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
• • 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
  • 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
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
  • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249994—Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
  • Y10T428/249998—Indefinite plurality of similar impregnated thin sheets [e.g., "decorative laminate" type, etc.]
• • 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
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• • 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
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/253—Cellulosic [e.g., wood, paper, cork, rayon, etc.]

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 / 051 15, or the equivalent patents EP-B-179 822 and US-A-4 839 1 13, describe the obtaining of spinning solutions based on cellulose formate, by reaction of the 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 / 05115 and WO96 / 09356 are characterized by a much more ordered or oriented structure, due to the crystal-liquid nature of the spinning solutions from which they come. They have very high mechanical properties in extension, in particular toughness of the order of 80 to 120 cN / tex, or even more, and initial modules which can exceed 2500 to 3000 cN / tex.
• acetone is a relatively expensive, volatile product, which 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 aim 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 properties of toughness and modulus are significantly improved compared to those of fibers coagulated simply with water.
• the coagulating agent of the invention capable of coagulating a crystal-liquid solution based on cellulosic materials, is characterized by the following points:
• Kd and Kp being respectively the diffusion and precipitation factors (slopes of the respective "Fick" lines), expressed in ⁇ m / s.
• 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;
• Figure 1 shows diagrams of "Fick" diagrams, while Figure 2 reproduces such diagrams recorded both for a coagulating agent according to the invention (Kp and Kj) and for water alone (K pe and rj e ).
• Kp and Kj a coagulating agent according to the invention
• K pe and rj e water alone
• 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.
• HCl 0.1 N decinormal hydrochloric acid
• 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 ⁇ l, by weighing this length of fiber. The title is given in tex (weight in grams of 1000 m of fiber).
• the mechanical properties in extension are measured in known manner using a ZWICK GmbH & Co (Germany) type 1435 or type 1445 traction machine.
• the fibers after have received a small preliminary protective twist (helix angle of approximately 6 °), undergo traction over an initial length of 400 mm at a nominal speed of 200 mm / min, or at a speed of 50 mm / min if their elongation at break does not exceed 5%. All the results given are an average over 10 measurements.
• the initial modulus Mi is defined as the slope of the linear part of the Force-Elongation curve, which occurs just after a standard pretension of 0.5 cN / tex.
• 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 quickly in solution, in other words of rapidly separating 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.
• liquid-crystal solutions based on cellulosic materials such as described for example in applications WO85 / 051 15 and WO96 / 09356 above, we normally observe not only one, but two different progression fronts when an agent coagulant, for example acetone or water, is brought into contact with said solutions: a first front called “diffusion front”, then a second front called “precipitation front”.
• the diffusion front corresponds to a simple progression of the coagulating agent in the solution, without precipitation of the cellulosic materials, while the precipitation front corresponds to the coagulation proper, that is to say to the precipitation of the cellulosic materials.
• the intermediate zone between the two fronts being simply impregnated, swollen by the coagulating agent but not yet coagulated (dark zone under polarized light, with loss of crystal-liquid coloration).
• the factor K being expressed in ⁇ m / sec 2 (micrometer per second 2 ).
• the two previously described fronts therefore correspond to two factors, the diffusion factor K ⁇ (1st front, of diffusion) and the precipitation factor K p (2nd front, of precipitation), Kp being at most equal to K_ when the precipitation front progresses as fast as the diffusion front; in other words, there exist for a time "t j " given two displacement values, "dj" for the diffusion, "cL” for the precipitation, with d p ⁇ dj.
• the experimental study of coagulation, in a static system, is carried out using an optical polarization microscope or an optical differential interference microscope (Olympus type BH2), equipped with a video camera.
• a little liquid-crystal solution is spread, for example using a spatula tip, on a slide and then covered with a cover slip, the thickness of the solution under the cover slip being calibrated to the thickness of said strip (lens correction), for example 0.170 mm; the coagulating agent is then brought into contact with this sample of solution, by depositing, for example using a pipette or a syringe, said agent around the coverslip in an amount sufficient to cover the entire surface around the sample.
• a constant level of said additive in the coagulating agent of 20% (% by total weight of coagulating agent).
• Figure 1 shows diagrams of "Fick” obtained for example for a coagulating agent according to the invention brought into contact with a liquid crystal solution based on cellulosic materials.
• the ratio (Kp / Kd) is determined from the slopes of the scattering line D (slope K ⁇ ) and the precipitation line P (slope K p ).
• 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).
• liquid-crystal solutions are prepared in a known manner, by dissolving the cellulosic materials in a suitable solvent or solvent mixture - called “spinning solvent” - as indicated for example in the abovementioned applications WO85 / 051 15 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.
• crystal-liquid solution is meant an optically anisotropic solution at room temperature (approximately 20 ° C.) and at rest, i.e. 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
• 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 then added (the humidity of which is in equilibrium with the ambient humidity of the air); the whole is mixed for a period of approximately 1 to 2 hours, for example, the temperature of the mixture being maintained between 10 and 20 ° C., until a solution is obtained.
• 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.
• 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 (stretching factor on spinning), before entering the coagulation zone, the thickness of the air-gap which can vary to a large extent, depending on the particular spinning conditions, for example from 10 mm to 100 mm.
• the stretched liquid veins After crossing the above non-coagulating layer, the stretched liquid veins enter a coagulation device where they then come into contact with the coagulating agent. Under the action of the latter, they are transformed, by precipitation of cellulosic materials (cellulose or cellulose derivative) into solid filaments which thus form a fiber.
• the coagulation devices to be used are known devices, composed for example of baths, pipes and or cabins, containing the coagulating agent and in which the fiber circulates during formation. It is preferable to use a coagulation bath placed under the die, at the outlet of the non-coagulating layer. This bath is generally extended at its base by a vertical cylindrical tube, called “spinning tube", through which the coagulated fiber passes and circulates the coagulating agent.
• the coagulating agent according to the invention capable of coagulating a crystal-liquid solution based on cellulosic materials, is characterized by the following points:
• coagulating agent in accordance with the invention is therefore meant any aqueous solution comprising an additive (ie a compound or a mixture of compounds) which, added to water in a determined proportion (20% by total weight of agent coagulant), allows to verify the above relation to the coagulation test.
• an additive ie a compound or a mixture of compounds
• the invention is not limited to a given percentage of additive in the coagulating agent.
• the preferred additives of the invention are soluble in water.
• amines for example 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 ammonium salt organic or inorganic, 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) PO4, NaNH4HPO 4 , CH3COONH4, HCOONH4.
• the coagulating agent of the invention verifies the following relationship:
• the increase in the Kp / Kd ratio, by adding an appropriate additive to the water was essentially done by a reduction in the Kd factor (in general, for water, Kd varies from 55 to 65 ⁇ m / s).
• the invention consists in bringing the diffusion front closer to the precipitation front using an appropriate additive, and this essentially by reducing the speed of diffusion of the water in the crystal-liquid solution. considered.
• the coagulating agent of the invention verifies the relationship Kp> 20, and even more preferably the relationship Kp> 30.
• 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) HP04 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%, even more preferably less than 5% (% by total weight coagulant).
• 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. After washing, the fiber is dried by everything 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.
• 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 I A with a coagulating agent not in accordance with the invention consisting of water alone, used at a temperature Te of 20 ° C:
• Example 1B with a coagulating agent in accordance with the invention consisting of an aqueous solution containing 10% Na (NH4) HP04, maintained at a temperature Te of 20 ° C:
• Example 1 C with an aqueous coagulating agent according to the invention, consisting of water and 20% (NH4) 2 HP04, 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 1A, but used at a temperature Te close to 0 ° C (+ 1 ° C):
• Example 1E with the same coagulating agent as for Example 1 C, 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 HP ⁇ 4, with concentrations of Ca additive and Te temperatures which vary.
• the coagulating agent in accordance with the invention gave the coagulation test, for the solution considered, the following characteristics:
• 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.
• FIG. 2 shows the Fick diagrams recorded in the coagulation test for the spinning solution of this test 3:
• the diffusion front denoted D e has the slope K e (equal to 58 ⁇ m / s) and the precipitation front denoted P e has the slope Kp e (equal to 29 ⁇ m / s 2 );
• the diffusion front noted D has a slope K (equal to 39 ⁇ m / s) and the precipitation front P a has a slope K p (equal to 32 ⁇ m / s).
• the regenerated cellulose fibers (DS between 0 and 1.5%) obtained in this test 3 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 2 5), 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.
• 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 has also been observed that the fibrillation is reduced on the fibers of the invention, compared with these former 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.
• 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 may for example be 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.

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• Chemical & Material Sciences (AREA)
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• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Liquid Crystal Substances (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Moulding By Coating Moulds (AREA)

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• 1997
  • 1997-10-15 RU RU99110497A patent/RU2184804C2/ru not_active IP Right Cessation
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  • 1997-10-15 EP EP19970912185 patent/EP0932710B1/de not_active Expired - Lifetime
  • 1997-10-15 AU AU49475/97A patent/AU4947597A/en not_active Abandoned
  • 1997-10-15 WO PCT/EP1997/005676 patent/WO1998017848A1/fr active IP Right Grant
  • 1997-10-15 BR BR9711937A patent/BR9711937A/pt not_active IP Right Cessation
  • 1997-10-15 CA CA 2268789 patent/CA2268789A1/fr not_active Abandoned
  • 1997-10-15 AT AT97912185T patent/ATE200695T1/de not_active IP Right Cessation
  • 1997-10-15 DE DE69704631T patent/DE69704631T2/de not_active Expired - Fee Related
  • 1997-10-15 JP JP51891598A patent/JP4216340B2/ja not_active Expired - Fee Related
  • 1997-10-15 CN CN97180817A patent/CN1086428C/zh not_active Expired - Fee Related
• 1999
  • 1999-04-16 US US09/293,102 patent/US6342296B1/en not_active Expired - Fee Related

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