EP0932709A1 - Coagulating agent for liquid crystal solutions with base of cellulose substances - Google Patents

Coagulating agent for liquid crystal solutions with base of cellulose substances

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Publication number
EP0932709A1
EP0932709A1 EP97910443A EP97910443A EP0932709A1 EP 0932709 A1 EP0932709 A1 EP 0932709A1 EP 97910443 A EP97910443 A EP 97910443A EP 97910443 A EP97910443 A EP 97910443A EP 0932709 A1 EP0932709 A1 EP 0932709A1
Authority
EP
European Patent Office
Prior art keywords
coagulating agent
tex
cellulose
spinning
fibers
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.)
Granted
Application number
EP97910443A
Other languages
German (de)
French (fr)
Other versions
EP0932709B1 (en
Inventor
Jean-Paul Meraldi
Rima Huston
Vlastimil Cizek
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.)
Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
Original Assignee
Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
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 Michelin Recherche et Technique SA Switzerland, Michelin Recherche et Technique SA France filed Critical Michelin Recherche et Technique SA Switzerland
Publication of EP0932709A1 publication Critical patent/EP0932709A1/en
Application granted granted Critical
Publication of EP0932709B1 publication Critical patent/EP0932709B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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 to 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 the 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.
  • 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 No. WO96 / 09356, describes a means for directly dissolving cellulose without formic acid 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 / 051 15 and WO96 / 09356 are characterized by a much more ordered or oriented structure, due to the liquid-crystal 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.
  • the processes described in the two above applications for obtaining these fibers with very high mechanical properties have the same drawback: the coagulation step is carried out in acetone.
  • acetone is a relatively expensive, volatile product, which also presents risks of explosion which require special safety measures.
  • Such drawbacks are not, moreover, 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 toughness of a conventional rayon type fiber (40-50 cN / tex), however obtained from a non-liquid crystal 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 propose 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 tenacity and modulus properties are significantly improved compared to those of fibers coagulated simply with water.
  • the aqueous coagulating agent of the invention capable of coagulating a liquid crystal 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, as well as any spun article obtained by such a process.
  • 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 toughness at least equal if not higher, a comparable resistance to fatigue, all combined with an initial module in extension significantly higher.
  • the invention further relates to the following products:
  • the reinforcement assemblies comprising at least one spun article in accordance with the invention, for example cables, twists, multifilament fibers twisted on themselves, such reinforcement assemblies being able to be, for example, hybrid, composite, ie comprising elements of different natures, possibly not in accordance with the invention;
  • the degree of substitution (denoted DS) of the fibers regenerated from a cellulose derivative, for example from cellulose formate, is measured in a 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 (NaOH IN) 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 (HCl 0.1 N), and the degree of substitution is thus deduced therefrom. 1-2. Optical properties of solutions
  • the optical isotropy or anisotropy of the solutions is determined by placing a drop of solution to be studied between crossed linear polarizers and analyzers with an optical polarization microscope, and then observing this solution at rest, i.e. by 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 a 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; humidity 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 module 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 (length of at least 600 mm) which has been subjected to prior conditioning, the test being carried out at ambient 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 at an angle of curvature of 90 degrees 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 reciprocating linear 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 bar with a diameter of 360 ⁇ m (micrometer) is used for a fiber whose average filament diameter is 13 ⁇ m (or an average filament titer of 0.20 tex, for a cellulose density equal to 1 , 52).
  • Fo being the breaking strength of the fiber before fatigue and F ⁇ its breaking strength after fatigue.
  • liquid-crystal solutions are prepared in 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.
  • liquid crystal solutions of cellulose derivatives based on at least one phosphoric acid these solutions being in particular solutions of cellulose esters, in particular solutions of cellulose formate, as described for example in application WO85 / 051 15 above, made by mixing cellulose, formic acid and phosphoric acid (or a liquid based on phosphoric acid), the formic acid being esterification acid, phosphoric acid being the solvent for cellulose formate;
  • 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 obtaining of the solution.
  • the mixing 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-walled mixer, comprising Z arms and an extrusion screw. (99% crystalline) and formic acid.
  • cellulose powder is 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 extrudate of solution 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 (spinning stretching factor), 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, for example composed 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 causing the polymer to precipitate rapidly in solution, 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 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, CH3 COONH4, HCOONH4.
  • ammonium salts which are not suitable (pH of the coagulating agent not greater than 6), there may be mentioned in particular (NH4) SO4, (NH4) HSC-4, (NH4) H 2 PO4, NH4NO3.
  • 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 / 051 15 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 Te below)
  • Te the temperature of the coagulating agent
  • the coagulating agent of the invention is used at a temperature Te greater than 10 ° C, more preferably close to ambient temperature (20 ° C) or higher.
  • adding a surfactant for example isopropanol or phosphate-based soaps, is another possible solution for eliminating or at least reducing the above difficulties.
  • 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 in accordance with 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. 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.
  • a cellulose derivative fiber it is also possible to directly treat the washed, but not dried, fiber through regeneration baths, for example in an aqueous sodium hydroxide solution, in order to regenerate the cellulose and to succeed after washing and drying with regenerated cellulose fiber.
  • 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 in accordance with 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. 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.
  • a cellulose derivative fiber it is also possible to directly treat the washed, but not dried, fiber through regeneration baths, for example in an aqueous sodium hydroxide solution, in order to regenerate the cellulose and to succeed after washing and drying with regenerated cellulose fiber.
  • 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 hour 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 stretched (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 on 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% .
  • the regenerated cellulose fibers (DS less than 2%) thus obtained have a titer of 47 tex per 250 filaments (or approximately 0.19 tex per filament), and the following mechanical properties:
  • Example 1A with a coagulating agent not in accordance with the invention consisting of water alone, used at a temperature Te of 20 ° C:
  • the tenacity of the coagulated fiber according to the invention is increased by 44% and its initial modulus by 37%, compared with the control coagulated with water alone.
  • Example 1D with the same coagulating agent as for Example 1 A, but used at a temperature Te close to 0 ° C (+ 1 ° C):
  • Example 1E with the same coagulating agent as for Example 1C, but used at a temperature Te of 0 ° C:
  • the toughness obtained here is greater than 50 cN / tex, improved by 30% compared to the control not in accordance with the invention (example 1D), the modulus is increased by 20%. It is therefore found in this test that the initial toughness and modulus can be increased, whether or not the coagulating agent is in accordance with the invention, by lowering the temperature Te to values close to 0 ° C; nevertheless, the formation of bonded filaments ("married filaments”) has been observed for such temperatures.
  • 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 around 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 (NH4) 2 HP04, with concentrations of Ca additive and Te temperatures which vary.
  • the regenerated cellulose fibers (DS between 0 and 1%) thus obtained have a titer of 47 tex for 250 filaments and the following mechanical properties:
  • a liquid crystal solution is prepared from cellulose (24%), orthophosphoric acid (70%) and formic acid (6%). After dissolving, 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, Ca additive concentration or Te temperature vary.
  • the regenerated cellulose fibers (DS between 0 and 1.5%) thus obtained have a titer of approximately 45 tex for 250 filaments (or 0.18 tex per filament on average), and the following properties:
  • 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) O5), that is to say that the cellulose is dissolved directly in the mixture of acids without going through a derivation step .
  • 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 indicated otherwise, 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.
  • Unregenerated cellulose fibers are thus obtained, ie obtained directly by spinning a cellulose solution, without going through the successive steps of deriving cellulose, spinning a solution of cellulose derivative, then regenerating fibers. cellulose derivative.
  • non-regenerated cellulose fibers have a titer of 47 tex for 250 filaments, and the following mechanical properties:
  • Example 4A with a coagulating agent not in accordance with the invention consisting of water alone, at a temperature Te of 20 ° 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 / 051 15 and WO96 / 09356).
  • the cellulosic fibers in accordance with the invention exhibit a strength-breaking lapse ⁇ 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 clearly 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, being able to reach 2000 cN / tex and more.
  • This combination of characteristics is completely unexpected for the person skilled in the art because a fatigue resistance practically equivalent to that of a conventional rayon fiber - originating from a non-crystal-liquid phase - was hitherto considered impossible for a high modulus cellulosic fiber from a crystal-liquid phase.
  • the fiber according to the invention verifies at least one of the following relationships:
  • 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; they 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.

Abstract

The invention concerns a coagulating agent for liquid crystal solutions with a base of cellulose substances, characterised in that it contains at least one water soluble additive selected from the group consisting of ammonia, amines of salt of these compounds, the additive being such that the pH of the said coagulating agent is greater than 6. A preferable additive is a salt elected from the group consisting of ammnonium formates, acetates and phosphates, mixed salts of these compounds, or mixtures of these constituents, in particular diammonium orthophosphates (NH4)2HPO4. The invention also concerns a method for spinning a liquid crystal solution with a base of cellulose substances, using a coagulating agent as per the invention, in particular the method called the "dry-jet-wet-spinning" as well as spun articles, fibers or films, obtained by these methods. The invention further concerns a cellulose fiber having toughness higher than 40 cN/tex, an initial modulus of elasticity higher than 1200 cN/tex and high fatigue strength: its breaking load degeneration DELTAF after 350 fatigue cycles in the so-called "specimen test", under a compression rate of 3.5% and a tensile stress of 0.25 cN/tex, is less than 30%.

Description

AGENT COAGULANT AQUEUX POUR SOLUTIONS CRISTAL-LIQUIDE A BASE DE MATIERES CELLULOSIQUES AQUEOUS COAGULATING AGENT FOR CRYSTAL-LIQUID SOLUTIONS BASED ON CELLULOSIC MATERIALS
La présente invention se rapporte aux matières cellulosiques, i.e. à la cellulose ou aux dérivés de la cellulose, aux solutions cristal-liquide à base de telles matières cellulosiques, en particulier aux solutions filables capables de donner après coagulation des articles filés tels que des fibres ou des films, à ces articles filés eux-mêmes, ainsi qu'aux procédés pour obtenir de tels articles filés.The present invention relates to cellulosic materials, ie to cellulose or to 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.
L'invention concerne plus particulièrement un agent coagulant aqueux apte à coaguler les solutions cristal-liquide à base de matières cellulosiques, l'utilisation d'un tel agent coagulant pour la coagulation de telles solutions, notamment dans un procédé de filage, ainsi qu'une fibre cellulosique nouvelle présentant une combinaison inattendue de caractéristiques mécaniques.The invention relates more particularly to an aqueous coagulating agent capable of coagulating the 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.
Il est connu depuis longtemps que la réalisation de solutions cristal-liquide est essentielle pour l'obtention par filage de fibres à hautes ou très hautes propriétés mécaniques, comme l'ont montré notamment les brevets US-A-3 767 756 portant sur les fibres aramides, et US-A- 4 746 694 portant sur les fibres de polyesters aromatiques. Le filage de solutions cristal- liquide de cellulose permet également d'obtenir des fibres à hautes propriétés mécaniques, notamment par les procédés dits de "dry-jet-wet spinning", comme décrit par exemple dans les demandes de brevet internationales PCT/CH85/00065 et PCT/CH95/00206 pour des solutions cristal-liquide à base de cellulose et d'au moins un acide phosphorique.It has been known for a long time that the production of liquid-crystal solutions is essential for obtaining by spinning fibers with high or very high mechanical properties, as shown in particular by the patents US-A-3,767,756 relating to fibers. aramids, and US-A-4,746,694 relating to aromatic polyester fibers. The spinning of liquid crystal-cellulose solutions 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.
La demande de brevet PCT/CH85/00065, publiée sous le No WO85/05115, ou les brevets équivalents EP-B-179 822 et US-A-4 839 113, décrivent l'obtention de solutions de filage à base de formiate de cellulose, par réaction de la cellulose avec de l'acide formique et de l'acide phosphorique, ces solutions présentant un état de cristal-liquide. Ces documents décrivent également le filage de ces solutions, selon la technique dite de "dry-jet-wet spinning", pour l'obtention de fibres en formiate de cellulose, ainsi que des fibres en cellulose régénérées à partir de ces fibres en formiate.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.
La demande de brevet PCT/CH95/00206, publiée sous le No WO96/09356, décrit un moyen pour dissoudre directement, sans acide formique, de la cellulose dans un agent solvant afin d'obtenir une solution cristal-liquide, cet agent solvant contenant plus de 85 % en poids d'au moins un acide phosphorique. Les fibres obtenues après filage de cette solution sont des fibres en cellulose non régénérée.Patent application PCT / CH95 / 00206, published under No. WO96 / 09356, describes a means for directly dissolving cellulose without formic acid 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.
Comparées à des fibres cellulosiques conventionnelles telles que les fibres rayonne ou viscose, ou à d'autres fibres conventionnelles non cellulosiques telles que les fibres de nylon ou de polyester par exemple, toutes filées à partir de liquides optiquement isotropes, les fibres de cellulose décrites dans ces deux demandes WO85/051 15 et WO96/09356 se caractérisent par une structure beaucoup plus ordonnée ou orientée, en raison du caractère cristal-liquide des solutions de filage dont elles sont issues. Elles présentent de très hautes propriétés mécaniques en extension, notamment des ténacités de l'ordre de 80 à 120 cN/tex, voire plus, et des modules initiaux pouvant dépasser 2500 à 3000 cN/tex. Cependant, les procédés décrits dans les deux demandes ci-dessus pour l'obtention de ces fibres à très hautes propriétés mécaniques présentent un même inconvénient: l'étape de coagulation est conduite dans de l'acétone.Compared to conventional cellulosic fibers such as rayon or viscose fibers, or to other conventional non-cellulosic fibers such as nylon or polyester fibers for example, all spun from optically isotropic liquids, the cellulose fibers described in these two applications WO85 / 051 15 and WO96 / 09356 are characterized by a much more ordered or oriented structure, due to the liquid-crystal 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. However, the processes described in the two above applications for obtaining these fibers with very high mechanical properties have the same drawback: the coagulation step is carried out in acetone.
Or, l'acétone est un produit relativement coûteux, volatil, présentant en outre des risques d'explosion qui nécessitent des mesures de sécurité particulières. De tels inconvénients ne sont d'ailleurs pas propres à l'acétone, mais communs en fait à de nombreux solvants organiques utilisés dans l'industrie du filage, en particulier comme agents coagulants.However, acetone is a relatively expensive, volatile product, which also presents risks of explosion which require special safety measures. Such drawbacks are not, moreover, specific to acetone, but in fact common to many organic solvents used in the spinning industry, in particular as coagulating agents.
Il était donc tout à fait souhaitable de trouver une alternative à l'emploi d'acétone en la remplaçant par un agent coagulant plus avantageux du point de vue industriel et plus facile d'emploi, même au prix d'une diminution de certaines caractéristiques mécaniques des fibres obtenues, d'autant plus que les très hautes propriétés mécaniques décrites ci-dessus peuvent être surabondantes pour certaines applications techniques.It was therefore entirely desirable to find an alternative to the use of acetone by replacing it with a coagulating agent which is more advantageous from an industrial point of view and easier to use, even at the cost of a reduction in certain mechanical characteristics. fibers obtained, especially since the very high mechanical properties described above can be superabundant for certain technical applications.
Certes, il s'est avéré techniquement possible de remplacer l'acétone par de l'eau pour coaguler les solutions cristal-liquide décrites dans les deux demandes WO85/051 15 et WO96/09356 précitées. Mais l'expérience a montré que l'emploi d'eau en lieu et place de l'acétone conduisait à des difficultés de filage et à des fibres cellulosiques ayant des ténacités très faibles comparées à celles décrites ci-dessus, ces ténacités ne dépassant guère 30-35 cN/tex, n'atteignant au plus que 35-40 cN/tex lorsque la fibre en cours de formation est soumise par exemple à des contraintes de tension particulièrement élevées, nuisibles par ailleurs à la qualité du produit obtenu. De telles valeurs de 30 à 40 cN/tex sont dans tous les cas inférieures aux ténacités connues d'une fibre conventionnelle du type rayonne (40-50 cN/tex), pourtant obtenue à partir d'une solution de filage non cristal-liquide, i.e. optiquement isotrope.Admittedly, it has proved technically possible to replace acetone with water to coagulate the crystal-liquid solutions described in the two applications WO85 / 051 15 and WO96 / 09356 mentioned above. However, experience has shown that the use of water in place of acetone leads to spinning difficulties and to cellulosic fibers having very low toughness compared to those described above, these toughness hardly exceeding 30-35 cN / tex, reaching no more than 35-40 cN / tex when the fiber being formed is subjected, for example, to particularly high tension stresses, which are moreover detrimental to the quality of the product obtained. Such values of 30 to 40 cN / tex are in all cases lower than the known toughness of a conventional rayon type fiber (40-50 cN / tex), however obtained from a non-liquid crystal spinning solution. , ie optically isotropic.
Ainsi, pour le filage des solutions cristal-liquide à base de matières cellulosiques, l'eau s'est révélée un agent coagulant incapable de produire des fibres présentant des propriétés mécaniques satisfaisantes, en particulier une ténacité au moins égale à celle d'une fibre rayonne conventionnelle, pour des applications techniques, par exemple pour le renforcement d'articles en caoutchouc ou de pneumatiques.Thus, for spinning liquid-crystal solutions based on cellulosic materials, 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.
Un premier but de la présente invention est de proposer un nouvel agent coagulant, à base d'eau, plus avantageux du point de vue industriel que l'acétone et plus efficace que l'eau seule. capable de produire des fibres dont les propriétés de ténacité et de module sont nettement améliorées par rapport à celles de fibres coagulées simplement avec de l'eau.A first object of the present invention is to propose 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 tenacity and modulus properties are significantly improved compared to those of fibers coagulated simply with water.
L'agent coagulant aqueux de l'invention, apte à coaguler une solution cristal-liquide à base de matières cellulosiques, est caractérisé en ce qu'il comporte au moins un additif soluble dans l'eau choisi dans le groupe constitué par l'ammoniac, les aminés ou les sels de ces composés, l'additif étant tel que le pH dudit agent coagulant est supérieur à 6.The aqueous coagulating agent of the invention, capable of coagulating a liquid crystal 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.
L'invention concerne également un procédé de filage d'une solution cristal-liquide à base de matières cellulosiques, pour l'obtention d'un article filé, mis en oeuvre avec un agent coagulant conforme à l'invention, ainsi que tout article filé obtenu selon un tel procédé. Un autre but de l'invention est de proposer une fibre cellulosique nouvelle pouvant être obtenue par le procédé conforme à l'invention ; cette fibre nouvelle, comparée à une fibre rayonne conventionnelle, a une ténacité au moins égale sinon supérieure, une résistance à la fatigue comparable, le tout combiné à un module initial en extension nettement plus élevé.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, as well as any spun article obtained by such a process. 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 toughness at least equal if not higher, a comparable resistance to fatigue, all combined with an initial module in extension significantly higher.
La fibre cellulosique de l'invention a les caractéristiques suivantes :The cellulosic fiber of the invention has the following characteristics:
- sa ténacité T est supérieure à 40 cN/tex ;- its tenacity T is greater than 40 cN / tex;
- son module initial en extension Mi est supérieur à 1200 cN/tex ;- its initial module in Mi extension is greater than 1200 cN / tex;
- sa déchéance en force-rupture ΔF après 350 cycles de fatigue au test dit "test de barreau", sous un taux de compression de 3,5 % et une contrainte de tension de 0,25 cN/tex, est inférieure à 30 %.- its lapse in breaking strength ΔF after 350 fatigue cycles in the so-called "bar test" test, under a compression rate of 3.5% and a tension stress of 0.25 cN / tex, is less than 30% .
L'invention concerne en outre les produits suivants:The invention further relates to the following products:
- les assemblages de renforcement comportant au moins un article filé conforme à l'invention, par exemple des câbles, des retors, des fibres multifilamentaires tordues sur elles-mêmes, de tels assemblages de renforcement pouvant être par exemple hybrides, composites, i.e. comportant des éléments de natures différentes, éventuellement non conformes à l'invention ;- the reinforcement assemblies comprising at least one spun article in accordance with the invention, for example cables, twists, multifilament fibers twisted on themselves, such reinforcement assemblies being able to be, for example, hybrid, composite, ie comprising elements of different natures, possibly not in accordance with the invention;
- les articles renforcés par au moins un article filé et/ou un assemblage conformes à l'invention, ces articles étant par exemple des articles en caoutchouc(s) ou en matière(s) plastique(s), par exemple des nappes, des courroies, des tuyaux, des enveloppes de pneumatiques, en particulier des armatures de carcasse de pneumatique.- Articles reinforced with at least one spun article and / or an assembly in accordance with the invention, these articles being for example articles made of rubber (s) or of plastic material (s), for example plies, belts, hoses, tire covers, in particular tire carcass reinforcements.
L'invention, ainsi que ses avantages, seront aisément compris à la lumière de la description et des exemples non limitatifs qui suivent.The invention, as well as its advantages, will be easily understood in the light of the description and of the nonlimiting examples which follow.
I. MESURES ET TESTS UTILISESI. MEASUREMENTS AND TESTS USED
1-1. Degré de substitution1-1. Degree of substitution
Le degré de substitution (noté DS) des fibres régénérées à partir d'un dérivé cellulosique, par exemple à partir du formiate de cellulose, est mesuré de manière connue, comme indiqué ci- après : environ 400 mg de fibre sont coupés en morceaux de 2 à 3 cm de long, puis pesés avec précision et introduits dans un Erlenmeyer de 100 ml contenant 50 ml d'eau. On ajoute 1 ml de soude normale (NaOH IN). L'ensemble est mélangé à température ambiante, pendant 15 minutes. On régénère ainsi complètement la cellulose en transformant en groupes hydroxyle les derniers groupes substituants qui avaient résisté au traitement de régénération sur fibres continues. La soude en excès est titrée avec une solution d'acide chlorhydrique décinormale (HC1 0,1 N), et on en déduit ainsi le degré de substitution. 1-2. Propriétés optiques des solutionsThe degree of substitution (denoted DS) of the fibers regenerated from a cellulose derivative, for example from cellulose formate, is measured in a 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 (NaOH IN) 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 (HCl 0.1 N), and the degree of substitution is thus deduced therefrom. 1-2. Optical properties of solutions
L'isotropie ou l'anisotropie optique des solutions est déterminée en plaçant une goutte de solution à étudier entre polariseur et analyseur linéaires croisés d'un microscope optique de polarisation, puis en observant cette solution au repos, c'est-à-dire en l'absence de contrainte dynamique, à la température ambiante.The optical isotropy or anisotropy of the solutions is determined by placing a drop of solution to be studied between crossed linear polarizers and analyzers with an optical polarization microscope, and then observing this solution at rest, i.e. by the absence of dynamic stress, at room temperature.
De manière connue, une solution optiquement anisotrope, dite aussi cristal-liquide, est une solution qui dépolarise la lumière, c'est-à-dire qui présente, ainsi placée entre polariseur et analyseur linéaires croisés, une transmission de la lumière (texture colorée). Une solution optiquement isotrope, c'est-à-dire qui n'est pas cristal-liquide, est une solution qui, dans les mêmes conditions d'observation, ne présente pas la propriété de dépolarisation ci-dessus, le champ du microscope restant noir.In known manner, an optically anisotropic solution, also called liquid-crystal, is 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.
1-3. Propriétés mécaniques des fibres1-3. Mechanical properties of fibers
Par "fibres", on entend ici des fibres multifilamentaires (encore appelées "filés"), constituées de manière connue d'un grand nombre de filaments élémentaires de faible diamètre (faible titre). Toutes les propriétés mécaniques ci-après sont mesurées sur des fibres ayant été soumises à un conditionnement préalable. Par "conditionnement préalable", on entend le stockage des fibres pendant au moins 24 heures, avant mesure, dans une atmosphère standard selon la norme européenne DIN EN20139 (température de 20 ± 2°C ; hygrométrie de 65 ± 2 %). Pour des fibres en matières cellulosiques, un tel conditionnement préalable permet de stabiliser leur taux d'humidité à un niveau d'équilibre inférieur à 15 % en poids de fibre sèche.By "fibers" is meant here multifilament fibers (also called "spun"), constituted in a 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; humidity 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.
Le titre des fibres est déterminé sur au moins trois échantillons, chacun correspondant à une longueur de 50 m, par pesée de cette longueur de fibre. Le titre est donné en tex (poids en grammes de 1000 m de fibre).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).
Les propriétés mécaniques en extension (ténacité, module initial, allongement à la rupture) sont mesurées de manière connue à l'aide d'une machine de traction ZWICK GmbH & Co (Allemagne) de type 1435 ou de type 1445. Les fibres, après avoir reçu une faible torsion de protection préalable (angle d'hélice de 6° environ), subissent une traction sur une longueur initiale de 400 mm à une vitesse nominale de 200 mm/min, ou à une vitesse de 50 mm/min si leur allongement à la rupture ne dépasse pas 5 %. Tous les résultats donnés sont une moyenne sur 10 mesures.The mechanical properties in extension (toughness, initial modulus, elongation at break) 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.
La ténacité (force-rupture divisée par le titre), notée T, et le module initial en extension, noté Mi, sont indiqués en cN/tex (centinewton par tex). Le module initial Mi est défini comme la pente de la partie linéaire de la courbe Force- Allongement, qui intervient juste après une prétension standard de 0,5 cN/tex. L'allongement à la rupture, noté Ar, est indiqué en pourcentage (%). 1-4. Résistance au "test de barreau"The tenacity (force-breaking divided by the title), noted T, and the initial module in extension, noted Mi, are indicated in cN / tex (centinewton by tex). The initial module 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. The elongation at break, denoted Ar, is indicated as a percentage (%). 1-4. Resistance to the "bar test"
Un test simple dit "test de barreau" est mis en oeuvre pour déterminer la résistance à la fatigue des fibres étudiées.A simple test called "bar test" is used to determine the fatigue strength of the fibers studied.
On utilise pour ce test un court tronçon de fibre (longueur d'au moins 600 mm) qui a été soumise à un conditionnement préalable, le test étant conduit à la température ambiante (environ 20°C). Ce tronçon, soumis à une tension de 0,25 cN/tex grâce à un poids constant fixé à une de ses extrémités libre, est tendu sur un barreau en acier poli, et courbé autour de ce dernier selon un angle de courbure de 90 degrés environ. Un dispositif mécanique auquel est fixée l'autre extrémité du tronçon de fibre assure le glissement forcé et répété de la fibre sur le barreau en acier poli, selon un mouvement linéaire alternatif de fréquence (100 cycles par minute) et d'amplitude (30 mm) déterminées. Le plan vertical contenant l'axe de la fibre se trouve toujours sensiblement perpendiculaire au plan vertical contenant le barreau qui est lui- même horizontal.For this test, a short section of fiber (length of at least 600 mm) is used which has been subjected to prior conditioning, the test being carried out at ambient 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 at an angle of curvature of 90 degrees 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 reciprocating linear 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.
Le diamètre du barreau est choisi pour provoquer une compression de 3,5 % lors de chaque passage des filaments de la fibre autour du barreau. A titre d'exemple, on utilise un barreau de diamètre 360 μm (micromètre) pour une fibre dont le diamètre moyen des filaments est de 13 μm (soit un titre filamentaire moyen de 0,20 tex, pour une densité de cellulose égale à 1,52).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. For example, a bar with a diameter of 360 μm (micrometer) is used for a fiber whose average filament diameter is 13 μm (or an average filament titer of 0.20 tex, for a cellulose density equal to 1 , 52).
On arrête le test au bout de 350 cycles et on mesure la déchéance de la force-rupture après fatigue, notée ΔF, selon l'équation:The test is stopped after 350 cycles and the lapse of the breaking force after fatigue is measured, denoted ΔF, according to the equation:
ΔF (%) = 100 [F0 - Fι ] / FoΔF (%) = 100 [F 0 - Fι] / Fo
Fo étant la force-rupture de la fibre avant fatigue et F\ sa force-rupture après fatigue.Fo being the breaking strength of the fiber before fatigue and F \ its breaking strength after fatigue.
II. CONDITIONS DE REALISATION DE L'INVENTIONII. CONDITIONS FOR CARRYING OUT THE INVENTION
On décrit tout d'abord les conditions de préparation des solutions cristal-liquide à base de matières cellulosiques (§ II- 1), puis les conditions de filage de ces solutions pour l'obtention de fibres (§ II-2).We first describe the conditions for preparing liquid-crystal solutions based on cellulosic materials (§ II-1), then the conditions for spinning these solutions to obtain fibers (§ II-2).
II- 1. Préparation des solutionsII- 1. Preparation of solutions
Les solutions cristal-liquide sont préparées de manière connue, en dissolvant les matières cellulosiques dans un solvant ou un mélange solvant approprié - dit "solvant de filage" - comme indiqué par exemple dans les demandes WO85/05115 et WO96/09356 précitées.The liquid-crystal solutions are prepared in 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.
Par "solution", on entend ici de manière connue une composition liquide homogène dans laquelle aucune particule solide n'est visible à l'oeil nu. Par "solution cristal-liquide", on entend une solution optiquement anisotrope à température ambiante (20°C environ) et au repos, i.e. en l'absence de toute contrainte dynamique.By "solution" is meant here in a known manner a homogeneous liquid composition in which no solid particle is visible to the naked eye. By "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.
De manière préférentielle, l'agent coagulant de l'invention est utilisé pour coaguler des solutions cristal-liquide contenant au moins un acide, cet acide appartenant plus préférentiellement au groupe constitué par l'acide formique, l'acide acétique, les acides phosphoriques, ou les mélanges de ces acides.Preferably, 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.
L'agent coagulant de l'invention peut être avantageusement utilisé pour coaguler:The coagulating agent of the invention can be advantageously used to coagulate:
- les solutions cristal-liquide de dérivés cellulosiques à base d'au moins un acide phosphorique, ces solutions étant notamment des solutions d'esters de cellulose, en particulier des solutions de formiate de cellulose, telles que décrites par exemple dans la demande WO85/051 15 précitée, réalisées en mélangeant de la cellulose, de l'acide formique et de l'acide phosphorique (ou un liquide à base d'acide phosphorique), l'acide formique étant l'acide d'estérification, l'acide phosphorique étant le solvant du formiate de cellulose;liquid crystal solutions of cellulose derivatives based on at least one phosphoric acid, these solutions being in particular solutions of cellulose esters, in particular solutions of cellulose formate, as described for example in application WO85 / 051 15 above, made by mixing cellulose, formic acid and phosphoric acid (or a liquid based on phosphoric acid), the formic acid being esterification acid, phosphoric acid being the solvent for cellulose formate;
- les solutions cristal-liquide de cellulose à base d'au moins un acide phosphorique telles que décrites par exemple dans la demande WO96/09356 précitée, préparées en dissolvant directement la cellulose, c'est-à-dire sans dérivation, dans un solvant approprié contenant plus de 85 % en poids d'au moins un acide phosphorique répondant à la formule moyenne suivante:- liquid crystal solutions of cellulose based on at least one phosphoric acid as described, for example, in the aforementioned application WO96 / 09356, prepared by directly dissolving the cellulose, that is to say without derivation, in a solvent suitable containing more than 85% by weight of at least one phosphoric acid corresponding to the following average formula:
[n(P2O5), p(H2O)] , avec: 0,33 < (n/p) < 1,0 .[n (P 2 O 5 ), p (H 2 O)], with: 0.33 <(n / p) <1.0.
La cellulose de départ peut se présenter sous différentes formes connues, notamment sous forme d'une poudre, préparée par exemple par pulvérisation d'une plaque de cellulose à l'état brut. De préférence, sa teneur initiale en eau est inférieure à 10 % en poids, et son DP (degré de polymérisation) est compris entre 500 et 1000.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. Preferably, its initial water content is less than 10% by weight, and its DP (degree of polymerization) is between 500 and 1000.
Les moyens de malaxage appropriés pour l'obtention d'une solution sont connus de l'homme du métier: ils doivent être aptes à pétrir, malaxer correctement, de préférence à une vitesse réglable, la cellulose et les acides jusqu'à l'obtention de la solution. Le malaxage peut être conduit par exemple dans un mélangeur comportant des bras en Z, ou dans un mélangeur à vis en continu. Ces moyens de malaxage sont de préférence équipés d'un dispositif d'évacuation sous vide et d'un dispositif de chauffage et de refroidissement permettant d'ajuster la température du mélangeur et de son contenu, afin d'accélérer par exemple les opérations de dissolution, ou de contrôler la température de la solution en cours de formation.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 obtaining of the solution. The mixing 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 titre d'exemple, pour une solution de formiate de cellulose, on peut utiliser le mode opératoire suivant: on introduit dans un malaxeur à double enveloppe, comportant des bras en Z et une vis d'extrusion, un mélange approprié d'acide orthophosphorique (cristallin à 99 %) et d'acide formique. Cn ajoute ensuite de la poudre de cellulose (dont l'humidité est en équilibre avec l'humidité ambiante de l'air) ; le tout est mélangé pendant une période d'environ 1 à 2 heures, par exemple, la température du mélange étant maintenue entre 10 et 20°C, jusqu'à l'obtention d'une solution. Pour une solution conforme à la demande WO96/09356, on pourra procéder de la même façon, en remplaçant l'acide formique par exemple par un acide polyphosphorique.By way of example, for a cellulose formate solution, the following procedure can be used: a suitable mixture of orthophosphoric acid is introduced into a double-walled mixer, comprising Z arms and an extrusion screw. (99% crystalline) and formic acid. Next, cellulose powder is 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. For a solution in accordance with application WO96 / 09356, it is possible to proceed in the same way, by replacing formic acid for example with a polyphosphoric acid.
Les solutions ainsi obtenues sont prêtes à filer, elles peuvent être transférées directement, par exemple par l'intermédiaire d'une vis d'extrusion placée à la sortie du mélangeur, vers une machine de filage pour y être filées, sans autre transformation préalable que des opérations habituelles telles que des étapes de dégazage ou de filtration par exemple.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.
II-2. Filage des solutionsII-2. Spinning solutions
En sortie des moyens de malaxage et de dissolution, la solution est transférée de manière connue vers un bloc de filage où elle alimente une pompe de filature. A partir de cette pompe de filature, on extrude la solution à travers au moins une filière, précédée d'un filtre. Au cours du cheminement jusqu'à la filière, la solution est progressivement amenée à la température de filage désirée.At the outlet of the mixing and dissolving means, 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.
Chaque filière peut comporter un nombre variable de capillaires d'extrusion, par exemple un seul capillaire en forme de fente pour le filage d'un film, ou dans le cas d'une fibre plusieurs centaines de capillaires, par exemple de forme cylindrique (diamètre de 50 à 80 micromètres par exemple). On considérera à partir de maintenant le cas général du filage d'une fibre multifilamentaire.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). We will now consider the general case of spinning a multifilament fiber.
En sortie de filière, on obtient donc un extrudat liquide de solution, constitué d'un nombre variable de veines liquides élémentaires. De préférence, les solutions sont filées selon la technique dite de "dry-jet-wet-spinning" utilisant une couche fluide non coagulante, en général de l'air ("air-gap"), placée entre la filière et les moyens de coagulation. Chaque veine liquide élémentaire est étirée dans cet air-gap, d'un facteur généralement compris entre 2 et 10 (facteur d'étirage au filage), avant de pénétrer dans la zone de coagulation, l'épaisseur de l'air-gap pouvant varier dans une large mesure, selon les conditions particulières de filage, par exemple de 10 mm à 100 mm.At the outlet of the die, a liquid extrudate of solution is therefore obtained, consisting of a variable number of elementary liquid veins. Preferably, 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. Each elementary liquid vein is stretched in this air-gap, by a factor generally between 2 and 10 (spinning stretching factor), 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.
Après traversée de la couche non coagulante ci-dessus, les veines liquides étirées pénètrent dans un dispositif de coagulation où elles entrent alors au contact de l'agent coagulant. Sous l'action de ce dernier, elles se transforment, par précipitation des matières cellulosiques (cellulose ou dérivé cellulosique) en filaments solides qui forment ainsi une fibre. Les dispositifs de coagulation à employer sont des dispositifs connus, composés par exemple de bains, tuyaux et/ou cabines, contenant l'agent coagulant et dans lesquels circule la fibre en cours de formation. On utilise de préférence un bain de coagulation disposé sous la filière, en sortie de la couche non coagulante. Ce bain est généralement prolongé à sa base par un tube cylindrique vertical, dit "tube de filage", dans lequel passe la fibre coagulée et circule l'agent coagulant.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, for example composed 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.
Par "agent coagulant", on entend de manière connue un agent apte à coaguler une solution, c'est-à-dire un agent susceptible de faire précipiter rapidement le polymère en solution, en d'autres termes de le séparer rapidement de son solvant ; l'agent coagulant doit être à la fois un non-solvant du polymère et un bon solvant du solvant du polymère.The term “coagulating agent” means in known manner an agent capable of coagulating a solution, that is to say an agent capable of causing the polymer to precipitate rapidly in solution, 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.
Conformément à l'invention, l'agent coagulant utilisé est un agent coagulant aqueux comportant au moins un additif soluble dans l'eau choisi dans le groupe constitué par l'ammoniac, les aminés ou les sels de ces composés, l'additif étant tel que le pH dudit agent coagulant est supérieur à 6.According to the invention, 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.
Parmi les additifs répondant à la définition ci-dessus, on citera par exemple l'ammoniaque (ammoniac aqueux), des aminés aliphatiques ou hétérocycliques telles que l'éthanolamine, la diéthanolamine, la triéthanolamine, l'éthylènediamine, la diéthylènetriamine, la triéthylamine, l'imidazole, le 1-méthyl imidazole, la morpholine, la pipérazine, les aminés préférentielles étant des aminés primaires ou secondaires comportant de 1 à 5 atomes de carbone.Among the additives corresponding to the above definition, there may be mentioned for example 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.
De préférence, on utilise comme additif un sel d'ammonium, organique ou inorganique, et plus préférentiellement un sel choisi dans le groupe constitué par les formiates, les acétates et les phosphates d'ammonium, les sels mixtes de ces composés, ou les mélanges de ces constituants, ce sel d'ammonium pouvant être en particulier un sel d'un acide présent dans la solution cristal-liquide, par exemple (NH4)2HPO4, (NH4)3PO4, CH3 COONH4, HCOONH4.Preferably, an organic or inorganic ammonium salt is used as 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, CH3 COONH4, HCOONH4.
Parmi les sels d'ammonium ne convenant pas (pH de l'agent coagulant non supérieur à 6), on citera notamment (NH4) SO4, (NH4)HSC-4, (NH4)H2PO4, NH4NO3 .Among the ammonium salts which are not suitable (pH of the coagulating agent not greater than 6), there may be mentioned in particular (NH4) SO4, (NH4) HSC-4, (NH4) H 2 PO4, NH4NO3.
L'agent coagulant de l'invention est préférentiellement mis en oeuvre sur des solutions cristal- liquide à base de cellulose ou de formiate de cellulose dissous dans au moins un acide phosphorique, telles que décrites par exemple dans les demandes WO85/051 15 et WO96/09356 précitées : on utilise alors avantageusement l'orthophosphate diammonique (NH4)2HPO4.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 / 051 15 and WO96 / 09356 mentioned above: diammonic orthophosphate (NH4) 2 HPO4 is then advantageously used.
La concentration en additif de l'agent coagulant (notée Ca) peut varier dans une large mesure, par exemple de 2 à 25 % (% en poids total d'agent coagulant), voire plus, selon les conditions particulières de réalisation de l'invention.The concentration of additive in the coagulating agent (denoted Ca) 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.
Concernant la température de l'agent coagulant (notée Te ci-après), on a observé que des températures basses, notamment voisines de 0°C, pouvaient dans certains cas entraîner le collage entre eux de certains filaments au cours de leur formation ("married filaments"). Ceci perturbe les opérations de filage et est généralement préjudiciable à la qualité du filé obtenu ; ainsi, de préférence, l'agent coagulant de l'invention est utilisé à une température Te supérieure à 10°C, plus préférentiellement voisine de la température ambiante (20°C) ou supérieure. On a constaté que l'ajout d'un tensio-actif, par exemple de l'isopropanol ou des savons à base de phosphate, était une autre solution possible pour supprimer ou tout du moins réduire les difficultés ci-dessus.With regard to the temperature of the coagulating agent (noted Te below), it has been observed that low temperatures, in particular close to 0 ° C., could in certain cases cause certain filaments to bond 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 Te greater than 10 ° C, more preferably close to ambient 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.
Selon le procédé conforme à l'invention, le taux de solvant de filage apporté par la solution dans l'agent coagulant est de préférence maintenu à un niveau inférieur à 10 %, de manière encore plus préférentielle inférieur à 5 % (% en poids total d'agent coagulant), en tout cas contrôlé de manière à ce que le pH dudit agent coagulant soit, conformément à l'invention, supérieur à 6.According to the process according to the invention, 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.
La profondeur totale d'agent coagulant traversée par les filaments en cours de formation dans le bain de coagulation, mesurée de l'entrée du bain jusqu'à l'entrée du tube de filage, peut varier dans une large mesure, par exemple de quelques millimètres à plusieurs centimètres. Néanmoins, on a observé qu'une profondeur trop faible d'agent coagulant pouvait entraîner elle aussi la formation de "married filaments" ; ainsi, de préférence, la profondeur de l'agent coagulant est choisie supérieure à 20 mm.The total depth of coagulating agent traversed by the filaments being formed in the coagulation bath, measured from the entry of the bath to the entry of the spinning tube, can vary to a large extent, for example by a few millimeters to several centimeters. However, it has been observed that too small a depth of coagulant could also lead to the formation of "married filaments"; thus, preferably, the depth of the coagulating agent is chosen to be greater than 20 mm.
L'homme du métier saura définir l'agent coagulant le plus approprié en fonction des caractéristiques particulières de la solution cristal-liquide à coaguler, et saura adapter des paramètres tels que concentration en additif, température ou profondeur d'agent coagulant, aux conditions particulières de mise en oeuvre de l'invention, à la lumière de la description et des exemples de réalisation qui suivent.Those skilled in the art will be able to define the most suitable coagulating agent as a function of the particular characteristics of the liquid-crystal solution to be coagulated, and will be able to adapt parameters such as concentration of additive, temperature or depth of coagulating agent, to the particular conditions. of implementation of the invention, in the light of the description and of the embodiment examples which follow.
De préférence, l'agent coagulant conforme à l'invention est utilisé dans un procédé de filage dit de "dry-jet-wet-spinning", comme décrit précédemment, mais il pourrait être utilisé également dans d'autres procédés de filage, par exemple un procédé dit de "wet-spinning", c'est-à-dire un procédé de filage dans lequel la filière est immergée dans l'agent coagulant.Preferably, the coagulating agent in accordance with 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. example a process called "wet-spinning", that is to say a spinning process in which the die is immersed in the coagulating agent.
En sortie des moyens de coagulation, la fibre est reprise sur un dispositif d'entraînement, par exemple sur des cylindres motorisés, pour être lavée de manière connue, de préférence avec de l'eau, par exemple dans des bains ou des cabines. Après lavage, la fibre est séchée par tout moyen convenable, par exemple par défilement en continu sur des rouleaux chauffants maintenus de préférence à une température inférieure à 200°C.At the outlet of the coagulation means, 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. After washing, the fiber is dried by any suitable means, for example by continuous scrolling on heating rollers preferably maintained at a temperature below 200 ° C.
Dans le cas d'une fibre en dérivé cellulosique, on peut aussi traiter directement la fibre lavée, mais non séchée, à travers des bains de régénération, par exemple dans une solution aqueuse de soude, afin de régénérer la cellulose et d'aboutir après lavage et séchage à une fibre en cellulose régénérée.In the case of a cellulose derivative fiber, it is also possible to directly treat the washed, but not dried, fiber through regeneration baths, for example in an aqueous sodium hydroxide solution, in order to regenerate the cellulose and to succeed after washing and drying with regenerated cellulose fiber.
III. EXEMPLES DE REALISATIONIII. EXAMPLES OF REALIZATION
Les exemples qui suivent, conformes ou non conformes à l'invention, sont des exemples de réalisation de fibres par filage de solutions cristal-liquide de cellulose ou de formiate de cellulose ; ces solutions connues sont préparées conformément à la description du chapitre II précédent.The examples which follow, in accordance with or not in accordance with the invention, are examples of the production of fibers by spinning liquid crystal solutions of cellulose or cellulose formate; these known solutions are prepared in accordance with the description in chapter II above.
Dans tous ces exemples, sauf indications différentes, les pourcentages des compositions des solutions ou des agents coagulants sont des pourcentages en poids total de solution ou d'agent coagulant, respectivement. Les valeurs de pH indiquées sont les valeurs mesurées au pH- mètre. encore plus préférentielle inférieur à 5 % (% en poids total d'agent coagulant), en tout cas contrôlé de manière à ce que le pH dudit agent coagulant soit, conformément à l'invention, supérieur à 6.In all these examples, unless otherwise indicated, 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.
La profondeur totale d'agent coagulant traversée par les filaments en cours de formation dans le bain de coagulation, mesurée de l'entrée du bain jusqu'à l'entrée du tube de filage, peut varier dans une large mesure, par exemple de quelques millimètres à plusieurs centimètres. Néanmoins, on a observé qu'une profondeur trop faible d'agent coagulant pouvait entraîner elle aussi la formation de "married filaments" ; ainsi, de préférence, la profondeur de l'agent coagulant est choisie supérieure à 20 mm.The total depth of coagulating agent traversed by the filaments being formed in the coagulation bath, measured from the entry of the bath to the entry of the spinning tube, can vary to a large extent, for example by a few millimeters to several centimeters. However, it has been observed that too small a depth of coagulant could also lead to the formation of "married filaments"; thus, preferably, the depth of the coagulating agent is chosen to be greater than 20 mm.
L'homme du métier saura définir l'agent coagulant le plus approprié en fonction des caractéristiques particulières de la solution cristal-liquide à coaguler, et saura adapter des paramètres tels que concentration en additif, température ou profondeur d'agent coagulant, aux conditions particulières de mise en oeuvre de l'invention, à la lumière de la description et des exemples de réalisation qui suivent.Those skilled in the art will be able to define the most suitable coagulating agent as a function of the particular characteristics of the liquid-crystal solution to be coagulated, and will be able to adapt parameters such as concentration of additive, temperature or depth of coagulating agent, to the particular conditions. of implementation of the invention, in the light of the description and of the embodiment examples which follow.
De préférence, l'agent coagulant conforme à l'invention est utilisé dans un procédé de filage dit de "dry-jet-wet-spinning", comme décrit précédemment, mais il pourrait être utilisé également dans d'autres procédés de filage, par exemple un procédé dit de "wet-spinning", c'est-à-dire un procédé de filage dans lequel la filière est immergée dans l'agent coagulant.Preferably, the coagulating agent in accordance with 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. example a process called "wet-spinning", that is to say a spinning process in which the die is immersed in the coagulating agent.
En sortie des moyens de coagulation, la fibre est reprise sur un dispositif d'entraînement, par exemple sur des cylindres motorisés, pour être lavée de manière connue, de préférence avec de l'eau, par exemple dans des bains ou des cabines. Après lavage, la fibre est séchée par tout moyen convenable, par exemple par défilement en continu sur des rouleaux chauffants maintenus de préférence à une température inférieure à 200°C.At the outlet of the coagulation means, 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. After washing, the fiber is dried by any suitable means, for example by continuous scrolling on heating rollers preferably maintained at a temperature below 200 ° C.
Dans le cas d'une fibre en dérivé cellulosique, on peut aussi traiter directement la fibre lavée, mais non séchée, à travers des bains de régénération, par exemple dans une solution aqueuse de soude, afin de régénérer la cellulose et d'aboutir après lavage et séchage à une fibre en cellulose régénérée.In the case of a cellulose derivative fiber, it is also possible to directly treat the washed, but not dried, fiber through regeneration baths, for example in an aqueous sodium hydroxide solution, in order to regenerate the cellulose and to succeed after washing and drying with regenerated cellulose fiber.
III. EXEMPLES DE REALISATIONIII. EXAMPLES OF REALIZATION
Les exemples qui suivent, conformes ou non conformes à l'invention, sont des exemples de réalisation de fibres par filage de solutions cristal-liquide de cellulose ou de formiate de cellulose ; ces solutions connues sont préparées conformément à la description du chapitre II précédent.The examples which follow, in accordance with or not in accordance with the invention, are examples of the production of fibers by spinning liquid crystal solutions of cellulose or cellulose formate; these known solutions are prepared in accordance with the description in chapter II above.
Dans tous ces exemples, sauf indications différentes, les pourcentages des compositions des solutions ou des agents coagulants sont des pourcentages en poids total de solution ou d'agent coagulant, respectivement. Les valeurs de pH indiquées sont les valeurs mesurées au pH- mètre. ESSAI 1In all these examples, unless otherwise indicated, 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. TEST 1
Dans ce premier essai, une solution cristal-liquide de formiate de cellulose est préparée à partir de 22 % de cellulose en poudre (DP initial de 600), de 61 % d'acide orthophosphorique (cristallin à 99 %) et de 17 % d'acide formique. Après mise en solution (1 h de mélangeage), la cellulose présente un DS (degré de substitution) de 33 % et un DP (degré de polymérisation, mesuré de manière connue) d'environ 480.In this first test, 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 hour 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.
La solution est ensuite filée, sauf indication différente, selon les conditions générales décrites au § II-2. précédent, à travers une filière constituée de 250 trous (capillaires de diamètre 65 μm), à une température de filage de 50°C environ ; les veines liquides ainsi formées sont étirées (facteur d'étirage au filage égal à 6) dans un air-gap de 25 mm puis sont coagulées au contact de divers agents coagulants (profondeur traversée: 30 mm), conformes ou non à l'invention, sans utiliser d'agent tensio-actif. Les fibres en formiate de cellulose ainsi obtenues sont lavées à l'eau (15°C), puis envoyées en continu sur une ligne de régénération, à une vitesse de 150 m/min, pour y être régénérées dans une solution aqueuse de soude à température ambiante (concentration en soude: 30 % en poids), lavées avec de l'eau (15°C) et enfin séchées par passage sur des cylindres chauffants (180°C) pour ajuster leur taux d'humidité à moins de 15 %.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 μm), at a spinning temperature of around 50 ° C; the liquid veins thus formed are stretched (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 on 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% .
Les fibres en cellulose régénérée (DS inférieur à 2 %) ainsi obtenues ont un titre de 47 tex pour 250 filaments (soit environ 0,19 tex par filament), et les propriétés mécaniques suivantes:The regenerated cellulose fibers (DS less than 2%) thus obtained have a titer of 47 tex per 250 filaments (or approximately 0.19 tex per filament), and the following mechanical properties:
- exemple 1A : avec un agent coagulant non conforme à l'invention constitué d'eau seule, utilisé à une température Te de 20°C:- Example 1A: with a coagulating agent not in accordance with the invention consisting of water alone, used at a temperature Te of 20 ° C:
T = 34 cN/tex ; Mi = 1430 cN/tex ; Ar = 5,l % .T = 34 cN / tex; Mi = 1430 cN / tex; Ar = 5.1%.
- exemple 1B : avec un agent coagulant conforme à l'invention constitué d'une solution aqueuse contenant 10 % de Na(NH4)HP04 - pH = 8,1 - maintenue à une température Te de 20°C:- Example 1B: with a coagulating agent in accordance with the invention consisting of an aqueous solution containing 10% Na (NH4) HP04 - pH = 8.1 - maintained at a temperature Te of 20 ° C:
T = 41 cN/tex ; Mi = 1935 cN/tex ; Ar = 4,7 % .T = 41 cN / tex; Mi = 1935 cN / tex; Ar = 4.7%.
Par rapport au témoin (exemple 1 A), on constate une augmentation de ténacité de plus de 20 % et une augmentation de module initial de 35 %.Compared to the control (example 1 A), there is an increase in toughness of more than 20% and an increase in initial modulus of 35%.
- exemple 1 C : avec un agent coagulant aqueux conforme à l'invention, constitué d'eau et de 20 % de (NH4)2HP04 - pH = 8,1 - utilisé à une température Te de 20°C:- Example 1 C: with an aqueous coagulating agent according to the invention, consisting of water and 20% of (NH4) 2 HP04 - pH = 8.1 - used at a temperature Te of 20 ° C:
T = 49 cN/tex ; Mi = 1960 cN/tex ; Ar = 6,4 % .T = 49 cN / tex; Mi = 1960 cN / tex; Ar = 6.4%.
On constate ici que la ténacité de la fibre coagulée selon l'invention est augmentée de 44 % et son module initial de 37 %, par rapport au témoin coagulé avec de l'eau seule.It can be seen here that the tenacity of the coagulated fiber according to the invention is increased by 44% and its initial modulus by 37%, compared with the control coagulated with water alone.
- exemple 1D : avec le même agent coagulant que pour l'exemple 1 A, mais utilisé à une température Te proche de 0°C (+ 1°C):- Example 1D: with the same coagulating agent as for Example 1 A, but used at a temperature Te close to 0 ° C (+ 1 ° C):
T = 39 cN/tex ; Mi = 1650 cN/tex ; Ar = 5,0 % .T = 39 cN / tex; Mi = 1650 cN / tex; Ar = 5.0%.
- exemple 1E : avec le même agent coagulant que pour l'exemple 1C, mais utilisé à une température Te de 0°C:- Example 1E: with the same coagulating agent as for Example 1C, but used at a temperature Te of 0 ° C:
T = 52 cN/tex ; Mi = 1975 cN/tex ; Ar = 4,7 % .T = 52 cN / tex; Mi = 1975 cN / tex; Ar = 4.7%.
La ténacité obtenue ici est supérieure à 50 cN/tex, améliorée de 30 % par rapport au témoin non conforme à l'invention (exemple 1D), le module est augmenté de 20 %. On constate donc dans cet essai que ténacité et module initial peuvent être augmentés, que l'agent coagulant soit d'ailleurs conforme ou non à l'invention, en abaissant la température Te à des valeurs voisines de 0°C ; néanmoins, on a observé pour de telles températures la formation de filaments collés ("married filaments").The toughness obtained here is greater than 50 cN / tex, improved by 30% compared to the control not in accordance with the invention (example 1D), the modulus is increased by 20%. It is therefore found in this test that the initial toughness and modulus can be increased, whether or not the coagulating agent is in accordance with the invention, by lowering the temperature Te to values close to 0 ° C; nevertheless, the formation of bonded filaments ("married filaments") has been observed for such temperatures.
ESSAI 2:TEST 2:
Dans ce second essai, une solution cristal-liquide est préparée à partir de cellulose (22 %), d'acide orthophosphorique (66 %) et d'acide formique (12 %). Après mise en solution, la cellulose présente un DS de 29 % et un DP d'environ 490. Cette solution est ensuite filée comme indiqué pour l'essai 1 , sauf indication différente, en utilisant dans tous les exemples un agent coagulant conforme à l'invention ayant le même additif: solutions aqueuses de (NH4)2HP04, avec des concentrations en additif Ca et des températures Te qui varient.In this second test, 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 around 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 (NH4) 2 HP04, with concentrations of Ca additive and Te temperatures which vary.
Les fibres en cellulose régénérée (DS entre 0 et 1 %) ainsi obtenues ont un titre de 47 tex pour 250 filaments et les propriétés mécaniques suivantes:The regenerated cellulose fibers (DS between 0 and 1%) thus obtained have a titer of 47 tex for 250 filaments and the following mechanical properties:
- exemple 2A : avec Ca = 2,4 % ; pH = 8,0 ; Te = 10°C ,- Example 2A: with Ca = 2.4%; pH = 8.0; Te = 10 ° C,
T = 48 cN/tex ; Mi = 1820 cN/tex ; Ar = 5,9 % .T = 48 cN / tex; Mi = 1820 cN / tex; Ar = 5.9%.
- exemple 2B : avec Ca = 2,4 % ; pH = 8,0 ; Te = 20°C ,- Example 2B: with Ca = 2.4%; pH = 8.0; Te = 20 ° C,
T = 44 cN/tex ; Mi=1725cN/tex; Ar = 6,6 % .T = 44 cN / tex; Mi = 1725cN / tex; Ar = 6.6%.
- exemple 2C : avec Ca = 5 % ; pH = 8,0 ; Te = 10°C ,- Example 2C: with Ca = 5%; pH = 8.0; Te = 10 ° C,
T = 46 cN/tex ; Mi=1870cN/tex; Ar = 5,2 % .T = 46 cN / tex; Mi = 1870cN / tex; Ar = 5.2%.
- exemple 2D : avec Ca = 12 % ; pH - 8,1 ; Te = 0°C ,- 2D example: with Ca = 12%; pH - 8.1; Te = 0 ° C,
T = 49 cN/tex ; Mi = 2135cN/tex; Ar = 4,5 % .T = 49 cN / tex; Mi = 2135cN / tex; Ar = 4.5%.
- exemple 2E : avec Ca = 12 % ; pH = 8,1 ; Te = 20°C ,- Example 2E: with Ca = 12%; pH = 8.1; Te = 20 ° C,
T = 44 cN/tex ; Mi=1765cN/tex; Ar = 6,5 % .T = 44 cN / tex; Mi = 1765cN / tex; Ar = 6.5%.
- exemple 2F: avec Ca = 20 % ; pH = 8,2 ; Te = 1°C ,- Example 2F: with Ca = 20%; pH = 8.2; Te = 1 ° C,
T = 62 cN/tex ; Mi = 2215cN/tex; Ar = 5,6 % .T = 62 cN / tex; Mi = 2215cN / tex; Ar = 5.6%.
- exemple 2G: avec Ca = 20 % ; pH = 8,2 ; Te = 30°C ,- example 2G: with Ca = 20%; pH = 8.2; Te = 30 ° C,
T = 47 cN/tex ; Mi = 1770cN/tex; Ar = 7,3 % .T = 47 cN / tex; Mi = 1770cN / tex; Ar = 7.3%.
On constate dans cet essai qu'à partir d'un même additif, il est possible de faire varier la ténacité des fibres de 44 à 62 cN/tex, leur module initial de 1725 à 2215 cN/tex, en jouant simplement sur la température Te et/ou sur la concentration en additif Ca de l'agent coagulant. ESSAI 3It is noted in this test that from the same additive, it is possible to vary the tenacity of the fibers from 44 to 62 cN / tex, their initial modulus from 1725 to 2215 cN / tex, by simply varying the temperature. Te and / or on the concentration of Ca additive in the coagulating agent. TEST 3
Dans ce troisième essai, une solution cristal-liquide est préparée à partir de cellulose (24 %), d'acide orthophosphorique (70 %) et d'acide formique (6 %). Après mise en solution, la cellulose présente un DS de 20 % et un DP d'environ 480. Cette solution est ensuite filée comme indiqué pour l'essai 1 , sauf indication différente, en utilisant divers agents coagulants, tous conformes à l'invention, dont la composition, la concentration en additif Ca ou la température Te varient.In this third test, a liquid crystal solution is prepared from cellulose (24%), orthophosphoric acid (70%) and formic acid (6%). After dissolving, 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, Ca additive concentration or Te temperature vary.
Les fibres en cellulose régénérée (DS entre 0 et 1,5 %) ainsi obtenues ont un titre d'environ 45 tex pour 250 filaments (soit 0,18 tex par filament en moyenne), et les propriétés suivantes:The regenerated cellulose fibers (DS between 0 and 1.5%) thus obtained have a titer of approximately 45 tex for 250 filaments (or 0.18 tex per filament on average), and the following properties:
- exemple 3A : avec 10 % d'éthanolamine (NH2 CF^ CH OH) ; pH = 12,1 ; Te = 20°C,- Example 3A: with 10% ethanolamine (NH 2 CF ^ CH OH); pH = 12.1; Te = 20 ° C,
T = 43 cN/tex ; Mi = 1855 cN/tex ; Ar = 4,8 % .T = 43 cN / tex; Mi = 1855 cN / tex; Ar = 4.8%.
- exemple 3B : avec 5 % de HCOO(NH4) ; pH = 6,5 ; Te = 20°C,- Example 3B: with 5% HCOO (NH4); pH = 6.5; Te = 20 ° C,
T = 41 cN/tex ; Mi - 1805 cN/tex ; Ar = 5,7 % .T = 41 cN / tex; Mid - 1805 cN / tex; Ar = 5.7%.
- exemple 3C : avec 20 % de HCOO(NH4) ; pH = 7 ; Te ≈ 20°C,- Example 3C: with 20% HCOO (NH4); pH = 7; Te ≈ 20 ° C,
T = 56 cN/tex ; Mi = 2250 cN/tex ; Ar = 4,8 % .T = 56 cN / tex; Mi = 2250 cN / tex; Ar = 4.8%.
- exemple 3D : avec 10 % de HCOO(NH ) plus 10 % de (NH ) HP04 ; pH = 7,8 ; Te = 20°C,- 3D example: with 10% of HCOO (NH) plus 10% of (NH) HP0 4 ; pH = 7.8; Te = 20 ° C,
T = 52 cN/tex ; Mi = 2135 cN/tex ; Ar = 5,3 % .T = 52 cN / tex; Mi = 2135 cN / tex; Ar = 5.3%.
- exemple 3E : avec 20 % de (NH4 HPO4 ; pH = 8,2 ; Te = 30°C,- example 3E: with 20% of (NH4 HPO4; pH = 8.2; Te = 30 ° C,
T = 51 cN/tex ; Mi = 2035 cN/tex ; Ar = 5,2 % . ESSAI 4T = 51 cN / tex; Mi = 2035 cN / tex; Ar = 5.2%. TEST 4
Dans cet essai, une solution cristal-liquide de cellulose est préparée conformément à la description du chapitre II précédent et à la demande WO96/09356 précitée, à partir de 18 % de cellulose en poudre (DP initial 540), 65,5 % d'acide orthophosphorique et 16,5 % d'acide polyphosphorique (titrant 85 % en poids de P) O5 ), c'est-à-dire que la cellulose est dissoute directement dans le mélange d'acides sans passer par une étape de dérivation.In this test, 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) O5), that is to say that the cellulose is dissolved directly in the mixture of acids without going through a derivation step .
On peut procéder de la manière suivante: les deux acides sont préalablement mélangés, le mélange acide est refroidi à 0°C puis introduit dans un mélangeur à bras Z lui-même préalablement refroidi à -15°C ; puis la cellulose en poudre, préalablement séchée, est ajoutée et malaxée avec le mélange acide en maintenant la température du mélange à une valeur au plus égale à 15°C. Après mise en solution (0,5 h de mélangeage), la cellulose présente un DP de 450 environ. Cette solution est ensuite filée, sauf indication différente, comme indiqué pour l'essai 1 précédent à la différence près, notamment, qu'il n'y a pas d'étape de régénération. La température de filage est de 40°C, et celle de séchage de 90°C.We can proceed as follows: 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 indicated otherwise, 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.
On obtient ainsi des fibres en cellulose non régénérée, i.e. obtenues directement par filage d'une solution de cellulose, sans passer par les étapes successives de dérivation de la cellulose, de filage d'une solution de dérivé cellulosique, puis de régénération des fibres de dérivé cellulosique.Unregenerated cellulose fibers are thus obtained, ie obtained directly by spinning a cellulose solution, without going through the successive steps of deriving cellulose, spinning a solution of cellulose derivative, then regenerating fibers. cellulose derivative.
Ces fibres en cellulose non régénérée ont un titre de 47 tex pour 250 filaments, et les propriétés mécaniques qui suivent:These non-regenerated cellulose fibers have a titer of 47 tex for 250 filaments, and the following mechanical properties:
- exemple 4A : avec un agent coagulant non conforme à l'invention constitué d'eau seule, à une température Te de 20°C:- Example 4A: with a coagulating agent not in accordance with the invention consisting of water alone, at a temperature Te of 20 ° C:
T = 30 cN/tex ; Mi = 1560 cN/tex ; Ar = 6,4 % .T = 30 cN / tex; Mi = 1560 cN / tex; Ar = 6.4%.
- exemple 4B: avec 20 % de 20°C,- example 4B: with 20% of 20 ° C,
T = 45 cN/tex ; Mi = 1895 cN/tex ; Ar = 6,4 % .T = 45 cN / tex; Mi = 1895 cN / tex; Ar = 6.4%.
On observe ici une augmentation de 50 % sur la ténacité et de 21 % sur le module initial. 1 bWe observe here an increase of 50% on the toughness and 21% on the initial modulus. 1 b
En conséquence, on constate que les agents coagulants conformes à l'invention permettent d'obtenir des fibres cellulosiques, en cellulose régénérée ou en cellulose non régénérée, dont le module initial et la ténacité sont notablement supérieurs à ceux que l'on obtient en utilisant de l'eau seule comme agent coagulant.Consequently, it can be seen that 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.
Dans tous les exemples comparatifs précédents, la ténacité et le module initial sont tous deux augmentés d'au moins 20 % par rapport à ceux obtenus après une simple coagulation dans l'eau, le gain pouvant atteindre 50 % dans certains cas ; le module initial est très élevé, avec des valeurs pouvant dépasser 2000 cN/tex.In all the previous comparative examples, 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.
On a soumis des fibres cellulosiques de l'invention au test de barreau décrit au chapitre I précédent, et on a comparé leurs performances à la fois à celles de fibres rayonne conventionnelles, et à celles de fibres à très hautes propriétés mécaniques obtenues par filage de solutions cristal-liquide identiques à celles utilisées dans les quatre essais précédents, mais après coagulation dans l'acétone (conformément aux demandes WO85/051 15 et WO96/09356 précitées).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 / 051 15 and WO96 / 09356).
Les fibres cellulosiques conformes à l'invention présentent une déchéance en force-rupture ΔF qui est toujours inférieure à 30 %, comprise généralement entre 5 et 25 %, alors que les fibres coagulées dans l'acétone, issues des mêmes solutions cristal-liquide, montrent une déchéance qui est supérieure à 30 %, en général comprise entre 35 et 45 %.The cellulosic fibers in accordance with the invention exhibit a strength-breaking lapse ΔF 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%.
A titre d'exemple, après 350 cycles de fatigue au test de barreau, pour un taux de compression de 3,5 %, on a enregistré les déchéances de force-rupture suivantes:For example, after 350 cycles of fatigue in the bar test, for a compression ratio of 3.5%, the following force-breaking lapses were recorded:
- exemple 3C : ΔF = 12 % ;- example 3C: ΔF = 12%;
- exemple 3E : ΔF = 14 % ;- example 3E: ΔF = 14%;
- exemple 4B : ΔF = 25 % ;- Example 4B: ΔF = 25%;
- fibre selon WO85/05115 (T = 90 cN/tex ; Mi = 3050 cN/tex):- fiber according to WO85 / 05115 (T = 90 cN / tex; Mi = 3050 cN / tex):
ΔF = 38 % ;ΔF = 38%;
- fibre selon WO96/09356 (T = 95 cN/tex ; Mi = 2850 cN/tex):- fiber according to WO96 / 09356 (T = 95 cN / tex; Mi = 2850 cN / tex):
ΔF = 42 % ;ΔF = 42%;
- fibres rayonne conventionnelles (T = 43-48 cN/tex ; Mi = 900-1000 cN/tex):- conventional rayon fibers (T = 43-48 cN / tex; Mi = 900-1000 cN / tex):
ΔF = 8-12 % .ΔF = 8-12%.
Les fibres cellulosiques de l'invention ont donc une résistance à la fatigue nettement supérieure à celle enregistrée sur les fibres obtenues à partir des mêmes solutions cristal- liquide en matières cellulosiques, mais coagulées de manière connue dans de l'acétone. On a observé en outre que la fibrillation était diminuée sur les fibres de l'invention, par rapport à ces fibres antérieures coagulées dans l'acétone.The cellulosic fibers of the invention therefore have a resistance to fatigue clearly 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.
Ces fibres de l'invention se caractérisent par une combinaison de propriétés qui est nouvelle: ténacité égale ou supérieure, et résistance à la fatigue pratiquement équivalente à celle d'une fibre rayonne conventionnelle, le tout combiné à un module initial nettement supérieur à celui d'une telle fibre rayonne, pouvant atteindre 2000 cN/tex et plus. Cette combinaison de caractéristiques est tout à fait inattendue pour l'homme du métier car une résistance à la fatigue pratiquement équivalente à celle d'une fibre rayonne conventionnelle - issue d'une phase non cristal-liquide - était jusqu'ici considérée comme impossible pour une fibre cellulosique à haut module issue d'une phase cristal-liquide.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, being able to reach 2000 cN / tex and more. This combination of characteristics is completely unexpected for the person skilled in the art because a fatigue resistance practically equivalent to that of a conventional rayon fiber - originating from a non-crystal-liquid phase - was hitherto considered impossible for a high modulus cellulosic fiber from a crystal-liquid phase.
De préférence, la fibre selon l'invention vérifie au moins l'une des relations suivantes:Preferably, the fiber according to the invention verifies at least one of the following relationships:
- T > 45 cN/tex ; - Mi > 1500 cN/tex ; - ΔF < 15 % ,- T> 45 cN / tex; - Mi> 1500 cN / tex; - ΔF <15%,
et d'une manière encore plus préférentielle au moins l'une des relations suivantes:and even more preferably at least one of the following relationships:
- T > 50 cN/tex ;- T> 50 cN / tex;
- Mi > 2000 cN/tex .- Mi> 2000 cN / tex.
Cette fibre selon l'invention est avantageusement une fibre en cellulose régénérée à partir de formiate de cellulose, le degré de substitution de la cellulose en groupes formiate étant compris entre 0 et 2 %.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%.
Bien entendu, l'invention n'est pas limitée aux exemples précédemment décrits.Of course, the invention is not limited to the examples previously described.
C'est ainsi par exemple que différents constituants peuvent être éventuellement ajoutés aux constituants de base précédemment décrits (cellulose, acide formique, acides phosphoriques, agents coagulants), sans que l'esprit de l'invention soit modifié.Thus, for example, different 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.
Les constituants supplémentaires, de préférence chimiquement non réactifs avec les constituants de base, peuvent être par exemple des plastifiants, des ensimages, des colorants, des polymères autres que la cellulose susceptibles éventuellement d'être estérifiés pendant la réalisation de la solution ; il peut s'agir également de produits permettant par exemple d'améliorer la filabilité des solutions de filage, les propriétés d'usage des fibres obtenues, l'adhésivité de ces fibres à une matrice de gomme.The additional constituents, preferably chemically non-reactive with the basic constituents, can be, for example, plasticizers, sizes, dyes, polymers other than cellulose which may possibly be esterified during the production of the solution; they 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.
Le terme "formiate de cellulose" utilisé dans ce document couvre les cas où les groupes hydroxyle de la cellulose sont substitués par d'autres groupes que les groupes formiate, en plus de ces derniers, par exemple des groupes esters, notamment des groupes acétate, le degré de substitution de la cellulose en ces autres groupes étant de préférence inférieur à 10 %.The term "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%.
Les termes "filage" ou "articles filés" doivent être pris dans un sens très général, ces termes concernant les fibres comme les films, qu'ils soient obtenus par extrusion, notamment à travers une filière, ou par coulée de solutions cristal-liquide en matières cellulosiques.The terms "spinning" or "spun articles" must be taken in a very general sense, these terms relating to fibers such as films, whether obtained by extrusion, in particular through a die, or by casting of liquid-crystal solutions in cellulosic materials.
Pour conclure, en raison de leur niveau de propriétés et de leur procédé d'obtention simplifié, les fibres de l'invention présentent un intérêt industriel à la fois dans le domaine des fibres techniques et dans celui des fibres textiles. To conclude, due to their level of properties and their simplified production process, the fibers of the invention are of industrial interest both in the field of technical fibers and in that of textile fibers.

Claims

REVENDICATIONS
1. Agent coagulant aqueux pour solution cristal-liquide à base de matières cellulosiques, caractérisé en ce qu'il comporte au moins un additif soluble dans l'eau choisi dans le groupe constitué par l'ammoniac, les aminés ou les sels de ces composés, l'additif étant tel que le pH dudit agent coagulant est supérieur à 6.1. Aqueous coagulating agent for liquid-crystal solution based on cellulosic materials, characterized in that it comprises at least one water-soluble additive chosen from the group consisting of ammonia, amines or the salts of these compounds , the additive being such that the pH of said coagulating agent is greater than 6.
2. Agent coagulant selon la revendication 1 , caractérisé en ce que la solution cristal-liquide comporte au moins un acide.2. Coagulating agent according to claim 1, characterized in that the liquid-crystal solution comprises at least one acid.
3. Agent coagulant selon la revendication 2, caractérisé en ce que l'additif est un sel de cet acide.3. Coagulating agent according to claim 2, characterized in that the additive is a salt of this acid.
4. Agent coagulant selon la revendication 2, caractérisé en ce que l'acide est choisi dans le groupe constitué par l'acide formique, l'acide acétique, les acides phosphoriques, ou les mélanges de ces acides.4. Coagulating agent according to claim 2, characterized in that the acid is chosen from the group consisting of formic acid, acetic acid, phosphoric acids, or mixtures of these acids.
5. Agent coagulant selon les revendications 3 et 4, caractérisé en ce que le sel est choisi dans le groupe constitué par les formiates, les acétates et les phosphates d'ammonium, les sels mixtes de ces composés, ou les mélanges de ces constituants.5. Coagulating agent according to claims 3 and 4, characterized in that the salt is chosen from the group consisting of formates, acetates and ammonium phosphates, mixed salts of these compounds, or mixtures of these constituents.
6. Agent coagulant selon l'une quelconque des revendications 4 ou 5, caractérisé en ce que la solution de filage est à base de formiate de cellulose dissous dans au moins un acide phosphorique.6. Coagulating agent according to any one of claims 4 or 5, characterized in that the spinning solution is based on cellulose formate dissolved in at least one phosphoric acid.
7. Agent coagulant selon l'une quelconque des revendications 4 ou 5, caractérisé en ce que la solution de filage est à base de cellulose dissoute directement dans au moins un acide phosphorique.7. Coagulating agent according to any one of claims 4 or 5, characterized in that the spinning solution is based on cellulose dissolved directly in at least one phosphoric acid.
8. Agent coagulant selon l'une quelconque des revendications 6 ou 7, caractérisé en ce que l'additif est l 'orthophosphate diammonique (NH4)2HPO4.8. Coagulating agent according to any one of claims 6 or 7, characterized in that the additive is diammonium orthophosphate (NH4) 2 HPO4.
9. Procédé de filage d'une solution cristal-liquide à base de matières cellulosiques, pour l'obtention d'un article filé, caractérisé en ce qu'il est mis en oeuvre avec un agent coagulant conforme à l'une quelconque des revendications 1 à 8.9. A method of spinning a liquid-crystal solution based on cellulosic materials, for obtaining a spun article, characterized in that it is used with a coagulating agent according to any one of claims 1 to 8.
10. Procédé de filage selon la revendication 9, caractérisé en ce qu'il s'agit d'un procédé dit de "dry-jet-wet-spinning".10. A spinning method according to claim 9, characterized in that it is a process called "dry-jet-wet-spinning".
11. Procédé de filage selon l'une quelconque des revendications 9 ou 10, caractérisé en ce que la profondeur d'agent coagulant, traversée par l'article filé en cours de formation, est supérieure à 20 mm. 11. A spinning method according to any one of claims 9 or 10, characterized in that the depth of coagulating agent, traversed by the spun article during formation, is greater than 20 mm.
12. Procédé de filage selon l'une quelconque des revendications 9 à 1 1. caractérisé en ce que la température de l'agent coagulant est supérieure à 10°C.12. A spinning method according to any one of claims 9 to 1 1. characterized in that the temperature of the coagulating agent is greater than 10 ° C.
13. Article filé obtenu selon un procédé conforme à l'une quelconque des revendications 9 à 12.13. A spun article obtained according to a process in accordance with any one of claims 9 to 12.
14. Fibre cellulosique ayant les caractéristiques suivantes :14. Cellulose fiber having the following characteristics:
- sa ténacité T est supérieure à 40 cN/tex ;- its tenacity T is greater than 40 cN / tex;
- son module initial en extension Mi est supérieur à 1200 cN/tex ;- its initial module in Mi extension is greater than 1200 cN / tex;
- sa déchéance en force-rupture ΔF après 350 cycles de fatigue au test dit "test de barreau", sous un taux de compression de 3,5 % et une contrainte de tension de 0,25 cN/tex, est inférieure à 30 %.- its lapse in breaking strength ΔF after 350 fatigue cycles in the so-called "bar test" test, under a compression rate of 3.5% and a tension stress of 0.25 cN / tex, is less than 30% .
15. Fibre selon la revendication 14, caractérisée en ce qu'elle vérifie au moins l'une des relations suivantes:15. Fiber according to claim 14, characterized in that it verifies at least one of the following relationships:
- T > 45 cN/tex ; - Mi > 1500 cN/tex ; - ΔF < 15 % .- T> 45 cN / tex; - Mi> 1500 cN / tex; - ΔF <15%.
16. Fibre selon la revendication 15, caractérisée en ce qu'elle vérifie au moins l'une des relations suivantes:16. Fiber according to claim 15, characterized in that it verifies at least one of the following relationships:
- T > 50 cN/tex ;- T> 50 cN / tex;
- Mi > 2000 cN/tex .- Mi> 2000 cN / tex.
17. Fibre selon l'une quelconque des revendications 14 à 16, caractérisée en ce qu'elle est en cellulose régénérée à partir de formiate de cellulose, le degré de substitution de la cellulose en • groupes formiate étant compris entre 0 et 2 % .17. Fiber according to any one of claims 14 to 16, characterized in that it is made of cellulose regenerated from cellulose formate, the degree of substitution of the cellulose in • formate groups being between 0 and 2%.
18. Article en caoutchouc(s) ou en matière(s) plastique(s), notamment enveloppe de pneumatique, renforcé par au moins une fibre cellulosique selon l'une quelconque des revendications 14 à 17. 18. Article made of rubber (s) or of plastic material (s), in particular tire casing, reinforced with at least one cellulose fiber according to any one of claims 14 to 17.
EP97910443A 1996-10-18 1997-10-15 Coagulating agent for liquid crystal solutions with base of cellulose substances Expired - Lifetime EP0932709B1 (en)

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FR9612870 1996-10-18
FR9612870 1996-10-18
PCT/EP1997/005675 WO1998017847A1 (en) 1996-10-18 1997-10-15 Coagulating agent for liquid crystal solutions with base of cellulose substances

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EP0932709A1 true EP0932709A1 (en) 1999-08-04
EP0932709B1 EP0932709B1 (en) 2003-01-29

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JP (1) JP2001505623A (en)
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CN102232128B (en) * 2008-10-14 2013-08-21 赛佩荷兰服务有限公司 Process for the manufacture of cellulose-based fibres and the fibres thus obtained
JP2013507534A (en) * 2009-10-07 2013-03-04 グラシム インダストリーズ リミテッド Process for producing low fibrillated cellulose derivative fibers
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BR9711933A (en) 1999-08-24
US20020040747A1 (en) 2002-04-11
DE69718807D1 (en) 2003-03-06
RU2183229C2 (en) 2002-06-10
US6756001B2 (en) 2004-06-29
DE69718807T2 (en) 2003-11-13
CN1240488A (en) 2000-01-05
ES2188910T3 (en) 2003-07-01
US6427736B1 (en) 2002-08-06
CN1086427C (en) 2002-06-19
AU4782097A (en) 1998-05-15
CA2268792A1 (en) 1998-04-30
EP0932709B1 (en) 2003-01-29
JP2001505623A (en) 2001-04-24
ATE231934T1 (en) 2003-02-15
WO1998017847A1 (en) 1998-04-30
CA2268792C (en) 2006-07-11

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