EP3697953B1 - Fibres en nylon discontinues de capacité de charge élévée avec additifs, fils melanges et leurs tissées - Google Patents

Fibres en nylon discontinues de capacité de charge élévée avec additifs, fils melanges et leurs tissées Download PDF

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Publication number
EP3697953B1
EP3697953B1 EP18807746.5A EP18807746A EP3697953B1 EP 3697953 B1 EP3697953 B1 EP 3697953B1 EP 18807746 A EP18807746 A EP 18807746A EP 3697953 B1 EP3697953 B1 EP 3697953B1
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EP
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Prior art keywords
nylon
additive
fiber
fabric
staple fiber
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EP18807746.5A
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German (de)
English (en)
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EP3697953A1 (fr
Inventor
Douglas BLOOM
Allen MORTIMER
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Invista Textiles UK Ltd
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Invista Textiles UK Ltd
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Classifications

    • 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
    • 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
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • 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
    • D01D5/26—Formation of staple fibres
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • 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
    • D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D04H1/549—Polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/04—Heat-responsive characteristics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength

Definitions

  • the invention relates to high load bearing nylon staple fibers which contain an additive and methods for their production and their use in blended yarns, fabrics and other articles of manufacture.
  • Nylon has been manufactured and used commercially for a number of years.
  • the first nylon fibers were of nylon 6,6, poly(hexamethylene adipamide).
  • Nylon 6,6 fiber is still made and used commercially as the main nylon fiber.
  • Nylon fiber is used in yarns for textile fabrics, and for other purposes. For textile fabrics, there are essentially two main yarn categories, namely continuous filament yarns and yarns made from staple fiber, i.e. cut fiber.
  • Nylon staple fiber has conventionally been made by melt-spinning nylon polymer into filaments, collecting very large numbers of these filaments into a tow, subjecting the tow to a drawing operation and then converting the tow to staple fiber, e.g., in a staple cutter.
  • the tow usually contains many thousands of filaments and is generally of the order of several hundred thousand (or more) in total denier.
  • the drawing operation involves conveying the tow between a set of feed rolls and a set of draw rolls (operating at a higher speed than the feed rolls) to increase the orientation of nylon polymer in the filaments.
  • Drawing is often combined with an annealing operation to increase nylon crystallinity in the tow filaments before the tow is converted into staple fiber.
  • nylon staple fibers are readily blended, particularly with natural fibers, such as cotton (often referred to as short staple) and/or with other synthetic fibers, to achieve the advantages derivable from such blending.
  • a particularly desirable form of nylon staple fiber has been used for many years for blending with cotton, particularly to improve the durability and economics of the fabrics made from yarns comprising blends of cotton with nylon. This is because such nylon staple fiber has a relatively high load-bearing tenacity, as disclosed in Hebeler, U.S. Pat. Nos. 3,044,250 ; 3,188,790 ; 3,321,448 ; and 3,459,845 .
  • the load-bearing capacity of nylon staple fiber is conveniently measured as the tenacity at 7% elongation (T7), and the T7 parameter has long been accepted as a standard measurement and is easily read on an Instron machine.
  • the Hebeler process for preparing nylon staple fiber involves the nylon spinning, tow forming, drawing and converting operations hereinbefore described. Improvements in the Hebeler process for preparing nylon staple fiber have subsequently been made by modifying the nature of the tow drawing operation and by adding specific types of annealing (or high temperature treatment) and subsequent cooling steps to the overall process. For example, Thompson in U.S. Pat. Nos.
  • nylon staple fiber preparation wherein nylon 6,6 polymer, having for example a formic acid relative viscosity (RV) of 55, is spun into filaments which are then drawn, annealed, cooled and cut into staple fiber having a tenacity, T, at break of about 6.8-6.9, a denier per filament of about 2.44, and a load-bearing capacity, T7, of from about 2.4 to 3.2.
  • RV formic acid relative viscosity
  • T7 load-bearing capacity
  • Nylon staple fibers prepared in accordance with the Thompson technology have been blended into NYCO yarns (generally at a 50:50 nylon/cotton ratio) with these yarns being used to prepare NYCO fabrics.
  • NYCO fabrics e.g., woven fabrics, find application in military combat uniforms and apparel. While such fabrics have generally proven satisfactory for military or other rugged apparel use, military authorities, for example, are continually looking for improved fabrics which may be lighter in weight, lower in cost and/or more comfortable but still highly durable or even of improved durability.
  • PCT/US2015/055333 discloses high strength or load bearing nylon yarn with break tenacity greater than 7.5 g/den and or a tenacity at 10% elongation of greater than 4.0 g/den as well as yarns, fabrics and articles of manufacture and methods for their production.
  • denim and canvas fabrics in particular dark denim, and especially black denim, have become popular in the marketplace but are known in the industry to have fading or colorfastness issues.
  • black denim the coloration quickly fades after repeated launderings/wear.
  • nylon as a blend with cotton or cellulosic fibers significantly improves the yarn and resulting fabric's durability by improving abrasion resistance.
  • the black dyes used to dye the black denim fabric only stain the nylon and are not as dark or permanent on the nylon fiber as they are on the cotton fiber.
  • any blending of nylon staple with a cotton or cellulosic fiber requires high strength/high modulus.
  • additives such as pigments into a polymer prior to melt spinning of fibers has historically reduced fiber physical properties.
  • organic pigments tend to cross-link nylon, change its viscosity, form spherulites which weaken fibers, and cause increased draw tension and filament breaks. The more pigment that is added, the larger the strength loss.
  • These reduced fiber properties have prevented or limited blending of pigmented nylon staple with cellulosic fibers due to resulting low yarn and low fabric strength issues.
  • DuPont produced pigmented nylon staple in the mid to late 1990's for use in automotive upholstery.
  • the resulting nylon staple product had break tenacity under 5.5 grams/denier.
  • the only end use identified at that time was for the yarns to be spun in 100% form for auto/home upholstery.
  • U.S. Patent 5,290,850 discloses an improved process for melt spinning a pigmented hexamethylene adipamide fiber from a melt blend of a polymer and a colored pigment wherein the polymer is a random interpolyamide or block polymer having two different difunctional recurring amide-forming moieties other than those which form hexamethylene which exhibit tenacities greater than 7.5 grams per denier.
  • WO2011/056467A2 relates to nylon-blend fabrics such as nylon-cotton light weight fabric that has improved durability and breathability over traditional nylon-cotton fabrics.
  • US5290850 relates to pigmented nylon fibers made from certain random and/or block polyamides and to methods for reducing the draw tension necessary for orientating melt-spun pigmented nylon fibers.
  • the invention is defined by the appended claims.
  • adding any inorganic or organic pigment or additive to the polymer during the melt spinning process reduces the resulting fiber strength.
  • the fiber strength loss translates into lower yarn and resulting fabric strength.
  • the inventors herein have unexpectedly found that adding an additive into nylon polymer prior to fiber formation and drawing the fibers under a steam assist/annealing process results in the production of high strength/high modulus fibers that contain the additive.
  • an aspect of the present invention relates to nylon staple fiber comprising nylon polymer and an additive.
  • the nylon staple fiber with additive of the present invention exhibits a break tenacity greater than 58.5 g/tex (6.5 g/den).
  • the nylon staple fiber also exhibits a tenacity at 10% elongation of greater than 27 g/tex (3.0 g/den).
  • the additives included in these fibers are pigments as well as additives included for fire or flame (FR) resistance and/or ultraviolet (UV) protection.
  • the yarn further comprises at least one companion staple fiber.
  • the nylon content of the yarn is greater than 5%.
  • the nylon content of the yarn is greater than 30%.
  • the nylon content of the yarn is greater than 50%.
  • Such yarns can be made into fabrics and other articles of manufacture which are advantageously lightweight, comfortable, lower cost, and durable and hence especially suitable for use in or as, for example, military apparel such as combat uniforms or other rugged use apparel.
  • Another aspect of the present invention relates to articles of manufacture, at least a portion of which comprises nylon staple fiber or yarn of the present invention.
  • the article of manufacture is fabric.
  • the fabric is dyed a solid color and/or exhibits a uniform dark shade.
  • the fabric exhibits improved UV light fastness over the closest comparison fabrics lacking such pigment-containing or additive-containing components.
  • the fabric exhibits improved dye wash fastness over the closest comparison fabrics lacking such pigment-containing or additive-containing components.
  • the fabric is a camouflage print.
  • This fabric is typically constructed by use of pigmented synthetic fiber such as polyamide 6,6 or nylon 6,6, though the fabric can also be greige, or non-pigmented fabric. Where the fiber is pigmented, however, printing can still occur over top of the pigmented fabric.
  • the fabric exhibits a NIR (Near Infrared) reflectance in the range of 600-900 nm and/or a lower and flattened SWIR (Short Wave Infrared) reflectance in the range of 900-2500 nm. Further, the fabric increases infrared (IR) reflectance curve separation between individual colors used in printed fabrics in the SWIR spectrum, and provides further disruption and improved camouflage effectiveness against night vision goggle surveillance.
  • NIR Near Infrared
  • SWIR Short Wave Infrared
  • the fabric has improved flame resistant characteristics.
  • the fabric exhibits an improved electric arc rating over the closest comparison fabrics lacking such pigment-containing or additive-containing components
  • the article of manufacture is denim fabric.
  • the denim fabric is overdyed in a color similar to the pigment contained in the nylon staple fiber. Further, when the fiber is black, and the fabric is printed to a dark color, a more uniformly dyed product is obtained, because the black fiber will act to minimize or eliminate the appearance of white fiber showing through the fabric.
  • the article of manufacture is a non-woven fabric composite.
  • End uses for such composites include, but are not limited to, industrial (felts/backings/filtration/insulation), apparel (inclusive of liner fabrics), footwear, bag/pack hard gear, durable and semi-durable (disposable or semi disposable) clothing or PPE, including FR (chemically treated or in combination with inherent FR fiber technologies), bio chemical, or other specialty protective wear.
  • Yet another aspect of the present invention relates to a method for producing high strength or load bearing pigmented nylon staple fiber.
  • the method of the present invention comprises melt-spinning nylon polymer with pigment into filaments, then uniformly quenching the filaments and forming a tow from a multiplicity of these quenched filaments.
  • the tow is then subjected to drawing in the presence of steam.
  • the steam is introduced between feeding and drawing.
  • the drawn tow is then annealed and the resulting drawn and annealed tow is converted into staple fibers.
  • the annealing is performed under tension.
  • Nylon staple fiber produced in accordance with this method has a break tenacity greater than 58.5 g/tex (6.5 g/den).
  • the nylon staple fiber prepared in accordance with this method has a tenacity at 10% elongation of greater than 27 g/tex (3.0 g/den).
  • high strength or load bearing nylon staple fiber with additive exhibiting a break tenacity greater than 58.5 g/tex (6.5 g/den) and a tenacity at 10% elongation of greater than 27 g/tex (3.0 g/den), yarns, fabrics and other articles of manufacture, at least a portion of which are prepared from these fibers, and methods for their production.
  • the additives included in the nylon staple fiber are pigments, additives which provide UV protection, and additives for FR resistance.
  • the additive is a pigment present in an amount from about 10 parts per million to about 50,000 parts per million.
  • the pigment is carbon black.
  • suitable pigments are: ultramarine violet, a silicate of sodium and aluminum containing sulfur; han purple, BaCuSi 2 O 6 ; cobalt violet, cobaltous orthophosphate; manganese violet, NH 4 MnP 2 O 7 ; ultramarine, Na 8-10 Al 6 Si 6 O 24 S 2-4 ; Persian blue, (Na, Ca) 8 (AlSiO 4 ) 6 (S,SO 4 ,Cl) 1-2 ; cobalt blue, cobalt(II) stannate; Egyptian blue, (CaCuSi 4 O 10 ); han blue, BaCuSi 4 O 10 ; azurite, (Cu 3 (CO 3 ) 2 (OH 2 )); Prussian blue, ferric hexacyanoferrate; YInMn blue, (YIn 1-x Mn
  • non-woven fabric composites comprising high tenacity fiber and cellulosic or recycled synthetic or natural fiber.
  • durable and “durability” refer to the propensity of a fabric so characterized to have suitably high grab and tear strength as well as resistance to abrasion for the intended end use of such fabric, and to retain such desirable properties for an appropriate length of time after fabric use has begun.
  • the term "blend” or “blended”, in referring to a spun yarn, means a mixture of fibers of at least two types, wherein the mixture is formed in such a way that the individual fibers of each type of fiber are substantially completely intermixed with individual fibers of the other types to provide a substantially homogeneous mixture of fibers, having sufficient entanglement to maintain its integrity in further processing and use.
  • cotton count refers to the yarn numbering system based on a length of 840 yards, and wherein the count of the yarn is equal to the number of 840-yard skeins required to weigh 1 pound.
  • Some embodiments are based on the preparation of improved nylon staple fibers with additive having certain specified characteristics and on the subsequent preparation of yarns, and fabrics woven from such yarns, wherein these improved nylon staple fibers with additive are blended with at least one other fiber.
  • the other fibers may include cellulosics such as cotton, modified cellulosics such as fire-resistant (FR) treated cellulose, polyester, rayon, animal fibers such as wool, FR polyester, FR nylon, FR rayon, m-aramid, p-aramid, modacrylic, novoloid, melamine, polyvinyl chloride, antistatic fiber, PBO (1,4-benzenedicarboxylic acid, polymer with 4,6-diamino-1,3-benzenediol dihydrochloride), PBI (polybenzimidazole), and combinations thereof.
  • the nylon staple fibers of some embodiments can provide an increase in strength and/or abrasion resistance to yarns and fabrics. This is especially true for combination with relatively weaker fibers such as
  • nylon staple fibers with additive prepared and used herein include fiber denier, fiber tenacity and fiber load-bearing capacity defined in terms of fiber tenacity at 7% and 10% elongation.
  • Realization of the desired nylon staple fiber with additive material herein is based on the use in staple fiber manufacture of nylon polymeric filaments and tows having certain selected properties and processed using certain selected processing operations and conditions.
  • the inventors herein have found that introduction of steam between the feed and draw module and/or tension during annealing during production of the nylon staple fiber with additive significantly inhibits or prevents reduction in strength associated with addition of such fiber additives.
  • steam is introduced into the process by addition of a steam chamber between the feed and draw modules as this allows the excess water to be removed prior to annealing.
  • the steam chamber adds enough heat/steam to reduce the draw force of the nylon and help localize the draw to the steam chamber and not over or at the feed roll exit. Steam can be controlled by pressure.
  • nylon polymer itself which is used for the spinning of nylon filaments of the present invention can be produced in conventional manner.
  • Nylon polymer suitable for use in the process and filaments of some embodiments comprises synthetic melt spinnable or melt spun polymer.
  • Such nylon polymers can include polyamide homopolymers, copolymers, and mixtures thereof which are predominantly aliphatic, i.e., less than 85% of the amide-linkages of the polymer are attached to two aromatic rings.
  • Widely-used polyamide polymers such as poly(hexamethylene adipamide) which is nylon 6,6 and poly( ⁇ -caproamide) which is nylon 6 and their copolymers and mixtures thereof can be used in accordance with some embodiments.
  • polyamide polymers which may be advantageously used are nylon 12, nylon 4,6, nylon 6,10, nylon 6,12, nylon 12,12, and their copolymers and mixtures thereof.
  • Illustrative of polyamides and copolyamides which can be employed in the process, fibers, yarns and fabrics of some embodiments are those described in U.S. Pat. Nos. 5,077,124 , 5,106,946 , and 5,139,729 (each to Cofer et al. ) and the polyamide polymer mixtures disclosed by Gutmann in Chemical Fibers International, pages 418-420, Volume 46, December 1996 .
  • the polymer may further comprise a monomeric salt of sulfonated isopthalate (SIPA) or a monomeric methylpentamethyldiamine (MPMD).
  • SIPA sulfonated isopthalate
  • MPMD monomeric methylpentamethyldiamine
  • the monomer is added at an amount of about 0.04 to about 4 wt. % of the nylon polymer.
  • Nylon polymer used in the preparation of nylon staple fibers has conventionally been prepared by reacting appropriate monomers, catalysts, antioxidants and other additives, including, but not limited to, plasticizers, delustrants, pigments, dyes, light stabilizers, heat stabilizers, antistatic agents for reducing static, additives for modifying dye ability, agents for modifying surface tension, etc.
  • Polymerization has typically been carried out in a continuous polymerizer or batch autoclave.
  • the molten polymer produced thereby has then typically been introduced to a spin pack wherein it is forced through a suitable spinneret and formed into filaments which are quenched and then formed into tows for ultimate processing into nylon staple fiber.
  • spin pack is comprised of a pack lid at the top of the pack, a spinneret plate at the bottom of the pack and a polymer filter holder sandwiched between the former two components.
  • the filter holder has a central recess therein.
  • the lid and the recess in the filter holder cooperate to define an enclosed pocket in which a polymer filter medium, such as sand, is received.
  • There are provided channels interior to the pack to allow the flow of molten polymer, supplied by a pump or extruder to travel through the pack and ultimately through the spinneret plate.
  • the spinneret plate has an array of small, precision bores extending therethrough which convey the polymer to the lower surface of the pack.
  • the mouths of the bores form an array of orifices on the lower surface of the spinneret plate, which surface defines the top of the quench zone.
  • the polymer exiting these orifices is in the form of filaments which are then directed downwards through the quench zone.
  • RV relative viscosity
  • RV is the ratio of the viscosity of a solution of nylon polymer in a formic acid solvent to the viscosity of the formic acid solvent itself. RV is taken as an indirect indication of nylon polymer molecular weight. For purposes herein, increasing nylon polymer RV is considered synonymous with increasing nylon polymer molecular weight.
  • nylon polymer of greater molecular weight i.e., nylon polymer having RV values of greater than 70-75 and up to 140 or even 190 and higher can be advantageous.
  • high RV nylon polymer of this type has improved resistance to flex abrasion and chemical degradation. Accordingly, such high RV nylon polymer is especially suitable for spinning into nylon staple fiber which can advantageously be used for the preparation of papermaking felts.
  • Procedures and apparatus for making high RV nylon polymer and staple fiber therefrom are disclosed in U.S. Pat. No. 5,236,652 to Kidder and in U.S. Pat. Nos. 6,235,390 ; 6,605,694 ; 6,627,129 and 6,814,939 to Schwinn and West .
  • nylon staple fibers with additive of improved tenacity are blended with one or more other fibers such as cotton staple fibers, textile yarns of improved strength as well as lower weight can be realized.
  • Fabrics such as NYCO fabrics woven from such yarns exhibit the advantages hereinbefore described with respect to durability, optional lighter weight, improved comfort and/or potential lower cost as well as the benefit of the selected additive color, UV protection or FR resistance.
  • nylon polymer with additive which is melt spun into tow-forming filaments through one or more spin pack spinnerets and quenched, will have an RV value ranging from 45 to 100, including from 55 to 100, from 46 to 65, from 50 to 60, and from 65 to 100.
  • Nylon polymer of such RV characteristics can be prepared, for example, using a melt blending of polyamide concentrate procedure such as the process disclosed in the aforementioned Kidder '652 patent.
  • Kidder discloses certain embodiments in which a catalyst is added for the purpose of increasing the formic acid relative viscosity (RV).
  • Higher RV nylon polymer available for melting and spinning such as nylon having an RV of from 65 to 100, can also be provided by means of a solid phase polymerization (SPP) step wherein nylon polymer flakes or granules are conditioned to increase RV to the desired extent.
  • solid phase polymerization (SPP) procedures are well-known and disclosed in greater detail in the aforementioned Schwinn/West '390, '694, '129 and '939 patents.
  • the nylon polymer material with additive having the requisite RV characteristics as specified herein is fed to a spin pack, for example via a twin screw melter device.
  • a volumetric or gravimetric feeder is used for addition of the additive.
  • the nylon polymer with additive is spun by extrusion through one or more spinnerets into a multiplicity of filaments.
  • filament is defined as a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length.
  • the filament cross section can be any shape, but is typically circular.
  • fiber can also be used interchangeably with the term "filament”.
  • Each individual spinneret position may contain from 100 to 1950 filaments in an area as small as 9 inches by 7 inches (22.9 cm x 17.8 cm).
  • Spin pack machines may contain from one to 96 positions, each of which provides bundles of filaments which eventually get combined into a single tow band for drawing/downstream processing with other tow bands.
  • the molten filaments which have been extruded through each spinneret are typically passed through a quench zone wherein a variety of quenching conditions and configurations can be used to solidify the molten polymer filaments with additive and render them suitable for collection together into tows. Quenching is most commonly carried out by passing a cooling gas, e.g., air, toward, onto, with, around and through the bundles of filaments being extruded into the quenching zone from each spinneret position within the spin pack.
  • a cooling gas e.g., air
  • One suitable quenching configuration is cross-flow quenching wherein a cooling gas such as air is forced into the quenching zone in a direction which is substantially perpendicular to the direction that the extruded filaments are travelling through the quench zone.
  • Cross-flow quenching arrangements are described, among other quenching configurations, in U.S. Pat. Nos. 3,022,539 ; 3,070,839 ; 3,336,634 ; 5,824,248 ; 6,090,485 , 6,881,047 and 6,926,854 .
  • the extruded nylon filaments with additive used to eventually form the desired nylon staple fibers with additive are spun, quenched and formed into tows with both positional uniformity and uniformity of quenching conditions such as described in published U.S. Patent Application Nos. 2011/0177737 and 2011/0177738 .
  • Quenched spun filaments can then be combined into one or more tows.
  • Such tows formed from filaments from one or more spinnerets are then subjected to a two stage continuous operation wherein the tows are drawn and annealed in the presence of steam.
  • Drawing of the tows is generally carried out primarily in an initial or first drawing stage or zone wherein bands of tows are passed between a set of feed rolls and a set of draw rolls (operating at a higher speed) to increase the crystalline orientation of the filaments in the tow.
  • the extent to which tows are drawn can be quantified by specifying a draw ratio which is the ratio of the higher peripheral speed of the draw rolls to the lower peripheral speed of the feed rolls.
  • the effective draw ratio is calculated by multiplying the 1st draw ratio and the 2nd draw ratio.
  • the first drawing stage or zone may include several sets of feed and draw rolls as well as other tow guiding and tensioning rolls such as snubbing pins.
  • Draw roll surfaces may be made of metal, e.g., chrome, or ceramic. Ceramic draw roll surfaces have been found to be particularly advantageous in permitting use of the relatively higher draw ratios specified for use in connection with the staple fiber preparation process herein. Ceramic rolls improve roll life as well as provide a surface that is less prone to wrap.
  • An article appearing the International Fiber Journal International Fiber Journal, 17, 1, February 2002: “Textile and Bearing Technology for Separator Rolls", Zeitz and el .) as well as U.S. Pat. No. 4,794,680 , also disclose the use of ceramic rolls in to improve roll life and reduce fiber adherence to roll surface.
  • the total amount of draw to which the filament tows herein are subjected can be quantified by specifying a total effective draw ratio which takes into account drawing that occurs in both a first initial drawing stage or zone and in a second zone or stage where annealing and some additional drawing are conducted simultaneously.
  • the tows of nylon filaments with additive are subjected to a total effective draw ratio of from 2.3 to 5.0, including from 3.0 to 4.0.
  • a total effective draw ratio can range from 3.12 to 3.40.
  • the total effective draw ratio can range from 3.5 to 4.0.
  • first or initial drawing stage or zone most of the drawing of the tows, as noted hereinbefore, occurs in the first or initial drawing stage or zone. In particular, from 85% to 97.5%, including from 92% to 97%, of the total amount of draw imparted to the tows will take place in the first or initial drawing stage or zone.
  • the drawing operation in the first or initial stage will generally be carried out at whatever temperature the filaments have when passed from the quench zone of the melt spinning operation. Frequently, this first stage drawing temperature will range from 80°C to 125° C.
  • steam is introduced between feeding and drawing.
  • a steam chamber located between the feed and draw modules is used.
  • the partially drawn tows are passed to a second annealing and drawing stage or zone wherein the tows are simultaneously heated and further drawn. Heating of the tows to effect annealing serves to increase crystallinity of the nylon polymer of the filaments.
  • the filaments of the tows are subjected to an annealing temperature of from 145° C to 205° C, such as from 165° C to 205° C.
  • the temperature of the tow in this annealing and drawing stage may be achieved by contacting the tow with a steam-heated metal plate that is positioned between the first stage draw and the second stage drawing and annealing operation.
  • annealing/oven drying under tension helps remove excess moisture gained during steam draw.
  • the drawn and annealed tows are cooled to a temperature of less than 80° C, such as less than 75° C. Throughout the drawing, annealing and cooling operations described herein, the tows are maintained under controlled tension and accordingly are not permitted to relax.
  • the multifilament tows are converted into staple fiber with additive by any conventional manner, for example, using a staple cutter.
  • Staple fiber with additive formed from the tows will frequently range in length from 2 to 13 cm (0.79 to 5.12 inches).
  • staple fibers with additive may range from 2 to 12 cm (0.79 to 4.72 inches), from 2 to 12.7 cm (0.79 to 5.0 inches), or from 5 to 10 cm.
  • the staple fiber with additive herein can optionally be crimped.
  • the high tenacity nylon staple fiber with additive formed in accordance with the process herein will generally be provided as a collection of fibers, e.g., as bales of fibers, having a denier per fiber of from 1.0 to 3.0.
  • a total effective draw ratio of from 3.12 to 3.40, such as from 3.15 to 3.30 can be used in the process herein to provide staple fibers of the requisite load-bearing capacity.
  • the nylon staple fiber with additive of the invention has a tenacity at 10% elongation of at least 27 d/gen (3.0 g/den).
  • Fiber with properties above and with the added advantage of the present invention of additives in the fiber such as pigments, UV protectors and FR resistors can be used at lower blend ratios or spun into yarns using alternative spinning systems that significantly reduce fabric manufacturing costs and still meet existing fabrics specifications.
  • This fiber can be used to significantly reduce yarn spinning and finished fabric costs by allowing the use of lower nylon blend levels and/or alternative spinning system while maintaining fabric properties.
  • the nylon staple fibers with additive provided herein are especially useful for blending with other fibers for various types of textile applications.
  • Blends can be made, for example, with the nylon staple fibers of some embodiments in combination with other synthetic fibers such as rayon or polyester.
  • Examples of blends of the nylon staple fibers herein include those made with natural cellulosic fibers such as cotton, flax, hemp, jute and/or ramie.
  • Suitable methods for intimately blending these fibers may include: bulk, mechanical blending of the staple fibers prior to carding; bulk mechanical blending of the staple fibers prior to and during carding; or at least two passes of draw frame blending of the staple fibers subsequent to carding and prior to yarn spinning.
  • the high load-bearing capacity nylon staple fibers with additive herein may be blended with cotton staple fibers and spun into textile yarn.
  • Such yarns may be spun in conventional manner using commonly known short and long staple spinning methods including ring spinning, air jet or vortex spinning, open end spinning, or friction spinning.
  • the resulting textile yarn will generally have a cotton fiber to nylon fiber weight ratio of from 10:90 to 90: 10, including from 30:70 to 70:30, and frequently a cotton:nylon weight ratio of 50:50. It is well-known in the art that nominal variation of the fiber content, e.g., 52:48 is also considered to be a 50:50 blend.
  • nylon/cotton (NYCO) yarns of some embodiments can be used in conventional manner to prepare NYCO woven fabrics of especially desirable properties for use in military or other rugged use apparel.
  • NYCO woven fabrics of especially desirable properties for use in military or other rugged use apparel.
  • such yarns may be woven into 2x1 or 3x1 twill NYCO fabrics.
  • Spun NYCO yarns and 3x1 twill woven fabrics comprising such yarns are in general described and exemplified in U.S. Pat. No. 4,920,000 to Green .
  • NYCO woven fabrics comprise both warp and weft (fill) yarns.
  • the woven fabrics of some embodiments are those which have the NYCO textile yarns herein woven in an least one, and optionally both, of these directions.
  • fabrics herein of especially desirable durability and comfort will have yarns woven in the weft (fill) direction comprising nylon staple fibers with additive herein and will have yarns woven in the warp direction comprising nylon staple fibers with additive herein.
  • the woven fabrics of some embodiments made using yarns which comprise the high load bearing nylon staple fibers with additive herein can use less of the nylon staple fibers than conventional NYCO fabrics while retaining many of the desirable properties of such conventional NYCO fabrics.
  • fabrics can be made to be relatively lightweight and low cost while still desirably durable.
  • fabrics can be made using equal or even greater amounts of the nylon staple fibers with additive herein in comparison with nylon fiber content of conventional NYCO fabrics with such fabrics herein providing superior durability properties.
  • nylon staple fiber of the present invention with pigment additive is used to produce an article of manufacture such as a denim fabric.
  • black dyed 100% cotton denim fabric has fade and wear issues after repeated launderings.
  • non-pigmented, high strength nylon staple can be added to improve fabric durability and strength, fading issues remain.
  • Adding a pigmented, high strength nylon staple of the present invention comprising an additive such as carbon black reduces the black color appearance loss and improves wear life.
  • alternative pigments for colors such as blue, green and tan can also be used.
  • pigmented fibers with 1-5% by weight of, for example, carbon black or denim blue coloration can be used in denim to reduce fabric fading issues and improve durability. Incorporation of these fibers into fabrics is particularly useful in articles of manufacture which are dyed a solid color and/or wherein improved uniformity in dyeing such as in dark shades is desired.
  • the denim fabric may be overdyed in a color similar to the pigment contained in the nylon staple fiber.
  • Camouflage printed fabrics may also be produced from the nylon staple fiber with additive of the present invention.
  • Such fabrics are expected to exhibit improved dye wash fastness.
  • NIR Near Infrared
  • SWIR Short Wave Infrared
  • nylon staple pigmented fibers of the present invention with carbon black in the range of 10 to 1000 ppm can be used to improve concealment of articles of manufacture such as uniforms containing the fiber when viewed under SWIR/NIR night vision goggles.
  • incorporation of a pigmented nylon staple fiber of the present invention comprising a conventional dyestuff can lower the NIR reflectance in the range of 600-900 nm without requiring any pre- or post-treatments or use of a metalized or special pigment formulations and without significantly changing the shade in the visible spectrum, thus enhancing the camouflage disruption and effectiveness against night vision goggle surveillance.
  • incorporation of a pigmented nylon staple fiber of the present invention comprising a conventional dyestuff can lower and flatten the Short Wave Infrared reflectance (SWIR) in the range of 900-2500 nm without requiring pre- or post-treatments or use of metalized or special pigment formulations required for solid color and printed camouflage NYCO fabrics, and without significantly changing the shade in the visible spectrum thus enhancing the camouflage disruption and effectiveness against night vision goggle surveillance.
  • SWIR Short Wave Infrared reflectance
  • incorporation of a pigmented nylon staple fiber of the present invention comprising a conventional dyestuff can increase the level of separation between print colors in the SWIR in the range of 900-2500 nm without requiring pre- or post-treatments or use of metalized or special pigment formulations, thus enhancing the camouflage disruption and effectiveness against night vision goggle surveillance.
  • Such fabrics of the present invention are also expected to exhibit an improved electric arc rating.
  • incorporation of nylon staple fiber with an additive providing UV protection or an additive providing FR resistance into an article of manufacture such as a fabric results in improved UV light fastness and/or flame retardance.
  • the present invention also relates to non-woven fabric composites comprising high tenacity fiber of the present invention.
  • the high tenacity fiber can be combined with various cellulosic or recycled synthetic or natural fiber technologies.
  • the high tenacity fiber is combined with recycled denim.
  • End uses for the non-woven fabric composites include, but are not limited to, industrial (felts/backings/filtration/insulation), apparel (inclusive of liner fabrics), footwear, bag/pack hard gear, durable and semi-durable (disposable or semi disposable) clothing or PPE, including FR (chemically treated or in combination with inherent FR fiber technologies), bio chemical, or other specialty protective wear.
  • Test Methods and Examples demonstrate the present invention and its capability for use.
  • the invention is capable of other and different embodiments, and its several details are capable of modifications in various apparent respects, without departing from the scope of the present invention. Accordingly, the Test Methods and Examples are to be regarded as illustrative in nature and non-limiting.
  • the formic acid RV of nylon materials used herein refers to the ratio of solution and solvent viscosities measured in a capillary viscometer at 25° C.
  • the solvent is formic acid containing 10% by weight of water.
  • the solution is 8.4% by weight nylon polymer dissolved in the solvent. This test is based on ASTM Standard Test Method D 789.
  • the formic acid RVs are determined on spun filaments, prior to or after drawing, and can be referred to as spun fiber formic acid RVs.
  • All Instron measurements of staple fibers herein are made on single staple fibers, taking appropriate care with the clamping of the short fiber, and making an average of measurements on at least 10 fibers. Generally, at least 3 sets of measurements (each for 10 fibers) are averaged together to provide values for the parameters determined.
  • Denier is the linear density of a filament expressed as weight in grams of 9000 meters of filament. Denier can be measured on a Vibroscope from Textechno of Kunststoff, Germany. Denier times (10/9) is equal to decitex (dtex). Denier per filament can be determined gravimetrically in accordance with ASTM Standard Test Method D 1577. A Favimat machine having a vibration based linear density measurement such as used in a Vibroscope can also be used to determine DPF or denier per filament of the individual fiber and is comparable to ASTM D1577.
  • Tenacity at break is the maximum or breaking force of a filament expressed as force per unit cross-sectional area.
  • the tenacity can be measured on an Instron model 1130 available from Instron of Canton, Mass, and is reported as grams per denier (grams per dtex). Filament tenacity at break (and elongation at break) can be measured according to ASTM D 885.
  • Filament tenacity at 7% elongation is the force applied to a filament to achieve 7% elongation divided by filament denier. T7 can be determined according to ASTM D 3822. Tenacity at 10% elongation can be run on a Favimat, which is comparable to ASTM D3822.
  • Strength of the spun nylon/cotton yarns herein can be quantified via a Lea Product value or yarn breaking tenacity.
  • Lea Product and skein breaking tenacity are conventional measures of the average strength of a textile yarn and can be determined in accordance with ASTM D 1578.
  • Lea Product values are reported in units of pounds force. Breaking tenacity is reported in units of cN/tex.
  • Fabric weight or basis weight of the woven fabrics herein can be determined by weighing fabric samples of known area and calculating weight or basis weight in terms of grams/m 2 or oz/yd 2 in accordance with the procedures of the standard test method of ASTM D 3776.
  • Fabric grab strength can be measured in accordance with ASTM D 5034. Grab strength measurements are reported in pounds-force in both warp and fill directions.
  • Fabric tear strength can be measured in accordance with ASTM D 1424 titled Standard Test Method for Tearing Strength of Fabrics by Falling-Pendulum Type (Elmendorf) Apparatus. Grab strength measurements are reported in pounds-force in both warp and fill directions.
  • AATCC 61 is used to evaluate the colorfastness to laundering of textiles expected to withstand frequent launderings. Test specimens are attached to multi-fiber swatches and stainless steel balls are loaded into stainless steel canisters to replicate abrasion. The canisters are then loaded into the machine and the 45 minute test begins. After laundering, specimens are dried, conditioned, and evaluated with both the Gray Scale for Color Change and the Gray Scale for Staining. Dimensional changes of fabrics after laundering are also tested and applied to evaluations, according to AATCC Test Method 135.
  • test method provides the general principles and procedures which are currently in use for determining the colorfastness to light of textile materials.
  • the test options described are applicable to textile materials of all kinds and for colorants, finishes and treatments applied to textile materials.
  • NIR and SWIR analyses are performed using any of commercially available color spectrophotometric instruments such as an UltraScan Pro spectrophotometer, available from HunterLab.

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Claims (15)

  1. Fibre discontinue de nylon comprenant :
    un polymère de nylon ; et
    un additif,
    dans laquelle la fibre discontinue de nylon présente une ténacité à la rupture supérieure à 58,5 g/tex (6,5 g/den) ;
    dans laquelle la ténacité de la fibre discontinue de nylon à un allongement de 10 % est supérieure à 27 g/tex (3,0 g/den), dans laquelle la ténacité à la rupture et la ténacité à un allongement de 10 % sont mesurées conformément aux procédés respectifs décrits dans la description ; et
    dans laquelle l'additif est sélectionné parmi un pigment, un additif pour une protection contre les ultraviolets (UV) ou un additif pour une résistance aux flammes ou au feu (FR).
  2. Fibre discontinue de nylon selon la revendication 1, dans laquelle l'additif est un pigment présent en une quantité allant d'environ 10 parties par million à environ 50 000 parties par million.
  3. Fibre discontinue de nylon selon la revendication 1, dans laquelle le polymère de nylon est sélectionné à partir du groupe consistant en le nylon 6,6, le nylon 6 et des combinaisons de ceux-ci.
  4. Fibre discontinue de nylon selon la revendication 1, dans laquelle le polymère de nylon comprend en outre un sel monomère d'isopthalate sulfoné (SIPA) en une quantité allant d'environ 0,04 à environ 4 % en poids de polymère de nylon.
  5. Fibre discontinue de nylon selon la revendication 1, dans laquelle le polymère de nylon comprend en outre un méthylpentaméthyldiamine monomère (MPMD) en une quantité allant d'environ 0,04 à environ 4 % en poids de polymère de nylon.
  6. Fil filé à partir de la fibre discontinue de nylon selon l'une quelconque des revendications 1 à 5.
  7. Fil selon la revendication 6, comprenant en outre au moins une fibre discontinue complémentaire ; facultativement
    dans lequel la fibre discontinue complémentaire est sélectionnée à partir du groupe consistant en des dérivés cellulosiques, des dérivés cellulosiques modifiés, des fibres animales, le polyester ignifuge, le nylon ignifuge, la rayonne ignifuge, la cellulose traitée ignifuge, la m-aramide, la p-aramide, la modacrylique, le novoloïde, la mélamine, le chlorure de polyvinyle, la fibre antistatique, le PBO (acide 1,4-benzènedicarboxylique, polymère avec 4,6-diamino-1,3-benzènediol dihydrochlorure) et le PBI (polybenzimidazole), et des combinaisons de ceux-ci.
  8. Fil selon l'une quelconque des revendications 3 ou 7, dans lequel la teneur en nylon est supérieure ou égale à 5 %.
  9. Article de fabrication dont au moins une partie comprend une fibre discontinue de nylon selon l'une quelconque des revendications 1-5 ou un fil selon l'une quelconque des revendications 6 à 8.
  10. Article de fabrication selon la revendication 9, qui est un tissu.
  11. Article de fabrication selon la revendication 9, qui est un tissu denim ; facultativement
    dans lequel le tissu denim est surteint en une couleur similaire au pigment contenu dans la fibre discontinue de nylon.
  12. Article de fabrication selon la revendication 9, qui est un composite de tissu non tissé ; facultativement
    dans lequel le composite de tissu non tissé comprend en outre une fibre cellulosique ou synthétique recyclée ou naturelle ; facultativement
    dans lequel la fibre cellulosique ou synthétique recyclée ou naturelle comprend du denim recyclé.
  13. Article de fabrication selon la revendication 9, dans lequel le tissu est teint d'une couleur unie et/ou présente une teinte foncée uniforme ; ou
    dans lequel le tissu présente une solidité à la lumière UV améliorée ; ou
    dans lequel le tissu présente une solidité des teintures au lavage améliorée ; ou
    dans lequel le tissu est un imprimé camouflage ; ou
    dans lequel le tissu présente une réflectance dans le proche infrarouge (NIR) réduite située dans la plage allant de 600 à 900 nm ; ou
    dans lequel le tissu présente une réflectance infrarouge à ondes courtes (SWTR) plus faible et plate située dans la plage allant de 900 à 2 500 nm ; ou
    dans lequel le tissu est ignifuge ; ou
    dans lequel le tissu présente un indice de niveau de protection contre un arc électrique amélioré.
  14. Procédé de production d'une fibre discontinue de nylon à haute résistance ou porteuse de charge avec un additif, ledit procédé comprenant les étapes consistant à :
    filer par fusion un polymère de nylon avec un additif en filaments ;
    tremper uniformément les filaments ;
    former un câble à partir d'une multiplicité de ces filaments trempés ;
    soumettre le câble à l'étirage en présence de vapeur,
    effectuer un recuit du câble étiré ; et
    convertir le câble étiré et recuit résultant en fibres discontinues ;
    dans lequel la vapeur est introduite entre l'alimentation et l'étirement ; et
    dans lequel l'additif est sélectionné parmi un pigment, un additif pour une protection contre les ultraviolets (UV) ou un additif pour une résistance au feu (FR).
  15. Procédé selon la revendication 14, dans lequel le recuit est réalisé sous tension.
EP18807746.5A 2017-10-20 2018-10-18 Fibres en nylon discontinues de capacité de charge élévée avec additifs, fils melanges et leurs tissées Active EP3697953B1 (fr)

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CN111225998A (zh) 2020-06-02
US20200283933A1 (en) 2020-09-10
JP7242664B2 (ja) 2023-03-20
CN111225998B (zh) 2023-01-24
WO2019079584A1 (fr) 2019-04-25
JP2021500483A (ja) 2021-01-07
BR112020007709A2 (pt) 2020-10-20
EP3697953A1 (fr) 2020-08-26
MX2020003277A (es) 2020-07-20

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