EP0051189B2 - 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

Info

Publication number
EP0051189B2
EP0051189B2 EP81108416A EP81108416A EP0051189B2 EP 0051189 B2 EP0051189 B2 EP 0051189B2 EP 81108416 A EP81108416 A EP 81108416A EP 81108416 A EP81108416 A EP 81108416A EP 0051189 B2 EP0051189 B2 EP 0051189B2
Authority
EP
European Patent Office
Prior art keywords
spinning
solvent
acrylonitrile
fibers
nozzle
Prior art date
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.)
Expired - Lifetime
Application number
EP81108416A
Other languages
German (de)
English (en)
Other versions
EP0051189A1 (fr
EP0051189B1 (fr
Inventor
Ulrich Dr. Reinehr
Kurt Bernklau
Toni Herbertz
Hermann-Josef Jungverdorben
Hans Karl Burghartz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6115591&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0051189(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0051189A1 publication Critical patent/EP0051189A1/fr
Application granted granted Critical
Publication of EP0051189B1 publication Critical patent/EP0051189B1/fr
Publication of EP0051189B2 publication Critical patent/EP0051189B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

  • A. Lehnen and G. Satlow in synthetic fibers and the textile industry March 1975 pages 251-254 report on the improved soiling behavior of textile floor coverings made of polyamide 6,6 yarns with a deeply lobed trilobal cross-sectional shape.
  • 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.
  • 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 identify the geometry of the profile nozzle used, a profile nozzle being understood to mean any nozzle bore with the exception of the simple ruden nozzle bore. Simple geometric shapes are used in particular.
  • the invention therefore relates to a process for the production of acrylonitrile fibers and threads with a sharp cross-sectional profile, wherein the thread-forming synthetic polymers are spun after a dry spinning process from a highly viscous solution through a profile nozzle, the nozzle hole area of which is less than 0.2 mm 2 and the leg width of which is less than 0.
  • the solution consists of acrylonitrile homo- and copolymers with at least 85% by weight of copolymerized acrylonitrile units and a viscosity of at least 120 falling ball seconds, measured at 80 ° C or at least 75 falling ball seconds, measured at 100 ° C, has, the solution being prepared by preparing appropriately concentrated suspensions of the thread-forming polymer in the desired solvent and in addition a non-solvent for the polymer which is miscible with the spinning solvent to a wide extent and these suspensions for a short time at tempera heated to just below the boiling point of the spinning solvent used.
  • the viscosity in falling ball seconds, measured at 80 or at 100 ° C was determined by the method of K. Jost, Reologica Acta, Vol. 1 (1958), page 303.
  • the leg width of a profile nozzle is the distance between the outer limit of the given profile shape in mm. but not understood the distance to the center of the nozzle hole. In the case of nozzle hole shapes whose leg width cannot be easily defined, for example a profile nozzle with triangular holes, 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 of 0.02-0.06 mm and nozzle hole areas of up to 0.1 mm 2 are particularly preferably used. At A flow of the cross-sectional shapes is determined in nozzle hole areas larger than 0.2 mm 2 . You get fuzzy, bulbous to formlessly deformed strange structures.
  • Spinning solutions of the stated viscosity which also contain a higher concentration of the thread-forming polymer, are obtained according to DE-A-27 06 032 by preparing appropriately concentrated suspensions of the thread-forming polymer, which are easy to convey, in the desired solvent and this suspension by briefly Heating to temperatures just below the boiling point of the spinning solvent used, converted into spinning solutions that are stable in viscosity.
  • the suspensions for the preparation of such spinning solutions are obtained by adding a non-solvent for the polymer to be spun to the spinning solvent and then adding the polymer with stirring. All substances which are a non-solvent for the polymer and which 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 can 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, glycerol, mono- and tetraethylene glycol and sugar are used as preferred non-solvents because of their easy handling and removal in the spinning shaft without residue formation and recovery.
  • non-solvents are used, the boiling point of which is below the boiling point of the spinning solvent, the known types with acrylic fibers with water retention capacity below 10%, for example 4.5-6%, are obtained.
  • acrylic fibers with a water retention capacity of greater than 10% are obtained, as already described in DE-A-25 54 124, which are distinguished by special wearing properties. While in the first case the non-solvent is removed in the spinning shaft, in the second case the non-solvent has to be washed out of the solidified fiber in a further process step following the spinning process.
  • 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, there is no longer any flowable, transportable suspension, but rather a thick, sluggish paste. 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 as can be seen from Table 11 for a 35% spinning solution or for a 36% spinning solution, only slightly influences 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 are found 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 cladding 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 produced according to the invention can have individual titer 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 0.069 6 (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 titer material is collected on spools and a band with a total titer of 187,000 dtex is folded.
  • the fiber cable is then stretched 1: 4 times in boiling water and, in the usual way, to fibers of single end titer 2.6 dtex aftertreated.
  • 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 1,500 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 11 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 in the introduction, in falling ball seconds at 80 ° C.
  • Example 1 The other spinning and post-treatment conditions correspond to the explanations of Example 1.
  • Fiber strength 2.7 cN / dtex; Tear resistance: 31%.
  • 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 dissolved again, as described in Example 1, filtered and spun dry from a 90-hole nozzle with trilobal nozzle holes (cf. 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 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 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 ball 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 0.069 6 (mm) 2 and the leg width is 0.04 mm.
  • the shaft temperature is 160 ° C and the air temperature is 100 ° C.
  • the enforced air flow is 30 m l / Stunge.
  • the take-off speed is 350 m / min.
  • the 475 dtex titer material 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 and in the usual way. Post-treated fibers with a final titer of 1.6 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 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 111 below 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 5 is used.
  • the spinning solution is prepared as described there and spun into fibers from the profiled nozzles given in Table 111 and then aftertreated. It was spun from 90 lynx 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 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 is 30 m 3 fh.
  • the take-off speed is 250 m / min.
  • the spun material of titer 2,100 dtex is collected on bobbins, folded into a ribbon with a total titer of 210,000 dtex and, as described in Example 5, post-treated into 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 chemical composition of Example 5 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.
  • 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 1,770 dtex is collected on bobbins, folded into a ribbon 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%.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (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)

Claims (3)

1. Procédé de préparation de fibres et filaments d'acrylonitrile à profil de section net dans lequel on file les polymères synthétiques fibrogènes par une technique de filage à sec à partir d'une solution à haute viscosité au travers d'une filière profilée dont la surface d'orifice de filière est inférieure à 0,2 mm2 et la largeur de jambe inférieure à 0,17 mm, caractérisé en ce que la solution consiste en homo- et co-polymères de l'acrylonitrile à au moins 85% en poids de motifs d'acrylonitrile polymérisés et présente une viscosité d'au moins 120 s à la chute de la bille, mesurée à 80°C, ou d'au moins 75 s à la chute de la bille, mesurée à 100°C, et en ce que l'on prépare la solution en préparant des suspensions à la concentration correspondante du polymère fibrogène dans le solvant désiré et, en outre, un non-solvant du polymère, qui est miscible dans de larges limites avec le solvant de filage, et en chauffant ces suspensions un court instant à des températures jusque juste au-dessous du point d'ébullition du solvant de filage utilisé.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise et tant que non-solvant de l'eau, du glycérol, du monoéthylène-glycol, du tétraéthylène-glycol ou un sucre.
3. Procédé selon la revendication 1, caractérisé en ce que la viscosité de la solution de filage, mesurée à 80°C, est de 120 à 300 s à la chute de la bille, et mesurée à 100°C, de 75 à 300 s à la chute de la bille.
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 EP0051189A1 (fr) 1982-05-12
EP0051189B1 EP0051189B1 (fr) 1985-08-07
EP0051189B2 true EP0051189B2 (fr) 1990-07-04

Family

ID=6115591

Family Applications (1)

Application Number Title Priority Date Filing Date
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

Country Status (4)

Country Link
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

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US3092873A (en) * 1958-10-17 1963-06-11 Celanese Corp Spinneret
US3131428A (en) * 1958-12-19 1964-05-05 Celanese Corp Spinneret and spinning method
US3169089A (en) * 1960-04-22 1965-02-09 Celanese Corp Filaments
NL284441A (fr) * 1961-10-26
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
DE2554124C3 (de) * 1975-12-02 1986-07-10 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von hydrophilen Fasern und Fäden aus Acrylnitrilpolymerisaten
DE2658179C2 (de) * 1976-12-22 1983-02-03 Bayer Ag, 5090 Leverkusen Herstellung grobtitriger Acrylfasern
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
DE2901860A1 (de) * 1979-01-18 1980-07-31 Bayer Ag Kontinuierliches verfahren zur herstellung von faeden oder fasern aus schwerloeslichen synthetischen polymeren

Also Published As

Publication number Publication date
JPS57106713A (en) 1982-07-02
JPH0214443B2 (fr) 1990-04-09
US4810448A (en) 1989-03-07
DE3171719D1 (en) 1985-09-12
EP0051189A1 (fr) 1982-05-12
EP0051189B1 (fr) 1985-08-07
DE3040970A1 (de) 1982-06-03

Similar Documents

Publication Publication Date Title
AT395863B (de) Verfahren zur herstellung eines cellulosischen formkoerpers
DE2948298C2 (fr)
EP0044534B1 (fr) Filaments et fibres à haut module, en polyacrylonitrile, et leur procédé de fabrication
DE2554124B2 (de) Hydrophile fasern und faeden aus synthetischen polymeren
DE3541034C2 (fr)
DE2951803C2 (fr)
EP0051189B2 (fr) Procédé pour la fabrication des filaments et fibres en polyacrylonitrile, à section profilée filés à sec
DE2607996A1 (de) Hydrophile fasern und faeden aus synthetischen polymeren
EP0019870B1 (fr) Fibres et filaments formés de mélanges de copolymères d'acrylonitrile et méthode pour leur fabrication
DE2713456C2 (de) Verfahren zur Herstellung von hydrophilen Fasern
EP0051203B1 (fr) Procédé pour la fabrication des filaments et fibres creuses en polyacrylonitrile, filés à sec
DE2736302C3 (de) Verfahren zur Herstellung von Polypyrrolidonfäden
DE3201350C2 (de) Verfahren zur Herstellung von Acrylfasern mit Antipilling-Eigenschaften
EP0069268B1 (fr) Procédé pour la fabrication de filaments et fibres creuses de polyacrylonitrile par filage au fondu
DE2657144A1 (de) Verfahren zur herstellung hydrophiler fasern
DE3418943A1 (de) Verfahren zur herstellung von faeden und fasern aus acrylnitrilpolymerisaten
EP0029949B1 (fr) Procédé de fabrication suivant un procédé de filage à sec de fibres et filaments hygroscopiques, à gaine et âme, ayant une section transversale stable
DE2909785A1 (de) Verfahren zur herstellung von faeden oder fasern aus acrylnitril enthaltenden polymerisaten mit erhoehtem wasserretentionsvermoegen
DE3630244C2 (de) Kontinuierliches Trockenspinn- und Nachbehandlungsverfahren des Spinngutes für hochschrumpffähige Acrylnitrilfäden und -fasern und entsprechende Fäden und Fasern
DE1771180C3 (de) Verfahren zur Herstellung von Reyon-Papier oder Vliesstoffen im Naßverfahren
DE2607659A1 (de) Hydrophile fasern und faeden aus synthetischen polymeren
DE2703545A1 (de) Bikomposit-acrylfasern und verfahren zu ihrer herstellung
EP0013764B1 (fr) Fibres hydrophiles de polycarbonate ayant une température de transition de second ordre élevée et procédé pour la fabrication de ces fibres
DE2737404A1 (de) Hydrophile fasern und faeden aus synthetischen polymeren
DE1760989A1 (de) Verbesserte Polypivalolactonfasern und Verfahren zu ihrer Herstellung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19811016

AK Designated contracting states

Designated state(s): DE FR GB IT

ITF It: translation for a ep patent filed

Owner name: SOCIETA' ITALIANA BREVETTI S.P.A.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB IT

REF Corresponds to:

Ref document number: 3171719

Country of ref document: DE

Date of ref document: 19850912

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HOECHST AKTIENGESELLSCHAFT, FRANKFURT

Effective date: 19860506

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881016

GBPC Gb: european patent ceased through non-payment of renewal fee
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19891031

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19900704

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR GB IT

EN3 Fr: translation not filed ** decision concerning opposition
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940913

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960702

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO