EP0934434B1 - Procede de fabrication de fibres aramide haute tenacite - Google Patents

Procede de fabrication de fibres aramide haute tenacite Download PDF

Info

Publication number
EP0934434B1
EP0934434B1 EP97913738A EP97913738A EP0934434B1 EP 0934434 B1 EP0934434 B1 EP 0934434B1 EP 97913738 A EP97913738 A EP 97913738A EP 97913738 A EP97913738 A EP 97913738A EP 0934434 B1 EP0934434 B1 EP 0934434B1
Authority
EP
European Patent Office
Prior art keywords
filaments
grams per
coagulating
jetted
coagulating liquid
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
EP97913738A
Other languages
German (de)
English (en)
Other versions
EP0934434A1 (fr
Inventor
Takeji Furumai
Kouzou Imaeda
Stephen D. Moore
Mikio Ohno
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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
Priority claimed from US08/950,250 external-priority patent/US5853640A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0934434A1 publication Critical patent/EP0934434A1/fr
Application granted granted Critical
Publication of EP0934434B1 publication Critical patent/EP0934434B1/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
    • D01D5/06—Wet spinning methods
    • 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
    • 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
    • D01D5/08—Melt spinning methods

Definitions

  • This invention relates to a process for making aramid fibers of especially high tenacity by means of a combination of process elements including particular spinneret capillary size, particular coagulating conditions, and particular drying tension, known for instance, from US-A- 4 348 559.
  • Yarns of the present invention have a tenacity of at least 24.7 dN/tex (28 gpd) and can be made utilizing the device depicted in Fig. 1. These yarns are made, generally, in accordance with the process disclosed in United States Patent No. 3,767,756 utilizing poly(p-phenylene terephthalamide) (PPD-T) having an inherent viscosity of at least 4.0 dissolved in sulfuric acid having a concentration of at least 98%.
  • PPD-T solution is extruded from a spinneret, through an air gap and into a coagulating bath.
  • the spinneret has capillaries with a diameter of 0.051 millimeter (2.0 mils) or less.
  • capillaries of more than 0.051 millimeter (2 mils) yield fiber filaments which are believed to have poorer molecular orientation resulting in reduced strength and, therefore, not as strong as are made using capillaries of smaller diameter.
  • capillaries of less than about 0.025 millimeter (1 mil) are difficult to use and do not yield fibers of acceptable quality.
  • Fig. 1 is a cross-sectioned view of a preferred coagulating bath 1.
  • Bath 1 is a circular structure consisting of an insert disc 2 fitted into supporting structure 3.
  • Supporting structure 3 includes inlet 4 for introduction of quench liquid 5 under pressure into distribution ring 6 which contains filler 7 suitable to enhance uniform delivery of quench liquid around the periphery of coagulating bath 1.
  • Introduction of coagulating liquid to the bath may be from a peripheral manifold containing baffles or packing to provide uniform distribution and nonturbulent flow of coagulating liquid toward the orifice.
  • the manifold can surround the bath.
  • the manifold can still surround the bath but coagulating liquid would be provided only on the sides of the bath which are parallel to the slot. It is necessary only that the flow of coagulating liquid toward the orifice be nonturbulent in the proximity of the orifice.
  • filler 7 may be glass beads, a series of screens, a honeycomb structure, sintered metal plates, or other similar device.
  • quench liquid After passing through filler 7, the quench liquid passes through perforated plate or screen 8 and flows uniformly without appreciable turbulence or back mixing horizontally toward the center of bath 1 where quench liquid 5 contacts filaments 9 extruded from spinneret 10 whereby both quench liquid 5 and filaments 9 pass together through orifice 11 in a downward direction into spin tube 14.
  • the bottom of the bath may be contoured as illustrated by the areas indicated by A and B to facilitate uniform nonturbulent flow toward opening 11.
  • An area about the orifice may also taper toward the orifice.
  • the depth of the coagulating bath is no more than 20% of the bath width in the area of nonturbulent flow.
  • a suitable bath width is about 6.35 cm (2.5 inches) in combination with an orifice having a diameter of 3.1 mm which has a tapered approach having a beginning diameter of about 12 mm.
  • a suitable bath width is about 23 cm in combination with an orifice diameter of 9 mm which may have a tapered approach having a beginning diameter of about 28 mm.
  • Insert disc 2 includes circular jet device 12 which operates similarly to the jet device disclosed in U.S. Pat. No, 4,298,565.
  • Orifice 11 preferably has a lip 13, i.e., orifice 11 is of slightly smaller diameter than spin tube 14, to help keep filaments 9 from adhering to the walls of orifice 11 and spin tube 14.
  • Quench liquid 5 is introduced through opening 15 through passageway 16 to one or more jet openings 17 whereby the quench liquid 5 passes along with filaments 9 and other quench liquid 5 in a downward direction through the spin tube to exit 18 toward a forwarding device (not shown).
  • the filaments are washed and/or neutralized and dried before wind-up of yarns produced by the process.
  • the angle for the liquid directed by jet openings 17 in relation to the filaments is preferable for the angle ( ⁇ ) in the range of 0 to 85 degrees. While satisfactory results are also obtainable for ⁇ -90 degrees, this selection of theta, however, makes the process very critical to control and is, therefore, not as desirable in commercial operation. 30 degrees is a particularly suitable angle for use in a commercial production process. Jet openings 17 are located adjacent orifice 11 and direct the jetted coagulating fluid downwardly toward the filaments within about 2 milliseconds from the time the filaments enter the spin tube.
  • the process provides the most improvement when the spinneret, spin orifice, jet and any extension of the spin tube are carefully aligned on the same axis and when the jet elements are carefully designed and aligned to provide perfectly symmetrical jetting about the threadlines. Any misalignment of jet elements or the lodging of any solid particles in jet openings so as to destroy symmetry can reduce or eliminate the improvements.
  • Such symmetry may be provided from two or more jet orifices, or from slots symmetrically spaced with respect to the thread line.
  • the flows of the overflowing coagulating liquid (Q 1 ) and jetted coagulating liquid (Q 2 ) are controlled and are maintained constant to achieve the improvement in accordance with the present invention.
  • the mass-flow ratio (R) of the mass-flow rate of the filaments is controlled to be greater than about 250. Preferably, the mass-flow ratio (R) is greater than about 300.
  • flow-rate of overflowing coagulating fluid is controlled by adjustment of the depth of bath above orifice 11 (dimension h) by metering the inflow into the bath but also depends on the diameter of spin tube 14.
  • Dimension h is ordinarily less than one inch (2.5 cm) and preferably about 0.5 inch (1.3 cm). If h is too small, air will be drawn into spin tube 14 by the pumping action of the advancing filaments, and such is deleterious to both tensile properties and mechanical quality of the yarn produced. Thus, h must be great enough to assure no entrainment of gas bubbles. The above considerations lead to calculation of a suitable diameter of spin tube 14.
  • the overflow rate of quench liquid (Q 1 ) through the orifice is greatly influenced by the moving threadline through the same orifice, this effect must also be taken into account.
  • the overflow rate through a 9.5mm (0.375 in.) diameter orifice under a hydrostatic head of 15.9 mm (0.625 in.) is approximately 1.5 liter/min (0.4 gallons/min) in the absence of a moving threadline, and 8.7 liter/min (2.3 gallons/min) in the presence of a threadline of 1000 filaments of 0.17 tex per filament (1.5 denier per filament) moving at 686 m/min.
  • the orifice size i.e., diameter of cross-sectional area is suitably selected.
  • the flow-rate of jetted coagulating liquid (Q 2 ) is preferably controlled by metered pumping through a jet opening of selected size.
  • the minor cross-sectional dimension of the jet e.g., hole diameter or flow width
  • the axial velocity of jetted coagulating liquid should not greatly exceed 200% of that of the yarn being processed and preferably does not exceed about 150% of the yarn velocity to prevent buffeting the threadline which can result in a reduction in measured yarn tenacity. It is therefore necessary to employ a suitable jetted liquid flow-rate and jet openings or slots which provide the mass-flow ratio of combined coagulating liquid to filament mass of greater than about 250, preferably greater than about 300, and the momentum ratio of jetted to overflowing coagulating liquids of greater than about 6.0 which also provide a suitable velocity for the jetted coagulating liquid in relation to yarn speed.
  • the average linear velocity of the combined coagulating liquids in the spin tube is maintained at a velocity less than the velocity of the filaments exiting from the spin tube. This prevents a loss of yarn tenacity due to "looping" of filaments in the yarn and possible process continuity problems due to the absence of sufficient tension before the feed rolls.
  • the present invention is useful for a wide range of spinning speeds and is particularly useful for spinning speeds of at least 300 m/min and preferably at least about 350 m/min although higher spinning speeds do result in a reduction in tenacity when compared with lower spinning speeds. While the advantages is tenacity produced by the process of the invention continue to increase with both increasing mass-flow ratio (R) and momentum ratio ( ⁇ ) and thus can compensate for tenacity decreases due to continued increases in spinning speed, it is believed that mass-flow ratios (R) of above 5000 and momentum ratios ( ⁇ ) above 50 will not yield any further significant improvement and will not be economically attractive for technical production, especially heavy deniers such as 1500 denier.
  • the fibers once spun and passed through the coagulating bath, are washed and dried to complete the manufacture. Fibers must be thoroughly washed to remove all traces of acid and eliminate acid-related fiber degradation.
  • Water alone or combinations of water and alkaline solutions can be used for fiber washing.
  • a convenient method for washing is to spray the threadline, as it leaves the coagulating bath on rolls, with aqueous alkaline solutions (e.g. saturated NaHCO 3 or 0.05 N NaOH), to reduce the acid content to about 0.01% (on a dry fiber basis).
  • the fibers can conveniently be dried on heated rolls (e.g. 160°C).
  • the preferred washing method for this invention is to wash the fibers with a spray and pass them continuously to dryer rolls maintained at about 150°C.
  • One important element of the process of this invention involves drying the fibers under high tension of from about 3.33 to 7.77 grams per dtex (3.0 to 7.0 grams per denier (gpd)). Drying tensions of less than about 3.33 grams per dtex (3.0 gpd) result in fibers which have reduced molecular orientation resulting in reduced strength and drying tensions of greater than 7.77 grams per dtex (7.0 gpd) cause excessive threadline breakage and related operational difficulties. Drying tensions of about 3.33 to 5.55 grams per dtex (3.0 to 5.0 gpd) are particularly preferred.
  • Tenacity is reported as breaking stress divided by linear density. Modulus is reported as the slope of the initial stress/strain curve converted to the same units as tenacity. Elongation is the percent increase in length at break. Both tenacity and modulus are first computed in g/denier units which, when multiplied by 0.8826, yield dN/tex units. Each reported measurement is the average of 10 breaks.
  • Denier is the weight, in grams, of 9000 meters and dtex is the weight, in grams, of 10,000 meters of yarn or filament.
  • Tensile properties for yarns are measured at 24°C and 55% relative humidity after conditioning under the test conditions for a minimum of 14 hours. Before testing, each yarn is twisted to a 1.1 twist multiplier (for example, nominal 1500 denier yarn is twisted about 0.8 turn/centimeter). Each twisted specimen has a test length of 25.4 cm and is elongated 50% per minute (based on the original unstretched length) using a typical recording stress/strain device.
  • TM twist multiplier
  • Tensile properties for yarns are different from and lower than tensile properties for individual filaments and such values for yarns cannot successfully and accurately be estimated from filament values.
  • the ratio ⁇ is independent of the units selected.
  • the basic unit of liquid flow rate Q herein is gal/min.
  • Q x 3899 mass-flow in g/min
  • basic units are speed (Y) in yd/min and denier (D) in g/9000m.
  • YD x (0.9144/9000) mass-flow in g/min.
  • the mass-flow then becomes Q/YD x 3.8376 x 10 7 .
  • poly(paraphyenylene terephthalamide) having an inherent viscosity of about 6.3 dL/g before solutioning and about 5.5 dL/g in fiber form was spun into apparatus as illustrated in U.S. Patent No. 4,340,559 using tray G.
  • the diameter of the spin tube was 0.76 cm (0.3 inch) and jets of 0.21 and 0.42 millimeters (8 and 16 mils) were employed with an angle of 30 degrees between the jetted stream and the threadline.
  • the solvent employed in making spin dope was about 100.1% sulfuric acid and the concentration of polymer in the spin dope of about 19.4 wt.%.
  • the spinnerets of 0.051 and 0.064 millimeters (2.0 and 2.5 mils) were employed.
  • the number of capillaries of spinnerets employed included 133, 266, 400, 500, 560 and 666 capillaries.
  • the air-gap, i.e., the distance of filament travel from the exit face of the spinneret to the first contact with coagulating liquid, was about 0.635 cm (0.25 inch).
  • the coagulating liquid was maintained at about 3°C.
  • Yarn tensions of about 1.11 grams per dtex (1.0 gpd) during washing and neutralization were employed for all of the examples described below.
  • Examples of the invention utilized a mass-flow ratio (R) of 325 to 1680, along with spinnerets with capillaries of 0.051 millimeter.
  • the yarns were dried under tension of greater than 2.22 grams per dtex (2 grams per denier) and the yarns had linear densities of 18 to 167 tex (160 to 1500 denier).
  • Comparative examples utilized the same polymer and the same spinning apparatus under the same conditions, except that the mass-flow ratios, the momentum ratios, the drying tensions, and the spinneret capillary sizes were different as shown in TABLE 1.
  • Invention Comparative Conditions 1 2 A B C D E F Capillary Diam (mm) 0.051 0.051 0.064 0.051 0.064 0.064 0.064 (mil) (2.0) (2.0) (2.5) (2.0) (2.5) (2.5) (2.5) (2.5) No.

Landscapes

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

Claims (4)

  1. Procédé de production de fil de poly(p-phénylène téréphtalamide) ayant une ténacité d'au moins 31,1 grammes par dtex (28 grammes par denier) comprenant les étapes ci-dessous: (a) extrusion de filaments d'une solution acide contenant au moins 30 grammes de poly(p-phénylène téréphtalamide) ayant une viscosité inhérente d'au moins 4 par 100 millilitres d'acide, à partir d'une filière (10) et à travers une couche de fluide inerte non coagulant, dans un bain de coagulation (1) et ensuite à travers un tube de filature (14), ensemble avec du liquide de coagulation à débordement; (b) éjection par jet du liquide de coagulation additionnel, de manière symétrique autour des filaments, dans une direction allant vers le bas, formant un angle compris entre 0 et 85 degrés par rapport aux filaments, dans le cadre de 2,0 millisecondes suivant l'entrée des filaments dans le tube de filature (14), (i) maintien d'un rapport entre le débit massique du liquide de coagulation à débordement et le débit massique du liquide de coagulation éjecté supérieur à 250, (ii) maintien d'une vitesse linéaire moyenne des liquides de coagulation à débordement et éjecté combinés dans le tube de filature (14) inférieure à la vitesse des filaments sortant du tube de filature (14), et (iii) maintien de débits constants des liquides de coagulation éjecté et à débordement; et (c) séchage des filaments,
       caractérisé par l'utilisation d'une filière (10) ayant des capillaires avec des diamètres atteignant 0,051 millimètres (2 millièmes de pouce) et par le séchage des filaments en présence d'une tension d'au moins 3,33 grammes par dtex (3,0 grammes par denier).
  2. Procédé selon la revendication 1, dans lequel le rapport entre le débit massique des liquides de coagulation à débordement et éjecté combinés et le débit massique des filaments est supérieur à 300.
  3. Procédé selon la revendication 1, dans lequel le diamètre des capillaires de la filière est compris entre 0,025 millimètre (1 millième de pouce) et 0,051 millimètres (2 millièmes de pouce).
  4. Procédé selon la revendication 1, dans lequel les filaments sont séchés en présence d'une tension comprise entre 3,33 grammes par dtex (3,0 grammes par denier) et 7,77 grammes par dtex (7,0 grammes par denier).
EP97913738A 1996-10-25 1997-10-22 Procede de fabrication de fibres aramide haute tenacite Expired - Lifetime EP0934434B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US2945296P 1996-10-25 1996-10-25
US29452P 1996-10-25
US950250 1997-10-14
US08/950,250 US5853640A (en) 1997-10-14 1997-10-14 Process for making high tenacity aramid fibers
PCT/US1997/019148 WO1998018984A1 (fr) 1996-10-25 1997-10-22 Procede de fabrication de fibres aramide haute tenacite

Publications (2)

Publication Number Publication Date
EP0934434A1 EP0934434A1 (fr) 1999-08-11
EP0934434B1 true EP0934434B1 (fr) 2003-02-26

Family

ID=26704957

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97913738A Expired - Lifetime EP0934434B1 (fr) 1996-10-25 1997-10-22 Procede de fabrication de fibres aramide haute tenacite

Country Status (7)

Country Link
EP (1) EP0934434B1 (fr)
JP (1) JP3888645B2 (fr)
KR (1) KR100431679B1 (fr)
CN (1) CN1076405C (fr)
DE (1) DE69719351T2 (fr)
EA (1) EA001176B1 (fr)
WO (1) WO1998018984A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW577940B (en) * 2001-08-11 2004-03-01 Acordis Ag Precipitating bath
DE602005018657D1 (de) * 2004-06-25 2010-02-11 Toray Industries Innverfahren sowie vorrichtung und verfahren zur herstellung eines faserbündels
CN101218381B (zh) * 2005-07-06 2011-05-11 可隆株式会社 芳基聚酰胺丝及其制造方法
EP2078106B1 (fr) * 2006-10-31 2012-06-06 E.I. Du Pont De Nemours And Company Procédé pour la production de fil
US7976943B2 (en) * 2007-10-09 2011-07-12 E. I. Du Pont De Nemours And Company High linear density, high modulus, high tenacity yarns and methods for making the yarns
KR101050860B1 (ko) 2008-03-31 2011-07-20 코오롱인더스트리 주식회사 파라 아라미드 섬유
BRPI0909475B1 (pt) * 2008-03-31 2019-04-30 Kolon Industries, Inc. Fibra de para-aramida e método de preparar a mesma
KR100930204B1 (ko) * 2008-06-27 2009-12-07 주식회사 코오롱 아라미드 섬유 및 그 제조방법
PL2321452T3 (pl) * 2008-08-29 2012-08-31 Teijin Aramid Bv Sposób wytwarzania wielu włókien z poliamidu aromatycznego, o dużej wytrzymałości i wysokim module
EP2398942B1 (fr) 2009-02-17 2012-11-14 Teijin Aramid B.V. Procédé de fabrication d'un fil continu en un polyamide aromatique
KR101192918B1 (ko) 2010-12-27 2012-10-18 코오롱인더스트리 주식회사 아라미드 섬유의 제조방법
CN103328698B (zh) * 2011-01-13 2016-04-06 纳幕尔杜邦公司 共聚物纤维和纱线及其制备方法
KR101394653B1 (ko) 2012-10-18 2014-05-12 주식회사 효성 고강도의 방향족 폴리아미드 멀티필라멘트 및 이의 제조방법
KR101959209B1 (ko) * 2013-06-28 2019-03-19 코오롱인더스트리 주식회사 아라미드 섬유의 제조방법
CN103498207B (zh) * 2013-10-21 2016-05-18 中蓝晨光化工研究设计院有限公司 一种适用于干喷-湿纺法制造芳纶ⅲ纤维的凝固成形装置
CN105671659B (zh) * 2016-04-08 2018-04-06 中芳特纤股份有限公司 一种用于对位芳纶纤维高速纺丝的凝固浴加速装置
CN108486678B (zh) * 2018-04-28 2020-08-28 义乌华鼎锦纶股份有限公司 一种石墨烯/聚酰胺6复合纤维的制备方法
CN109537074A (zh) * 2018-12-28 2019-03-29 中国纺织科学研究院有限公司 用于纤维素纺丝的凝固成型装置
CN110747524B (zh) * 2019-11-26 2022-04-15 中芳特纤股份有限公司 一种对位芳纶干喷湿纺的凝固浴装置及其纺丝方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4340559A (en) * 1980-10-31 1982-07-20 E. I. Du Pont De Nemours And Company Spinning process
US4898704A (en) * 1988-08-30 1990-02-06 E. I. Du Pont De Nemours & Co. Coagulating process for filaments
US5173236A (en) * 1991-03-08 1992-12-22 E. I. Du Pont De Nemours And Company Method for spinning para-aramid fibers of high tenacity and high elongation at break
US5330698A (en) * 1993-04-19 1994-07-19 E. I. Du Pont De Nemours And Company Process for making high elongation PPD-T fibers

Also Published As

Publication number Publication date
JP2002515949A (ja) 2002-05-28
EA001176B1 (ru) 2000-10-30
DE69719351T2 (de) 2003-10-30
EA199900408A1 (ru) 1999-10-28
JP3888645B2 (ja) 2007-03-07
CN1234839A (zh) 1999-11-10
DE69719351D1 (de) 2003-04-03
WO1998018984A1 (fr) 1998-05-07
EP0934434A1 (fr) 1999-08-11
KR20000052793A (ko) 2000-08-25
CN1076405C (zh) 2001-12-19
KR100431679B1 (ko) 2004-05-17

Similar Documents

Publication Publication Date Title
EP0934434B1 (fr) Procede de fabrication de fibres aramide haute tenacite
US4340559A (en) Spinning process
US4298565A (en) Spinning process
WO1998018984A9 (fr) Procede de fabrication de fibres aramide haute tenacite
US5417909A (en) Process for manufacturing molded articles of cellulose
KR0177261B1 (ko) 셀룰로오스 섬유의 제조방법, 및 이 방법을 수행하기 위한 장치
EP0168879B1 (fr) Procédé de fabrication de filaments de polyamides aromatiques
US4971539A (en) Device for coagulating filaments
US4728473A (en) Process for preparation of polyparaphenylene terephthalamide fibers
US4965033A (en) Process for spinning high-strength, high-modulus aromatic polyamides
US5853640A (en) Process for making high tenacity aramid fibers
CA2167378A1 (fr) Filature de polyamides avec trempe dans un bain aqueux
JP3799061B2 (ja) 光学的に異方性の紡糸液からフィラメントを作る方法
US5945054A (en) Process for manufacturing filaments from an optically anisotropic spinning solution
US3124926A (en) Woodell
IE902168A1 (en) Improved coagulating process for filaments
JP2004300616A (ja) モノフィラメントの溶融紡糸装置
JPS646284B2 (fr)
JPH0949141A (ja) レーヨン混繊糸の製造方法

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: 19990326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

17Q First examination report despatched

Effective date: 20001117

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RIN1 Information on inventor provided before grant (corrected)

Inventor name: OHNO, MIKIO

Inventor name: MOORE, STEPHEN, D.

Inventor name: IMAEDA, KOUZOU

Inventor name: FURUMAI, TAKEJI

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69719351

Country of ref document: DE

Date of ref document: 20030403

Kind code of ref document: P

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20031127

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20131016

Year of fee payment: 17

Ref country code: DE

Payment date: 20131016

Year of fee payment: 17

Ref country code: FR

Payment date: 20131009

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20131010

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69719351

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20150501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20141022

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141022

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150630

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

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150501

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141031