure ist.
  4. Koagulationsmittel nach Anspruch 2, dadurch gekennzeichnet, daß die Säure unter Ameisensäure, Essigsäure, Phosphorsäuren oder den Gemischen dieser Säuren ausgewählt ist.
  5. Koagulationsmittel nach den Ansprüchen 3 und 4, dadurch gekennzeichnet, daß das Salz unter den Formiaten, Acetaten und Phosphaten von Ammonium, den gemischten Salzen dieser Verbindungen oder den Gemischen dieser Bestandteile ausgewählt ist.
  6. Koagulationsmittel nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, daß es sich um eine Spinnlösung auf der Basis von Celluloseformiat handelt, das in mindestens einer Phosphorsäure gelöst ist.
  7. Koagulationsmittel nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, daß es sich um eine Spinnlösung auf der Basis von Cellulose handelt, wobei die Cellulose unmittelbar in mindestens einer Phosphorsäure gelöst ist.
  8. Koagulationsmittel nach einem der Ansprüche 6 oder 7, dadurch gekennzeichnet, daß der Zusatzstoff das Diammoniumorthophosphat (NH4)2HPO4 ist.
  9. Verfahren zum Verspinnen einer flüssigkristallinen Lösung auf der Basis von Cellulosematerial zur Herstellung von versponnenen Gegenständen, dadurch gekennzeichnet, daß mindestens ein Koagulationsmittel nach einem der Ansprüche 1 bis 8 eingesetzt wird.
  10. Verfahren zum Verspinnen nach Anspruch 9, dadurch gekennzeichnet, daß es sich um ein sogenanntes "dry-jet-wet-spinning"-Verfahren handelt.
  11. Verfahren zum Verspinnen nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, daß die Tiefe des Koagulationsmittels, die von dem versponnenen Artikel bei der Bildung durchquert wird, über 20 mm liegt.
  12. Verfahren zum Verspinnen nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, daß die Temperatur des Koagulationsmittels über 10 °C liegt.
  13. Cellulosefaser mit den folgenden Eigenschaften:
    - ihre Bruchfestigkeit Bf liegt über 40 cN/tex;
    - ihr anfangsbezogener Modul Mi liegt über 1200 cN/tex;
    - die Abnahme der Reißkraft ΔF nach 350 Ermüdungszyklen im sogenannten "Stabtest" liegt bei einem Kompressionsgrad von 3,5 % und einer Zugspannung von 0,25 cN/tex unter 30 %.
  14. Faser nach Anspruch 13, dadurch gekennzeichnet, daß sie mindestens eine der folgenden Bedingungen erfüllt:
    - Bf > 45 cN/tex;
    - Mi > 1500 cN/tex;
    - ΔF < 15 %.
  15. Faser nach Anspruch 14, dadurch gekennzeichnet, daß sie mindestens eine der folgenden Bedingungen erfüllt:
    - Bf > 50 cN/tex;
    - Mi > 2000 cN/tex.
  16. Faser nach einem der Ansprüche 13 bis 15, dadurch gekennzeichnet, daß sie aus einer aus Celluloseformiat regenerierten Faser besteht, wobei der Grad der Substitution der Cellulose mit Formiatgruppen im Bereich von 0 bis 2 % liegt.
  17. Gegenstand aus Kautschuk(en) oder Kunststoff(en), insbesondere ein Luftreifen, der mit mindestens einer Cellulosefaser nach einem der Ansprüche 13 bis 16 verstärkt ist.
EP97910443A 1996-10-18 1997-10-15 Wässrige koagulationsmittel für flüssigkristalllösungen aus cellulosematerialen Expired - Lifetime EP0932709B1 (de)

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FR9612870 1996-10-18
FR9612870 1996-10-18
PCT/EP1997/005675 WO1998017847A1 (fr) 1996-10-18 1997-10-15 Agent coagulant aqueux pour solutions cristal-liquide a base de matieres cellulosiques

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JP4216340B2 (ja) * 1996-10-18 2009-01-28 ミシュラン ルシェルシュ エ テクニーク ソシエテ アノニム セルロース材料を主成分とする液晶溶液用の水性凝固剤
KR100488604B1 (ko) * 2003-07-25 2005-05-11 주식회사 효성 라이오셀 멀티 필라멘트
DE102004007616B4 (de) * 2004-02-17 2005-12-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von Fasern und anderen Formkörpern aus Cellulosecarbamat und/oder regenerierter Cellulose
CN102232128B (zh) * 2008-10-14 2013-08-21 赛佩荷兰服务有限公司 制造基于纤维素的纤维的方法和由此获得的纤维
EP2486175B1 (de) * 2009-10-07 2015-05-20 Grasim Industries Limited Verfahren zur herstellung von niedrig fibrillierenden cellulosefasern
US9068063B2 (en) 2010-06-29 2015-06-30 Eastman Chemical Company Cellulose ester/elastomer compositions
US9273195B2 (en) 2010-06-29 2016-03-01 Eastman Chemical Company Tires comprising cellulose ester/elastomer compositions
US9708472B2 (en) 2011-12-07 2017-07-18 Eastman Chemical Company Cellulose esters in highly-filled elastomeric systems
US10077342B2 (en) 2016-01-21 2018-09-18 Eastman Chemical Company Elastomeric compositions comprising cellulose ester additives
WO2017137284A1 (de) * 2016-02-11 2017-08-17 Basf Se Verfahren zur herstellung von polymerfasern aus in ionischen flüssigkeiten gelösten polymeren durch einen luftspaltspinnprozess

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US20020153076A1 (en) 2002-10-24
US6427736B1 (en) 2002-08-06
WO1998017847A1 (fr) 1998-04-30
CA2268792C (fr) 2006-07-11
US6756001B2 (en) 2004-06-29
AU4782097A (en) 1998-05-15
BR9711933A (pt) 1999-08-24
DE69718807T2 (de) 2003-11-13
JP2001505623A (ja) 2001-04-24
CN1240488A (zh) 2000-01-05
US20020040747A1 (en) 2002-04-11
RU2183229C2 (ru) 2002-06-10
ES2188910T3 (es) 2003-07-01
CN1086427C (zh) 2002-06-19

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