WO1997006294A1 - Fibres cellulosiques a allongement rupture ameliore et procedes pour les obtenir - Google Patents
Fibres cellulosiques a allongement rupture ameliore et procedes pour les obtenir Download PDFInfo
- Publication number
- WO1997006294A1 WO1997006294A1 PCT/EP1996/003444 EP9603444W WO9706294A1 WO 1997006294 A1 WO1997006294 A1 WO 1997006294A1 EP 9603444 W EP9603444 W EP 9603444W WO 9706294 A1 WO9706294 A1 WO 9706294A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fiber
- cellulose
- fibers
- formate
- tex
- Prior art date
Links
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
- D01F2/24—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
- Y10T428/29—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 invention relates to fibers of cellulose derivatives and fibers of cellulose regenerated from these derivatives.
- cellulose derivatives is understood here to mean the compounds formed, as a result of chemical reactions, by substitution of the hydroxyl groups of the cellulose, these derivatives also being called substitution derivatives.
- regenerated cellulose means a cellulose obtained by a regeneration treatment carried out on a cellulose derivative.
- the invention relates more particularly to fibers of cellulose formate and to fibers of cellulose regenerated from this formate. as well as the processes for obtaining such fibers.
- Fibers of cellulose formate and fibers of cellulose regenerated from this formate have in particular been described in international patent application WO 85/05115 (PCT / CH85 / 00065), filed by the applicant, or in equivalent patents EP -B-179 822 and US-A-4 839 113.
- These documents describe the obtaining of spinning solutions based on cellulose formate, by reaction of the cellulose with formic acid and phosphoric acid. These solutions are optically anisotropic. that is, they have a liquid crystal state.
- These documents also describe the cellulose formate fibers obtained by spinning these solutions, according to the so-called "dry-jet-wet spinning" technique, as well as the cellulose fibers obtained after a regeneration treatment of these formate fibers.
- the cellulose fibers of the application WO 85/05115 are characterized by a much more ordered structure, due to the liquid-crystal nature of the spinning solutions from which they come. They thus have very high mechanical properties in extension, in particular very high values of toughness and modulus, but, on the other hand, are characterized by rather low elongation at break values, these values being on average between 3 % and 4%. and not exceeding 4.5%.
- the primary object of the invention is to provide fibers in cellulose formate as well as regenerated cellulose fibers which, compared to the fibers of application WO 85/05115, have a significantly improved elongation at break, as well as properties high energy at break.
- the second object of the invention is to obtain the above improvements without reducing the tenacity of the fibers, which is a major advantage of the invention.
- Another object of the invention is to obtain regenerated cellulose fibers from cellulose formate, the fatigue resistance of which, in particular in tires, is significantly improved compared to that of regenerated cellulose fibers on demand.
- WO 85/05115 cited above.
- Ds being the degree of substitution of the cellulose in formate groups (in%)
- Te being its tenacity in cN / tex
- Mi being its initial modulus in cN / tex
- Ar being its elongation at break in%
- Er being its energy at break in J / g.
- the cellulose fiber of the invention regenerated from cellulose formate, is characterized by the following relationships:
- Dg being the degree of substitution of the cellulose for formate groups (in%)
- T E being its toughness in cN / tex
- M I being its initial modulus in cN / tex
- a R being its elongation at break in%.
- E R being its energy at break in J / g.
- the cellulose formate fiber and the regenerated cellulose fiber above are both obtained by novel and specific methods which constitute other objects of the invention.
- the spinning process of the invention for obtaining the cellulose formate fiber of the invention, consisting in spinning a solution of cellulose formate in a solvent based on phosphoric acid, according to the so-called “dry” spinning method -jet-wet spinning ", is characterized in that the coagulation step of the fiber and the neutral washing step of the coagulated fiber are both carried out in acetone.
- the regeneration process of the invention for obtaining the regenerated cellulose fiber of the invention, consisting in passing a cellulose formate fiber through a regenerating medium, washing it and then drying it, is characterized in that the regenerating medium is an aqueous sodium hydroxide solution (NaOH) whose sodium hydroxide concentration, denoted Cs, is greater than 16% (% by weight).
- NaOH aqueous sodium hydroxide solution
- the invention further relates to the following products:
- the reinforcement assemblies each comprising at least one fiber according to the invention, for example cables, plies, fibers
- reinforcement assemblies which can be for example hybrid, that is to say composite, comprising elements of different natures, possibly not in accordance with the invention
- the articles reinforced with at least one fiber and / or an assembly in accordance with the invention are for example articles made of rubber or plastics, for example plies, belts, pipes, tire casings, in particular tire carcass reinforcements.
- the degree of polymerization is noted DP.
- the DP of the cellulose is measured in a known manner, this cellulose being in the form of a powder, or previously transformed into a powder.
- the inherent viscosity (IV) of the cellulose in solution is first determined, according to Swiss standard SNV 195 598 of 1970, but at different concentrations which vary between 0.5 and 0.05 g / dl.
- the inherent viscosity is defined by the equation:
- the intrinsic viscosity [ ⁇ ] is then determined by extrapolation at zero concentration of the inherent viscosity IV.
- the weight average molecular mass M w is given by the Mark-Houwink relation:
- the solution is first coagulated with water in a dispersing device. After filtration and washing with acetone, a powder is obtained which is then dried in a vacuum oven at 40 ° C for at least 30 minutes. After isolating the formate, the cellulose is regenerated by treating this formate at reflux with normal sodium hydroxide. The cellulose obtained is washed with water, dried and the DP is measured as described above.
- the degree of substitution of cellulose for cellulose formate is also called the degree of formylation.
- the degree of substitution determined by the method described here gives the percentage of alcohol functions of the cellulose which are esterified, that is to say transformed into formate groups. This means that a degree of substitution of 100% is obtained if the three alcohol functions of the cellulose unit are all esterified. or that a degree of substitution of 30%, for example, is obtained if 0.9 out of three alcohol functions, on average, is esterified.
- the degree of substitution is measured differently depending on whether one characterizes cellulose formate (formate in solution, or fibers in formate) or cellulose fibers regenerated from cellulose formate.
- this formate is first isolated from the solution as indicated previously in paragraph I-1. If it is measured on formate fibers, these fibers are first cut into pieces 2 to 3 cm long.
- cellulose formate thus prepared is weighed with precision and placed in an Erlenmeyer flask. 40 ml of water and 2 ml of normal sodium hydroxide (1 N NaOH) are added. The mixture is heated at 90 ° C. at reflux for 15 minutes under nitrogen. The cellulose is thus regenerated by retransforming the formate groups into hydroxyl groups. After cooling, the excess soda is titrated back with a solution of decinormal hydrochloric acid (0.1 N HCl), and the degree of substitution is thus deduced therefrom.
- decinormal hydrochloric acid 0.1 N HCl
- the degree of substitution is noted Ds when it is measured on cellulose formate fibers.
- D S degree of substitution
- 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 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 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 EN 20139 (temperature of 20 ⁇ 2 ° C; hygrometry of 65 ⁇ 2%).
- 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 of the fibers are measured in known manner using a tensile machine
- the fibers after having received a slight preliminary protective twist (helix angle of approximately 6 °), undergo a traction over an initial length of 400 mm at a speed of 200 mm / min (or at a speed of 50 mm / min only when their elongation at break does not exceed 5%). All the results given are an average of 10 measurements.
- the toughness (breaking force divided by the title) and the initial modulus are indicated in cN / tex (centinewton per tex - reminder: 1 cN / tex equal to approximately 0.11 g / den (gram per denier)).
- the initial modulus is defined as the slope of the linear part of the Force-Elongation curve, which occurs just after the standard pretension of 0.5 cN / tex.
- the elongation at break is indicated as a percentage.
- the energy at break is given in J / g (joule per gram), that is to say per unit mass of fiber.
- Cellulose formate solutions are made by mixing cellulose, formic acid, and phosphoric acid (or an acid-based liquid
- the cellulose can be in different forms, in particular in the form of a powder, prepared for example by spraying a plate of raw cellulose.
- its initial water content is less than 10% by weight, and its DP between 500 and 1000.
- Formic acid is esterification acid, phosphoric acid (or liquid based on phosphoric acid) being the solvent for cellulose formate, called “solvent” or “spinning solvent” in the description below. -after.
- solvent or solvent for cellulose formate
- phosphoric used is orthophosphoric acid (H 3 PO 4 ), but one can use other phosphoric acids, or a mixture of phosphoric acids.
- the phosphoric acid can, depending on the case, be used solid, in the liquid state, or dissolved in formic acid.
- the water content of these two acids is less than 5% by weight; they can be used alone or optionally contain, in small proportions, other organic and / or mineral acids, such as acetic acid, sulfuric acid or hydrochloric acid for example.
- the cellulose concentration of the solution can vary to a large extent; concentrations C of between 10% and 30% (% by weight of cellulose - calculated on the basis of non-esterified cellulose - on the total weight of the solution) are for example possible, these concentrations being in particular a function of the degree of polymerization cellulose.
- phosphoric can also be adjusted within a wide range.
- cellulose formate When making cellulose formate, the use of formic acid and phosphoric acid makes it possible to obtain both a high degree of substitution for cellulose formate, generally greater than 20%, without excessive reduction the initial degree of polymerization of the cellulose, as well as a homogeneous distribution of these formate groups, both in the amorphous zones and in the crystalline zones of the cellulose formate.
- 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.
- solution is meant here, in a known manner, a homogeneous liquid composition in which no solid particle is visible to the naked eye.
- 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.
- Cellulose powder (the humidity of which is in equilibrium with the ambient humidity of the air) is introduced into a double-jacket mixer, comprising Z-shaped arms and an extrusion screw.
- a mixture of orthophosphoric acid (99% crystalline) and formic acid is then added, containing for example three quarters of orthophosphoric acid per quarter of formic acid (parts by weight).
- 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.
- the spinning 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 further processing. prior to usual operations such as degassing or filtration steps for example.
- the spinning solutions used for implementing the invention are optically anisotropic solutions.
- these spinning solutions have at least one of the following characteristics:
- the concentration of phosphoric acid is between 50% and 75% (% by weight); the degree of substitution of the cellulose for formate groups in the solution is between 25% and 50%, more preferably between 30% and
- the degree of polymerization of the cellulose, in solution is between 350 and 600;
- the spinning solutions are spun according to the so-called “dry-jet-wet-spinning” technique: this technique uses a non-coagulating fluid layer, generally air, placed at the outlet of the die, between the die and the means of coagulation.
- a non-coagulating fluid layer generally air
- the spinning solution is transferred to the 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. It is during the journey to the die that the solution is gradually brought to the desired spinning temperature, generally between 35 ° C and 90 ° C, depending on the nature of the solutions, preferably between 40 ° C and 70 ° C.
- the term "spinning temperature” therefore means the temperature of the spinning solution at the time of its extrusion through the die.
- Each die can include a variable number of extrusion capillaries, this number being able to vary for example from 50 to 1000.
- the capillaries are generally of cylindrical shape, their diameter being able to vary for example from 50 to 80 ⁇ m
- a liquid extnidate which consists of a variable number of elementary liquid veins.
- Each elementary liquid vein is stretched (see below spinning drawing factor) in a non-coagulating fluid layer, before entering the coagulation zone.
- This non-coagulating fluid layer is generally a layer of gas, preferably air, the thickness of which can vary from a few mm to several tens of mm (millimeters), for example from 5 mm to 100 mm, depending on the conditions. specific spinning; in known manner, the thickness of the non-coagulating layer is understood to mean the distance separating the underside of the die, arranged horizontally, and the entry to the coagulation zone (surface of the coagulating liquid).
- the temperature of the coagulating medium, noted Tc is not a critical parameter for the implementation of the invention.
- Tc temperature of the coagulating medium
- Tc a negative temperature
- the temperature Tc will be chosen the lower the lower the concentration C of the spinning solution.
- the level of spinning solvent in the coagulating medium is preferably stabilized at a level of less than 15%, even more preferably less than 10% (% by weight of coagulating medium).
- the coagulation means to be used are known devices, composed for example of baths, pipes and / or cabins, containing the coagulating medium 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 the coagulating medium circulates.
- the depth of the coagulating medium in the coagulation bath measured from the entry of the bath to the entry of the spinning tube, can vary from a few millimeters to a few centimeters for example, depending on the particular conditions of implementation of
- the coagulation bath can be extended if necessary by additional coagulation devices, for example by other baths or cabins, placed at the outlet of the spinning tube, for example after a horizontal deflection point.
- the method of the invention is implemented so that at least one of the following characteristics is verified: a) the rate of residual solvent in the fiber, at the outlet of the coagulation means (denoted Rs) , is less than 100% by weight of dry formate fiber; b) the stress of tension undergone by the fiber, at the exit of the means of
- ⁇ c coagulation
- the fiber is left in contact with the coagulating medium until a significant portion of spinning solvent is extracted from the fiber.
- an effort is made to maintain the tensions undergone by the fiber at a moderate level: to control this, these tensions will be measured immediately at the output of the coagulation means, using tensiometers appropriate.
- the invention will preferably be implemented so that the following two relationships are verified:
- the procedure is for example as follows: fiber is taken at the outlet of the coagulation means, with its coagulating medium; then it is wiped on the surface with absorbent paper, without pressure, so as to eliminate most of the coagulating medium (acetone) which is contained in the surface layer surrounding the fiber, and which itself contains a certain fraction of solvent of spinning (phosphoric acid or liquid based on phosphoric acid) already extracted from the fiber; the fiber is then washed completely with water, in a laboratory device, so as to completely extract the phosphoric acid which it contains, then this phosphoric acid is titrated in return with sodium hydroxide; for more precision, the measurement is repeated 5 times and the average is calculated.
- the fiber is taken up on a device
- the speed of the spun product, on this drive device is called “spinning speed” (or also calling or driving speed): it is the speed of travel of the fiber through the spinning installation. , once the fiber is formed.
- the ratio between the spinning speed and the speed of extrusion of the solution through the die defines what is known, in known manner, the drawing stretch factor (abbreviated as FEF), which is for example between 2 and 10.
- neutral washing is meant any washing operation making it possible to extract all or almost all of the spinning solvent from the fiber.
- water is indeed the "natural" swelling medium of the fibers of cellulose or of cellulose derivatives (see for example example US-A-4,501,886), and therefore the medium likely to offer, a priori, the best washing efficiency.
- the patents or patent applications EP-B-220642, US-A-4,926,920, WO 94/17136 like the aforementioned application WO 85/05115 (page 72, examples II-1 and following) , describe the use of water, at the outlet of the coagulation means, for washing fibers of cellulose formate.
- acetone used as a washing medium despite a washing power which is, in known manner, significantly lower than that of water, leads to fibers which have a once completed (ie washed until neutral, then dried), very markedly improved properties, as regards firstly their elongation at break, when they are compared to the fibers described in application WO 85/05115.
- the step of coagulating the fiber and the step of neutral washing of the coagulated fiber must both be carried out in acetone.
- the temperature of the washing acetone is not a critical parameter of the process. It goes without saying, however, that excessively low temperatures are avoided so as to favor the washing kinetics.
- the temperature of the washing acetone denoted T1
- T1 will be chosen positive (by this is meant a temperature equal to or greater than 0 ° C), and even more preferably greater than + 10 ° C.
- washing means can be used, consisting for example of baths containing washing acetone and in which the fiber to be washed flows.
- the washing times in acetone can vary, typically, from a few seconds to a few tens of seconds, depending on the particular conditions of implementation of the invention.
- both the washing medium and the coagulating medium may contain constituents other than acetone, without the spirit of the invention being modified, provided that these other constituents are present only in minor proportion. ; the total proportion of these other constituents will preferably be less than 15%, more preferably less than 10% (% by total weight of coagulating medium or of washing medium). More particularly, if water is present in the coagulation or washing acetone, its content will preferably be less than 5%.
- the cellulose formate fiber is dried by any suitable means, in order to remove the washing acetone.
- the level of acetone at the outlet of the drying means is adjusted to a rate of less than 1% by weight of dry fiber.
- the drying operation one can operate for example by continuously scrolling the fiber on heating rollers, or use, as a main or
- a drying temperature at least equal to 60 ° C is used, more preferably between 60 ° C and 90 ° C.
- the method of the invention can be implemented in a very wide range of spinning speeds, which can vary from several tens to several hundred meters per minute, for example to 400 m / min or 500 m / min, or even more .
- the spinning speed is at least equal to 100 m / min, more preferably at least equal to 200 m / min.
- the washing step will preferably be carried out so as to that the level of residual spinning solvent in the finished fiber, ie washed and dried, does not exceed 0.1% to 0.2% by weight, relative to the weight of dry fiber.
- the cellulose formate fiber thus spun can also be sent directly to the regeneration means, online and continuously, in order to prepare a regenerated cellulose fiber.
- a process for regenerating a fiber into a cellulose derivative consists in treating this fiber in a regenerating medium so as to eliminate almost all of the substituent groups (so-called saponification treatment), in washing the fiber thus regenerated, then to dry it, these three operations being in principle carried out continuously on the same treatment line called "regeneration line".
- the regenerating medium usually used is an aqueous solution of soda (sodium hydroxide NaOH) weakly concentrated, containing only a few% soda (% by weight), for example from 1 to 3% (see for example PCT / AU91 / 00151).
- soda sodium hydroxide NaOH
- the Applicant has found that the filaments of the cellulose formate fibers (whether or not they conform to the invention) undergo partial, superficial dissolution, as soon as that the sodium hydroxide concentration reached and exceeded approximately 6% by weight, the regenerating medium then becoming a true solvent for cellulose formate.
- Such dissolution, even partial, is completely detrimental to the mechanical properties of the fiber: presence of bonded filaments, drop in resistance of the attacked filaments, difficulties in washing the fiber, etc.
- the process of the invention for obtaining a regenerated cellulose fiber according to the invention, by regeneration of a cellulose formate fiber, is characterized in that the regenerating medium is an aqueous solution of highly concentrated sodium hydroxide, the concentration of soda, noted Cs, is greater than 16% (% by weight).
- a concentration Cs greater than 18% is used, and even more preferably, a concentration of between 22% and 40%; it has in fact been found that such concentration ranges were, as a general rule, more particularly beneficial to the elongation at break of the regenerated fiber, the optimal concentration range being between 22% and 30%.
- the regeneration process of the invention it is preferably started from a cellulose formate fiber according to the invention, having in particular an elongation at break Ar greater than 6%.
- the regeneration line consists concretely, and conventionally, of regeneration means, followed by washing means, themselves followed by drying means. All these devices are not critical for the implementation of the invention, and those skilled in the art will be able to define them without difficulty.
- the regeneration and washing means may consist in particular of baths, pipes, tanks, cabins, in which the regenerating medium or the washing medium circulate. It is possible, for example, to use cabins each equipped with two motorized cylinders around which the fiber to be treated is wound, this fiber then being showered with the liquid medium used (regenerating or washing).
- the residence times in the regeneration means will of course have to be adjusted so as to regenerate the formate fibers substantially, and thus to verify the following relationship on the final regenerated fiber:
- the washing medium is preferably water. Indeed, after the operation of
- the cellulose fiber can be washed with its natural swelling medium, that is to say with water, the latter having the best washing efficiency.
- Water is used at room temperature, or at a higher temperature, if necessary, to increase the washing kinetics.
- a neutralizing agent for the soda not consumed for example formic acid.
- the drying means may consist, for example, of ventilated heating tunnels through which the washed fiber circulates, or alternatively in heating cylinders on which the fiber is wound.
- the drying temperature is not critical, and can vary over a wide range, in particular from 80 ° C. to 240 ° C. or more, depending on the particular conditions of implementation of the invention, in particular according to the speeds. of passage on the regeneration line. Preferably a temperature not exceeding 200 ° C is used.
- the fiber is taken from a take-up reel, and its residual moisture level is checked.
- the drying conditions temperature and duration
- the residual humidity level is between 10% and 15%, even more preferably of the order of 12% to 13% by weight of dry fiber.
- the washing and drying times required vary from a few seconds to a few tens of seconds, depending on the means employed and the particular conditions for carrying out the invention.
- the tension stresses at the input of the regeneration means, washing means and drying means will preferably be chosen lower. at 10 cN / tex. and even more preferably less than 5 cN / tex.
- the regeneration speed (denoted Vr), that is to say the speed of passage of the fiber through the regeneration line, can vary from several tens to several hundred meters per minute, for example up to 400 or 500 m / min or more; advantageously, this speed Vr is at least equal to 100 m / min, more preferably at least equal to 200 m / min.
- the regeneration method of the invention is preferably implemented in line and continuously with the spinning method of the invention, in such a way that the entire production chain, from the extrusion of the solution through the until the regenerated fiber is dried, or uninterrupted.
- the tests described below can be either tests in accordance with the invention, or tests not in accordance with the invention.
- a total of 14 spinning tests of cellulose formate fibers are carried out, according to the spinning process of the invention, and in particular conforming to the
- the coagulation step and the neutral washing step of the coagulated fiber are both carried out in acetone.
- Table 1 gives both the specific conditions for carrying out the process of the invention, and the properties of the fibers obtained.
- Test No . test number (referenced from A-1 to A-14);
- N number of filaments of the fiber
- Vf spinning speed (in m / min);
- Tc temperature of the coagulating medium (in ° C);
- ⁇ c tension stress undergone by the fiber at the exit of the coagulation means (in cN / tex);
- Te fiber tenacity (in cN / tex);
- Mi initial fiber modulus (in cN / tex);
- Ds degree of substitution of cellulose for formate groups. in fiber (in%);
- these solutions contain (% by weight) from 16 to 22% of cellulose, from 60 to 65% of phosphoric acid, and from 18 to 19% of formic acid (total), the weight ratio (formic acid / phosphoric acid ) initial being approximately 0.30;
- the degree of substitution of the cellulose in the solutions is between 40 and 45% for the solutions containing 16% by weight of cellulose, between 30 and 40% for the other more concentrated solutions;
- the channels include 500 or 1000 capillaries of cylindrical shape, with a diameter of 50 or 65 ⁇ m;
- the spinning temperatures are between 40 and 50 ° C;
- the FEF values are between 2 and 6 (between 2 and 4 for tests A-1, A-5 to A-9, A-14; between 4 and 6 for other tests);
- the non-coagulating fluid layer consists of an air layer (thickness varying from 10 to 40 mm depending on the tests);
- the level of phosphoric acid in the coagulating medium is stabilized at a level of less than 10% (% by weight of coagulating medium);
- the temperature of the washing acetone (Tl) is always positive, between 15 and 20 ° C;
- the drying of the fiber is carried out at 70 ° C, by passage over heating cylinders, with in addition a blowing of nitrogen heated to 80 ° C; the acetone level at the outlet of the drying means is less than 0.5% (% by weight of dry fiber);
- the residual phosphoric acid level is less than 0.1% (% by weight of dry fiber).
- the DP of the cellulose, in the solution is between 400 and 450, which shows in particular a low depolymerization after dissolution.
- the values of Ds are between 25 and 50%. It can be seen that in these examples, they are all between 30 and 45%: in practice, they are identical to the values of degrees of substitution measured on the spinning solutions.
- the neutral washing step of the coagulated fiber is carried out with water (as in the request WO 85/05115 cited above), and not with acetone.
- This washing water is industrial water, at a temperature close to 15 ° C.
- the fibers contain 250 to 1000 filaments.
- Table 2 gives both the specific conditions for carrying out the process of the invention, and the properties of the fibers obtained.
- the abbreviations and the units used in this table 2 are the same as for the previous table 1.
- these fibers of table 2 can have quite interesting characteristics of tenacity and initial modulus; in particular, after a conventional regeneration step according to the prior art (weakly concentrated aqueous NaOH solution), they can be transformed into regenerated fibers having very high toughness (110 to 120 cN / tex, or even more) combined with very high initial modulus values (3000 to 3500 cN / tex, or even more).
- a total of 23 regeneration tests of cellulose formate fibers are carried out, in accordance with the regeneration process of the invention, according to the indications provided in paragraph II-3 above.
- the regenerating medium is an aqueous sodium hydroxide solution, the Cs concentration of which is in all cases greater than 16%.
- Table 3 gives both specific conditions for carrying out the process of the invention, and the properties of the fibers obtained.
- Test No . test number (referenced from C-1 to C-23);
- N number of filaments of the regenerated fiber
- Cs concentration of sodium hydroxide in the regenerating medium (% by weight);
- Vr regeneration speed (in m / min);
- T I title of the fiber (in tex);
- T E tenacity of the fiber (in cN / tex);
- a R elongation at break of the fiber (in%)
- the starting cellulose formate fibers a sample of which (a few hundred meters) was systematically taken at the outlet of the spinning means, to check their mechanical properties, all conform to the invention; in particular, they all have a
- the regenerating medium used is at room temperature (about 20 ° C);
- the regeneration, washing, and drying means consist of cabins equipped with motorized cylinders on which the fiber to be treated is wound;
- the regeneration speed Vr indicated in table 3 (from 55 to 200 m / min) is therefore equal to the spinning speed Vf;
- the drying of the washed fiber is carried out on heating cylinders, at different temperatures varying from 80 ° C to 240 ° C, according to the specific scheme below: from 80 ° C to 120 ° C for tests C-2, C-3, C-5, C-10, C-17; at 240 ° C for test C-11; from 160 ° C to 190 ° C for the other tests;
- the residence times in the regeneration means are of the order of
- the fibers At the outlet of the drying means, the fibers have a residual moisture content of the order of 12% to 13% (% by weight of dry fiber).
- their elongation at break A R is greater than 7% (examples C-4 to C-11, C-13 to C-16, C-19 and C-20), even more preferably greater than 8% (example C-4).
- the filamentary title (title of the fiber T I divided by the number N of filaments) is equal to approximately 1.8 dtex (decitex) (most common filamentary title for cellulosic fibers)
- the latter can vary to a large extent, for example from 1.4 dtex to 4.0 dtex, or even more, by adjusting the spinning conditions in known manner.
- the regenerated fibers of tests Cl 9 and C-20 have, respectively, a
- a total of 9 regeneration tests of cellulose formate fibers (referenced from D-1 to D-9) are carried out, according to a regeneration process not in accordance with the invention.
- the regeneration conditions are the same as those used for the fibers in accordance with the invention of table 3 above, with one exception: the regenerating medium is an aqueous sodium hydroxide solution whose Cs soda concentration is at most equal to 16% .
- Table 4 gives both the specific conditions for carrying out the process of the invention, and the properties of the fibers obtained.
- the abbreviations and the units used in this table 4 are the same as for the previous table 3.
- each filament is constituted at least in part by layers nested one inside the other surrounding the axis of the filament; it is further noted that in each layer, in general, the optical direction and the direction of crystallization vary quasi-periodically along the axis of the filament.
- Such a structure or morphology is commonly described in the literature under the name of "band structure”.
- the regenerated cellulose fibers of the invention have many other advantages when compared with the fibers described in the aforementioned basic application WO 85/05115 on the one hand, with conventional fibers of the type radiates on the other hand.
- the fibers of the invention Compared with the fibers described in basic application WO 85/05115, the fibers of the invention notably have a very significantly improved fatigue resistance, both in laboratory test and in pneumatic rolling.
- the fatigue resistance can be analyzed by subjecting assemblies of these fibers to various known laboratory tests, in particular to the fatigue test known under the name of "Disc Fatigue Test"(see for example US 2,595,069, standard ASTM D885-591 revised 67T).
- This test which is well known to those skilled in the art (see for example US 4,902,774), essentially consists in incorporating plied fibers of the fibers to be tested, previously glued, in rubber blocks, then, after baking, to tire the gum test tubes. thus formed in compression, between two rotating discs, a very large number of cycles (for example between 100,000 and 1,000,000 cycles). After fatigue, the plies are extracted from the test pieces and their residual breaking strength is compared to the breaking strength of control plies extracted from non-tired test pieces.
- the fibers of the invention compared to the fibers of basic application WO 85/05115, systematically show clearly improved endurance on the "Disc Fatigue Test".
- fibers according to the invention having a preferred elongation at break greater than 7%, as well as fibers according to application WO 85/05115, all having an elongation at break less than 5%, have been assembled to form plied (type "A” and "B", respectively) having the same formula 180x2 (tex) 420/420 (t / m).
- each ply consists of two yarns (multifilament fibers), each having a count of 180 tex before twisting, which are first twisted individually at 420 rpm in one direction during a first step, then twisted the two together at 420 rpm in the opposite direction during a second step.
- the helix angle is approximately 27 ° and the coefficient of torsion (or torsional factor) K is approximately 215, with:
- twists of type "A” (according to the invention) and of type “B” (according to WO 85/051 15) were subjected to the "Disc Fatigue Test" above (6 hours at 2700 cycles / min, with a maximum compression rate of the test piece of approximately 16% in each cycle); the following force-breaking lapses were recorded on the extracted twists (data in relative values, with a base 100 for the maximum lapsing recorded on a type “B” plied):
- the fatigue resistance of the regenerated fibers of the invention is therefore significantly improved - by a factor of two to three on average - compared to the regenerated fibers of the initial application WO 85/05115.
- the capacity of technical fibers to reinforce tires can be analyzed, in a known manner, by reinforcing a rubber sheet with plies of the fibers to be tested, previously glued, by incorporating the fabric thus formed in a tire structure, for example in a carcass ply reinforcement, then subjecting the tire thus reinforced to a rolling test.
- Such rolling tests are widely known to those skilled in the art, they can for example be implemented on automatic machines making it possible to vary a large number of parameters (pressure, load, temperature, etc.) during rolling. .
- the plies are extracted from the tire tested, and their residual breaking strength is compared to that of control plies extracted from control tires which have not been rolled.
- the fibers of the invention when used to reinforce a radial tire carcass, show an endurance which is significantly improved compared to the fibers according to WO 85/05115.
- the fibers according to the prior art did not resist (rupture of the plies of type "B" above), due to particularly severe driving conditions, the fibers of the invention
- the regenerated fibers of the invention have other quite advantageous characteristics compared to conventional rayon fibers.
- the resistance to humidity of cellulosic fibers can be analyzed using various known tests, a simple test consisting for example of completely soaking the fibers in a water bath, for a determined time, then measuring the strength- rupture of the fibers in the wet state, by pulling them immediately out of the water bath after having simply drained them.
- the breaking strength in the wet state for the fibers of the invention, represents 80 to 90%, depending on the case, of the nominal breaking strength (ie in the dry state, measured as indicated in paragraph I-4.).
- the nominal breaking strength ie in the dry state, measured as indicated in paragraph I-4.
- rayon fibers it only represents around 60% of the nominal breaking strength.
- the fibers of the invention are therefore much less sensitive to moisture than conventional rayon fibers, they have better dimensional stability in a humid environment.
- the fibers of the invention can be assembled, as described
- the fibers of the invention in the twisted state , have a toughness which is even greater than the tenacity of untwisted rayon fibers.
- the tenacities of the plies according to the invention are generally much greater than the tenacities on plies which can be obtained from fibers of the rayon type whose tenacity hardly exceeds, so known, 45-50 cN / tex before twisting. They can therefore be used in a smaller quantity in articles usually reinforced with conventional rayon fibers.
- the fibers of the invention the primary characteristic of which is a
- the improvement brought by the invention does not consist in a simple displacement towards another optimum of a given combination [tenacity-elongation at break], with an energy at break remaining substantially the same (total surface under the curve of traction Force - Elongation remaining substantially constant); it consists in fact of a very appreciable improvement in any combination [toughness-elongation at break], making it possible to "extend" the force-elongation curves obtained for the fibers of the initial application WO 85/05115, and thus obtaining a very markedly improved energy at break (increased surface area under the Force-Elongation curve).
- 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 with these other groups being preferably less than 10%.
- 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. It can also be various additives 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.
- the invention also covers the cases where a die is made up of one or more non-cylindrical capillaries, of various shapes, for example of a single capillary in the form of a slit, the term "fiber" used in the description and the claims before then be understood in a more general sense, which may include in particular the case of a cellulose formate film or of a regenerated cellulose film.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69612863T DE69612863T2 (de) | 1995-08-10 | 1996-08-05 | Cellulosefasern mit hoher bruchdehnung und deren herstellungsverfahren |
AT96927680T ATE201241T1 (de) | 1995-08-10 | 1996-08-05 | Cellulosefasern mit hoher bruchdehnung und deren herstellungsverfahren |
CA002226305A CA2226305C (fr) | 1995-08-10 | 1996-08-05 | Fibres cellulosiques a allongement rupture ameliore et procedes pour les obtenir |
JP50811997A JP3941836B2 (ja) | 1995-08-10 | 1996-08-05 | 改良された破断点伸びを有するセルロース繊維、及びその製造方法 |
US09/011,423 US6093490A (en) | 1995-08-10 | 1996-08-05 | Cellulose fibers with improved elongation at break, and methods for producing same |
BR9610076A BR9610076A (pt) | 1995-08-10 | 1996-08-05 | Fibra de formiato de celulose e de celulose regenerada a partir de formiato de celulose processos de fiação de uma solução de formiato de celulose em um solvente à base de ácido fosforico e de obtenção de uma fibra de celulose regenerada montagem de reforço e artigo |
AU67419/96A AU701914B2 (en) | 1995-08-10 | 1996-08-05 | Cellulose fibres with improved elongation at break, and methods for producing same |
EP96927680A EP0848767B1 (fr) | 1995-08-10 | 1996-08-05 | Fibres cellulosiques a allongement rupture ameliore et procedes pour les obtenir |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR95/09905 | 1995-08-10 | ||
FR9509905A FR2737735A1 (fr) | 1995-08-10 | 1995-08-10 | Fibres cellulosiques a allongement rupture ameliore |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/544,249 Division US6261689B1 (en) | 1995-08-10 | 2000-04-05 | Cellulose fibers with improved elongation at break, and methods for producing same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997006294A1 true WO1997006294A1 (fr) | 1997-02-20 |
Family
ID=9481986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/003444 WO1997006294A1 (fr) | 1995-08-10 | 1996-08-05 | Fibres cellulosiques a allongement rupture ameliore et procedes pour les obtenir |
Country Status (13)
Country | Link |
---|---|
US (2) | US6093490A (fr) |
EP (1) | EP0848767B1 (fr) |
JP (2) | JP3941836B2 (fr) |
CN (1) | CN1077614C (fr) |
AT (1) | ATE201241T1 (fr) |
AU (1) | AU701914B2 (fr) |
BR (1) | BR9610076A (fr) |
CA (1) | CA2226305C (fr) |
DE (1) | DE69612863T2 (fr) |
ES (1) | ES2156619T3 (fr) |
FR (1) | FR2737735A1 (fr) |
RU (1) | RU2169217C2 (fr) |
WO (1) | WO1997006294A1 (fr) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6527997B1 (en) * | 1997-02-06 | 2003-03-04 | Michelin Recherche Et Technique S.A. | Process of making cellulose formate fibers of liquid crystal origin |
US7222481B2 (en) | 2002-01-17 | 2007-05-29 | Michelin Recherche Et Technique S.A. | Hybrid cables, a process for obtaining such and composite fabrics incorporating such |
WO2016091812A1 (fr) | 2014-12-09 | 2016-06-16 | Compagnie Generale Des Etablissements Michelin | Câblé textile haut module à au moins triple torsion |
WO2016091810A1 (fr) | 2014-12-09 | 2016-06-16 | Compagnie Generale Des Etablissements Michelin | Câblé textile cellulosique à au moins triple torsion |
WO2016091811A1 (fr) | 2014-12-09 | 2016-06-16 | Compagnie Generale Des Etablissements Michelin | Câblé textile aramide à au moins triple torsion |
WO2016156263A1 (fr) | 2015-03-31 | 2016-10-06 | Compagnie Generale Des Etablissements Michelin | Elément de renfort hybride à torsions différenciées |
WO2018202981A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2018202982A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2018202983A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2018202980A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2019122620A1 (fr) | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une nappe de frettage perfectionnée |
WO2019122621A1 (fr) | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Procédé de fabrication d'un élément filaire de renfort |
WO2019122619A1 (fr) | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une nappe de frettage perfectionnée |
WO2019180367A1 (fr) | 2018-03-20 | 2019-09-26 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant un câblé textile aramide perfectionne à au moins triple torsion |
WO2019180369A1 (fr) | 2018-03-20 | 2019-09-26 | Compagnie Generale Des Etablissements Michelin | Câblé textile aramide perfectionne à au moins triple torsion |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2700772A1 (fr) * | 1993-01-27 | 1994-07-29 | Michelin Rech Tech | Composition, susceptible de donner des fibres ou des films, à base de formiate de cellulose. |
NL1001692C2 (nl) * | 1995-11-20 | 1997-05-21 | Akzo Nobel Nv | Werkwijze voor de bereiding van geregenereerde cellulose filamenten. |
CN1078271C (zh) * | 1996-02-14 | 2002-01-23 | 阿克佐诺贝尔公司 | 高断裂伸长纤维素纤维和长丝、纱线及其生产方法 |
BR9711933A (pt) * | 1996-10-18 | 1999-08-24 | Michelin Rech Tech | Agente coagulante aquoso para solu-Æo de cristal l¡quido - base de materiais celulÄsicos processo de fia-Æo artigo fiado fibra celulÄsica e artigo de borrach(s) ou de material(ais) pl stico(s) |
WO2005054297A2 (fr) | 2003-11-28 | 2005-06-16 | Eastman Chemical Company | Interpolymeres de cellulose, procede d'oxydation de ces derniers |
US7722796B1 (en) * | 2005-08-05 | 2010-05-25 | Wright State University | Fabrication of small diameter continuous fibers |
TWI393807B (zh) * | 2010-03-26 | 2013-04-21 | Taiwan Textile Res Inst | 高伸長率纖維素母粒之製備方法與應用 |
US20110319531A1 (en) | 2010-06-29 | 2011-12-29 | Eastman Chemical Company | Cellulose ester compositions |
US9273195B2 (en) | 2010-06-29 | 2016-03-01 | Eastman Chemical Company | Tires comprising cellulose ester/elastomer compositions |
KR101916650B1 (ko) | 2010-08-05 | 2018-11-08 | 코르덴카 게엠베하 운트 코. 카게 | 개별 필라멘트들의 증가된 선형 밀도를 가지는 셀룰로오스 멀티필라멘트 얀들로 만들어진 코드 |
JP5611776B2 (ja) * | 2010-11-08 | 2014-10-22 | 東洋ゴム工業株式会社 | 弾性継手 |
PL2683858T3 (pl) * | 2011-03-08 | 2018-03-30 | Sappi Netherlands Services B.V. | Sposób suchego przędzenia obojętnej i modyfikowanej anionowo celulozy |
US20130150484A1 (en) | 2011-12-07 | 2013-06-13 | Eastman Chemical Company | Cellulose esters in pneumatic tires |
EP2951339B1 (fr) * | 2013-01-29 | 2017-03-15 | Cordenka GmbH & Co. KG | Fil multi-filaments en viscose très résistant avec numéros de fil peu élevés |
JP6096321B2 (ja) | 2013-01-29 | 2017-03-15 | コンティネンタル・ライフェン・ドイチュラント・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | エラストマー材料から作られる物品用の、好ましくは空気入り車両タイヤ用の補強層、および空気入り車両用タイヤ |
EP2781367B1 (fr) * | 2013-03-18 | 2016-12-14 | Continental Reifen Deutschland GmbH | Nappe de renforcement pour objets composés de matériau élastomère, de préférence pour pneus de véhicule et pneu de véhicule |
EP2781633A1 (fr) | 2013-03-18 | 2014-09-24 | Continental Reifen Deutschland GmbH | Corde hybride constituée d'au moins deux fils multifilaments entortillés l'un avec l'autre |
US10077342B2 (en) | 2016-01-21 | 2018-09-18 | Eastman Chemical Company | Elastomeric compositions comprising cellulose ester additives |
FR3050401B1 (fr) | 2016-04-25 | 2018-04-06 | Compagnie Generale Des Etablissements Michelin | Pneu avion ayant une armature de carcasse a endurance amelioree |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2465763A1 (fr) * | 1979-09-21 | 1981-03-27 | Asahi Chemical Ind | Adjuvant en mesophase contenant un derive de cellulose et un acide inorganique |
WO1985005115A1 (fr) * | 1984-04-27 | 1985-11-21 | Michelin Recherche Et Technique | Compositions anisotropes en esters cellulosiques; procedes pour obtenir ces compositions; fibres en esters cellulosiques ou en cellulose |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1010806B (zh) * | 1986-11-25 | 1990-12-12 | 北美菲利浦消费电子仪器公司 | 改进了对比度的显示投影系统 |
FR2700772A1 (fr) * | 1993-01-27 | 1994-07-29 | Michelin Rech Tech | Composition, susceptible de donner des fibres ou des films, à base de formiate de cellulose. |
FR2715406A1 (fr) * | 1994-01-26 | 1995-07-28 | Michelin Rech Tech | Composition contenant du formiate de cellulose et pouvant former un gel élastique et thermoréversible. |
FR2759094B1 (fr) * | 1997-02-06 | 1999-03-05 | Michelin Rech Tech | Fibres cellulosiques d'origine cristal-liquide ayant un allongement a la rupture important ; procedes pour les obtenir |
-
1995
- 1995-08-10 FR FR9509905A patent/FR2737735A1/fr active Pending
-
1996
- 1996-08-05 CN CN96197243A patent/CN1077614C/zh not_active Expired - Fee Related
- 1996-08-05 CA CA002226305A patent/CA2226305C/fr not_active Expired - Fee Related
- 1996-08-05 ES ES96927680T patent/ES2156619T3/es not_active Expired - Lifetime
- 1996-08-05 AU AU67419/96A patent/AU701914B2/en not_active Ceased
- 1996-08-05 RU RU98103987/04A patent/RU2169217C2/ru not_active IP Right Cessation
- 1996-08-05 AT AT96927680T patent/ATE201241T1/de not_active IP Right Cessation
- 1996-08-05 BR BR9610076A patent/BR9610076A/pt not_active IP Right Cessation
- 1996-08-05 DE DE69612863T patent/DE69612863T2/de not_active Expired - Fee Related
- 1996-08-05 JP JP50811997A patent/JP3941836B2/ja not_active Expired - Fee Related
- 1996-08-05 WO PCT/EP1996/003444 patent/WO1997006294A1/fr active IP Right Grant
- 1996-08-05 EP EP96927680A patent/EP0848767B1/fr not_active Expired - Lifetime
- 1996-08-05 US US09/011,423 patent/US6093490A/en not_active Expired - Lifetime
-
2000
- 2000-04-05 US US09/544,249 patent/US6261689B1/en not_active Expired - Lifetime
-
2006
- 2006-11-28 JP JP2006320139A patent/JP4034808B2/ja not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2465763A1 (fr) * | 1979-09-21 | 1981-03-27 | Asahi Chemical Ind | Adjuvant en mesophase contenant un derive de cellulose et un acide inorganique |
WO1985005115A1 (fr) * | 1984-04-27 | 1985-11-21 | Michelin Recherche Et Technique | Compositions anisotropes en esters cellulosiques; procedes pour obtenir ces compositions; fibres en esters cellulosiques ou en cellulose |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6527997B1 (en) * | 1997-02-06 | 2003-03-04 | Michelin Recherche Et Technique S.A. | Process of making cellulose formate fibers of liquid crystal origin |
US7222481B2 (en) | 2002-01-17 | 2007-05-29 | Michelin Recherche Et Technique S.A. | Hybrid cables, a process for obtaining such and composite fabrics incorporating such |
WO2016091812A1 (fr) | 2014-12-09 | 2016-06-16 | Compagnie Generale Des Etablissements Michelin | Câblé textile haut module à au moins triple torsion |
WO2016091810A1 (fr) | 2014-12-09 | 2016-06-16 | Compagnie Generale Des Etablissements Michelin | Câblé textile cellulosique à au moins triple torsion |
WO2016091811A1 (fr) | 2014-12-09 | 2016-06-16 | Compagnie Generale Des Etablissements Michelin | Câblé textile aramide à au moins triple torsion |
US10689780B2 (en) | 2014-12-09 | 2020-06-23 | Compagnie Generale Des Etablissements Michelin | High modulus textile cord with an at least triple twist |
WO2016156263A1 (fr) | 2015-03-31 | 2016-10-06 | Compagnie Generale Des Etablissements Michelin | Elément de renfort hybride à torsions différenciées |
US10688828B2 (en) | 2015-03-31 | 2020-06-23 | Compagnie Generale Des Etablissments Michelin | Hybrid reinforcing element with differential twist |
WO2018202983A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2018202980A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2018202982A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2018202981A1 (fr) | 2017-05-05 | 2018-11-08 | Compagnie Generale Des Etablissements Michelin | Pneumatique pour véhicule |
WO2019122620A1 (fr) | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une nappe de frettage perfectionnée |
WO2019122621A1 (fr) | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Procédé de fabrication d'un élément filaire de renfort |
WO2019122619A1 (fr) | 2017-12-22 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant une nappe de frettage perfectionnée |
WO2019180367A1 (fr) | 2018-03-20 | 2019-09-26 | Compagnie Generale Des Etablissements Michelin | Pneumatique comprenant un câblé textile aramide perfectionne à au moins triple torsion |
WO2019180369A1 (fr) | 2018-03-20 | 2019-09-26 | Compagnie Generale Des Etablissements Michelin | Câblé textile aramide perfectionne à au moins triple torsion |
Also Published As
Publication number | Publication date |
---|---|
BR9610076A (pt) | 1999-03-02 |
CA2226305A1 (fr) | 1997-02-20 |
AU701914B2 (en) | 1999-02-11 |
JPH11510569A (ja) | 1999-09-14 |
CA2226305C (fr) | 2004-03-09 |
JP3941836B2 (ja) | 2007-07-04 |
CN1077614C (zh) | 2002-01-09 |
US6261689B1 (en) | 2001-07-17 |
RU2169217C2 (ru) | 2001-06-20 |
DE69612863T2 (de) | 2001-08-30 |
ES2156619T3 (es) | 2001-07-01 |
DE69612863D1 (de) | 2001-06-21 |
EP0848767B1 (fr) | 2001-05-16 |
JP4034808B2 (ja) | 2008-01-16 |
CN1198194A (zh) | 1998-11-04 |
EP0848767A1 (fr) | 1998-06-24 |
JP2007084997A (ja) | 2007-04-05 |
AU6741996A (en) | 1997-03-05 |
FR2737735A1 (fr) | 1997-02-14 |
ATE201241T1 (de) | 2001-06-15 |
US6093490A (en) | 2000-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0848767B1 (fr) | Fibres cellulosiques a allongement rupture ameliore et procedes pour les obtenir | |
EP0650508B1 (fr) | Composition, susceptible de donner des fibres ou des films, a base de formiate de cellulose | |
EP0179822B1 (fr) | Compositions anisotropes en esters cellulosiques; procedes pour obtenir ces compositions; fibres en esters cellulosiques ou en cellulose | |
CN105658852B (zh) | 香烟过滤嘴用莱赛尔材料及其制备方法 | |
EP0782603B1 (fr) | Solutions cristal-liquide a base de cellulose et d'au moins un acide phosphorique | |
EP0712427B1 (fr) | Composition contenant du formiate de cellulose et pouvant former un gel elastique et thermoreversible | |
EP0932709B1 (fr) | Agent coagulant aqueux pour solutions cristal-liquide a base de matieres cellulosiques | |
EP0958413B1 (fr) | Fibres cellulosiques d'origine cristal-liquide ayant un allongement a la rupture important et procedes pour les obtenir | |
WO1992012285A1 (fr) | Traitement par plasma d'un monofilament aramide | |
EP0836622B1 (fr) | Procede d'obtention d'une solution de formiate de cellulose par impregnation puis malaxage de plaques de cellulose | |
EP0932710B1 (fr) | Agent coagulant aqueux pour solutions cristal-liquide a base de matieres cellulosiques | |
CA2074262C (fr) | Monofilament aramide ayant une peau faiblement structuree - procede pour obtenir ce monofilament |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 96197243.2 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG US UZ VN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1996927680 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2226305 Country of ref document: CA Ref document number: 2226305 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09011423 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 1997 508119 Country of ref document: JP Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1996927680 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1996927680 Country of ref document: EP |