EP0672201B1 - Procede de sechage rapide d'une fibre de polybenzazole - Google Patents

Procede de sechage rapide d'une fibre de polybenzazole Download PDF

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Publication number
EP0672201B1
EP0672201B1 EP94902469A EP94902469A EP0672201B1 EP 0672201 B1 EP0672201 B1 EP 0672201B1 EP 94902469 A EP94902469 A EP 94902469A EP 94902469 A EP94902469 A EP 94902469A EP 0672201 B1 EP0672201 B1 EP 0672201B1
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Prior art keywords
fiber
percent
drying
temperature
rmc
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EP94902469A
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German (de)
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EP0672201A1 (fr
Inventor
Jang-Hi Im
Chieh-Chun Chau
Hiroki 3-4-402 Ohginosato MURASE
Tooru 5-36 Yamagami-Cho Kitagawa
Takaharu 30-3 Kinugawa 1-Chome Ichiryu
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Toyobo Co Ltd
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Dow Chemical Co
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Priority claimed from US08/142,526 external-priority patent/US5429787A/en
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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
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying

Definitions

  • the present invention relates to improved processes for drying polybenzazole e fibers.
  • Polybenzazole (“PBZ”) fibers include polybenzoxazole (“PBO”) or polybenzothiazole (“PBT”) fibers.
  • Lyotropic liquid crystalline PBZ is typically made into fibers by dry-jet, wet-spinning techniques, in which a solution that contains the PBZ polymer and an acid solvent (known as a "dope") is spun through a spinneret to form dope filaments, that are combined into one or more dope fibers. These dope fibers are drawn across an air gap, and then contacted with a fluid that dilutes the solvent and is a non-solvent for the polymer. This contact with fluid causes the polymer to separate from the solvent. See jointly owned, Allowed, U.S.
  • Patent Applications US-A-4 507 302 (Method for Spinning a Polybenzazole Fiber) and US-A-4 619 933 (Method for Rapid Spinning of a Polybenzazole Fiber) for a description of the PBZ fiber spinning process.
  • Polybenzazole fibers typically contain a very high degree of residual moisture after they are washed.
  • the residual moisture content is frequently between 30 and 200 weight percent, and may even be higher in some fibers.
  • the percent residual moisture content, (hereinafter percent RMC) is calculated on a parts per hundred basis as follows: [(initial fiber weight - dried fiber weight)/dried fiber weight] ⁇ 100%.
  • PBZ fiber can be damaged by exposing it to the typical amount of heat (about 400°C) used in heat treating while the fiber contains more than about twelve percent RMC. Therefore, in order to be heat treated without being damaged, a PBZ fiber usually must have a percent RMC of less than about twelve percent.
  • the present invention is in a first aspect a process as recited in independent claim 1.
  • the second aspect of this invention is a process as recited in independent claim 2.
  • Figure 1 shows a plot of Percent Residual Moisture Content of Polybenzoxazole Fiber vs. Temperature in °C.
  • a negatively sloped curved line 10 representing the boundary between an area 30, representing "safe” drying conditions and an area 20, representing “unsafe” drying conditions.
  • This line 10 is referred to as the non-damage drying ("NDD") line for PBO fiber.
  • Figure 2 shows the NDD line 10 on a plot of Percent Residual Moisture Content (RMC) of Polybenzoxazole Fiber vs. Temperature in °C, along with a series of vertical and horizontal lines 12 representing the drying profile for a PBO fiber wherein the temperature the PBO fiber is exposed to is continuously increased as the moisture content of the fiber is reduced.
  • RMC Percent Residual Moisture Content
  • Figure 3 shows the NDD line 10 on a plot of Percent Residual Moisture Content of Polybenzoxazole Fiber vs. Temperature in °C, along with drying profile lines 1 and 2 representing the reduction of RMC in two separate PBO fibers as they are exposed to progressively elevated temperatures.
  • polybenzazole includes polybenzoxazole (“PBO”) homopolymers, polybenzothiazole (“PBT”) homopolymers and random, sequential and block copolymers of PBO or PBT.
  • PBO polybenzoxazole
  • PBT polybenzothiazole
  • Polybenzoxazole, polybenzothiazole and random, sequential and block copolymers of polybenzoxazole and polybenzotniazoie are described in references such as Wolfe et al., Liquid Crystalline Polymer Compositions, Process and Products, U.S. Patent 4,703,103 (October 27, 1987); Wolfe et al., Liquid Crystalline Polymer Compositions, Process and Products, U.S.
  • Patent 4,533,692 (August 6, 1985); Wolfe et al., Liquid Crystalline Poly(2,6-Benzothiazole) Compositions, Process and Products, U.S. Patent 4,533,724 (August 6, 1985); Wolfe, Liquid Crystalline Polymer Compositions, Process and Products, U.S. Patent 4,533,693 (August 6, 1985); Evers, Thermooxidatively Stable Articulated p-Benzobisoxazole and p-Benzobisthiazole Polymers, U.S. Patent 4,359,567 (November 16, 1982); and Tsai et al., Method for Making Heterocyclic Block Copolymer , U.S. Patent 4,578,432 (March 25, 1986).
  • Units within the PBZ polymer are preferably chosen so that the polymer is lyotropic liquid-crystalline.
  • Preferred monomer units are illustrated in Formulae (a)-(h).
  • the polymer more preferably consists essentially of monomer units selected from those illustrated in (a)-(h), and most preferably consists essentially of a number of identical units selected from those illustrated in (a)-(c).
  • Solvents suitable for formation of dopes of PBZ polymers include cresol as well as non-oxidizing acids capable of dissolving the polymer.
  • suitable acid solvents include polyphosphoric acid, methanesulfonic acid and highly concentrated sulfuric acid and mixtures of those acids.
  • a highly preferred solvent is polyphosphoric acid or methanesulfonic acid.
  • a most highly preferred solvent is polyphosphoric acid.
  • the concentration of the polymer in the solvent is preferably at least about 7 weight percent, more preferably at least about 10 weight percent and most preferably at least about 14 weight percent.
  • the maximum concentration is limited primarily by practical factors, such as polymer solubility and, as already described, dope viscosity. Because of these limiting factors, the concentration of polymer is usually no more than about twenty weight percent.
  • Suitable polymers or copolymers and dopes can be synthesized by known procedures, such as those described in Wolfe et al., U.S. Patent 4,533,693 (August 6, 1985); Sybert et al., U.5. Patent 4,772,678 (September 20, 1988); and Harris, U.S. Patent 4,847,350 (July 11, 1989).
  • PBZ polymers can be advanced rapidly to high molecular weight at relatively high temperatures and high shear in a dehydrating solvent acid, according to Gregory et al., U.S. Patent No. 5,089,591 (February 18, 1992).
  • the dope is spun into fibers by known dry jet, wet-spin techniques in which the dope is spun through a spinneret to form dope filaments that are collected together to form one or more dope fibers.
  • Fiber spinning techniques for PBZ polymers are known in the references already mentioned in the Background of the Invention section.
  • the dope fiber(s) After passing through an air gap the dope fiber(s) is/are contacted with a fluid that dilutes the solvent and is a non-solvent for the polymer. This process is known as coagulation. After coagulation, most of the remaining residual solvent is washed/leached from each fiber, leaving the fiber wet. See jointly owned, U.S. Patent Application US-A-4 519 693 (Improved Process for Coagulation and Washing of Polybenzazole Fibers), for a description of the coagulation process.
  • the amount of residual moisture in the fiber after it has been washed can vary from more than 30 percent RMC all the way up to 200 percent RMC.
  • the percent residual moisture content of the fiber should preferably be twelve percent RMC or less, more preferably ten percent RMC or less, more highly preferably six percent RMC or less, most preferably four percent RMC or less and most highly preferably two percent RMC or less.
  • NDD line 10 represents the maximum safe temperature that a PBO fiber can be exposed to at each specific percent RMC without causing drying-induced damage to the fiber.
  • the NDD line acts as a boundary between areas of "safe" drying conditions, area 30 on Figure 1, and "unsafe” drying conditions, area 20 on Figure 1.
  • the highest drying temperatures that can be selected for drying each PBO fiber can be chosen simply by knowing the percent RMC of the fiber when it will first be exposed to the temperature. It is desi rable to select the highest drying temperature possible for each fiber percent RMC in order to minimize the amount of time it takes to dry the fi ber down to about twelve percent RMC or less.
  • the number of drying temperatures used can be selected as a matter of process convenience, though it has been found desirable and necessary to have two or more drying temperatures, with each temperature selected to be progressively hotter than the previous temperature, in order to minimize the amount of time it takes to dry the fiber to a percent RMC about twelve percent or less.
  • Figure 2 illustrates a multiple-temperature drying process in which twenty-three progressively hotter temperatures are used to dry a PBO fiber from a starting percent RMC above forty percent to a final percent RMC below five percent.
  • the temperatures selected relative to the percent RMC of the fiber in this drying profile are as close as possible to the NDD line without crossing it. This manner of selection insures the most rapid drying process for the fiber without creating voids in the fiber during drying.
  • the morphology and physical state of the PBZ fiber being dried can vary with the dope composition, the polymer formulation and the specific fiber processing conditions, therefore, the highest temperature a PBZ fiber can be exposed to at each percent RMC without being damaged can vary.
  • the NDD line for each PBZ fiber and for the same PBZ polymer processed under different conditions can and will vary, with the amount of variance depending upon the degree in differences between any or ail of, but not limited to, the following factors,
  • one type of standard equipment used to dry fibers includes matched pairs of heated rolls.
  • the fiber is wrapped over these rolls many times in order to increase the amount of contact time the fiber has with the heated roll.
  • Contact time is defined as the amount of time the fi ber is in direct contact with the set point temperature of the heated roll (or other heating device that can be used for drying PBZ fiber).
  • a fiber in contact with a heated roll is at the same temperature as the surface of the roll.
  • the surface temperature of the roll is the same as the set point temperature of the roll, that is, a heated roll with a set point temperature of 180°C should have a surface temperature of 180°C.
  • the set point temperature of a heating device is defined herein as the temperature the heating mechanism of the heating device is set at.
  • the fiber In addition to contact time with the heated roll, the fiber must travel between each pair of heated rolls before it recontacts a roll or before it travels on to the next pair of heated rolls.
  • the time the fiber is not in contact with a heated roll or any other direct source of heat during the drying process is referred to as non-contact time.
  • the total residence time of a fiber during the drying process is the contact time (CT) plus the non-contact time (NCT).
  • CT contact time
  • NCT non-contact time
  • this invention contemplates that as the fiber is exposed to progressively increasing temperatures, that if the fiber is being dried by heated rolls, then there will be brief moments during the drying process when the fiber is not exposed to the full set point temperature of the heated rolls.
  • the fiber continues to undergo drying during its NCT with the heated roll, but that the drying of the fiber during NCT is not as efficient drying as that drying the fiber undergoes during its CT with the heated roll.
  • One way to increase the efficiency of the drying process is to insulate the cabinets that the pairs of heated rolls are usually positioned in, and to blow hot air or a gas that does not damage the fiber, such as nitrogen, helium, argon or carbon dioxide, into the cabinets so that the temperature throughout the cabinet is the same as the set point temperature of the heated rolls.
  • Another way to more efficiently dry fibers is to pass them through progressively heated ovens in which the temperature of each oven is progressively increased such that the fibers are continually exposed to the set point temperature of each oven.
  • the residence time of the fiber is made up of only contact time without any non-contact time.
  • Contact time is, as has already been stated, much more efficient drying time than is non-contact time.
  • these more efficient methods of drying it is possible to reduce the residence time required to reach a certain percent RMC in the fiber as follows.
  • the residence time to achieve a certain percent RMC is about two-thirds or less of what is required when drying is carried out with the contact time and a non-contact time component (such as when drying is carried out using heated rolls positioned in non-insulated drying cabinets).
  • the total amount of residence time, when there is both a CT and a NCT component to the residence time, required to dry a PBZ fiber to less than about twelve percent RMC is no more than about 20 minutes, preferably no more than about 10 minutes, more preferably no more than about 5 minutes, and most preferably no more than about 3 minutes.
  • the total amount of residence time, where there is only a CT component (no NCT component) of residence time, required to dry a PBZ fiber to less than about twelve percent RMC should preferably be no more than about 6 minutes, more preferably be no more than about 3 minutes, and most preferably be no more than about 2 minutes.
  • the total amount of residence time, when there is both a CT and a NCT component to the residence time, required to dry a PBZ fiber to less than about two percent RMC should preferably be no more than about 20 minutes, more preferably be no more than about 15 minutes, and most preferably be no more than about 10 minutes.
  • the total amount of residence time, when there is only a CT component (no NCT component) of residence time, required to dry a PBZ fiber to a level of percent RMC of less than two percent RMC should preferably be no more than about 14 minutes, more preferably be no more than about 10 minutes, and most preferably be no more than about 7 minutes.
  • the drying process In order to dry the fiber to a certain residual moisture content in the amount of time specified in the preceding paragraphs, the drying process must start at a certain minimum temperature. Accordingly, the minimum first temperature the fiber should be exposed to is at least about 140°C, preferably at least about 150°C, more preferably at least about 160°C, more highly preferably at least about 170°C, and most preferably at least about 180°C. It is desirable to minimize the amount of time it takes to dry the fiber. It has been found that selecting intermediate process temperatures close to those temperatures on the NDD line, without going higher than those temperatures on the NDD line (as illustrated by the series of vertical and horizontal lines 12 in Figure 2) allows the most rapid drying of PBZ fiber, without creating voids. Typically, final drying temperatures do not excess 300°C, preferably do not exceed 280°C and most preferably do not exceed 260°C.
  • the drying process is concluded when the percent RMC of the fiber has reached the desired level. Drying is preferably continued until the fiber exiting the drying equipment contains at most about twelve percent RMC, preferably at most about 10 percent RMC, more preferably at most about 8 percent RMC, more highly preferably at most about 6 percent RMC, most preferably at most about 4 percent RMC and most highly preferably at most about 2 percent RMC.
  • percent residual moisture content is determined by a gravimetric method as follows: Approximately 0.5 grams of fiber sample is collected and weighed on a balance. The samples are heated in an oven at 250°C for thirty minutes to remove the residual moisture and weighed again. The percent RMC is determined by calculating [(initial sample weight - dried sample weight)/dried sample weight] x 100 percent.
  • the void content and distribution are determined using a visual microscopic method. Three inch long samples of fiber are cut and end-taped on microscopic slides and observed under a light microscope at 200X magnification. Voids usually appear as blotches or dark striations along the fiber. They can vary in size, number and thickness among fiber samples. The void content is qualitatively rated as void free, slight voids and many voids.
  • a spinning dope that contains 14 percent cis-polybenzoxazole (I.V. 30 g/dL) dissolved in polyphosphoric acid was extruded at 160°C from a spinneret that contained 166 orifices, with each orifice having a diameter of 0.22 mm.
  • the resulting filaments were drawn across an air gap of 22 cm and immersed in an aqueous coagulation bath maintained at a temperature of about 22°C.
  • the fiber was dried using 3 matched pairs of heated drying rolls with each pair of heated drying rolls set up in separate, uninsulated drying cabinets. Each pair of heated drying rolls has the same set point temperature.
  • the residence time in each cabinet is the sum of the amount of time the fiber is in contact with the rolls (CT) plus the amount of time the fiber is not in contact with each roll (non-contact time or NCT). After drying, the physical properties of the dried fiber are measured.
  • Figure 3 shows the drying profile lines of the fibers described in the following examples.
  • the line marked 1 was the drying profile line for Fiber 1.
  • Fiber 1 was moved at 200 meters/minute through the drying process. Drying profile line 1 for Fiber 1 show that this fiber was dried at 180°C (residence time 42 seconds), until its moisture level was below 25 percent, then it was dried at 240°C (residence time 121 seconds) until its moisture level was below 15 percent.
  • the drying profile line 1 crosses the NDD line at position 5.
  • the fiber had a tensile strength of 33.8 g/d(4.66 GPa), a tensile modulus of 1671 g/d(230 GPa) and an elongation to break of 2.46 percent. This fiber had many visible voids present.
  • THIS FIBER IS NOT AN EXAMPLE OF THIS INVENTION.
  • the line marked 2 was the drying profile line for Fiber 2.
  • Fiber 2 was moved at 100 meters/minute through the drying process.
  • Line 2 showed that Fiber 2 was dried first at 170°C (residence time of 84.3 seconds), until its moisture level was below 20 percent then it was dried at 200°C (residence time of 84.3 seconds) until its moisture level was below 10 percent and then it was dried at 240°C (residence time of 79.3) until its moisture level was below 3 percent.
  • this fiber's ending percent RMC was 3.0 percent.
  • the fiber's ending percent residual moisture content drops to 1.0 percent.
  • This fiber had a tensile strength of 38.0 to 39.3 g/d(5.24 to 5.42 GPa), a tensile modulus of 1616 to 1624 g/d(223 to 224 GPa) and an elongation to break of 2.86 to 3.00 percent. This fiber did not have visible voids at the conclusion of the drying process.
  • a polybenzoxazole fiber was provided with a certain percent RMC.
  • One segment of this fiber was dried at a 100/meters minute line speed using heated rolls positioned in a non-insulated cabinet (residence time with contact time and non-contact time components).
  • the first pair of heated rolls had a set point temperature of 180°C
  • the second pair of heated rolls had a set point temperature of 200°C
  • the third pair of heated rolls had a set point temperature of 220°C.
  • the total residence time for the PBO fiber was the sum of all the residence times (33.7 sec CT at each set point temperature and 50.6 seconds N CT at each set point temperature).
  • the total residence time for the PBO fi ber dried in this manner to reach 4.8 percent RMC was 4.2 minutes.
  • the same fiber was dried at 100 m/minute using heated rolls positioned in insulated cabinets wherein the interior temperature of each cabinet was maintained at the set point temperature of the heated rolls contained within it (residence time with only a contact time component).
  • the set point temperature pattern of the rolls were the same as the set point temperatures of the fiber dried with both a CT and a NCT component.
  • the total residence time for the PBO fiber dried in this manner to reach 4.8 percent RMC was 2.4 minutes.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Preliminary Treatment Of Fibers (AREA)

Abstract

L'on peut rapidement sécher des fibres de polybenzazole sans qu'elles soient trop endommagées en les exposant à au moins deux températures de référence, ces températures étant selectionnées par rapport à la teneur en humidité résiduelle de la fibre. Le temps de séjour nécessaire à la fibre à chaque montée progressive de température peut être réduit si la fibre est toujours exposée totalement à la température de référence de l'équipement de séchage.

Claims (7)

  1. Procédé pour réduire la teneur en humidité d'une fibre de polybenzazole d'une valeur supérieure à 30 % en poids jusqu'à une valeur de 12 % en poids ou moins pour la fibre, qui comprend le chauffage de la fibre avec au moins deux dispositifs de chauffage disposés en série, le premier dispositif présentant une température de point de consigne d'au moins 140° C environ,
    caractérisé en ce que
    (a) la température de point de consigne de chaque dispositif de chauffage est fixée à une valeur supérieure à celle du dispositif précédent, ce qui laisse des laps de temps pendant lesquels la fibre n'est pas exposée à une température de point de consigne totale lorsqu'elle va d'un dispositif de chauffage à un autre ;
    (b) les températures de point de consigne des dispositifs de chauffage sont fixées par rapport à la teneur en humidité résiduelle de la fibre et sont choisies pour empêcher la formation de vides visibles au microscope optique pour un grossissement de 200, et
    (c) on effectue le procédé en moins de 20 minutes.
  2. Procédé pour réduire la teneur en humidité d'une fibre polybenzazole d'une valeur supérieure à 30 % en poids jusqu'à une valeur de 12 % en poids ou moins pour la fibre, qui comprend l'exposition de la fibre successivement à deux ou plus de deux températures d'au moins 140° C environ,
    caractérisé en ce que
    (a) chaque température choisie est supérieure à la température précédente ;
    (b) les températures sont choisies par rapport à la teneur en humidité résiduelle de la fibre pour empêcher la formation de vides visibles au microscope optique pour un grossissement de 200, et
    (c) on effectue le procédé en moins de 20 minutes.
  3. Procédé conforme à la revendication 1 ou 2, dans lequel la teneur en humidité résiduelle de la fibre est réduite à 10 % en poids ou moins pour la fibre.
  4. Procédé conforme à la revendication 1 ou 2, qui est effectué en moins de 6 minutes.
  5. Procédé conforme à la revendication 1 ou 2, dans lequel le nombre de températures auxquelles ladite fibre est exposée, vaut 2.
  6. Procédé conforme à la revendication 1 ou 2, dans lequel ladite fibre de polybenzazole est une fibre de polybenzothiazole.
  7. Fibre de polybenzazole séchée par le procédé conforme à la revendication 1 ou 2.
EP94902469A 1992-12-03 1993-11-30 Procede de sechage rapide d'une fibre de polybenzazole Expired - Lifetime EP0672201B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US142526 1980-04-21
US98508092A 1992-12-03 1992-12-03
US985080 1992-12-03
US08/142,526 US5429787A (en) 1992-12-03 1993-11-02 Method for rapid drying of a polybenzazole fiber
PCT/US1993/011592 WO1994012704A1 (fr) 1992-12-03 1993-11-30 Procede de sechage rapide d'une fibre de polybenzazole

Publications (2)

Publication Number Publication Date
EP0672201A1 EP0672201A1 (fr) 1995-09-20
EP0672201B1 true EP0672201B1 (fr) 1997-08-06

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EP (1) EP0672201B1 (fr)
AU (1) AU5682994A (fr)
CA (1) CA2148610A1 (fr)
DE (1) DE69312958T2 (fr)
ES (1) ES2105609T3 (fr)
WO (1) WO1994012704A1 (fr)

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WO2012097254A1 (fr) * 2011-01-13 2012-07-19 E. I. Du Pont De Nemours And Company Production et séchage de fibres copolymères
CN103314142B (zh) * 2011-01-13 2017-03-01 纳幕尔杜邦公司 共聚物纤维的制备和干燥
KR101911110B1 (ko) * 2011-01-13 2018-10-23 이 아이 듀폰 디 네모아 앤드 캄파니 공중합체 섬유의 제조 및 건조

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JPH03104921A (ja) * 1989-09-14 1991-05-01 Mitsui Petrochem Ind Ltd ポリベンゾチアゾール類繊維、ポリベンゾオキサゾール類繊維またはポリベンゾイミダゾール類繊維の製造方法
CA2044407A1 (fr) * 1990-06-15 1991-12-16 William C. Uy Additifs de filage anisotropes de viscosite reduite
JPH04194022A (ja) * 1990-11-28 1992-07-14 Mitsui Petrochem Ind Ltd ポリベンゾチアゾール類繊維、ポリベンゾオキサゾール類繊維またはポリベンゾイミダゾール類繊維の製造方法
JPH04202257A (ja) * 1990-11-29 1992-07-23 Mitsui Petrochem Ind Ltd 全芳香族ヘテロ環状高分子組成物、その繊維、フィルムおよび製造方法

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AU5682994A (en) 1994-06-22
DE69312958T2 (de) 1998-03-12
DE69312958D1 (de) 1997-09-11
WO1994012704A1 (fr) 1994-06-09
ES2105609T3 (es) 1997-10-16
CA2148610A1 (fr) 1994-06-09
EP0672201A1 (fr) 1995-09-20

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