EP0428632B1 - Fibre non lineaire de polyamide aromatique ou ensemble de fibres et leur procede de preparation - Google Patents

Fibre non lineaire de polyamide aromatique ou ensemble de fibres et leur procede de preparation Download PDF

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Publication number
EP0428632B1
EP0428632B1 EP90901290A EP90901290A EP0428632B1 EP 0428632 B1 EP0428632 B1 EP 0428632B1 EP 90901290 A EP90901290 A EP 90901290A EP 90901290 A EP90901290 A EP 90901290A EP 0428632 B1 EP0428632 B1 EP 0428632B1
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Prior art keywords
fibers
fiber
nonlinear
percent
fibrous structure
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EP0428632A4 (en
EP0428632A1 (fr
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Francis P. Mccullough, Jr.
R. Vernon Snelgrove
Bhuvenesh C. Goswami
David M. Hall
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Dow Chemical Co
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Dow Chemical Co
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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/002—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by knitting, weaving or tufting, fixing and then unravelling
    • 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
    • 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • 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
    • 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D04H1/4342—Aromatic polyamides
    • 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
    • D04H1/43918—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres nonlinear fibres, e.g. crimped or coiled fibres

Definitions

  • the invention resides in a nonlinear fiber or fiber assembly and method of preparation according to the preamble of claims 1, 9 and 19 and known, for instance from US-A-4 756 941.
  • the fibers are derived from aromatic polyamide precursor fibers having imparted thereto a substantially permanently set nonlinear or crimped configuration capable of a reversible deflection of greater than 1.2 times the length of the nonlinear fibers when measured at ambient temperature and which possess a percent bending strain value of less than 50.
  • the fibers also possess improved tenacity over mechanically crimped fibers of the prior art.
  • the state of the art generally discloses the manufacture of fibers from polymeric compositions such as polyacrylonitrile (PAN) by the conventional technique of spinning the fibers which can then be collected into multifiber assemblies, such as tows, and can thereafter be oxidatively stabilized. Such fibers may then be subjected to a carbonizing procedure to provide the fibers with a nonlinear configuration.
  • PAN polyacrylonitrile
  • the prior art also discloses linear aromatic polyamide fibers having a high tensile strength.
  • To provide such fibers with a certain degree of electrical conductivity and a "graphitic" nature required the application of elevated temperatures to obtain a high degree of carbonization.
  • the fibers produced from such a high temperature treatment are very brittle and incapable of standing up to stress, such as a repeated bending of the fibers, particularly when they have been subjected to a temperature above 700°C.
  • U.S. Patent No. 4,120,914 discloses the preparation of highly crimped fibers of poly(p-phenylene terephthalamide) which, as a result of the crimping, suffer mechanical damage resulting in an appreciable decrease in fiber tenacity.
  • the crimping is performed by a steam stuffer box crimper.
  • Stuffer box crimping results in the production of sharp V-type bends in the fibers such that the outer portion of the fiber bend is damaged due to a severe stress and the underside of the fiber bend is damaged due to severe compression. These sharp bends therefore are the cause of severely weakened portions in the fiber, including fibrillation. These fibers suffer an increase in bending strain, leading to unacceptable fiber breakage, especially with fibers that are relatively rigid, stiff and brittle, or that are subsequently heat treated.
  • U.S. Patent No. 4,401,588 to Turner discloses a process for making an active carbon fabric from an aramid fabric by heating the fabric to a temperature of from 850°C to 950°C in an inert atmosphere.
  • U.S. Patent No. 3,560,135 to Han discloses that heating mechanically crimped aromatic polyamide fibers to a temperature of from 257°C to 400°C for a time period of from 1 to 10 minutes increases their hydrolytic durability and solvent resistance. However, there is a loss in tenacity, as a result of the crimping and the presence of fibrils.
  • U.S. Patent No. 4,193,252 to Sheppherd et al. discloses the making of partially carbonized and carbon (graphitic) fibers from stabilized rayon. It has been found that the partially carbonized and carbonized rayon fibers do not retain their reversible deflection, easily break under tension, and lose their crimp or kinks at relatively low temperatures or under tension. More importantly, the fibers are flammable.
  • U.S. Patent No. 4,642,664 to Goldberg et al. discloses the use of partially carbonized aromatic polyamides for use as conductors in electrical devices. However, only linear fibers that have been heat treated to a temperature above 400°C are disclosed in the patent.
  • U.S. Patent No. 4,756,941 teaches the use of nonlinear fibers derived from a stabilized polyacrylonitrile or petroleum or coal tar spun fiber in carpet bachings in order to provide a more effective antistatic carpet. These nonlinear fibers are prepared by imparting a nonlinear configuration to the starting fiber and heating the fibers at a temperature of above 200°C. These fibers can be blended with nylon fibers. No reference is made to a starting material consiting of aromatic polyamide fibers.
  • the problem underlying the present invention is the provision of nonlinear fibers having an improved tenacity over mechanically crimped fibers of the prior art. Further, the fibers of the invention are distinguishable over the carbonaceous fibers derived from polyacrylonitrile based fibers by possessing greater relative strength and abrasion resistance. Also, fibers made from an aromatic polyamide, such as p-aramid, are liquid crystals. The term "liquid crystals" herein applies to organic compounds which are in an intermediate or mesomorphic state between a solid and a liquid.
  • uniform diameter when used herein relates to the diameter of the fiber as drawn prior to crimping.
  • the fiber may contain minute variations, which are common during normal fiber processing operations, such slight variations can be disregarded in determining the uniformity in fiber diameter.
  • crimp or “crimped portions” as utilized herein, refers to nonlinear portions, kinks, bends or waviness that is imparted to the fibers.
  • the crimped fibers of the invention include different configurations such as sinusoidal, coil-like or a combination thereof.
  • nonlinear as used herein applies to fibers or fiber structures that are crimped, as hereinbefore defined, but that are free of sharp V-shaped bends or fibrils.
  • the reversible deflection of a nonlinear fiber comprises two components, pseudoelongation and fiber elongation.
  • Pseudoelongation results from an elongation of the nonlinear configuration of the fiber, while fiber elongation is the elongation to fiber break after the fiber has been made linear.
  • the term "pseudoextensibility" as used herein applies to the elongation of nonlinear fibers as the result of crimps and/or false twists therein when the fiber is straightened to its linear configuration.
  • the sharpness of the crimp can be quantified in terms of its bending strain.
  • the term "bending strain” as used herein is as defined in Physical Properties of Textile Fibres , W.E. Morton and J.W.S. Hearle, The Textile Institute, Manchester, 1975, pages 407-409.
  • carbonaceous fiber is understood to mean that the carbon content of the original aromatic polyamide fiber has been increased as a result of an irreversible chemical reaction caused by heat treating the fiber.
  • aromatic polyamide fibers can be carbonized or partially carbonized by heat treatment of the fibers at elevated temperatures and for a period of time to increase the carbon content of the fibers. That is, the fibers as disclosed in U.S. Patent No. 4,642,644 can be heat treated until they are partially carbonized or completely carbonized.
  • stabilized herein applies to aromatic polyamide fibers or fiber structures which are oxidized, in an oxidizing atmosphere, at a temperature of typically less than about 400°C, preferably at a temperature of from 175°C to 400°C, for a period of time sufficient to oxidize the fibers. It will be understood that the fibers can be oxidized by chemical oxidants, rather than in an oxidizing atmosphere, at lower temperatures.
  • the fibers of the invention can be prepared from stabilized or nonstabilized aromatic polyamide precursor fibers.
  • substantially permanently set used herein applies to nonlinear aromatic polyamide fibers which have been heat treated under the conditions as set forth hereinafter until they are crimped and possess a degree of nonlinearity and, accordingly, a degree of resiliency and flexibility such that the fibers, when stretched to a substantially linear shape but without exceeding the tensile strength of the fibers, will revert to their original nonlinear shape once the tension on the fibers is released.
  • the foregoing term also implies that the fibers can be stretched and released over many cycles without breaking the fibers.
  • fiber structure herein applies to a fiber tow comprising a multiplicity of filaments, a yarn, a multiplicity of entangled nonlinear aromatic polyamide fibers forming a shape reforming wool-like fluff, a batting, webbing or felt of nonwoven fibers, a knitted or woven cloth or fabric, or the like. More particularly, the fiber structure of the present invention, particularly when in the shape of a wool-like fluff, is lightweight, resilient, and compressible. The fluff, at ambient temperature, has good shape and volume retention and is stable to numerous compression and unloading cycles without breakage of the fibers.
  • KEVLAR-29 (a trademark of E.I. du Pont de Nemours & Co.) is a p-aramid with a high tensile strength of 400,000 psi (2.758 GPa) but a moderate modulus of 9 X 106 psi (62 GPa) and an elongation to break of 4.0 percent.
  • KEVLAR-49 (a trademark of E.I. du Pont de Nemours & Co.) is a p-aramid with the same tensile strength as KEVLAR-29 but of a higher modulus of 18 X 106 psi (124 GPa) with an elongation to break of 2.5 percent.
  • aromatic polyamide fibers can be provided with a crimped or nonlinear configuration and without any sharp V-type bends, fibrils or other damage.
  • the fibers of the invention do not exhibit any loss in mechanical properties and thus provide a novel fiber or fiber structure having new and unexpected properties and capabilities.
  • crimped or nonlinear aromatic polyamide fibers of the invention provide superior loft and compression when in the form of a fluff as compared to fibers of the prior art that have been subjected to gear crimping or stuffer box crimping procedures in which the fibers are provided with sharp V-shaped bends or are otherwise damaged.
  • the process of the invention provides aromatic polyamide fibers, such as p-aramid, with at least a pseudoextensibility which is necessary for processing the fibers into a fabric.
  • the resultant nonlinear fibers when in the form of a yarn or wool-like fluff, have improved loft, bulkiness and friction without creating weak spots such as would occur with mechanically crimped fibers having sharp bends, fibrils and the like due to high gear pressure applied to the fibers by the gear crimping mechanism.
  • Such fiber damage is generally exhibited by fibers having gouged out portions, severely compressed or stressed portions, fibrils, creased or crazed portions, and the like.
  • a process for making nonlinear, aromatic polyamide fibers comprising the steps of imparting a nonlinear configuration to the fibers, heating said fibers at a temperature of above 200°C to provide said fibers with a reversible deflection ratio of greater than 1.2:1 when measured at ambient temperature and a bending strain value of less than 50 percent.
  • the fibers of the invention also provide for an improved tenacity over mechanically crimped fibers.
  • the tenacity of the fibers is at least about per 0.000111 g/m (18 g/dn), preferably from 0.018 to per 0.000111 g/m (18 to 25 g/dn) or greater.
  • Fibers of the invention will maintain their reversible deflection when measured at ambient temperature. Fibers, when measured at a temperature in excess of 100°C and up to 130°C, still maintained their reversible deflection characteristics. However, reversible deflection of the fibers when measured at the higher temperature of 100°C to 130°C will depend on the particular aromatic polyamide that is selected and other physical characteristics, such as fiber diameter. The higher temperatures are those which the nonlinear fibers of the invention will commonly encounter in any washing or fiber treatment operation.
  • the fibers of the invention are substantially free of variations in fiber diameter at each bend portion thereof.
  • the fibers have not more than a 15 percent variation, i.e. reduction, in fiber diameter over the length of the fiber.
  • the fibers of the present invention provide an improvement over present state of the art aromatic polyamide fibers which have been subjected to standard gear crimping or stuffer box crimping techniques.
  • the prior crimping techniques generally result in fibrillation and/or other damage to the fiber, as mentioned herein before, at the sites of the crimp or bend as well as a substantial variation in fiber diameter of greater than 15 percent. These factors result in a weakening of the fiber and thus affect the performance of the fiber during processing and when placed in an environment where the fiber is subject to repeated bending or flexing. The loss of fiber properties becomes even more pronounced when the weakened or damaged fibers are subsequently heat treated.
  • Fibers that are substantially weakened at the bent portions due to conventional crimping techniques exhibit a bending strain value of greater than 50 percent. If attempts are made to decrease the bending strain value by mechanical crimping with rounded crimps, such as may be produced by a round gear tooth crimping mechanism, there is a corresponding loss in the reversible deflection ratio. Gear crimping with flat faced gears usually results in the production of fibers exhibiting greater damage, particularly fibrillation, and thus these fibers have a bending strain value which is substantially greater than 50 percent and generally as high as about 80 percent.
  • the crimped or nonlinear fibers of the invention may be blended with the carbonaceous fibers of the afore-mentioned European Patent Publication Serial No. 0199567 or with the carbonaceous fibers of U.S. Patent No. 4,868,037.
  • the combination of carbonaceous fibers and nonlinear polyamide fibers in yarn permits the manufacture of fabrics which are resistant to chemical attack, which possesses good abrasive strength and a loft which permits the permeation of air.
  • the physical characteristics of the crimped or nonlinear fibers of the invention can be better controlled than the state of the art fibers that are produced with the use of standard gear crimping or stuffer box crimping techniques, particularly where these standard techniques are applied to fibers of larger diameters or fiber tows having a larger number of fibers and/or larger diameter fibers.
  • the graph provided herein illustrates the improvement in tenacity and elongation of KEVLAR-29 when treated according to the invention.
  • an aromatic polyamide precursor fiber is formed into a crimped or nonlinear configuration with the fiber exhibiting a substantially uniform diameter along its length.
  • the nonlinear precursor fiber is then heated, preferably without applying any tension or stress to the fiber, at an elevated temperature.
  • the so-formed crimped or nonlinear fiber is thereby provided with a substantially permanent set and a reversible deflection ratio of greater than 1.2:1, preferably 2:1, when measured at ambient temperatures, a bending strain value of less than 50 percent, preferably less than 30 percent, and is free of any sharp V-shaped bends and/or fibrils.
  • the fibers can be simultaneously provided with a crimped or nonlinear configuration and heat treated at a temperature higher than 200°C to provide the fibers with a substantially permanent set.
  • heat setting is conducted in a water-free atmosphere.
  • aromatic polyamides include polyparabenzamide and polyparaphenylene terephthalamide.
  • Polyparabenzamide and their processes of preparation are disclosed in U.S. Patent Nos. 3,109,836; 3,225,011; 3,541,056; 3,542,719; 3,547,895; 3,558,571; 3,575,933; 3,600,350; 3,671,542; 3,699,085; 3,753,957; and 4,025,494.
  • Polyparaphenylene terephthalamide (p-aramid) is available commercially as KEVLAR, a trademark of E.I. du Pont de Nemours, and processes of preparing the same are disclosed in U.S. Patent Nos.
  • wholly aromatic polyamides are (poly(2,7-phenanthridone)terephthalamide), poly(paraphenylene-2,6-naphthalamide), poly(methyl-1,4-phenylene) terephthalamide Additional specific examples of wholly aromatic polyamides are disclosed by P.W. Morgan in “Macromolecules," Vol. 10, No. 6, pp. 1381-90 (1977).
  • the aromatic polyamide fibers of the invention are provided with a substantially permanently set nonlinear configuration when heated in a nonlinear configuration, for example, a coiled or sinusoidal configuration, at a temperature above 200°C, preferably at a temperature of from 200°C to 550°C, and more preferably at a temperature of from 200°C to 420°C in a water free atmosphere.
  • the time period of heating the fiber depends on the temperature, diameter of fiber, type of aromatic polyamide polymer used, etc. A more permanent heat set is imparted when the fibers are heated at higher temperatures to thereby increase the carbon content, although it will be understood that the fibers become more brittle as the temperature is increased above 500°C.
  • Stabilized or nonstabilized aromatic polyamide fibers which are heat treated, in a nonlinear configuration and in an inert atmosphere result in a fiber with a substantially permanent set and higher tenacity as compared to fibers which are heat treated in oxygen or air. It is preferable to do this heat treatment in a substantially unstressed condition.
  • the fibers of the invention have a substantially uniform diameter, especially in the bent portions, and preferably have a sinusoidal or coil-like configuration or a more complicated structural configuration of a combination of the two.
  • the precursor fibers are typically formed by conventional methods into a fiber having a nominal diameter of from 4 to 25 microns and an aspect ratio of greater than 10:1.
  • the fibers are collected as an assembly of a multiplicity of continuous fibers in tows.
  • the tows optionally, may then be stabilized in the conventional manner such as described in U.S. Patent No. 4,642,664.
  • the tows (or staple yarn made from chopped or stretch broken fiber staple) are thereafter formed into a substantially uniform coil-like and/or sinusoidal form by knitting or weaving the tow or yarn into a fabric or cloth.
  • the so-formed knitted fabric or cloth is thereafter heat treated at the hereinbefore stated temperatures, in an inert atmosphere or in air for a period of time sufficient to produce an internal modification of the polymer structure such that the fiber is substantially irreversibly heat set into a nonlinear configuration exhibiting a reversible deflection of greater than 1.2:1 when measured at ambient temperature.
  • the heat treatment be conducted while the nonlinear fibers are in a relaxed or unstressed condition. Greater improvement in physical properties are found with fibers which are simultaneously formed into a nonlinear configuration and heat treated, particularly when heat treated in a water free atmosphere.
  • the resulting deknitted tows or yarn, or even the cloth per se may then be subjected to other methods of treatment known in the art, such as garnetting (to create an opening), a procedure in which the fiber structure is separated into an entangled mass of a multiplicity of nonlinear, curly fibers in the form of a wool-like fluffy material wherein the individual fibers retain their coil-like or sinusoidal configuration yielding a shape reforming mass of the entangled fibers of considerable loft.
  • garnetting to create an opening
  • the fibers when substantially permanently set in accordance with the present invention into the desired nonlinear structural configuration retain their resilient and reversible deflection characteristics when measured at ambient temperature and, preferably, will retain their reversible deflection when measured at a temperature of about 130°C.
  • fibers when heat treated to a temperature of from 525°C to 625°C for a period of time of from 2 to 3 minutes, had an increase of carbon content from about 70.6 percent to about 75 percent. Although these fibers had a higher carbon content, they were still nongraphitic.
  • the fibers of the invention may be blended with other synthetic or natural fibers including, for example, nongraphitic carbonaceous fibers.
  • Other fibers may be used in an amount of up to 90 percent by weight, based on the total weight of the fibers, so as to obtain the benefits of abrasion resistance from the aromatic polyamide fibers as well as the handle of the other fibers
  • the blended fibers are advantageously used in protective clothing, such as fire fighting garments.
  • the nonlinearity and increased tenacity of the fibers of the invention greatly improves the conditions for manufacture of the fibers into the desired end products since there are fewer fiber breaks and since the nonlinearity of the fibers provides for a substantial increase in loft.
  • the substantially permanently set crimped or nonlinear fibers improve the bending strain value of the fibers and thus the compressibility of the fibers when in the form of a wool-like fluff or batting.
  • the fibers may have imparted to them an electrically conductive property by heating the fibers, or fiber structure, to a temperature above 700°C in a nonoxidizing atmosphere as described in the aforementioned U.S. Patent No. 4,642,664.
  • the process of the present invention results in nonlinear aromatic polyamide fibers which are free of many defects with weaken the fibers. It has been found that mechanical gear crimping or stuffer box crimping of aromatic polyamide fibers by standard methods result in damage to the fibers at the bent portions of the fibers, i.e., at the portions where the fiber is doubled back on itself as is the case in the use of a stuffer box, or where the fiber is compressed between the gears of a gear crimping mechanism. Such damage becomes more pronounced when the fibers are subsequently heat treated.
  • Crimped or nonlinear fibers of the invention when heat treated at a temperature of 300°C or 500°C for 10 minutes were found to be substantially uniform in diameter and free of damage and/or fibrils at their crimped or bent portions.
  • the cloth was heat set at a temperature of 227°C for a time period of 20 minutes.
  • the deknitted it produced a tow which had an elongation or reversible deflection ratio of greater than 2:1.
  • the deknitted tow was cut into various length of from 5 to 25 cm and fed into a Platts Shirley Analyzer.
  • the fibers of the tow were separated by a carding treatment into a wool-like fluff in which the fibers had a high interstitial spacing and a high degree of interlocking as a result of the coiled configuration of the fibers.
  • a similar result was achieved with KEVLAR-49 fibers.
  • the fluff may be densified by needled punching, treated with a thermoplastic binder such as a polyester binder, or the like, to form a mat or felt-like structure having fire resistance and good abrasion strength.
  • a thermoplastic binder such as a polyester binder, or the like
  • the wool-like fluff of Example 2 was fabricated into a thermal jacket employing about 200 g of the fluff as the sole filler for the jacket.
  • the jacket had an insulating effect similar to that of a down (feather) filled jacket having from 425g to 710g of down as the insulating fill.
  • the fibers may be blended with other natural or polymeric linear or nonlinear fibers including, for example, nylon, rayon polyester, cotton, wool, and the like, or carbonaceous nongraphitic fibers.
  • a circular knit fabric composed of non-stabilized p-aramid fibers was placed in a laboratory tube furnace under a nitrogen purge. The sample was heated to a temperature of 250°C and held for 10 minutes. The sample was then cooled under nitrogen and removed. The fabric, when opened, contained fibers having a sinusoidal shape which could not be pulled out at ambient temperatures, i.e., the fibers had a substantially permanent set and could not be forced into a linear configuration by stretching of the fibers.
  • the samples prepared were:
  • the fibers had an amplitude of 21 ⁇ 2 mm and 120 coils per meter (three crimps per inch).
  • the nonlinear fibers of the invention had superior mechanical properties over nonlinear fibers which were mechanically crimped. A sharp deterioration of the properties of the fibers occurred when the heat treatment temperature was raised above 500°C.

Claims (23)

  1. Fibre non-linéaire présentant des plis ou des frisures et un rapport d'aspect supérieur à 10:1, caractérisée par le fait que la fibre est une fibre de polyamide aromatique non linéaire présentant un pourcentage de contrainte par pliage inférieur à 50 pour-cent tel que déterminé par l'équation:

    S = r R x 100
    Figure imgb0014

       où S est le pourcentage de contrainte par pliage, r est le rayon de la fibre et R est le rayon de courbure du pli ou de la frisure.
  2. Fibre selon la revendication 1, présentant un taux d'élasticité réversible supérieur à 1,2:1 lors d'une mesure à la température ambiante.
  3. Fibre selon la revendication 1, ladite fibre non-linéaire étant texturée de façon pratiquement permanente et présentant un taux d'élasticité réversible supérieur à 1,2:1 lors d'une mesure à une température de 130°C.
  4. Fibre selon les revendications 1, 2 ou 3, présentant un pourcentage de contrainte par pliage inférieur à 30%.
  5. Fibre selon l'une quelconque des revendications 1 à 4, présentant une résistance d'au moins environ 0,018 Ns²/m pour une fibre de 0,000111 g/m (18 grammes par denier).
  6. Fibre selon l'une quelconque des revendications 1 à 5, ne présentant pas plus de 15 pour-cent de variation du diamètre de la fibre aux plis ou aux frisures.
  7. Fibre selon l'une quelconque des revendications 1 à 6, ladite fibre étant pratiquement exempte de plis vifs de type V et de fibrilles.
  8. Fibre selon l'une quelconque des revendications 1 à 7, ladite fibre étant partiellement carbonisée.
  9. Structure fibreuse comportant une multiplicité de fibres non linéaires présentant des plis ou des frisures, caractérisée par le fait que les fibres sont des fibres de polyamide aromatique non linéaires présentant un pourcentage de contrainte par pliage inférieur à 50 pour-cent tel que déterminé par l'équation:

    S = r R x 100
    Figure imgb0015

       où S est le pourcentage de contente par pliage, r est le rayon de la fibre et R est le rayon de courbure du pli ou de la frisure.
  10. Structure fibreuse selon la revendication 9, présentant un taux d'élasticité réversible supérieur à 1,2:1 lors d'une mesure à la température ambiante.
  11. Structure fibreuse selon la revendication 9; ladite fibre non linéaire étant texturée de façon pratiquement permanente et présentant un taux d'élasticité réversible supérieur à 1,2:1 lors d'une mesure à une température de 130°C.
  12. Structure fibreuse selon l'une des revendications 9, 10 ou 11, présentant un pourcentage de contrainte par pliage inférieur à 30 pour-cent.
  13. Structure fibreuse selon l'une quelconque des revendications 9 à 12, présentant une résistance d'au moins environ 0,018 Ns²/m pour une fibre de 0,000111 g/m (18g/dn).
  14. Structure fibreuse selon l'une quelconque des revendications 9 à 13, ne présentant pas plus de 15 pour-cent de variation en diamètre de la fibre aux plis ou aux frisures.
  15. Structure fibreuse selon l'une quelconque des revendications 9 à 14, ladite fibre étant pratiquement exempte de plis vifs du type V et de fibrilles.
  16. Structure fibreuse selon l'une quelconque des revendications 9 à 15, ladite fibre étant partiellement carbonisée.
  17. Structure fibreuse selon l'une quelconque des revendications 9 à 16, comportant un mélange desdites libres de polyamide aromatique non linéaires avec d'autres libres choisies parmi des fibres naturelles, des fibres synthétiques et des fibres carbonées non linéaires.
  18. Structure fibreuse selon l'une quelconque des revendications 9 à 17, dans laquelle ladite multiplicité de fibres de polyamide se présentant sous forme d'une mèche ou d'un fil, d'une masse duveteuse laineuse de fibres emmêlées, de nappe, de feutre ou de voile non tissé ou de tricot tricoté ou de tissu tissé.
  19. Procédé de fabrication de libres non linéaires, comportant les étapes consistant à donner une configuration non linéaire aux libres, puis à chauffer lesdites libres à une température supérieure à 200°C pour donner auxdites libres un taux d'élasticité réversible supérieur à 1,2:1 lors d'une mesure à la température ambiante, caractérisé par le fait que les libres de départ sont des fibres de polyamide aromatique et que l'on donne aux fibres un pourcentage de contrainte par pliage inférieur à 50 pour-cent tel que déterminé par l'équation:

    S = r R x 100
    Figure imgb0016

       où S est le pourcentage de contrainte par pliagé, r est le rayon de la fibre et R est le rayon de courbure des plis ou des frisures.
  20. Procédé selon la revendication 19, dans lequel lesdites fibres sont chauffées à une température allant de 200°C à 550°C.
  21. Procédé selon la revendication 19, dans lequel les fibres sont traitées à chaud de façon pratiquement permanente sous atmosphère non aqueuse et sont exemptes de tous plis vifs de type V ou de fibrilles.
  22. Procédé selon l'une des revendications 19, 20 ou 21 dans lequel lesdites fibres sont chauffées en condition relaxée et sans tension.
  23. Procédé selon l'une quelconque des revendications 19 à 22 ne présentant pas plus de 15 pour-cent de variation dans le diamètre des fibres aux plis ou aux frisures.
EP90901290A 1988-11-30 1989-11-30 Fibre non lineaire de polyamide aromatique ou ensemble de fibres et leur procede de preparation Expired - Lifetime EP0428632B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US27808488A 1988-11-30 1988-11-30
US27808188A 1988-11-30 1988-11-30
US278081 1988-11-30
US278084 1988-11-30
PCT/US1989/005414 WO1990006229A1 (fr) 1988-11-30 1989-11-30 Fibre non lineaire de polyamide aromatique ou ensemble de fibres et leur procede de preparation

Publications (3)

Publication Number Publication Date
EP0428632A1 EP0428632A1 (fr) 1991-05-29
EP0428632A4 EP0428632A4 (en) 1992-06-17
EP0428632B1 true EP0428632B1 (fr) 1995-07-05

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EP (1) EP0428632B1 (fr)
JP (1) JPH0670284B2 (fr)
KR (1) KR900701527A (fr)
AT (1) ATE124731T1 (fr)
AU (1) AU624664B2 (fr)
BR (1) BR8907206A (fr)
DE (1) DE68923373T2 (fr)
DK (1) DK181690D0 (fr)
FI (1) FI903766A0 (fr)
HU (1) HUT54563A (fr)
RU (1) RU1838472C (fr)
WO (1) WO1990006229A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4957794A (en) * 1990-01-02 1990-09-18 E. I. Dupont De Nemours And Company Aramid fluff
US5173240A (en) * 1991-04-26 1992-12-22 E. I. Du Pont De Nemours And Company Tension-free heat-treatment of aramid fiber and fibrids
US8932965B1 (en) 2008-07-30 2015-01-13 International Textile Group, Inc. Camouflage pattern with extended infrared reflectance separation
US10433593B1 (en) 2009-08-21 2019-10-08 Elevate Textiles, Inc. Flame resistant fabric and garment
US8209785B2 (en) 2010-02-09 2012-07-03 International Textile Group, Inc. Flame resistant fabric made from a fiber blend
US8793814B1 (en) 2010-02-09 2014-08-05 International Textile Group, Inc. Flame resistant fabric made from a fiber blend

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120914A (en) * 1977-02-04 1978-10-17 E. I. Du Pont De Nemours And Company Aromatic polyamide fiber blend for protective clothing
US4752514A (en) * 1986-05-06 1988-06-21 E. I. Du Pont De Nemours And Company Cellular fiber with collapsed cells at bends
US4756941A (en) * 1987-01-16 1988-07-12 The Dow Chemical Company Method and materials for manufacture of anti-static carpet and backing
US4857404A (en) * 1988-08-24 1989-08-15 The Dow Chemical Company Fluorinated carbonaceous fibers

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ATE124731T1 (de) 1995-07-15
JPH0670284B2 (ja) 1994-09-07
DK181690A (da) 1990-07-30
FI903766A0 (fi) 1990-07-27
DE68923373D1 (de) 1995-08-10
AU624664B2 (en) 1992-06-18
WO1990006229A1 (fr) 1990-06-14
BR8907206A (pt) 1991-03-05
EP0428632A4 (en) 1992-06-17
HUT54563A (en) 1991-03-28
DK181690D0 (da) 1990-07-30
EP0428632A1 (fr) 1991-05-29
AU4662289A (en) 1990-06-26
KR900701527A (ko) 1990-12-03
DE68923373T2 (de) 1995-11-09
HU900534D0 (en) 1991-02-28
JPH03503427A (ja) 1991-08-01
RU1838472C (ru) 1993-08-30

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