EP0775221B1 - Procede de fabrication d'une etoffe non tissee de polybenzazole - Google Patents

Procede de fabrication d'une etoffe non tissee de polybenzazole Download PDF

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Publication number
EP0775221B1
EP0775221B1 EP95928723A EP95928723A EP0775221B1 EP 0775221 B1 EP0775221 B1 EP 0775221B1 EP 95928723 A EP95928723 A EP 95928723A EP 95928723 A EP95928723 A EP 95928723A EP 0775221 B1 EP0775221 B1 EP 0775221B1
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EP
European Patent Office
Prior art keywords
filaments
polybenzazole
dope
deposited
aspirator
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
EP95928723A
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German (de)
English (en)
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EP0775221A1 (fr
EP0775221A4 (fr
Inventor
Kazuyuki Yabuki
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.)
Toyobo Co Ltd
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Toyobo Co Ltd
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Publication date
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Publication of EP0775221A1 publication Critical patent/EP0775221A1/fr
Publication of EP0775221A4 publication Critical patent/EP0775221A4/fr
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Publication of EP0775221B1 publication Critical patent/EP0775221B1/fr
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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
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically

Definitions

  • This invention relates to articles of polybenzazole polymer and, more specifically, to fabrics of polybenzazole fiber.
  • Nonwoven fabrics are known materials which comprise assemblies of textile fibers held together by mechanical interlocking in a random web or mat, by fusing of thermoplastic fibers, or by bonding the fibers with a cementing medium such as starch, glue, casein, rubber, latex, cellulose derivative, or synthetic resins.
  • Polybenzazole fibers are known fibers which are prepared by extruding filaments of a polybenzazole dope, drawing the filaments across an air gap, combining the filament to form a multifilament structure, and then washing and drying the structure under conditions sufficient to remove the acid solvent and the water from the filament. An efficient process for the preparation of nonwoven fabrics of polybenzazole would be desirable.
  • US-A-5,233,821 discloses fabrics containing polybenzazole fibers having high cut resistance that can be used to make cut resistant and flame resistant garments.
  • the dope is spun into fibers by known dry jet wet spin techniques in which the dope is drawn through a spinneret across an air gap and into a coagulation bath, thereby coagulating the single fibers.
  • garments and fabrics containing commingled or composite fibers are disclosed.
  • this invention is a continuous process for preparing nonwoven fabrics of polybenzazole filaments which comprises spinning at least two polybenzazole dope filaments simultaneously and intermingling and depositing the filaments on a collecting device, whereby the filaments are mechanically interlocked, washing and drying the intermingled and deposited filaments to obtain a non-woven fabric.
  • the process of the invention provides a means of preparing nonwoven polybenzazole fabrics in a continuous, on-line process which permits the polybenzazole dope to be extruded at a very high speed, since the speed of the on-line process is not limited by the line speed which would be necessary to wash and dry single filaments in an on-line process. Further, since the fabric moves through the washing and drying equipment at a much slower rate of speed than a single fiber, fewer washing and drying cabinets may be required to effectively wash and dry the fabric.
  • polybenzazole refers to polybenzoxazole (PBO) homopolymers, polybenzothiazole (PBT) homopolymers, and random, sequential, or block copolymerized polymer of PBO and PBT.
  • PBO polybenzoxazole
  • PBT polybenzothiazole
  • Polybenzoxazole, polybenzothiazole, and random, sequential, or block copolymerized polymers thereof are described, for example, in "Liquid Crystalline Polymer Compositions, Process and Products" by Wolfe et.
  • the structural units present in PBZ polymer are preferably selected so that the polymer is lyotropic liquid crystalline.
  • Preferred monomer units are illustrated below in Formulae I-VIII.
  • the polymer more preferably consists essentially of monomer units selected from those illustrated below, and most preferably consists essentially of cis-polybenzoxazole, trans-polybenzoxazole, or trans-polybenzothiazole.
  • Suitable polybenzazole 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.S. Patent 4,772,678 (September 20, 1988); Harris, U.S. Patent 4,847,350 (July 11, 1989); and Gregory et al., U.S. Patent 5,089,591 (February 18, 1992).
  • suitable monomers are reacted in a solution of non-oxidizing and dehydrating acid (the acid solvent) under non-oxidizing atmosphere with vigorous mixing and high shear at a temperature that is increased in step-wise or ramped fashion from no more than 120°C to at least 190°C.
  • Suitable solvents for the preparation of PBZ polymer dope include cresols and non-oxidizing acids.
  • suitable acid solvents include polyphosphoric acid, methane sulfonic acid, and highly concentrated sulfuric acid or mixtures thereof.
  • the solvent acid is polyphosphoric add or methane sulfonic acid, but is most preferably polyphosphoric acid.
  • the polymer concentration in the solvent is preferably at least 7 percent by weight, more preferably at least 10 percent by weight, and most preferably at least 13 percent by weight.
  • the maximum concentration is limited by the practical factors of handling, such as polymer solubility and dope viscosity.
  • the polymer concentration normally does not exceed 30 percent by weight, and is preferably no greater than about 20 percent by weight. Oxidation inhibitors, de-glossing agents, coloring agents, and anti-static agents may also be added to the dope.
  • the solutions of polybenzazole polymers may be stored for a period of time prior to spinning. However, it is particularly desirable to conduct a continuous polymerization, direct spinning method in which polymerization is conducted continuously and a spinning dope is supplied directly to a spinning device without prior storage.
  • the process of the present invention is preferably run in a continuous fashion with a spinning speed of at least about 50 meters/minute (m/min).
  • the spinning speed is more preferably at least about 200 m/min, more preferably at least about 400 m/min and most preferably at least about 600 m/min.
  • the draw tension is preferably at least about 1 gram/denier, more preferably at least about 3 grams/denier, but is preferably no greater than about 10 grams per denier, more preferably no greater than about 5 grams per denier. Since it is difficult to achieve this level of tension with an air or gas aspirator, the filaments are preferably drawn utilizing an aspirator which uses the flow of a liquid to reduce the air pressure in the aspirator (hereafter, "liquid aspirator”), and then deposited on the collecting device.
  • liquid aspirator an aspirator which uses the flow of a liquid to reduce the air pressure in the aspirator
  • a set of draw rolls positioned between the spin-die and the aspirator may be used to draw the filament, which then may be deposited on the collecting device utilizing either a gas or liquid aspirator.
  • the aspirator moves in a swinging motion relative to the collecting device, in order to more effectively and evenly scatter the fiber on the surface of the device.
  • the filaments After the filaments are extruded they are intermingled and deposited on a substantially planar collecting surface.
  • the filaments may be intermingled by any suitable method, such as by passing the filaments through a device which utilizes an aspirator to create turbulence and draw or convey the filaments through it to the collecting surface.
  • the temperature of the aspirator gas or liquid may be increased above ambient conditions to soften the dope, if desired, which will cause the filaments in contact with each other to adhere. In such cases, when the filaments are subsequently washed and dried, the filaments will continue to adhere, creating a more rigid fabric than would be obtained otherwise.
  • a heated liquid is to be used in the aspirator, it is preferably a liquid which is not a solvent for the acid contained in the dope, so that the acid is not removed before the filament is deposited on the collecting surface.
  • the aspirator fluid is a solvent for the acid, such as water
  • a portion of the solvent may be removed as the filament passes through the aspirator and the dope filament will not adhere as effectively after being deposited on the collecting device.
  • fluids which may be used which are not solvents for either the add or polybenzazole polymer include alkylene glycols.
  • the flow rate of the fluid through the aspirator is preferably at least about 20 m/sec.
  • the spun filament is deposited on a substantially planar collecting surface.
  • the filament first passes through an aspirator or other device which may be used to direct the filament onto the substantially planar collecting surface.
  • the collecting surface should be substantially flat and level enough to hold the extruded dope filaments, it may be made of a flexible material such as net conveyer but is not a godet or roll as is typically used in a fiber spinning process. Any solid material may be used to make the collecting surface, but is preferably one which is chemically resistant to the effect of the acid in the polybenzazole dope and any gases or liquids to which it may be exposed during the process.
  • the polybenzazole filaments are preferably deposited on the collecting device in amounts and under conditions sufficient to form a random network having an average width of at least about 1 cm. However, it is more efficient from a processing standpoint to prepare a random network having a much greater width, such as at least about 0.2 m, so that a correspondingly wider nonwoven fabric will be obtained.
  • the filament After the filament is deposited on the collecting device, it may be washed and dried using methods which are typically employed in the manufacture of polybenzazole fibers.
  • the filaments are preferably washed to remove at about 80 percent of the solvent acid present in the dope, more preferably at least about 90 percent, and most preferably at least about 95 percent Examples of suitable washing fluids include water, methanol, and aqueous solutions of the solvent acid. If the solvent acid is polyphosphoric acid, the filaments are preferably washed to a residual phosphorous content of less than about 8,000 ppm, more preferably less than about 5,000 ppm.
  • the filaments are preferably dried to a moisture content of less than 3.0 percent by weight, more preferably less than 2.0 percent by weight, more preferably less than 1.0 percent by weight, and most preferably less than 0.5 percent by weight, and any suitable drying device may be employed. If desired, the filament may also be heat-treated to improve its tensile modulus as described, for example, in U.S. Patent 5,288,442.
  • an apparatus having a spinning head (1) which is spinning filaments through a quench chamber (2), over a pair of polytetrafluoroethylene-coated godet rolls (3), through a compressed air aspirator (4), and onto a net conveyor (5) on which the filaments are collected.
  • the filaments then pass through a series of washing baths (6), (7), and (9), and a neutralization bath (8).
  • the washed filaments then pass through a dryer (10) and the resulting nonwoven fabric is wound on a winding roll (11).
  • an apparatus having a spinning head (12) which is spinning filaments through a quench chamber (13), through a water flow aspirator (14), and onto a net conveyor (15) on which the filaments are collected.
  • the filaments then pass through a series of washing baths (16), (17), and (19), and a neutralization bath (18).
  • the washed filaments then pass through a dryer (20) and the resulting nonwoven fabric is wound on a winding roll (21).
  • the nonwoven fabric obtained by washing and drying the filaments which have been processed according to the invention is a random web or mat of polybenzazole filaments.
  • the filaments As the filaments are deposited on the collecting device at a high rate of speed, they will become intermingled. They may also become intermingled as they pass through the aspirator.
  • the intermingling causes the filaments to become mechanically interlocked, and the filaments will remain intermingled as they are washed and dried.
  • the drawing and intermingling process may cause the filaments to break periodically before or as they are deposited, although such breakage will not significantly affect the process.
  • the mechanical interlocking of the filaments may be increased further, if desired, by use of a needle punch, water punch, or calender device designed for such purpose. If the dope filaments are deposited at a temperature at which the dope is soft, such as above about 80°C, the filaments will tend to adhere to each other, even after the filaments are washed and dried, which will also act to hold the fabric together.
  • a binder may also be applied to the fabric after it has been washed and dried, if desired.
  • the polybenzazole nonwoven fabric prepared by the washing and drying of the filaments according to the process of the invention has advantageous heat resistance, tearing power, tear strength, insulating, wear resistance, and flame resistance properties.
  • the tensile strength of the filaments is preferably at least about 25 g/d, and the tensile modulus is preferably at least about 700 g/d. If the fabric is heat-treated at a temperature of at least about 350°C, the tensile modulus of the filaments may increase to greater than 1500 g/d.
  • a solution of polybenzoxazole in polyphosphoric acid was prepared from 4,6-diamino-1,3-benzenediol di-hydrochloride and terephthalic acid.
  • the dope had a phosphorous pentoxide content of 83.17 percent and an intrinsic viscosity of 24.4 dL/g, as measured in methane sulfonic acid at 30°C, and was prepared using the method described in U.S. Patent 4,533,693.
  • the dope was passed through a metal screen filter and degassed in a twin screw extruder. The pressure was raised, and the dope was transferred to a spinning head using a metering pump and heated to 170°C.
  • the dope was spun through a spinneret with 334 orifices at 170°C, and then cooled to 60°C in a quench chamber.
  • the filaments were drawn over a pair of driven godet rolls having a surface treated with polytetrafluoroethylene, at a speed of 200 m/min.
  • the filaments were then drawn through an aspirator through which compressed air was fed, and deposited on a net conveyor moving at a speed of 20 cm/min.
  • the network of filaments was then washed in a 10 percent aqueous solution of polyphosphoric acid maintained at a temperature of 22 ⁇ 2°C.
  • the filaments were then subsequently washed in a water bath, and then immersed in a 0.1 N sodium hydroxide solution to be neutralized.
  • the filaments were then washed in a water bath, and dried for 5 minutes at 190°C.
  • the resulting non-woven fabric had a weight of 55 g/m2 and a water content of 0.8 percent.
  • Twenty single filaments were removed from the fabric to determine their average physical properties, which are as follows: 0.17 tex (1.5 denier) filament, 4.83 ⁇ Pa (35 g/denier (g/d)) tensile strength, 110 ⁇ Pa (800 g/d) tensile modulus, 4.5 percent elongation.
  • Polybenzoxazole filaments were prepared using the procedure described in Example 1 except that the temperature of the quench chamber is 80°C.
  • the extruded filaments were drawn using a water aspirator, and then deposited on a net conveyor. The filaments were then washed, dried, and neutralized using the procedure described in Example 1. Twenty single filaments were removed from the fabric to determine their average physical properties, which are as follows: 0.28 tex (2.5 denier) filament, 4.55 ⁇ Pa (33 g/denier (g/d)) tensile strength, 110 ⁇ Pa (800 g/d) tensile modulus, 4.4 percent elongation.

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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)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (5)

  1. Procédé continu de préparation d'étoffes non tissées de filaments de polybenzazole qui comprend le filage d'au moins deux filaments de dope de polybenzazole simultanément et l'entremêlement et le dépôt des filaments sur un dispositif collecteur, par lequel les filaments sont entrelacés mécaniquement, le lavage et le séchage des filaments entremêlés et déposés pour obtenir une étoffe non tissée.
  2. Procédé selon la revendication 1, dans lequel le polybenzazole est du polybenzoxazole,
  3. Procédé selon la revendication 1, dans lequel le polybenzazole est du polybenzothiazole.
  4. Procédé selon la revendication 1, dans lequel le filament filé est tiré avec un aspirateur liquide avant d'être déposé sur la surface collectrice.
  5. Procédé selon la revendication 1, dans lequel le filament filé est tiré avec une paire de cylindre à godet entraíné avant d'être déposé sur la surface collectrice.
EP95928723A 1994-08-03 1995-08-02 Procede de fabrication d'une etoffe non tissee de polybenzazole Expired - Lifetime EP0775221B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP18242094 1994-08-03
JP182420/94 1994-08-03
JP18242094A JP3541966B2 (ja) 1994-08-03 1994-08-03 ポリベンザゾール繊維不織布の製造方法
PCT/US1995/009818 WO1996004413A1 (fr) 1994-08-03 1995-08-02 Procede de fabrication d'une etoffe non tissee de polybenzazole

Publications (3)

Publication Number Publication Date
EP0775221A1 EP0775221A1 (fr) 1997-05-28
EP0775221A4 EP0775221A4 (fr) 1997-11-12
EP0775221B1 true EP0775221B1 (fr) 2002-12-18

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ID=16117977

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Application Number Title Priority Date Filing Date
EP95928723A Expired - Lifetime EP0775221B1 (fr) 1994-08-03 1995-08-02 Procede de fabrication d'une etoffe non tissee de polybenzazole

Country Status (6)

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EP (1) EP0775221B1 (fr)
JP (1) JP3541966B2 (fr)
CA (1) CA2194989A1 (fr)
DE (1) DE69529221T2 (fr)
ES (1) ES2186726T3 (fr)
WO (1) WO1996004413A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5534205A (en) * 1994-08-05 1996-07-09 The Dow Chemical Company Method for preparing polybenzoxazole or polybenzothiazole fibers
US5633161A (en) * 1995-03-29 1997-05-27 Millennium Pharmaceuticals, Inc. Murine gene fomy030 coding for tumor progression inhibitor
CN101495689B (zh) * 2006-07-31 2011-04-06 纳幕尔杜邦公司 含芳并唑类聚合物微纤维的非织造网及其制造方法
EP2591847A4 (fr) * 2010-07-07 2013-11-27 Mitsubishi Rayon Co Dispositif et procédé de séchage pour membranes à fibres creuses

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4780359A (en) * 1987-04-03 1988-10-25 Gates Formed-Fibre Products, Inc. Fire retardent structural textile panel
JPH0284511A (ja) * 1988-09-20 1990-03-26 Mitsui Petrochem Ind Ltd ポリベンゾチアゾール類延伸繊維、ポリベンゾオキサゾール類延伸繊維またはポリベンゾイミダゾール類延伸繊維の製造方法
US5164131A (en) * 1990-09-19 1992-11-17 The Dow Chemical Company Methods for synthesizing pulps and short fibers containing polybenzazole polymers
US5233821A (en) * 1991-02-25 1993-08-10 The Dow Chemical Company Protective garment containing polybenzazole

Also Published As

Publication number Publication date
DE69529221T2 (de) 2003-08-21
JPH0849156A (ja) 1996-02-20
WO1996004413A1 (fr) 1996-02-15
DE69529221D1 (de) 2003-01-30
CA2194989A1 (fr) 1996-02-15
ES2186726T3 (es) 2003-05-16
EP0775221A1 (fr) 1997-05-28
EP0775221A4 (fr) 1997-11-12
JP3541966B2 (ja) 2004-07-14
MX9700815A (es) 1997-09-30

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