EP0435975B1 - Aramidemonofilament und verfahren zur herstellung - Google Patents

Aramidemonofilament und verfahren zur herstellung Download PDF

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Publication number
EP0435975B1
EP0435975B1 EP90909123A EP90909123A EP0435975B1 EP 0435975 B1 EP0435975 B1 EP 0435975B1 EP 90909123 A EP90909123 A EP 90909123A EP 90909123 A EP90909123 A EP 90909123A EP 0435975 B1 EP0435975 B1 EP 0435975B1
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Prior art keywords
monofilament
monofilaments
aramid
spinning
following relationship
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EP90909123A
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French (fr)
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EP0435975A1 (de
Inventor
Jean-Paul Meraldi
Jo[L Ribiere
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Michelin Recherche et Technique SA Switzerland
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Michelin Recherche et Technique SA Switzerland
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Priority claimed from FR8908755A external-priority patent/FR2649127B1/fr
Priority claimed from FR9004790A external-priority patent/FR2660941B1/fr
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Publication of EP0435975A1 publication Critical patent/EP0435975A1/de
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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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • 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
    • Y10T428/2904—Staple length 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
    • 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
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2925—Helical or coiled
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]

Definitions

  • the invention relates to so-called "aramid” fibers, that is to say fibers of linear macromolecules formed from aromatic groups linked together by amide bonds of which at least 85% are directly linked to two aromatic rings, and more precisely aramid fibers produced from optically anisotropic spinning compositions.
  • the methods described in these documents essentially consist in dissolving in an appropriate solvent, generally concentrated sulfuric acid, an aromatic polyamide (polymer, copolymer or mixture of polymers) of molecular structure compatible with obtaining a crystal solution.
  • liquid at the spinning temperature a concentration generally between 12 and 20% by weight of polyamide, to extrude this solution through a die, to stretch through a layer of air the liquid veins leaving this die and to coagulate optimally, most often in an aqueous solution of sulfuric acid, to guarantee the high mechanical properties known for these aramid fibers.
  • the maximum filament strength claimed is approximately 6.7 dtex, which corresponds to a maximum filament diameter of approximately 24 ⁇ m. It is further specified that the operations of spinning unit filaments with a diameter between approximately 17 and 24 ⁇ m are already disturbed by coagulation difficulties.
  • Japanese patent application published under the number 61-55 210 very succinctly describes the production of a monofilament from paraphenylene diamine, terephthaloyl chloride and 4,4'-diaminodiphenyl ether.
  • This monofilament has a titer of 100 deniers and a tenacity of 16.8 g / denier, no indication being given on the initial module of this monofilament.
  • the properties indicated are only obtained after a hot super-stretching phase (stretching ratio equal to 1.8), the prior spinning operation as well as the above stretching operation being carried out in particular all two at very low speed.
  • This monofilament is actually derived from a semi-rigid aromatic copolyamide, the spinning solutions used for the production of this type of fiber being known moreover as being weakly concentrated in polymers and optically isotropic in the molten state and at rest.
  • aromatic polyamides containing a large fraction of bonds responsible for a low molecular extension, and the products which result therefrom by these ultra-stretching techniques after spinning are described for example in JP-A-62-00534, JP -A-63-92716, JP-A-63-165515.
  • the object of the invention is to provide an aramid monofilament having both a large diameter and high mechanical characteristics in the raw spinning state.
  • the aramid monofilament according to the invention is characterized in that there are the following relationships: 1.7 ⁇ Ti ⁇ 260; 40 ⁇ D ⁇ 480; T ⁇ 170 - D / 3; Mid ⁇ 2000; Ti being the title in tex, D being the diameter in ⁇ m (micrometer), T being the tenacity in cN / tex, Mi being the initial modulus in cN / tex, for this monofilament.
  • the invention also relates to a method for obtaining at least one such monofilament.
  • the monofilament according to the invention can be used either alone or in the form of assemblies, for example to reinforce articles, in particular articles made of plastics and / or rubbers, such articles being for example belts, pipes , reinforcement plies, tire casings, the invention also relates to these assemblies and these articles thus reinforced.
  • spun article covers any article produced by spinning, a monofilament being a particular spun article.
  • packaging is meant in this description the treatment of articles spun according to the German Federal standard DIN 53802-20 / 65 of July 1979.
  • the title of the spun articles is determined according to the Federal German standard DIN 53830 of June 1965. The measurement is carried out by weighing for each spun article on at least three previously conditioned samples, each corresponding to a length of 50 m. The title corresponds to the average of the measurements of the samples for the spun article considered, it is expressed in tex.
  • the densities of the spun articles are measured using the density gradient tube technique for plastics specified in ASTM D1505-68 (re-approved in 1975), method C using a mixture of 1,1,2-trichlorotrifluoroethane and 1,1,1-trichloroethane as the liquid system for the density gradient tube.
  • the samples used are short sections about 2 cm of loosely knotted spun articles. Before measurement, they are immersed for two hours in the component of the liquid system which has the lowest density. Then they remain 12 hours in said tube before being evaluated. Particular care is taken to avoid the retention of air bubbles on the surface of the spun articles.
  • the mechanical properties of the spun articles are measured using a traction machine of the company Zwick GmbH & Co (Federal Republic of Germany) of type 1435 or of type 1445, corresponding to the standards of Federal Germany DIN 51220 d 'October 1976, DIN 51221 of August 1976 and DIN 51223 of December 1977, according to the procedure described in the German Federal standard DIN 53834 of January 1979.
  • the spun articles are pulled over an initial length of 400 mm. All results are obtained with an average of 10 measurements.
  • T The tenacity (T) and the initial modulus (Mi) are indicated in cN / tex (centinewton per tex).
  • the elongation at break (Ar) is indicated as a percentage (%).
  • the initial modulus (Mi) is defined as the slope of the linear part of the curve representing the variations in force as a function of the elongation, this linear part occurring just after the standard pretension of 0.5 cN / tex.
  • the alpha parameter will be defined below for poly (p-phenylene terephthalamide) monofilaments.
  • the equatorial X-ray diffraction spectra are recorded in symmetrical transmission on one or more monofilaments assembled in parallel, arranged vertically.
  • the recording is carried out from 13 ° to 33 ° in 2 ⁇ (2 Theta) in increments of 0.08 and counting time of 10 s.
  • the calculation of the average intensity of the first five and last five points of the recording makes it possible after interpolation to determine and draw a baseline (or linear background) used for measuring the intensity of certain peaks.
  • a JBOL JEM 100CX transmission electron microscope is used with an acceleration voltage of 120 kV.
  • the observations in electronic microdiffraction are carried out on sagittal longitudinal sections the thickness of which is less than 100 nm.
  • the technique used is the so-called "convergent beam” technique.
  • This technique and the method of adjusting the device have been described by MJ Witcomb (Ultramicroscopy 7 - 1982 - pp 343-350).
  • the condenser diaphragm has a diameter of 20 ⁇ m, the first condenser lens is excited in the "spot size 3" position.
  • the diameter of the beam at the level of the sample is close to 400 nm.
  • the microscope is used under low dose irradiation conditions, low condenser current and without focusing of the second condenser lens.
  • the microdiffraction images are recorded on Agfa film type 23D56.
  • the optical anisotropy of the spinning compositions, in the molten state and at rest, is observed using a polarization microscope of the Olympus BH2 type, equipped with a heating plate.
  • the polymer used is a poly (p-pbenylene terephthalamide).
  • the poly (p-phenylene terephthalamide) (PPTA) is prepared according to the following known method: in a mixer swept by a stream of nitrogen, equipped with an agitator and a cooling device, an N- solution is introduced methylpyrrolidone containing a percentage by weight of calcium chloride greater than 5%. Then the ground p-phenylene diamine is added with stirring. After dissolution of the diamine, the contents of the mixer are cooled to approximately 10 ° C. The ground terephthaloyl dichloride is then added, in a substantially stoichiometric proportion, and stirring is continued. All reagents used are at room temperature (about 20 ° C) before introduction into the reactor. At the end of the reaction, the mixer is emptied, the product obtained is coagulated with water, washed and dried.
  • the spinning solution is prepared according to the following known method:
  • Concentrated sulfuric acid with a concentration by weight of acid close to 100%, is introduced into a planetary mixer whose double jacket is connected to a cryostat. With stirring and a stream of nitrogen, the acid is cooled to a temperature at least 10 ° C below its crystallization temperature; stirring is continued until a homogeneous mass with the appearance of snow is formed.
  • the polymer is then added; the temperature of the latter before introduction into the mixer is not critical, preferably the polymer is at room temperature.
  • the mixing of the acid and the polyamide is carried out with stirring, maintaining the temperature of the mixture at a value 10 ° C. lower than the crystallization temperature of the acid, until sufficient homogeneity is obtained.
  • the temperature in the mixer is then gradually increased to room temperature, while stirring. A solid, dry and non-cohesive powder is thus obtained.
  • this solid solution can be stored at room temperature without risk of degradation, before the spinning operation. Avoid any exposure extended to a humid atmosphere,
  • the quantity of polymer necessary to obtain the desired concentration is generally mixed with 8 kg of sulfuric acid. Before the spinning operation, a sample of solution is taken and weighed. It is then coagulated, washed carefully with water, dried under vacuum and weighed, in order to determine the concentration (% by weight, noted C below) of polymer in the solution.
  • the spinning compositions described in the present application are optically anisotropic in the molten state and at rest, that is to say in the absence of dynamic stress. Such compositions depolarize light when viewed through a microscope between crossed linear polarizers.
  • the solid spinning solution 2 previously deaerated at room temperature in a feed tank 3, is extruded using a single screw extruder 4 to the spinning block 5. It is melted during this extrusion phase, under high shear, at a temperature generally between 90 and 100 ° C.
  • Prolonged stays at a temperature notably above 100 ° C. can be the cause of degradation of the polymer, which is moreover easily controllable by an inherent viscosity measurement V.I (f) on the spun article.
  • V.I (f) an inherent viscosity measurement
  • the temperature of the spinning solution during its transfer to the spinning block 5 is maintained at a value less than 110 ° C., and preferably less than 100 ° C.
  • the spinning block 5 is essentially composed of a metering pump 6 and a spinning head 7 through which the liquid solution 2 is extruded.
  • Different elements such as filters, static mixers, for example, can optionally be incorporated in block 5, or placed at the inlet of the latter, FIG. 1 representing for example a filtration device 8.
  • the temperature of the spinning pump 6 is preferably less than 100 ° C for the same reasons as those mentioned above.
  • the spinning head 7 is essentially composed in a known manner of a distributor, filters, seals and a die. Only the die 9 is shown in Figure 1, for the sake of simplification, a portion of this die 9 being shown in more detail in Figure 2. Commonly, as shown in Figure 2, the die 9 has a single cylindrical capillary 10 of diameter d and of length 1, preceded by a convergent 11 of angle ⁇ , the latter possibly being whether or not preceded by a cylindrical pilot hole (not shown in Figure 2), Figure 2 being a section of the die 9 by a plane passing through the axis xx 'of the capillary 10, d being determined in a perpendicular plane to axis xx '.
  • the invention is not limited to the use of a die made up of a single capillary, the process being able to be extended to the simultaneous spinning of several monofilaments,
  • the speed V1 of the jet 12 is the average speed of passage of the solution 2 in the capillary 10 of the die 9, it can be calculated from the volume of solution 2 passing through this capillary 10 per unit of time.
  • the spinning temperature Tf is defined as the temperature of the solution 2 when crossing the capillary 10.
  • the jet 12 of liquid leaving the die 9 is stretched in a non-coagulating layer 13 of gas 14, preferably a layer of air, before entering the coagulation bath 15 (FIGS. 1 and 2).
  • the thickness "e" of the air layer, between the outlet face 16 of the die 9, this face being arranged horizontally, and the surface 17 of the coagulation bath 15 can vary from a few mm to several tens of mm.
  • the drawn liquid vein 18 After crossing the orientation fields developed in the die 9 and in the air layer 13, during which a reorientation has been given to the polymer molecules, the drawn liquid vein 18 thus obtained penetrates into the coagulating medium 19 of the bath 15 where we start to freeze this structure oriented by counteracting at best the molecular relaxation processes which are expressed during the coagulation phase, and this all the longer as the diameter of the monofilament to be produced is high.
  • coagulation means the process during which the wire is formed, that is to say during which the polyamide precipitates or crystallizes, whether it is in a solvated state, partially solvated, or not solvated.
  • coagulating medium is meant a liquid medium in which such a transformation takes place.
  • the coagulating medium 19 may be composed at least in part of water or of substances such as acids, bases, salts, or organic solvents such as, for example, alcohols, polyalcohols, ketones, or a mixture of these compounds.
  • the coagulating medium is an aqueous solution of sulfuric acid.
  • the wire 20 being formed is entrained with the coagulating medium 19 in the vertical tube 21, the length of which varies for example from a few cm to a few tens of cm and the internal diameter is for example a few mm, this tube can be straight or tightened for example at its lower end.
  • the combination of the coagulation bath 15 and this tube 21, sometimes called “coagulation tube” or “spinning tube”, is known to those skilled in the art for spinning conventional aramid fibers.
  • the use of the tube 21 is however not compulsory in the device 1.
  • the depth of coagulating liquid 19, in the coagulation bath 15, measured between the inlet surface 17 of the coagulation bath 15 and the inlet of the spinning tube 21 can vary for example from a few millimeters to several centimeters, a depth too significant which may adversely affect the quality of the product, taking into account the hydrodynamic tensions which may develop, in particular at the highest spinning speeds, when passing through this first coagulating layer.
  • One of the essential characteristics of the process according to the invention lies in the fact that the dynamic contact times of the wire 20 with the coagulating medium 19 must, in most cases, be significantly greater than the contact times which can be achieved after simple crossing of the bath 15 and the spinning tube 21 as previously described.
  • the extension of these contact times may be made by any suitable means.
  • coagulation baths 15 and / or tube 21 of very great depth or length typically several meters, it is preferred for example, taking into account in particular the problems of hydrodynamic tension mentioned above, to use at least an additional coagulation device 22 extending the bath 15 and the tube 21, this device 22 being placed at the outlet of the spinning tube 21, immediately after a reference point 25.
  • the device 22 is for example composed of baths, pipes, cabins in which circulates the coagulating medium 19, or an association of these different elements which are not shown in the drawing for the purpose of simplification, and whose length and configuration can be adapted with great flexibility to specific manufacturing conditions, in particular to the monofilament diameter of the spun product.
  • the wire 20 being formed is subjected to tensions of less than 3 cN / tex.
  • total dynamic contact time of the wire 20 with the coagulating medium 19 is meant the total time during which the monofilament is immersed in the coagulating medium or in contact with this same medium, during the passage of the wire 20 in the coagulation devices previously described, that is to say the bath 15, the tube 21 and the device 22.
  • the latter must ensure effective renewal of the coagulating medium on the surface of the monofilament in movement and during formation, the coagulating medium 19 being at the temperature Tc.
  • any additional coagulation device as described above cannot be assimilated to a simple washing device, in which one could, for example, use aqueous, neutral or basic solutions, at markedly high temperature, to improve the kinetics of extraction of the residual solvent after the coagulation phase.
  • the constitution of the coagulating medium 19 and its temperature Tc can be chosen to be identical or different in the devices 15, 21 and 22.
  • the wire 20 formed is washed to remove the residual acid which it contains, this washing is carried out optimally by any known means, for example by washing with water, or even with alkaline aqueous solutions, possibly at high temperature to improve the kinetics.
  • This washing can be carried out for example by collecting the wire 20, at the outlet of the device 22, on the coil 23 actuated by the motor 24, this coil being immersed for a few hours in a tank permanently supplied with fresh water.
  • the wire 20 is dried, for example either on a reel at room temperature, or even in an oven, or by passing the wire over heating cylinders.
  • the drying temperature is at most equal to 200 ° C.
  • the device 1 could be arranged so that the washing and drying operations are carried out continuously with the extrusion and coagulation operations.
  • the dried wire 20 has the diameter D previously defined.
  • the final sulfuric acid content, or in the base if a basic washing liquid is used is less than 0.01% by weight relative to the weight of dry yarn.
  • the stretching factor FEF is defined as the ratio between the speed V2 of the first drive device encountered by the wire 20 and the speed V1 of the jet 12 in the capillary 10, this drive device being for example incorporated in the device 22.
  • additives or substances such as, for example, plasticizers, lubricants, products which can improve the adhesiveness of the product to a gum matrix, can optionally be incorporated into the polymer, into the spinning solution, or applied to the surface of the monofilament, during the various stages of the process according to the invention described above.
  • the monofilaments obtained in accordance with the invention verify all of the following relationships: 1.7 ⁇ Ti ⁇ 260; 40 ⁇ D ⁇ 480; T ⁇ 170 - D / 3; Mid ⁇ 2000.
  • the tenacity T and the initial module Mi verify the following relationships: T ⁇ 190 - D / 3; Mi ⁇ 6800 - 10D.
  • the monofilaments in accordance with the invention are characterized by high or very high tenacity, and by high or very high initial modules.
  • these monofilaments in accordance with the invention are characterized by an elongation at break Ar always greater than 2.0%, preferably greater than 3.0%, or even greater than 4.0%.
  • these monofilaments in accordance with the invention are characterized by high values of inherent viscosity VI (f), all greater than 4.0 dl / g, equal to or greater than 4.5 dl / g, this inherent viscosity being preferably 5.0 dl / g or more.
  • the spinning of PPTA monofilaments in accordance with the invention leads to a crystalline structure different from the structure of a conventional PPTA fiber, this conventional structure being described for example by M.G. Northolt in Eur. Polym. J., 10, p. 799 (1974).
  • FIG. 3 shows the comparison of the equatorial X-ray diffraction patterns recorded for a known PPTA fiber (Kevlar® 49 - diagram referenced C3 ⁇ 1) and for the monofilament according to the invention corresponding to test No M-7 (diagram referenced C3 ⁇ 2).
  • the angles plotted on the abscissa correspond to 2 ⁇ (2 theta) in degrees and the intensity I plotted on the ordinate is expressed in relative units (u.r).
  • the known fiber does not have the lines (X) and (Y) that are observed on the monofilament according to the invention (diagram C3 ⁇ 2).
  • an increase in the alpha parameter is observed for these PPTA monofilaments according to the invention when the diameter of the monofilament produced increases, in other words an increase in the intensity of the additional line referenced (X) to the detriment of the intensity of the conventional reflection referenced (A), the intensity of the line referenced (B) appearing for its part affected comparatively.
  • the decrease in intensity of the peak (A) can be such that the latter is no longer manifested on the X-ray diffractogram except by a slight shoulder, and therefore that its angular position can no longer be precisely defined. by simply reading the recording. The intensity of the peak (A) is then measured at the average angular position known for this peak.
  • these monofilaments in accordance with the invention are characterized by high density values ⁇ , greater than 1,400 g / cm3, this density preferably being greater than 1.420 g / cm3, or even greater than 1.430 g / cm3, which is the guarantee of high crystallinity and high structural perfection, unexpected for such large diameters. It is known that the densities of conventional PPTA fibers of small monofilament diameters, in the absence of heat or thermo-mechanical treatment, are generally between 1,400 and 1,450 g / cm3 (see for example US-A-3,869,429, US-A-3,869,430, EP-A-138,011).
  • the coagulating medium is advantageously an aqueous solution of sulfuric acid.
  • the inherent viscosities VI (f) and VI (p), expressed in dl / g, are linked by the relation: VI (f) ⁇ VI (p) - 0.8, degradation of the polymer during different stages of dissolving, spinning and drying the fiber, thus remaining very limited.
  • PPTA monofilaments are produced according to the general conditions previously described in ⁇ II-A but in such a way that at least one of the characteristics of the process according to the invention is not observed.
  • Table 3 comprises 11 series of tests referenced A, B, E, G, H to K , M, P, Q.
  • the temperature Tc of the coagulating medium 19 in the coagulation bath 15 and in the tube 21, is equal to 8 ° C., but the temperature of this medium in the additional device 22 is equal to 60 ° C., so that this device 22 is no longer a coagulation device, but that it is used as a conventional washing device, such as one could use it in a spinning process.
  • traditional aramid fibers of small monofilament diameter, to improve the kinetics of extraction of the residual solvent is used as a conventional washing device, such as one could use it in a spinning process.
  • the dynamic contact time of the monofilament with the coagulating medium at a temperature Tc at most equal to 16 ° C., that is to say before entering the device 22, is only 0.14 s, which corresponds to a value of K equal to approximately 4 s / mm, therefore very low.
  • example M-ll a coil of about 2000 m is taken from the input of the additional coagulation device 22, the dynamic contact time with the coagulating medium then being only 0.14 s approximately, which corresponds to the low value of approximately 4 s / mm for K.
  • the monofilaments obtained not in accordance with the invention all have a diameter D of between 40 and 480 ⁇ m but that they do not verify at least one of the set of relationships verified by the monofilaments according to the invention. It is further noted that these monofilaments not in accordance with the invention have an always lower toughness and an initial modulus in the majority of cases lower than those of the monofilaments in accordance with the invention, with equivalent monofilament diameter.
  • these monofilaments which do not conform to the invention do not, in a large number of cases, verify the preferential relationship alpha ⁇ 0.70 - exp (-D / 80) (D being expressed in ⁇ m), unlike conforming monofilaments to the invention of the preceding examples which systematically verified this relationship.
  • these monofilaments not in accordance with the invention are characterized by low or very low density values since they are less than 1.38 g / cm3 or even as low as 1.33 g / cm3 (examples I-4 , Q-4).
  • These are in particular monofilaments produced from spinning solutions of concentrations equal to 18.5% or 19.5%, such concentrations being yet typically used for the production of conventional multifilament fibers with high density, generally between 1.40 and 1.45 g / cm3.
  • the spinning solutions used to make these multifilaments are prepared in the same way as the solutions used to make the monofilaments, in accordance with paragraph II-A-b.
  • monofilaments with a diameter substantially equal to 180 ⁇ m are produced, according to the conditions described in paragraphs II-A and II-B (series I), by varying the concentration of the polymer in the spinning solution. All the production conditions are in accordance with the invention, except for the concentration C which can take values of less than 20% by weight. These conditions as well as the physical and mechanical properties of the products obtained have already been given in tables 1 to 4 above.
  • test numbers, the titer Ti and the diameter D of the monofilaments obtained, their inherent viscosity VI (f) are simply recalled, and we follow, as a function of the concentration C of the spinning solution, the evolution of the tenacity T, of the density ⁇ and of the parameter alpha deduced from the X-ray analysis.
  • the tenacity is also expressed in relative units (ur) by taking the base 100 for the tenacity obtained on the spun monofilaments from the least concentrated solution (18.5%).
  • the spinning of these multifilaments is carried out in a known manner, by extrusion of the solution through a die composed of 100 capillaries with a diameter of 50 ⁇ m, the spinning temperature being equal to the extrusion temperature (90 ° C.), by drawing to through a layer of air 10 mm thick, the FEF being approximately 4, before passing through the coagulation device constituted by the bath 15 and the associated spinning tube 21, as described in paragraph II-Ac, the temperature of the coagulating medium being approximately 8 ° C.
  • the spinning speed V2 as defined previously in paragraph II-A-c is equal to 400 m / min.
  • the multifilaments thus spun are taken out of the above coagulation device to be then washed and dried under the same conditions as those used for the preceding monofilaments.
  • Table 6 gives the tenacity values T obtained for these multifilaments as a function of the concentration C.
  • the test number, the inherent viscosity VI (f) and the density p of these multifilaments are also specified.
  • the toughness is also expressed in relative units (ur) by taking the base 100 for the toughness measured on the fibers spun from the least concentrated solution (18.5%), in accordance with the presentation. retained in table 5.
  • C concentration
  • monofilaments are produced according to the conditions given in paragraphs II-A and II-B (series J), by varying the spinning temperature Tf by increasing the temperature of the spinning head 7. These tests are carried out to give monofilaments of the same diameter substantially equal to 180 ⁇ m. All the production conditions are in accordance with the invention, except the spinning temperature Tf which can be greater than 105 ° C. These conditions as well as the physical and mechanical properties of the products obtained have already been given in tables 1 to 4 above.
  • Table 8 gives the initial modulus Mi and tenacity T values obtained for these multifilaments as a function of the spinning temperature Tf.
  • the initial modulus and the toughness are also expressed in relative units (ur), taking the base 100 for the initial modulus and the tenacity obtained on the multifilaments spun at a spinning temperature of 75 ° C., in accordance with the presentation of table 7 previous.
  • the test number and the inherent viscosity VI (f) of the multifilaments obtained are also specified.
  • FIG. 6, deducted from Tables 7 and 8, represents, as a function of the spinning temperature Tf, expressed in ° C, the variations in tenacity T, in relative units (ur), for the multifilaments (curve C6 ⁇ 1) and for monofilaments (curve C6 ⁇ 2): the common base equal to 100, symbolized in FIG. 6 by T100, corresponds as previously indicated to the toughness obtained on the products spun at a spinning temperature of 75 ° C.
  • Tf spinning temperature
  • monofilaments are produced according to the conditions given in paragraph II-A and II-B (series H), by varying the temperature Tc of the coagulating medium. These tests are carried out to give monofilaments of the same diameter substantially equal to 180 ⁇ m. All the conditions of realization are in accordance with the invention, except the temperature of the coagulating medium which can be higher than 16 ° C. These conditions as well as the physical and mechanical properties of the products obtained have already been given in tables 1 to 4 above. In the following table 9, the test numbers, the titer Ti and the diameter D of the monofilaments, their inherent viscosity VI (f) are simply recalled, and the evolution of the toughness T is monitored as a function of the temperature Tc of the coagulating medium.
  • the toughness is also expressed in relative units (ur) by taking the hase 100 for the average toughness obtained on the monofilaments produced from a coagulating medium temperature of 7 ° C. (examples H-1, H-2 and H- 3).
  • Table 9 Trial number Tc (° C) Ti (tex) D ( ⁇ m) VI (f) (dl / g) T (cN / tex) T (ur) H-1 7 37.6 183 5.2 135 H-2 7 37.2 182 5.2 145 H-3 7 37.7 183 5.2 138 average value : 139 ⁇ 100 H-4 13 34.2 175 5.2 123 88 H-5 17 37.6 183 5.2 102 73 H-6 20 36.2 181 5.2 92 66 H-7 28 36.2 180 5.0 66 47 H-8 33 36.5 181 4.9 50 36
  • Table 10 gives the tenacity values T obtained for these multifilaments as a function of the temperature of the coagulating medium Tc.
  • the toughness is also expressed in relative units (ur), in accordance with the presentation chosen in the previous table, taking the base 100 for the toughness obtained on the multifilaments produced from a temperature of the coagulating medium of 7 ° C.
  • the test number and the inherent viscosity VI (f) of the multifilaments obtained are also specified.
  • Table 10 Trial number Tc (° C) VI (f) (dl / g) T (cN / tex) T (ur) T-1 7 5.3 187 100 T-2 13 5.3 180 96 T-3 21 5.3 180 96 T-4 34 5.3 178 95
  • FIG. 8 which illustrates these results represents, as a function of the temperature of the coagulating medium Tc, expressed in ° C, the variations in tenacity, in relative units (ur), for the multifilaments (curve C8 ⁇ 1) and for the monofilaments (curve C8 ⁇ 2): the common base equal to 100, symbolized in Figure 8 by T100, corresponds to the toughness obtained on the products produced from the lowest temperature of the coagulating medium, ie 7 ° C in the present case.
  • monofilaments are produced according to the conditions given in paragraphs II-A and II-B (series H, I, J, K, L, M, N, P), by varying the inherent viscosity of the polymer. These tests are carried out to give monofilaments with diameters between 159 and 183 ⁇ m. With the exception of the inherent viscosity of polymer VI (p), all the conditions of production are in accordance with the invention and also simultaneously fulfill all the preferential relationships set out in paragraph II-Ac. These production conditions as well as the physical and mechanical properties of the products obtained have already been given in tables 1 to 4 above.
  • Reading table 11 it can be seen that the increase in the inherent viscosity of the polymer VI (p), from 4.1 to 6.2 dl / g, results for the monofilaments produced by a very large increase in the tenacity, completely unexpected since it can even reach almost 150%.
  • conventional multifilament fibers are produced, consisting of monofilaments with an average diameter equal to approximately 13 ⁇ m (filament titer of approximately 0.18 tex), also by varying the inherent viscosity of the polymer in a range in accordance with the preceding one.
  • These fibers are produced in a known manner, in accordance with the production conditions indicated for the tests referenced R, S, and T in the three preceding paragraphs.
  • Table 12 gives the toughness values T obtained for these multifilaments as a function of the inherent viscosity of the polymer V.I (p).
  • the test number and the inherent viscosity VI (f) of the multifilaments obtained are also specified.
  • Figure 9 illustrates this fundamental difference in behavior. It represents as a function of the inherent viscosity of the polymer VI (p), expressed in dl / g, the variations in tenacity, in relative units (ur), for the multifilaments (curve C9 ⁇ 1) and for the monofilaments (curve C9 ⁇ 2): the common base equal to 100, symbolized in FIG. 9 by T100, corresponds to the toughness measured on the products spun from the polymer having the lowest inherent viscosity, ie 4.1 dl / g in the present case .
  • the coagulating medium 19 can be composed at least in part of water or of substances such as for example acids, bases, salts or organic solvents, or of a mixture of these compounds.
  • this coagulating medium 19 was an aqueous solution of weakly concentrated sulfuric acid, containing less than 5% by weight of acid.
  • monofilaments of different diameters are produced, all in accordance with the invention, using coagulating media of another composition, according to the process in accordance with the invention.
  • the temperature of the coagulating medium Tc is not kept constant during the crossing of the devices 15, 21 and 22. Nevertheless, this temperature always remains in accordance with the invention since at most equal to + 7 ° C.
  • the density of the products produced is always greater than 1,400 g / cm3, and at least equal to 1,420 g / cm3 in the majority of case.
  • alpha parameter verifies the preferential relationship observed for the previous examples of PPTA monofilaments in accordance with the invention, namely: alpha ⁇ 0.70 - exp (-D / 80).
  • the invention is not limited to the use of cylindrical extrusion capillaries, the process according to the invention can, for example, be implemented with capillaries of conical shape, or with non-circular extrusion holes of different shapes, for example holes of rectangular or oval shape, to produce for example monofilaments of oblong type.
  • the definitions of the invention given above apply very generally, the diameter D representing the smallest dimension of the monofilament, and the diameter d the smallest dimension of the extrusion hole, D and d being determined. in sections perpendicular to the longitudinal direction of the monofilament and to the direction of flow in the extrusion capillary, respectively.
  • the monofilament is previously coated in an epoxy-type resin.
  • Each aromatic polyamide used in the process according to the invention can be a homopolymer or a copolymer, this polyamide comprising aromatic and optionally non-aromatic sequences.
  • These sequences can for example be formed from radicals or groups of the phenylene, biphenylene, diphenyl ether, naphthylene, pyridylene, vinylene, polymethylene, polybenzamide, diaminobenzanilide type, these radicals or these groups being able to be substituted and / or unsubstituted, the substituents, when 'they are present, preferably being non-reactive.
  • This polyamide may optionally contain imide bonds.
  • the process according to the invention can be carried out with a mixture of such polyamides.
  • the monofilaments in accordance with the invention other than in PPTA are formed by copolyamides of the poly (p-phenylene terephthalamide) (PPTA) type.
  • PPTA poly (p-phenylene terephthalamide)
  • aromatic polyamides used in these examples are copolyamides essentially comprising p-phenylene terephthalamide sequences, and additional sequences, of aromatic or aliphatic nature.
  • copolyamides are prepared according to the method described in paragraph II-Aa with the following modifications: a molar fraction of p-phenylene diamine (PPDA) or of terephthalic acid dichloride (DCAT) is replaced by another diamine or another dichloride acid, respectively.
  • PPDA p-phenylene diamine
  • DCAT terephthalic acid dichloride
  • the acid chloride (s) and the diamine (s) are in substantially stoichiometric proportions.
  • substitution monomers are commercially available and are produced according to known methods which are not described here for the purpose of simplification. The purity of these monomers is given by the suppliers as being greater than 97% and they are used without further purification.
  • the coagulating medium 19 circulating in the devices 15, 21 and 22, as described in paragraph II-Ac is an aqueous solution of sulfuric acid containing less than 5% by weight acid.
  • the coagulating medium 19 is a highly concentrated aqueous solution of sulfuric acid since it contains 18% by weight of acid.
  • an aqueous solution containing 25% by weight of sulfuric acid and maintained at a temperature of -10 ° C. is used as coagulating medium 19 in the devices 15 and 21, while in the additional device 22 using a solution containing less than 5% by weight of this same acid, at a temperature of + 7 ° C.
  • An aromatic copolyamide is prepared in accordance with the description in paragraph V-A-a above, using the following monomers: PPDA, DCAT, 1,5-naphthylene diamine (NDA), with 3 moles of NDA per 100 moles of diamines.
  • a spinning solution is prepared according to the method described in paragraph II-A-b, using sulfuric acid with an acid concentration by weight of approximately 99.5%. From this solution, monofilaments are produced according to the general conditions previously described in paragraph V-A-b, but in such a way that at least one of the characteristics of the process according to the invention is not observed.

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Claims (34)

  1. Aramid-Monofilament,
    gekennzeichnet durch folgende Beziehungen für dieses Monofilament: 1,7 ≤ Ti ≤ 260;
    Figure imgb0077
     40 ≤ D ≤ 480;
    Figure imgb0078
     T ≥ 170 - D/3;
    Figure imgb0079
     Mi ≥ 2000,
    Figure imgb0080
    worin bedeuten:
    Ti die Feinheit in tex,
    D den Durchmesser in µm,
    T die Feinheitsfestigkeit in cN/tex
       und
    Mi den anfänglichen Modul in cN/tex.
  2. Aramid-Monofilament nach Anspruch 1, gekennzeichnet durch die folgende Beziehung: T ≥ 190 - D/3.
    Figure imgb0081
  3. Aramid-Monofilament nach Anspruch 2, gekennzeichnet durch die folgende Beziehung: T ≥ 210 - D/3.
    Figure imgb0082
  4. Aramid-Monofilament nach einem der Ansprüche 1 bis 3, gekennzeichnet durch die folgende Beziehung: Mi ≥ 6800 - 10D.
    Figure imgb0083
  5. Aramid-Monofilament nach Anspruch 4, gekennzeichnet durch die folgende Beziehung: Mi ≥ 7200 - 10D.
    Figure imgb0084
  6. Aramid-Monofilament nach einem der Ansprüche 1 bis 5, gekennzeichnet durch die folgende Beziehung für dieses Monofilament: Ar > 2,
    Figure imgb0085
     worin Ar die in % ausgedrückte Bruchdehnung bedeutet.
  7. Aramid-Monofilament nach Anspruch 6, gekennzeichnet durch die folgende Beziehung: Ar > 3.
    Figure imgb0086
  8. Aramid-Monofilament nach Anspruch 7, gekennzeichnet durch die folgende Beziehung: Ar > 4.
    Figure imgb0087
  9. Aramid-Monofilament nach einem der Ansprüche 1 bis 8, gekennzeichnet durch die folgende Beziehung: ρ > 1,400,
    Figure imgb0088
     worin ρ die in g/cm³ ausgedrückte Dichte bedeutet.
  10. Aramid-Monofilament nach Anspruch 9, gekennzeichnet durch die folgende Beziehung: ρ > 1,420.
    Figure imgb0089
  11. Aramid-Monofilament nach Anspruch 10, gekennzeichnet durch die folgende Beziehung: ρ > 1,430.
    Figure imgb0090
  12. Aramid-Monofilament nach einem der Ansprüche 1 bis 11, gekennzeichnet durch die folgende Beziehung: V.I(f) > 4,0,
    Figure imgb0091
     worin V.I(f) die in dl/g ausgedrückte inhärente Viskosität bedeutet.
  13. Aramid-Monofilament nach Anspruch 12, gekennzeichnet durch die folgende Beziehung: V.I(f) ≥ 4,5.
    Figure imgb0092
  14. Aramid-Monofilament nach Anspruch 13, gekennzeichnet durch die folgende Beziehung: V.I(f) ≥ 5,0.
    Figure imgb0093
  15. Aramid-Monofilament nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß es im wesentlichen p-Phenylenterephthalamid-Verknüpfungen enthält.
  16. Aramid-Monofilament nach einem der Amsprüche 1 bis 14, dadurch gekennzeichnet, daß es ein Poly(p-phenylenterephthalamid) (PPTA) ist.
  17. Aramid-Monofilament nach Anspruch 16, dadurch gekennzeichnet, daß die äquatoriale Aufnahme seines Röntgenbeugungsspektrums im Winkelbereich von 2θ = 13° bis 2θ = 33° für die Kupfer-Kα-Linie das Vorliegen von vier Linien ergibt, die nach steigenden Winkeln 2θ als (X), (A), (B) und (Y) bezeichnet sind,
    und die Beziehung α ≥ 0,05
    Figure imgb0094
     gilt, wobei definitionsgemäß α = I(X)/I(A) gilt und I(X) und I(A) die apparenten maximalen Intensitäten der Peaks (X) bzw. (A) bedeuten, die am Röntgenbeugungsdiagramm gemessen und bezüglich des linearen Untergrunds korrigiert sind.
  18. Aramid-Monofilament nach Anspruch 17, dadurch gekennzeichnet, daß der Parameter α der folgenden Beziehung genügt: α ≥ 0,70 - exp(-D/80).
    Figure imgb0095
  19. Aramid-Monofilament nach einem der Ansprüche 16 bis 18, dadurch gekennzeichnet, daß es eine kristalline Struktur aufweist, die im Kern und an der außenhaut unterschiedlich ist.
  20. Aramid-Monofilament nach einem der Ansprüche 1 bis 19, dadurch gekennzeichnet, daß es im rohgesponnenen Zustand vorliegt.
  21. Verfahren zur Herstellung eines oder mehrerer Monofilamente nach einem der Ansprüche 1 bis 20, gekennzeichnet durch folgende Schritte:
    a) Herstellung einer Lösung mindestens eines aromatischen Polyamids, bei dem mindestens 85 % der Amidbindungen (-CO-MH-) direkt an zwei aromatischen Kernen geburden sind, die inhärente Viskosität V.I(p) dieses Polyamids bzw. dieser Polyamide mindestens gleich 4,5 dl/g ist und die Konzentration C des Polyamids bzw. der Polyamide in der Lösung mindestens 20 Gew.-% beträgt, wobei diese Spinnzusammensetzung in geschmolzenem Zustand und im Ruhezustand optisch anisotrop ist,
    b) Extrudieren dieser Lösung in eine Spinndüse durch mindestens eine Kapillare hindurch, deren Durchmesser d größer als 80 µm ist, wobei die Verspinntemperatur Tf, d.h., die Temperatur der Lösung bei ihrem Durchtritt durch die Kapillare, höchstens gleich 105 °C ist,
    c) Abziehen des aus der Kapillare austretenden Flüssigkeitsstrahls in eine Schicht eines nicht koagulierenden Fluids,
    d) Einführen des so erhaltenen abgezogenen Flüssigkeitsstrahls in ein Koagulationsmedium, wobei das Monofilament so im Verlaufe seiner Entstehung während der Zeit t in dynamischem Kontakt mit dem Koagulationsmedium bleibt und die Temperatur Tc des Koagulationsmediums höchstens gleich 16 °C ist,
    und
    e) Waschen und Trocknen des Monofilaments, wobei der Durchmesser D des so fertiggestellten trockenen Monofilaments und die Zeit t durch die folgenden Beziehungen miteinander verknüpft sind: t = KD 2 ;
    Figure imgb0096
     K > 30,
    Figure imgb0097
     worin t in s, D in mm und K, das als "Koagulationskonsnante" bezeichnet wird, in s/mm ausgedrückt sind.
  22. Verfahren nach Anspruch 21, dadurch gekennzeichnet, daß mindestens eine der folgenden Beziehungen erfüllt ist: V.I(p) ≥ 5,3 dl/g;
    Figure imgb0098
     C ≥ 20,2 %;
    Figure imgb0099
     Tf ≤ 90 °C;
    Figure imgb0100
     Tc ≤ 10 °C;
    Figure imgb0101
     K ≥ 200 s/mm 2 .
    Figure imgb0102
  23. Verfahren nach Anspruch 21 oder 22, dadurch gekennzeichnet, daß mindestens eine der folgenden Beziehungen erfüllt ist: l/d ≤ 10;
    Figure imgb0103
     5° ≤ β ≤ 90°;
    Figure imgb0104
     3 mm ≤ e ≤ 20 mm;
    Figure imgb0105
     2 ≤ FEF ≤ 15,
    Figure imgb0106
     worin bedeuten:
    l die Länge der Kapillare in µm,
    β den Öffnungswinkel einer vor der Kapillare angeordneten konischen Kammer,
    e die Dicke der nicht koagulierenden Schicht und
    FEF den Verstreckfaktor beim Verspinnen.
  24. Verfahren nach einem der Ansprüche 21 bis 23, dadurch gekennzeichnet, daß das Koagulationsmedium eine -wässerige Schwefelsäurelösung ist.
  25. Verfahren nach einem der Ansprüche 21 bis 24, dadurch . gekennzeichnet, daß das Monofilament bei seiner Erzeugung Zugspannungen von weniger als 3 cN/tex unterworfen wird.
  26. Verfahren nach einem der Ansprüche 21 bis 25, dadurch gekennzeichnet, daß die Temperatur bei der Trocknung höchstens 200 °C beträgt.
  27. Verfahren nach einem der Ansprüche 21 bis 25, dadurch gekennzeichnet, daß die inhärenten Viskositäten V.I(f) und V.I(p), die in dl/g ausgedrückt sind, durch die Beziehung V.I(f) ≥ V.I(p) - 0,8
    Figure imgb0107
     miteinander verknüpft sind, wobei V.I(f) die inhärente viskosität des Monofilaments bedeutet.
  28. Verfahren nach einem der Ansprüche 21 bis 27, dadurch gekennzeichnet, daß die Lösung mit Schwefelsäure hergestellt wird, deren gewichtsbezogene Säurekonzentration etwa 100 % beträgt.
  29. Verfahren nach einem der Ansprüche 21 bis 28, dadurch gekennzeichnet, daß es unter Einsatz mindestens eines aromatischen Polyamids durchgeführt wird, das im wesentlichen p-Phenylenterephthalamid-Verknüpfungen aufweist.
  30. Verfahren nach einem der Ansprüche 21 bis 28, dadurch gekennzeichnet, daß es unter Einsatz von Poly(p-phenylenterephthalamid) durchgeführt wird.
  31. Verbundmaterial, das mindestens ein Aramid-Monofilament nach einem der Ansprüche 1 bis 20 enthält.
  32. Formkörper, der mit mindestens einem Aramid-Monofilament nach einem der Ansprüche 1 bis 20 verstärkt ist.
  33. Formkörper, der mit mindestens einem Verbundmaterial nach Anspruch 31 verstärkt ist.
  34. Gegenstand nach Anspruch 32 oder 33, dadurch gekennzeichnet, daß es sich um einen Luftreifen handelt.
EP90909123A 1989-06-28 1990-06-27 Aramidemonofilament und verfahren zur herstellung Expired - Lifetime EP0435975B1 (de)

Applications Claiming Priority (5)

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FR8908755 1989-06-28
FR8908755A FR2649127B1 (fr) 1989-06-28 1989-06-28 Monofilament en poly(p-phenylene terephtalamide) et procede pour obtenir un tel monofilament
FR9004790A FR2660941B1 (fr) 1990-04-11 1990-04-11 Monofilament aramide et procede pour l'obtenir.
FR9004790 1990-04-11
PCT/CH1990/000155 WO1991000381A1 (fr) 1989-06-28 1990-06-27 Monofilament aramide et procede pour l'obtenir

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JPH04500394A (ja) 1992-01-23
WO1991000381A1 (fr) 1991-01-10
NO910757D0 (no) 1991-02-26
HUT58835A (en) 1992-03-30
CA2033172C (fr) 2001-02-06
HU904843D0 (en) 1991-10-28
BR9006842A (pt) 1991-08-06
DE69027108D1 (de) 1996-06-27
OA09554A (fr) 1993-01-31
EP0435975A1 (de) 1991-07-10
NO910757L (no) 1991-04-24
NO178236B (no) 1995-11-06
DE69027108T2 (de) 1996-10-17
KR920701539A (ko) 1992-08-12
NO178236C (no) 1996-02-14
KR0143889B1 (ko) 1998-07-15
RU2096537C1 (ru) 1997-11-20
CA2033172A1 (fr) 1990-12-29
US5246776A (en) 1993-09-21
HU213944B (en) 1997-11-28
ATE138427T1 (de) 1996-06-15
AU634554B2 (en) 1993-02-25
FI910952A0 (fi) 1991-02-27
ES2089017T3 (es) 1996-10-01
JP3093786B2 (ja) 2000-10-03
AU5816790A (en) 1991-01-17

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