EP0051189A1 - Procédé pour la fabrication des filaments et fibres en polyacrylonitrile, à section profilée filés à sec - Google Patents

Procédé pour la fabrication des filaments et fibres en polyacrylonitrile, à section profilée filés à sec Download PDF

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Publication number
EP0051189A1
EP0051189A1 EP81108416A EP81108416A EP0051189A1 EP 0051189 A1 EP0051189 A1 EP 0051189A1 EP 81108416 A EP81108416 A EP 81108416A EP 81108416 A EP81108416 A EP 81108416A EP 0051189 A1 EP0051189 A1 EP 0051189A1
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EP
European Patent Office
Prior art keywords
spinning
cross
fibers
dry
spun
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
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EP81108416A
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German (de)
English (en)
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EP0051189B1 (fr
EP0051189B2 (fr
Inventor
Ulrich Dr. Reinehr
Kurt Bernklau
Toni Herbertz
Hermann-Josef Jungverdorben
Hans Karl Burghartz
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Bayer AG
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Bayer AG
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    • 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
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide

Definitions

  • polyamide and polyester fibers are preferably produced using the melt spinning process from profiled spinnerets in order to achieve special effects with regard to gloss, grip, luster and loss of goods.
  • the effects of changing the thread cross-sectional shape of synthetic fibers in detail on the failure and behavior of finished goods can be seen, for example, from the reports by F. Bolland in Chemiefaser 13 (1963), pages 42-45 and 106-109 and from the article H. Bieser and R. Hesse in Chemiefaser 17 (1967), pages 262-268. H.
  • cross-section-modified synthetic fibers for example cross-section-modified acrylic fibers, can also be produced by the wet spinning process.
  • acrylic fibers with a triangular fiber cross section are on the market, which are characterized by high color brilliance.
  • dumbbell-shaped cross section is always obtained, for example with an acrylonitrile copolymer made of 93.6% by weight acrylonitrile, 5.7% by weight methyl acrylate and 0.7% by weight sodium methallylsulfonate with the K value 81 from a 32% by weight spinning solution in dimethylformamide. If one tries to raise the solids content further, then Such spinning solutions gel on cooling even at temperatures around 50-80 ° C., so that trouble-free spinning becomes impossible.
  • the object of the present invention was to provide such a dry spinning process because of the versatile application possibilities of such fibers and threads.
  • any predetermined cross-sectional profile can be spun if spinning solutions with a viscosity exceeding a certain value are used and profile nozzles which have certain dimensions are used.
  • Fibers with a sharp cross-sectional profile are to be understood as fibers whose cross-section can be used to recognize the geometry of the profile nozzle used, a profile nozzle being understood to mean any nozzle bore with the exception of the simple round nozzle bore. Simple geometric shapes are used in particular.
  • the invention therefore relates to dry-spun polyacrylonitrile fibers with a sharp cross-sectional profile.
  • Suitable acrylonitrile polymers for the production of threads and fibers are acrylonitrile homopolymers and copolymers, the copolymers containing at least 50% by weight, preferably at least 85% by weight, of copolymerized acrylonitrile units.
  • the invention further relates to a method for Manufacture of acrylic fibers and threads with a sharp cross-sectional profile, characterized in that the thread-forming synthetic polymers are spun after a dry spinning process from a solution which has a viscosity of at least 120 ball falling seconds, measured at 80 ° C or at least 75 ball falling seconds, measured at 100 ° C, the nozzle hole area of the profile nozzle being less than 0.2 mm 2 and the leg width being less than 0.17 mm.
  • Spinning is followed by the usual further process steps of the acrylonitrile dry spinning process.
  • the viscosity in falling ball seconds was determined by the method of K. Jost, Reologica Acta, Vol. 1 (1958), page 303.
  • the leg width of a profile nozzle is understood to mean the distance in mm from the outer boundary of the predetermined profile shape, but not the distance to the center of the nozzle hole.
  • the distance between two opposite side centers is defined as the middle leg width as the leg width. It has been shown that sharp cross-sectional profiles can always be spun in the sense of the invention if the nozzle hole area is less than 0.2 mm 2 and the leg width is less than 0.17 mm.
  • Leg widths are particularly preferred from 0.02 - 0.06 mm and nozzle hole areas up to 0.1 mm 2 are used. For nozzle hole areas larger than 0.2 mm 2 a. Flowing of the cross-sectional shapes found. You get fuzzy, bulbous to formless. deformed playful structures.
  • Spinning solutions of the stated viscosity which also contain a higher concentration of the thread-forming polymer, are obtained according to DE-OS 27 06 032 by preparing appropriately concentrated suspensions of the thread-forming polymer, which are easy to convey, in the desired solvent and heating this suspension by briefly heating it up Converted temperatures to just below the boiling point of the spinning solvent used in viscosity-stable spinning solutions.
  • the suspensions for the preparation of such spinning solutions are obtained by, if necessary, spinning the solvent with a non-solvent for that to be spun Polymers added and then the polymer is added with stirring. All substances that are non-solvents for the polymer and can be mixed with the spinning solvent within wide limits are suitable as non-solvents in the sense of the invention.
  • the boiling points of the non-solvents can be both below and above the boiling point of the spinning solvent used.
  • Such substances which may be in solid or liquid state, are, for example, alcohols, esters or ketones and mono- and polysubstituted alkyl ethers and esters of polyhydric alcohols, inorganic or organic acids, salts and the like.
  • Water and, on the other hand, glycerin, mono- and tetraethylene glycol and sugar are used as preferred non-solvents because of their easy handling and removal in the spin shaft without residue formation and recovery.
  • the water content of such suspensions of polyacrylonitrile and dimethylformamide is in the range between 2 and 10% by weight, based on the total suspension. Below 2% by weight of water, a free-flowing, transportable suspension is no longer obtained, but rather a thick, slurry. On the other hand, if the water content is more than 10% by weight, the threads burst during the spinning process below the nozzle because of the excessive water vapor partial pressure when it emerges from the nozzle holes.
  • the percentage of water in the spinning solution influences, as shown in Table II for a 35% spinning solution or for a 36% spinning solution, only to a small extent the profile at the nozzle. It is crucial that the spinning solution has the specified minimum viscosity.
  • acrylonitrile copolymer made from 92% acrylonitrile 6% acrylic acid methyl ester and 2% sodium methallylsulfonate with a K value of 60
  • a suspension made of 45% copolymer solid, 4% water and 51% dimethylformamide can be produced, which is still flowable at room temperature and heated by heating Spinning solution gives, which has a viscosity of 142 ball falling seconds at 80 ° C.
  • the spinning of this spinning solution from profile nozzles results in fibers with a sharp cross-sectional profile in the sense of this invention.
  • the required viscosity of the spinning solution can also be achieved with a lower solids concentration.
  • the spinning solution has a minimum viscosity.
  • non-solvent fractions of 5-10% by weight have proven to be optimal in order to obtain profiled acrylic fibers with a water retention capacity greater than 10%.
  • the fibers also have a core-shell structure. The thickness of the fiber sheath can be varied within wide limits by the ratio of polymer solid to non-solvent content.
  • the minimum viscosity can be determined at two different temperatures, namely at 80 ° C and 100 ° C.
  • This measure takes into account the fact that, on the one hand, the determination of the viscosity in spinning solutions which contain water as the non-solvent is difficult because of the evaporation of the water at 100 ° C., on the other hand the determination of the viscosity in the case of other spinning solutions which contain a substance as the non-solvent whose boiling point is above that of the spinning solvent can become problematic at 80 ° C due to the tendency to gel.
  • the viscosity of water-containing spinning solutions can also be determined at 100 ° C when working in a closed system.
  • the water retention capacity (WR) is determined based on DIN specification 53 814 (see Melliant "Textile Reports” 4, 1973, page 350).
  • the higher boiling solvents such as dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and N-methylpyrrolidone, and the like can also be used as spinning solvents in the production of acrylic fibers with modified fiber cross sections.
  • the fibers according to the invention can have individual titers in the stretched state of 1 to 40 dtex.
  • DMF dimethylformamide
  • 38 kg of an acrylonitrile copolymer composed of 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate with a K value of 81 are then metered in with stirring at room temperature.
  • the suspension is pumped via a gear pump into a spinning kettle equipped with an agitator. Then the suspension, which has a solids content of 38% by weight and a water content of 3% by weight, based on the total solution, is heated in a double-walled tube with steam of 4.0 bar.
  • the dwell time in the tube is 7 minutes.
  • the temperature of the solution at the pipe outlet is 138 ° C.
  • the spinning solution which has a viscosity of 176 falling balls at 80 ° C, is filtered after leaving the heating device without intermediate cooling and fed directly to the spinning shaft.
  • the spinning solution is spun dry from a 90-hole nozzle with hexalobal nozzle holes (see FIG. 1).
  • the nozzle hole area is 0.0696 (mm) 2 and the leg width is 0.04 mm.
  • the shaft temperature is 160 ° C and the air temperature is 150 ° C.
  • the air flow rate is 30 m 3 / hour.
  • the take-off speed is 275 m / min.
  • the 750 dtex spinning material is collected on bobbins and closed a volume of 187,000 dtex total titre.
  • the fiber cable is then stretched 1: 4 times in boiling water and aftertreated in the usual way to give fibers with a final density of 2.6 dtex.
  • the fiber capillaries are embedded in methyl methacrylate and cross-cut.
  • the light microscopic images produced in the differential interference contrast method show that the sample cross sections have a completely uniform hexalobal structure.
  • the tensile strength is 2.9 cN / dtex and the elongation at break is 27%.
  • Table I shows the production of further modified fiber cross-sectional shapes, such as those obtained in dry spinning from profiled nozzles by the process according to the invention.
  • an acrylonitrile copolymer with the chemical composition and concentration of Example 1 is used.
  • the spinning solution is prepared as described there and spun into fibers from the profiled nozzles given in Table 1 and then aftertreated. It was spun from 90-hole nozzles.
  • the thread cross-sectional geometry is determined as stated in Example 1 and is documented with light microscopic images.
  • An acrylonitrile copolymer with the chemical composition of Example 1 with a K value of 81 is, as described there, dissolved, filtered and dry spun from a 90-hole nozzle with trilobal nozzle holes (see FIG. 8).
  • the nozzle hole area is 0.03 (mm) 2 and the leg width is 0.04 mm.
  • the shaft temperature is 150 ° C and the air temperature is 150 ° C.
  • the air flow rate is 30 m 3 / h.
  • the take-off speed is 125 m / min.
  • the spinning material with a titer of 1500 dtex is collected on spools, folded into a ribbon with a total titer of 150,000 dtex and, as described in Example 1, post-treated to fibers with a final titer of 5.0 dtex.
  • the following table II shows the limits of the method according to the invention for producing cross-section-modified acrylic fibers according to the dry spinning method using further examples.
  • an acrylonitrile copolymer with the chemical composition of Example 1 is used again and transferred to a spinning solution as described there.
  • the solids concentration and the type and percentage of non-solvent for PAN are varied. It is spun from one of the 90-hole nozzles described above with trilobal nozzle holes (cf. FIG. 8).
  • the spinning and aftertreatment conditions correspond to the information from example 2.
  • the viscosities are measured, as described at the beginning, in falling ball seconds at 80 ° C.
  • Example 1 67 kg of dimethylformamide are mixed with 3 kg of water in a kettle with stirring. Then 30 kg of an acrylonitrile homopolymer with a K value of 91 according to Fikentscher are metered in with stirring at room temperature.
  • the suspension which has a solids concentration of 30%, is again dissolved, as described in Example 1, filtered and from a 90-hole nozzle spun dry with trilobal nozzle holes (see FIG. 8).
  • the viscosity measured at 80 ° C was 138 falling seconds.
  • the nozzle hole area is 0.03 mm 2 and the leg width is 0.04 mm.
  • the other spinning and post-treatment conditions correspond to the explanations of Example 1.
  • DMF dimethylformamide
  • monoethylene glycol monoethylene glycol
  • 37 kg of an acrylonitrile copolymer of 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate with a K value of 81 are then metered in with stirring at room temperature.
  • the suspension is pumped via a gear pump in a spinning kettle equipped with an agitator. Then the suspension, which has a solids content of 37% by weight and a non-solvent content of 6% by weight, based on the total solution, is heated in a double-walled tube with steam of 4.0 bar.
  • the dwell time in the tube is 7 minutes.
  • the temperature of the solution at the pipe outlet is 138 ° C.
  • the spinning solution which has a viscosity of 186 falling seconds at 100 ° C, is filtered after leaving the heating device without intermediate cooling and fed directly to the spinning shaft.
  • the spinning solution is spun dry from a 90-hole nozzle with hexalobal nozzle holes (see FIG. 1).
  • the nozzle hole area is 0.0696 (mm) 2 and the leg width is 0.04 mm.
  • the shaft temperature is 160 ° C and the air temperature is 100 ° C.
  • the air flow rate is 30 m 3 / hour.
  • the take-off speed is 350 m / min.
  • the spun material with a titer of 475 dtex is collected on spools and folded into a band with a total titer of 142 500 dtex.
  • the fiber cable is then stretched 1: 4 times in boiling water, washed, dried at 110 ° C.
  • the fiber capillaries are embedded in methyl methacrylate and cross-cut.
  • the light microscopic images produced in the differential interference contrast method show that the sample cross sections have a completely uniform shape with a hexalobal core / shell structure.
  • the tear strength is 2.6 cN / dtex and the elongation at break is 34%.
  • the surface area is approximately 80%.
  • the water retention capacity is 12.6%.
  • Table III shows the production of further, modified fiber cross-sectional shapes, as are obtained in dry spinning from profiled nozzles by the process according to the invention.
  • an acrylonitrile copolymer with the chemical composition and concentration of Example 5 used.
  • the spinning solution is prepared as described there and spun into fibers from the profiled nozzles given in Table III and then aftertreated. It was spun from 90-hole nozzles.
  • the thread cross-sectional geometry was determined, as stated in Example 1, and documented with light microscopic images.
  • Example 5 55 kg of dimethylformamide are mixed with 7 kg of tetraethylene glycol in a kettle with stirring. Then 38 kg of an acrylonitrile copolymer having the chemical composition of Example 5 with a K value of 81 are metered in with stirring at room temperature.
  • the suspension which has a solids concentration of 38%, is again dissolved, as described in Example 5, filtered and spun dry from a 90-hole nozzle with trilobal nozzle holes (cf. FIG. 8).
  • the viscosity of the spinning solution measured at 100 ° C is 152 falling seconds.
  • the nozzle hole area is 0.03 mm2 and the leg width is 0.04 mm.
  • the shaft temperature is 160 ° C and the air temperature is 150 ° C.
  • the air flow is 30m J / h.
  • the take-off speed is 250 m / min.
  • the spinning material with a titer of 2100 dtex is collected on bobbins, folded into a band with a total titer of 210,000 dtex and after-treated as described in Example 5 to give fibers with a final titer of 6.7 dtex.
  • the sample cross-sections of the fibers which in turn have a core / sheath structure, show a completely uniform trilobal cross-sectional profile. Fiber strength 2.4 cN / dtex; Elongation at break: 34%; Water retention: 15.2%.
  • the following table IV shows the limits of the method according to the invention for producing cross-section-modified acrylic fibers according to the dry spinning method using further examples.
  • an acrylonitrile copolymer with the. used chemical composition of Example 5 and transferred to a spinning solution as described therein.
  • the solids concentration and the type and percentage of non-solvent for PAN are varied.
  • the spinning and post-treatment conditions correspond to the information from Example 2.
  • the viscosity in falling ball seconds is determined at 100 ° C.
  • Example 5 The other spinning and post-treatment conditions correspond to the explanations of Example 5.
  • the sample cross sections of the fibers which have a final titer of 3.1 dtex, show a completely uniform hexalobal cross-sectional profile with a core / shell structure.
  • Fiber strength 2.7 cN / dtex; Elongation at break: 31%. Water retention: 10.2%.
  • a portion of the spinning solution from Example 5 is fed to another spinning shaft after the filtration and is dry spun from a 90-hole nozzle with hexalobal nozzle holes (see FIG. 1).
  • the shaft temperature is 220 ° C and the air temperature is 360 ° C.
  • the air flow rate is 40 m 3 / hour.
  • the take-off speed is 125 m / min.
  • the spun material with a titre of 1770 dtex is collected on bobbins, folded into a band with a total titre of 177,000 dtex and then, as described in Example 5, post-treated into fibers with a final titre of 6.7 dtex.
  • the sample cross-sections of the fibers show a completely uniform hexalobal cross-sectional profile. However, they no longer have a core / shell structure, since most of the non-solvent is evaporated out in the spinning shaft.
  • the water retention capacity is 4.3%.
  • a part of the fiber cable from Example 5 with a total titer of 142,500 dtex was stretched and washed as described there, but then dried at 180 ° C. in a drum dryer with 20% shrinkage and in the usual way to fibers with a final titer of 1.6 dtex aftertreated.
  • the sample cross-sections of the fibers show a completely uniform hexalobal cross-sectional profile. However, they no longer have a core / shell structure, since the pore system due to the harsh drying conditions has been eliminated.
  • the water retention capacity is 3.9%.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP81108416A 1980-10-30 1981-10-16 Procédé pour la fabrication des filaments et fibres en polyacrylonitrile, à section profilée filés à sec Expired - Lifetime EP0051189B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803040970 DE3040970A1 (de) 1980-10-30 1980-10-30 Trockengesponnene polyacrylnitril-profilfasern und -faeden und ein verfahren zu ihrer herstellung
DE3040970 1980-10-30

Publications (3)

Publication Number Publication Date
EP0051189A1 true EP0051189A1 (fr) 1982-05-12
EP0051189B1 EP0051189B1 (fr) 1985-08-07
EP0051189B2 EP0051189B2 (fr) 1990-07-04

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EP81108416A Expired - Lifetime EP0051189B2 (fr) 1980-10-30 1981-10-16 Procédé pour la fabrication des filaments et fibres en polyacrylonitrile, à section profilée filés à sec

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US (1) US4810448A (fr)
EP (1) EP0051189B2 (fr)
JP (1) JPS57106713A (fr)
DE (2) DE3040970A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5994611A (ja) * 1982-11-22 1984-05-31 Mitsubishi Rayon Co Ltd ポリアクリロニトリルフィラメント糸の製造方法
GB8527752D0 (en) * 1984-11-21 1985-12-18 Mitsubishi Rayon Co Acrylic fiber
JPH0712646Y2 (ja) * 1989-06-20 1995-03-29 株式会社クボタ エンジンの大容量オイルパン
SG73992A1 (en) * 1995-12-18 2000-07-18 Standard Oil Co Melt spun acrylonitrile olefinically unsaturated fibers and a process to make fibers
CN101351581A (zh) * 2005-12-06 2009-01-21 因维斯塔技术有限公司 有三个主叶和三个小叶的六叶横截面纤丝，由具有该纤丝的纱线簇绒成的地毯，和用于制造该纤丝的毛细喷丝头孔
CN105273125A (zh) * 2014-06-06 2016-01-27 中国石油化工股份有限公司 适用于干法腈纶纺丝的聚丙烯腈干粉及制备方法
WO2021203027A1 (fr) * 2020-04-02 2021-10-07 Aladdin Manufacturing Corporation Filaments de type ruban et leurs systèmes et procédés de production

Citations (6)

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Publication number Priority date Publication date Assignee Title
US3169089A (en) * 1960-04-22 1965-02-09 Celanese Corp Filaments
DE1219165B (de) * 1958-10-17 1966-06-16 Celanese Corp Spinnduese
DE1435547A1 (de) * 1961-10-26 1969-07-17 Monsanto Co Textilfaden mit besonderem Querschnitt und Spinnduese fuer seine Herstellung
DE2554124A1 (de) * 1975-12-02 1977-06-08 Bayer Ag Hydrophile fasern und faeden aus synthetischen polymeren
DE2658179A1 (de) * 1976-12-22 1978-07-06 Bayer Ag Trockengesponnene grobtitrige acrylfasern
EP0013889A1 (fr) * 1979-01-18 1980-08-06 Bayer Ag Procédé pour la fabrication en continu de filaments ou de fibres à partir de polymères synthétiques difficilement solubles

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CA750852A (en) * 1967-01-17 E. Bishop Clarence Dry-spinning k-shape filaments
CA729518A (en) * 1966-03-08 E. Bishop Clarence Dry spun y-shaped filaments with bulbous ends
US2843449A (en) * 1954-04-13 1958-07-15 Eastman Kodak Co Dry spinning process
US3131428A (en) * 1958-12-19 1964-05-05 Celanese Corp Spinneret and spinning method
US3194002A (en) * 1962-07-25 1965-07-13 Eastman Kodak Co Multifilament yarn of non-regular cross section
US3340571A (en) * 1964-04-02 1967-09-12 Celanese Corp Spinneret for making hollow filaments
FR93435E (fr) * 1966-09-29 1969-03-28 Rhodiaceta Nouvelle filiere et fils spéciaux obtenus au moyen de cette filiere.
JPS5432859B2 (fr) * 1971-11-15 1979-10-17
JPS50135323A (fr) * 1974-04-16 1975-10-27
JPS546919A (en) * 1977-06-17 1979-01-19 Mitsubishi Rayon Co Ltd Production of acrylic noncircular cross-section filament yarns
DE2804376A1 (de) * 1978-02-02 1979-08-09 Bayer Ag Hydrophile hohlfasern

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1219165B (de) * 1958-10-17 1966-06-16 Celanese Corp Spinnduese
US3169089A (en) * 1960-04-22 1965-02-09 Celanese Corp Filaments
DE1435547A1 (de) * 1961-10-26 1969-07-17 Monsanto Co Textilfaden mit besonderem Querschnitt und Spinnduese fuer seine Herstellung
DE2554124A1 (de) * 1975-12-02 1977-06-08 Bayer Ag Hydrophile fasern und faeden aus synthetischen polymeren
DE2658179A1 (de) * 1976-12-22 1978-07-06 Bayer Ag Trockengesponnene grobtitrige acrylfasern
EP0013889A1 (fr) * 1979-01-18 1980-08-06 Bayer Ag Procédé pour la fabrication en continu de filaments ou de fibres à partir de polymères synthétiques difficilement solubles

Also Published As

Publication number Publication date
JPH0214443B2 (fr) 1990-04-09
US4810448A (en) 1989-03-07
JPS57106713A (en) 1982-07-02
DE3171719D1 (en) 1985-09-12
EP0051189B1 (fr) 1985-08-07
EP0051189B2 (fr) 1990-07-04
DE3040970A1 (de) 1982-06-03

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