EP0932710B1 - Wässrige koagulationsmittel für flüssigkristalllösungen auf basis von cellulosehaltigen materialen - Google Patents

Wässrige koagulationsmittel für flüssigkristalllösungen auf basis von cellulosehaltigen materialen Download PDF

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Publication number
EP0932710B1
EP0932710B1 EP19970912185 EP97912185A EP0932710B1 EP 0932710 B1 EP0932710 B1 EP 0932710B1 EP 19970912185 EP19970912185 EP 19970912185 EP 97912185 A EP97912185 A EP 97912185A EP 0932710 B1 EP0932710 B1 EP 0932710B1
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Prior art keywords
tex
coagulating agent
cellulose
solution
spinning
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French (fr)
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EP0932710A1 (de
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Jean-Paul Meraldi
Rima Huston
Vlastimil Cizek
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Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
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Michelin Recherche et Technique SA Switzerland
Michelin Recherche et Technique SA France
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    • 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 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 fiber new cellulosic with an unexpected combination of mechanical characteristics.
  • Patent application PCT / CH85 / 00065 published under the number W085 / 05115, or the patents equivalents EP-B-179 822 and US-A-4 839 113, describe obtaining spinning solutions at cellulose formate base, by reaction of cellulose with formic acid and acid phosphoric, these solutions having a liquid crystal state. These documents describe also spinning these solutions, using the so-called "dry-jet-wet spinning" technique, to obtaining cellulose formate fibers, as well as regenerated cellulose fibers at from these formate fibers.
  • Patent application PCT / CH95 / 00206 published under the number WO96 / 09356, describes a means to directly dissolve cellulose without formic acid in a solvent agent so to obtain a liquid-crystal solution, this solvent agent containing more than 85% by weight of minus a phosphoric acid.
  • the fibers obtained after spinning this solution are fibers made of non-regenerated cellulose.
  • fibers of cellulose described in these two applications WO85 / 05115 and WO96 / 09356 are characterized by a much more ordered or oriented structure, due to the liquid crystal character of 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. which require special safety measures. Such disadvantages are not incidentally not specific to acetone, but in fact common to many organic solvents used in the spinning industry, in particular as coagulating agents.
  • Such values from 30 to 40 cN / tex are in any case lower to the known toughness of a conventional rayon type fiber (40-50 cN / tex), however obtained from a non-liquid crystal spinning solution, i.e. optically isotropic.
  • a first object of the present invention is to propose a new coagulating agent, based water, more advantageous from an industrial point of view than acetone and more effective than water alone, capable of producing fibers whose tenacity and modulus properties are clearly improved over those of fibers coagulated simply with water.
  • the invention also relates to a method of 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 fiber conventional rayon, has a toughness at least equal if not greater, resistance to comparable fatigue, all combined with an initial module in significantly higher extension.
  • Figure 1 shows diagrams of "Fick" diagrams, while Figure 2 reproduces such diagrams recorded both for a coagulating agent according to the invention (K p and K d ) and for water alone (K pe and K de ).
  • the degree of substitution (noted DS) of the fibers regenerated from a cellulose derivative is measured in a known manner, as indicated below : about 400 mg of fiber are cut into pieces 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 soda (1N NaOH). The whole is mixed at room temperature, for 15 minutes. The cellulose is thus completely regenerated by transforming into groups hydroxyl the last substituent groups which had resisted the regeneration treatment on continuous fibers. The excess soda is titrated with a hydrochloric acid solution decinormal (0.1 N HCl), and the degree of substitution is deduced from this.
  • DS degree of substitution
  • the isotropy or optical anisotropy of the solutions is determined by placing a drop of solution to study between crossed linear polarizer and analyzer of an optical microscope polarization, then by observing this solution at rest, that is to say in the absence of constraint dynamic, at room temperature.
  • an optically anisotropic solution also called liquid crystal
  • a solution optically isotropic that is to say which is not liquid-crystal, is a solution which, in the same observation conditions, does not have the above depolarization property, the microscope field remaining black.
  • fibers is meant here multifilament fibers (also called “spun”), constituted in a known manner a large number of elementary filaments of small diameter (small title). All of the following mechanical properties are measured on fibers which have been subject to prior conditioning.
  • Pre-conditioning means the fiber storage 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 %).
  • prior conditioning makes it possible to stabilize their humidity at an equilibrium level of less than 15% by weight of dry fiber.
  • the titer of the fibers 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 1000 m of fiber).
  • Tenacity (force-breaking divided by the title), noted T, and the initial module in extension, noted Mi, are indicated in cN / tex (centinewton per 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 in percentage (%).
  • Coagulation mechanisms in the case of a ternary system (polymer / solvent / agent coagulant) have been described in the literature, for example in Textile Research Journal, Sept. 1966, pp. 813-821, for solutions of polyamides in sulfuric acid.
  • coagulating agent in known manner an agent capable of coagulating a solution, that is to say an agent capable of rapidly precipitating the polymer in solution, in other words to quickly separate it from its solvent; the coagulating agent must be both a non-solvent for the polymer and a good solvent for the solvent for the polymer.
  • the diffusion front corresponds to a simple progression of the coagulating agent in the solution, without precipitation cellulosic materials, while the precipitation front corresponds to coagulation proper, that is to say the precipitation of cellulosic materials under the action of the coagulating agent, the intermediate zone between the two fronts being simply impregnated, swollen by the coagulating agent but not yet coagulated (dark area under polarized light, with loss of liquid-crystal coloring).
  • the two fronts described above therefore correspond to two factors, the diffusion factor K d (1st front, of diffusion) and the precipitation factor K p (2nd front, of precipitation), K p being at most equal to Kd when the front of precipitation is advancing as fast as the diffusion front; in other words, there exist for a time "t i " given two displacement values, "d d " for the diffusion, "d p " for the precipitation, with d p ⁇ d d .
  • the experimental study of coagulation, in a static system, is carried out using a polarization optical microscope or a differential interference optical microscope (Olympus type BH2), equipped with a video camera.
  • a little liquid-crystal solution is spread out, for example using a spatula tip, on a slide and then covered with a cover glass, the thickness of solution under the cover glass being calibrated to the thickness of said strip (lens correction), for example 0.170 mm; we put then the coagulating agent in contact with this sample of solution, by depositing, for example at using a pipette or syringe, said agent around the coverslip in quantity sufficient to cover the entire area around the sample.
  • a constant level of said additive in the coagulating agent is used for the test 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 (K p / K d ) is determined from the slopes of the diffusion line D (slope K d ) and the precipitation line P (slope K p ).
  • bar test A simple test called "bar test” is used to determine the resistance to fatigue fibers studied.
  • a short section of fiber (length of at least 600 mm) which has been subject to prior conditioning, the test being carried out at room temperature (about 20 ° C).
  • This section subjected to a tension of 0.25 cN / tex thanks to a constant weight attached to one of its free ends, is stretched over a polished steel bar, and bent around it the latter at an angle of curvature of about 90 degrees.
  • a mechanical device to which is fixed the other end of the fiber section ensures the forced and repeated sliding of the fiber on the polished steel bar, in a linear reciprocating frequency movement (100 cycles per minute) and amplitude (30 mm) determined.
  • the vertical plane containing the fiber axis is is always approximately 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.
  • ⁇ F 100 [F 0 - F 1 ] / F 0 F 0 being the breaking strength of the fiber before fatigue and F 1 its breaking strength after fatigue.
  • liquid-crystal solutions are prepared in a known manner, by dissolving the materials cellulosics in a solvent or a suitable 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 hears an optically anisotropic solution at room temperature (around 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 belonging more preferentially to the group consisting of formic acid, acetic acid, acids phosphorics, or mixtures of these acids.
  • the starting cellulose can be in various known forms, in particular under form of a powder, prepared for example by spraying a cellulose plate in the state gross.
  • its initial water content is less than 10% by weight
  • its DP (degree polymerization) is between 500 and 1000.
  • Kneading means suitable for obtaining a solution are known to man of the trade: they must be able to knead, knead properly, preferably at a speed adjustable, cellulose and acids until the solution is obtained.
  • Mixing can be leads for example in a mixer comprising arms in Z, or in a screw mixer continuously.
  • These mixing means are preferably equipped with an evacuation device vacuum and a heating and cooling device to adjust the temperature of the mixer and its contents, for example to speed up the dissolution, or control the temperature of the solution being formed.
  • the mode can be used following procedure: introduced into a double jacket mixer, comprising arms Z and an extrusion screw, a suitable mixture of orthophosphoric acid (99% crystalline) and formic acid. Cellulose powder is then added (the humidity of which is in equilibrium with ambient air humidity); 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.
  • a solution in accordance with the request WO96 / 09356 we can proceed in the same way, replacing formic acid for example with an acid polyphosphoric.
  • the solutions thus obtained are ready to spin, they can be transferred directly, by example by means of an extrusion screw placed at the outlet of the mixer, towards a spinning machine to be spun there, with no further processing other than operations usual such as degassing or filtration steps for example.
  • the solution is transferred so known to a spinning block where it supplies a spinning pump. From this pump spinning, the solution is extruded through at least one die, preceded by a filter. During from the path to the die, the solution is gradually brought to the temperature of desired wiring.
  • Each die can include a variable number of extrusion capillaries, for example a single capillary in the form of a slit for spinning a film, or in the case of a fiber several hundreds of 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 slit for spinning a film, or in the case of a fiber several hundreds of 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 number variable of elementary liquid veins.
  • the solutions are spun according to the technique called “dry-jet-wet-spinning" using a non-coagulating fluid layer, in general air (“air-gap”), placed between the die and the coagulation means.
  • air-gap air
  • Each liquid vein elementary is stretched in this air-gap, by a factor generally between 2 and 10 (factor before drawing into the coagulation zone, the thickness of the air-gap can vary to a large extent, depending on the particular spinning conditions, for example from 10 mm to 100 mm.
  • the stretched liquid veins penetrate in 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) in 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 training courses. It is preferable to use a coagulation bath placed under the die, in exit from the non-coagulating layer. This bath is generally extended at its base by a tube vertical cylindrical, called “spinning tube", through which the coagulated fiber passes and the agent circulates coagulant.
  • coagulating agent in accordance with the invention is therefore meant any aqueous solution containing an additive (i.e. a compound or a mixture of compounds) which, added to water in a determined proportion (20% by total weight of coagulating agent), makes it possible to verify the above relationship to coagulation test.
  • an additive i.e. 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 that ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylamine, imidazole, 1-methyl imidazole, morpholine, piperazine, the preferred amines being primary or secondary amines comprising 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) 3 PO4, NaNH 4 HPO 4 , CH 3 COONH 4 , HCOONH 4 .
  • the coagulating agent of the invention verifies the following relationship: K p / K d >0.65; and even more preferably the following relation: K p / K d > 0.75.
  • the increase in the ratio K p / K d is essentially done by a decrease in the factor K d (in general, for water, K d varies from 55 to 65 ⁇ m / s 1 ⁇ 2 ).
  • 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 K p > 20, and even more preferably the relationship K p > 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 / 05115 and WO96 / 09356 mentioned above: diammonic orthophosphate (NH4) 2 HPO4 is then advantageously used.
  • diammonic orthophosphate (NH4) 2 HPO4 is then advantageously used.
  • the additive concentration of 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 conditions particular embodiments of the invention.
  • the temperature of the coagulating agent (noted Tc below), it has been observed that low temperatures, especially around 0 ° C, could in some cases cause the bonding between them of certain filaments during their formation ("married filaments"). This disrupts 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 higher temperature Tc at 10 ° C, more preferably close to room temperature (20 ° C) or higher.
  • a surfactant such as isopropanol or soap based phosphate
  • 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).
  • the total depth of coagulant crossed 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 widely, for example from a few millimeters to several centimeters. However, it was observed that a too small depth of coagulating agent could cause also the formation of "married filaments"; so, preferably, the depth of the agent coagulant is chosen greater than 20 mm.
  • the coagulating agent according to the invention is used in a so-called spinning process of "dry-jet-wet-spinning", as described above, but it could also be used in other spinning processes, for example a so-called “wet-spinning” process, 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, by 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 kept at a temperature below 200 ° C.
  • the washed fiber can also be treated directly, but not dried, through regeneration baths, for example in an aqueous solution of soda, in order to regenerate the cellulose and to end up, after washing and drying, with a fiber regenerated cellulose.
  • a liquid crystal solution of cellulose formate is prepared from 22% cellulose powder (initial DP 600), 61% orthophosphoric acid (99% crystalline) and 17% 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 a known manner) of approximately 480.
  • the solution is then spun, unless otherwise indicated, according to the general conditions described in ⁇ II-2. previous, through a die made up of 250 holes (capillaries of diameter 65 ⁇ m), at a spinning temperature of approximately 50 ° C; the liquid veins thus formed are drawn (spinning drawing factor equal to 6) in a 25 mm air-gap then coagulated with contact with various coagulating agents (depth crossed: 30 mm), whether or not in accordance with the invention without using a surfactant.
  • the cellulose formate fibers thus obtained are washed with water (15 ° C), then sent continuously to a regeneration line, to a speed of 150 m / min, to be regenerated in an aqueous sodium hydroxide solution 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 rate humidity below 15%.
  • a liquid-crystal solution is prepared from cellulose (22%), orthophosphoric acid (66%) and formic acid (12%). After dissolving, the cellulose has a DS of 29% and a DP of 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 (NH 4 ) 2 HPO 4 , with concentrations of additive Ca and varying temperatures Tc.
  • a liquid-crystal solution is prepared from cellulose (24%), orthophosphoric acid (70%) and formic acid (6%). After 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, including the composition, the concentration of Ca additive or the temperature Tc vary.
  • a liquid crystal solution of cellulose is prepared in accordance with the description of the preceding chapter II and with the abovementioned application WO96 / 09356, from 18% of powdered cellulose (initial DP 540), 65.5% of orthophosphoric acid and 16.5% polyphosphoric acid (grading 85% by weight of P 2 O 5 ), that is to say that the cellulose is dissolved directly in the mixture of acids without going through a derivation step.
  • the two acids are mixed beforehand, the acid mixture is cooled to 0 ° C. and then introduced into a Z-arm mixer 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 different, as indicated for test 1 above with the difference, in particular, that it there is no regeneration step. The spinning temperature is 40 ° C, and that of drying at 90 ° C.
  • the coagulating agents in accordance with the invention allow to obtain cellulose fibers, regenerated cellulose or non-regenerated cellulose, the initial modulus and toughness are significantly higher than those obtained using water alone as a coagulating agent.
  • the toughness and the initial module 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 Chapter I previous, and we compared their performance both to that of rayon fibers and those of fibers with very high mechanical properties obtained by spinning liquid crystal solutions identical to those used in the previous four tests, but after coagulation in acetone (in accordance with applications WO85 / 05115 and WO96 / 09356 above).
  • the cellulosic fibers according to 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, from the same liquid-crystal solutions, show a decline which is greater than 30%, generally between 35 and 45%.
  • the cellulosic fibers of the invention therefore have a markedly fatigue resistance higher than that recorded on the fibers obtained from the same liquid-crystal solutions in cellulosic materials, but coagulated in a known manner 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 module significantly higher than that of such a rayon fiber, up to 2000 cN / tex and more.
  • This fiber according to the invention is advantageously a cellulose fiber regenerated from cellulose formate, the degree of substitution of 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 realization of the solution; it can also be products allowing for example 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 groups cellulose hydroxyl are substituted by groups other than formate groups, in addition of these, for example ester groups, especially acetate groups, the degree of substitution of cellulose for these other groups preferably being less than 10%.
  • the fibers of the invention are of industrial interest both in the field of fibers and in that of textile fibers.

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

Claims (19)

  1. Koagulationsmittel für flüssigkristalline Lösungen auf der Basis von Cellulosematerial, gekennzeichnet durch folgende Punkte:
    es enthält Wasser und mindestens einen Zusatz;
    wenn es mit der Lösung in Kontakt gebracht wird, sind die Kinetik der Diffusion des Koagulationsmittels in der Lösung und die Kinetik des Fällens des Cellulosematerials durch die Einwirkung des Mittels, die unter dem Mikroskop im "Koagulationstest" bei einem Gehalt des Zusatzes von 20 Gew.-% bestimmt werden, durch die folgende Beziehung gegeben: 0,55<Kf/Kd≤1,
    wobei Kd bzw. Kf den Diffusionskoeffizienten bzw. Fällkoeffizienten (Steigungen der "Fick" Geraden) in µm/s½ bedeuten.
  2. Koagulationsmittel nach Anspruch 1, gekennzeichnet durch folgende Beziehung: Kf/Kd>0,65.
  3. Koagulationsmittel nach Anspruch 2, gekennzeichnet durch folgende Beziehung: Kf/Kd>0,75.
  4. Koagulationsmittel nach einem der Ansprüche 1 bis 3, gekennzeichnet durch folgende Beziehung: Kf>20.
  5. Koagulationsmittel nach Anspruch 4, gekennzeichnet durch folgende Beziehung: Kf>30.
  6. Koagulationsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Zusatz unter den Formiaten, Acetaten und Phosphaten von Ammonium, den gemischten Salzen dieser Verbindungen oder den Gemischen dieser Bestandteile ausgewählt ist.
  7. Koagulationsmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es sich um eine Spinnlösung auf Celluloseformiat-Basis handelt, wobei das Celluloseformiat in mindestens einer Phosphorsäure gelöst ist.
  8. Koagulationsmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es sich um eine Spinnlösung auf Cellulose-Basis handelt, wobei die Cellulose unmittelbar in mindestens einer Phosphorsäure gelöst ist.
  9. Koagulationsmittel nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, daß der Zusatz das Diammoniumorthophosphat (NH4)2HPO4 ist.
  10. Verfahren zum Verspinnen einer flüssigkristallinen Lösung auf der Basis von Cellulosematerial zur Herstellung von versponnenen Gegenständen, dadurch gekennzeichnet, daß mindestens ein Koagulationsmittel nach einem der Ansprüche 1 bis 9 eingesetzt wird.
  11. Verfahren zum Verspinnen nach Anspruch 10, dadurch gekennzeichnet, daß es sich um ein sogenanntes "dry-jet-wet-spinning"-Verfahren handelt.
  12. Verfahren zum Verspinnen nach einem der Ansprüche 10 oder 11, dadurch gekennzeichnet, daß die Tiefe des Koagulationsmittels, die von dem versponnenen Artikel bei der Bildung durchquert wird, über 20 mm liegt.
  13. Verfahren zum Verspinnen nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, daß die Temperatur des Koagulationsmittels über 10 °C liegt.
  14. Versponnener Gegenstand, der nach einem Verfahren gemäß einem der Ansprüche 10 bis 13 hergestellt ist.
  15. Cellulosefaser mit den folgenden Eigenschaften:
    ihre Bruchfestigkeit B liegt über 40 cN/tex;
    ihr anfänglicher Modul M; liegt über 1200 cN/tex;
    die Abnahme der Reißkraft ΔF nach 350 Ermüdungszyklen im sogenannten "Stabtest" liegt bei einem Kompressionsgrad von 3,5 % und einer Zugspannung von 0,25 cN/tex unter 30 %.
  16. Faser nach Anspruch 15, dadurch gekennzeichnet, daß sie mindestens eine der folgenden Bedingungen erfüllt:
    B > 45 cN/tex;
    Mi > 1500 cN/tex;
    ΔF < 15 %.
  17. Faser nach Anspruch 16, dadurch gekennzeichnet, daß sie mindestens eine der folgenden Bedingungen erfüllt:
    B > 50 cN/tex;
    Mi > 2000 cN/tex.
  18. Faser nach einem der Ansprüche 15 bis 17, dadurch gekennzeichnet, daß sie aus einer aus Celluloseformiat regenerierten Faser besteht, wobei der Substitutionsgrad der Cellulose bezüglich der Formiatgruppen im Bereich von 0 bis 2 % liegt.
  19. Gegenstand aus Kautschuk(en) oder Kunststoff(en) und insbesondere Luftreifen, der mit mindestens einer Cellulosefaser nach einem der Ansprüche 15 bis 18 verstärkt ist
EP19970912185 1996-10-18 1997-10-15 Wässrige koagulationsmittel für flüssigkristalllösungen auf basis von cellulosehaltigen materialen Expired - Lifetime EP0932710B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9612871 1996-10-18
FR9612871 1996-10-18
PCT/EP1997/005676 WO1998017848A1 (fr) 1996-10-18 1997-10-15 Agent coagulant aqueux pour solutions cristal-liquide a base de matieres cellulosiques

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EP0932710A1 EP0932710A1 (de) 1999-08-04
EP0932710B1 true EP0932710B1 (de) 2001-04-18

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EP0932709B1 (de) 1996-10-18 2003-01-29 Michelin Recherche Et Technique S.A. Wässrige koagulationsmittel für flüssigkristalllösungen aus cellulosematerialen
US6836759B1 (en) * 2000-08-22 2004-12-28 Microsoft Corporation Method and system of handling the selection of alternates for recognized words
KR101370200B1 (ko) * 2005-12-23 2014-03-05 바스프 에스이 용융 이온액 기재 용액계, 그의 제조 및 재생 탄수화물의제조를 위한 용도

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CA1133658A (en) * 1979-09-21 1982-10-19 Kenji Kamide Mesophase dope containing cellulose derivative and inorganic acid
AU580060B2 (en) * 1984-04-27 1988-12-22 Michelin Recherche Et Technique S.A. Anisotropic cellulose-ester compositions
MX9701280A (es) * 1994-08-19 1997-05-31 Akzo Nobel Nv Procedimiento para formar productos de extrusion de celulosa.
FR2724662B1 (fr) * 1994-09-19 1997-01-24 Michelin Rech De Tech Sa Solutions cristal-liquide a base de cellulose et d'au moins un acide phosphorique
NL1001692C2 (nl) * 1995-11-20 1997-05-21 Akzo Nobel Nv Werkwijze voor de bereiding van geregenereerde cellulose filamenten.
EP0932709B1 (de) * 1996-10-18 2003-01-29 Michelin Recherche Et Technique S.A. Wässrige koagulationsmittel für flüssigkristalllösungen aus cellulosematerialen
NL1004958C2 (nl) * 1997-01-09 1998-07-13 Akzo Nobel Nv Werkwijze voor het bereiden van cellulose vezels.
JPH10300337A (ja) * 1997-04-24 1998-11-13 Sanyo Electric Co Ltd 貯蔵庫の棚装置
FR2768354B1 (fr) * 1997-09-12 1999-10-22 Usinor Face laterale pour l'obturation de l'espace de coulee d'une installation de coulee continue de bandes metalliques entre cylindres, et installation de coulee ainsi equipee

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CN1241225A (zh) 2000-01-12
CN1086428C (zh) 2002-06-19
BR9711937A (pt) 1999-09-21
DE69704631T2 (de) 2001-08-30
WO1998017848A1 (fr) 1998-04-30
AU4947597A (en) 1998-05-15
ATE200695T1 (de) 2001-05-15
RU2184804C2 (ru) 2002-07-10
JP4216340B2 (ja) 2009-01-28
CA2268789A1 (fr) 1998-04-30
ES2156369T3 (es) 2001-06-16
US6342296B1 (en) 2002-01-29
EP0932710A1 (de) 1999-08-04
DE69704631D1 (de) 2001-05-23

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