EP1888823A1

EP1888823A1 - Polyamide yarns, filaments and fibers with enhanced properties

Info

Publication number: EP1888823A1
Application number: EP06778588A
Authority: EP
Inventors: Gilles Robert
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2005-06-10
Filing date: 2006-06-09
Publication date: 2008-02-20
Also published as: RU2008100053A; FR2886949A1; WO2006131658A1; IL187965A; UA90312C2; TW200708543A; SG162746A1; JP2008542576A; US20100021679A1; BRPI0613318A2; MX2007015404A; KR20080010457A; IL187965A0; TWI323269B; RU2372422C2; FR2886949B1; CN101228302A; KR100947195B1

Abstract

The invention concerns polyamide yarns, fibers and filaments wherein are dispersed nanometric particles, the method for preparing said yarns, fibers and filaments and uses thereof.

Description

POLYAMIDE THREADS, FILAMENTS AND POLYAMIDE FIBERS WITH IMPROVED PROPERTIES

The present invention relates to filaments, fibers, and synthetic son, in particular based on polyamide, having improved mechanical properties, and in particular improved elongation resistance and crush stress (transverse plasticity).

The present invention also relates to the spinning process of said filaments, and the use of said filaments, fibers and yarns in various fields, especially in processes involving filtration, pressing or spinning operations. . A particularly appropriate use is that of paper felt.

[0003] Polyamide fibers with improved mechanical properties are already widely known. In particular, the patent application WO 99/60057 discloses polyamide-based matrices in which are dispersed nanoparticles of delaminated silicates. Similarly, the international application WO 01/12678 describes a process for the preparation of polyamide comprising dissociated silicates.

Japanese Patent Application JP-B2-2716810 teaches that polyamide filaments containing from 0.05 to 30 parts by weight of silicates, for example of a multilayered clay, have excellent mechanical properties, such as toughness , elongation, rigidity, stretching, and others.

However, there is still a need for polyamide fibers, yarns or filaments having further improved properties. Thus, a first object of the present invention is to provide filaments, fibers, and polyamide son having a high rate of elongation at break.

A second objective of the present invention is defined by filaments, fibers, and polyamide son having a high rate of elongation at break, and a high transverse plasticity threshold stress.

Another object of the present invention is to provide filaments, fibers, and polyamide yarns having a high degree of elongation at break, as well as a constraint at the threshold of high transverse plasticity, and having a relatively low level of nanoscale particles.

Another object of the present invention is to provide filaments, fibers, and polyamide son having a high rate of elongation at break, a stress at the threshold of high transverse plasticity, while having only one rate relatively small nanoscale particles and having, for a given elongation rate, a higher stress than the filaments, fibers or son, known in the prior art. Still other objects will appear in the following description of the invention. According to a first aspect, the present invention relates to filaments, fibers, and yarns comprising a polyamide matrix in which are dispersed between 0.01% and 5% by weight, preferably between 0.02% and 3% by weight. , more preferably between 0.05% and 2% by weight of nanometric particles and having a transverse plasticity threshold stress of between 40 and 150 MPa, preferably between 45 and 95 MPa, with a degree of elongation at break included between 20% and 140%, advantageously between 40% and 100%, for a relative humidity of 50%, at 23 ^° C.

The polyamide matrix from which are manufactured son, fibers and filaments of the invention comprises. any type of polyamide known per se, and in particular any polyamide usually used in the field of textile articles or yarns, fibers, etc. with technical applications.

Although this is not a limit to the present invention, the matrix of son, fibers and filaments is a polyamide or a copolyamide or a mixture of polyamides whose weight average molecular weight is between 25000 g / mol and 100000 g / mol, preferably between 30000 g / mol and 90000 g / mol, advantageously between 40000 g / mol and 85000 g / mol. By way of example and without limitation, the polyamides that can be used in the present invention include PA 6.6, PA 6, PA 6 / 6.6 copolymer, semi-aromatic polyamides, such as polyamide. 6T, the Amodel ^® (marketed by Amoco), HTN ^® (marketed by DuPont), and other polyamides 11, 12, 4-6, and the like, and mixtures thereof in all proportions. The polyamides may be of linear or branched structure, such as star polyamide marketed by Rhodia under the trademark Technylstar ^® .

For the purposes of the invention, it is preferred to use PA 6.6 or PA 6, or alternatively the PA 6 / 6.6 copolymer, alone or in mixtures in all proportions of two or more of them.

The son, fibers and filaments according to the invention are obtained by melt spinning a charged composition, as explained further in the present description. Furthermore, any step, conventional in the field of the manufacture of son, fibers and filaments, intended for example to dimensionally stabilize said son, fibers and filaments (thermofixation) or to give them volume through a compression box (crimping), can be applied. Any other method of manufacturing yarns, fibers and filaments is also suitable. The son, fibers and filaments used in the present invention may have sections of any shape, whether round, flat, serrated or fluted, or in the form of beans, but also multilobed, in particular trilobed or pentalobées , X-shaped, ribbon, hollow, square, triangular, elliptical and others. Their sectional shape is however not an essential feature of the invention. All section shapes resulting from the method of manufacturing said yarns, fibers and filaments are acceptable. Likewise, the yarns, fibers and filaments used in the present invention may be of constant diameter and / or section or have variations. Finally, by son, fibers and polyamide filaments according to the invention, it must be understood the spun articles in general, for example also son, fibers and multi-component filaments (for example of the "heart-skin" type). ) at least one of the components is a polyamide as defined above. By wire is meant a monofilament, a continuous multi-filament yarn, a spun yarn, obtained from a single type of fiber or several types of fibers in intimate mixture. The continuous wire can also be obtained by assembling q

several multi-filament yarns. By fiber is meant a filament or a set of cut, cracked or converted filaments.

In general, the yarns, fibers and filaments of the present invention are characterized by their strand titer which is generally greater than 1, 9 decitex (i.e., 1.9 g / 10,000 meters). and less than or equal to 130 decitex (dtex), advantageously less than 100 dtex. Preferably, the titre of the yarns, fibers and filaments of the invention will be between 1.9 and 100 dtex, and even more preferably between 1, 9 and 66 dtex.

For the purposes of the present invention, the term "nanometric particles" means fillers with a form factor equal to or greater than 3, preferably between 4 and 1000 inclusive, and more preferably between 5 and 500 inclusive. At least one of the dimensions of the nanoscale particles in the sense of the present invention is of the order of a nanometer to a few tens of nanometers.

The nanometric particles may be in individual form or in the form of agglomerates.

According to an advantageous variant of the present invention, the nanometric particles dispersed in the polyamide matrix have a form factor of between 4 and 1000 inclusive, and the smallest particle size is less than or equal to 100 nm, preferably less than or equal to 75 nm, advantageously less than or equal to 50 nm.

The minimum value of the smallest dimension is not important in itself.

A minimum value of the smallest dimension below one nanometer is, however, inappropriate.

The amount of nanometric particles present in the son, fibers and filaments according to the present invention is generally between 0.01% by weight and 5% by weight, preferably between 0.02% by weight and 3% by weight. more preferably between 0.05% and 2% by weight.

Suitable nanoscale particles in the context of the present invention are reinforcing fillers, preferably in lamellar form, of any type known per se and are advantageously chosen from those commonly used in the field of fiber reinforcement, filaments. or polyamide thread. In particular, any mineral particle having the particularity of being in the form of lamellar particles is usable in the context of the present invention, and as such, there may be mentioned in particular certain oxides, sulfides or phosphates of metals or of non-metals. metals, such as titanium, cerium, silicon, zirconium, cadmium, zinc, and preferably zirconium phosphate.

The inorganic particles may be used as such or in "interleaved" form, that is to say after having been subjected to the action of at least one intercalation agent, mineral and / or organic.

It should be understood that mixtures of the various particles or fillers listed above can be used in any proportion.

By way of example, said particles may be mineral particles, such as phyllosilicates of the mica type, comprising in particular clays, smectite clays, swelling smectite clays, including in particular:

• variable equidistance dioctahedral smectite clays such as Montmorillonites (including askanite, confolensite, erinite, galapectite, malthacite and other synonyms of the term Montmorillonite, corresponding, among other things, to minor substitutions of structural cations), the Beidellites (including chromiumbidellite, ferribeidellite, ferromontmorillonite, glaserite, nontronite, protonontronite, volkonskoite and other clays with a name synonymous with the generic term Beidellite), and their corresponding ones bearing a trade name, in particular and in a non-specific manner exhaustive, Amargosites, Cloisites, Bentonites, Otaylites, etc. ;

• trioctahedral smectite clays with variable equidistances such as stevensites (including ghassulite), hectorites (including the corresponding synthetic clay, laponite), saponites (including bowlingites, sauconites, griffithites and synonyms of these terms, corresponding inter alia to minor replacements of structural cations such as ferrisaponites, lembergites, and other cardenites), Vermiculites (including batavite, and other clay synonyms of the family Vermiculites such as culsageeite, kerrite, lennilite, phallite, philadelphite, vaalite, maconite, etc.), as well as their correspondents bearing a commercial name.

It may also be made illites, sepiollites, palygorskites, muscovites, allevardites, amesites, talcs, fluorohectorites, stevensites, micas, fluoromicas, vermicullites, fluorovermicullites and halloysites.

These clays all have the distinction of being materials with compact agglomerations of lamellar particles more or less stacked on each other. The nanoscale particles are advantageously lamellar particles which can be considered as sheets stacked on each other forming compact stacks, called tactoids. These tactoids may or may not be intercalated, optionally partially or completely exfoliated (or swollen) according to conventional techniques known to those skilled in the art, in particular by means of swelling agents, inorganic or organic, for example mineral bases, such as as sodium hydroxide, or organic, such as hexamethylenediamine, or alternatively caprolactam.

According to one embodiment of the present invention, the nanoscale particles are zirconium phosphate particles, alone or in combination with other fillers; for example such as those mentioned above. The zirconium phosphate may be in different crystalline forms, especially in crystalline form "alpha" or crystalline form "gamma", denoted "α-ZrP" and "γ-ZrP" respectively in the remainder of this disclosure. The zirconium phosphate and its various crystalline forms that can be used in the context of the present invention are for example described in patent applications WO-A-2003/070818 and WO-A-2004/096903, the contents of which are incorporated herein by reference.

More preferred is the crystalline form "alpha" of zirconium phosphate, intercalated or not, preferably intercalated, as described for example in the patent application WO-A-2002/16264, the content of which is also incorporated here. by reference. there

According to a most preferred embodiment, the yarns, fibers and filaments according to the present invention comprise a polyamide matrix in which are dispersed between 0.01% and 1% by weight, preferably between 0.01% and 0.5% by weight, nanoparticles of zirconium phosphate, preferably in crystalline form α ("α-ZrP"), as described in patent application WO-A-2002/16264. The spun yarns, yarns, fibers and filaments according to the present invention have quite interesting mechanical characteristics and in particular a transverse plasticity threshold stress quite interesting greater than 40 MPa. Stress at the threshold of transverse plasticity means the transverse compressive strength, as indicated in the illustrative examples of the present invention appearing after this disclosure.

In addition, the yarns, fibers and filaments of the present invention have a high tenacity, generally between 30 and 85 cN / tex, more particularly between 35 to 75 cN / tex. The remarkable properties of the son, filaments and fibers described above are obtained in particular by a particular spinning method defined below and which represents another object of the present invention.

Thus, the present invention also relates to the process for preparing yarns, fibers and filaments, by melt spinning a filled composition comprising at least one polyamide matrix in which are dispersed between 0.01% and 5% by weight. , preferably between 0.02% and 3% by weight, more preferably between 0.05% and 2% by weight of nanometric particles, said method being characterized in that the ratio of call rate / extrusion rate is included between 20 and 300, preferably between 30 and 200, more preferably between 40 and 180, for example between 50 and 90.

The polyamide used is as defined above in the present description. The nanoscale particles are also as defined above. The nanometric particles may be incorporated into the matrix by introduction into the polymerization medium, that is to say in the monomer or monomers, before the polymerization reaction, or else incorporated into the polymer matrix by introduction into the molten polymer, for example by masterbatch. The term melt spinning of a composition in charge corresponds to the melt spinning technique known to those skilled in the art where a polymer composition, here the polyamide matrix loaded nanoscale particles, is melted and then extruded through a die for forming yarns, fibers and filaments, with a controlled extrusion speed. At the end of the die, the son, fibers and filaments are optionally cooled, according to conventional techniques (air or water), and called on a call roller at a speed called calling speed. The calling speed is generally between 150 m / min and 2000 m / min, preferably between 200 m / min and 1500 m / minute. The extrusion rate is generally between 5 and 25 m / minute.

According to one embodiment of the method of the present invention, the extrusion speed is between 5 and 25 m / minute and the speed of call, between 300 and 1500 m / minute, while maintaining the ratio call speed / extrusion speed defined above. By way of example and without limitation, the method of the invention can be implemented with a call speed set at 800 m / minute for an extrusion speed of 10, 12 or 15 m. /minute.

Generally, the son, fibers and filaments are then stretched again, hot or cold, for example by a factor of up to 3, see up to 5.

The spun articles, son, fibers or filaments are made according to the usual spinning techniques that can be performed immediately after the polymerization of the matrix, the latter being in molten form. It can be made from a granule comprising the composition. The spun articles according to the invention may be subjected to all the treatments that may be performed in subsequent steps in the spinning step. They can in particular be stretched, textured, curled, heated, twisted, dyed, sized, cut, etc. These additional operations can be carried out continuously and be integrated after the spinning device or be carried out in a discontinuous manner. The list of operations subsequent to spinning has no limiting effect.

The spun articles, yarns, fibers and filaments obtained according to the process of the present invention and having the previously defined characteristics are found a use in many fields of application thanks to their good physical properties.

The spun articles, yarns, fibers and filaments of the invention have remarkable physical properties, in view of the small amount of reinforcing fillers that they comprise, and in particular good values of stress at the threshold of transverse plasticity. .

The invention also relates to articles comprising yarns, fibers and / or filaments as described above. The yarns, fibers, filaments according to the invention can be used in woven, knitted or non-woven form. [0054] Many applications are conceivable for the spun articles, threads, fibers and filaments according to the invention, and mention may be made of for example uses in the fields of filtration, pressing, screen printing, but also for the manufacture of carpets, rugs, mats, etc. The fibers according to the invention are in particular suitable for the manufacture of felt for paper machines ("paper felt"), and in particular for the nonwovens of paper machine felts used in the paper industry.

The spun articles, yarns, fibers, filaments according to the invention can also be used as carpet yarns. They can also be used, in particular monofilaments, for obtaining fabrics in the field of screen printing for printing transfers, or in the field of filtration.

The spun articles, yarns, fibers, filaments of the invention, and especially the multifilers, may also be used in the manufacture of ropes, in particular climbing ropes, or belts, in particular conveyor belts. Finally son of the invention can be used for the manufacture of nets, especially fishing nets. .

Other details or advantages of the invention will emerge more clearly from the following examples which are not limiting for the present invention. Examples

EXAMPLE 1 Preparation of the Nanometric Particles of α-ZrP Zirconium phosphate α-ZrP, as prepared in Example 4 of the patent application WO-A-02/16264, is used from a aqueous solution of zirconium oxychloride (in the form of 32.8% ZrO ₂ powder) at 2.1 mol / L in ZrO ₂ .

In a 1 L reactor with stirring, 50 ml of hydrochloric acid (Prolabo ^® 36%, d = 1.19), 50 ml of phosphoric acid (Prolabo ^® 85%, d = 1, 695) and 150 ml of deionized water. After stirring the mixture, 140 ml of the aqueous solution of 2.1 M zirconium oxychloride are added continuously at a rate of 5.7 ml / min. The stirring is maintained for one hour after the end. addition of the zirconium oxychloride solution. After removal of the mother liquors, the precipitate is washed by centrifugation at 4500 rpm, with 1200 ml of phosphoric acid (HsPO ₄ at 20 g / l), and then with deionized water, until reach a conductivity of 6.5 mS (supernatant). A cake of the precipitate based on zirconium phosphate is obtained. The cake is then dispersed in 1 L of 10 M aqueous phosphoric acid solution. The dispersion thus obtained is transferred to a 2 L reactor and then heated to 115 ^° C. This temperature is maintained for 5 hours. The dispersion obtained is washed by centrifugation with deionized water to a conductivity of less than 1 mS (supernatant). The cake from the last centrifugation is redispersed so as to obtain a solids content of 20%, the pH of the dispersion is between 1 and 2. A dispersion of a crystallized compound based on sodium phosphate is obtained. zirconium of lamellar structure (electron microscopy with TEM transmission), whose lamellae are in hexagonal form with a size between 200 and 500 nm. The particles consist of a stack of substantially parallel plates, the thickness of the stacks in the direction perpendicular to the wafers being about 200 nm. X-ray diffraction analysis (XRD) demonstrates the crystallized phase Zr (HPO ₄ ) ₂ , 1H ₂ O, with a solids content of 18.9% by weight. , a pH of 1.8 and a conductivity of 8 mS.

The particles are neutralized by addition of hexamethylenediamine (HMD). 5 To this dispersion was added an aqueous solution of HMD at 70% until a pH of 5. The dispersion thus obtained is homogenized using an Ultraturrax ^®. The final dry extract is adjusted by addition of deionized water (dry extract: 15% by weight).

EXAMPLE 2 Polyamide Compositions Containing Nanometric Particles Based on Zirconium Phosphate α-ZrP Treated by Hexamethylenediamine A polyamide 6 is synthesized from caprolactam according to a conventional method, by introducing into the polymerization medium a dispersion The proportion of the zirconium phosphate compound introduced is 2% by weight. A polymer containing no nanometric particles (comparative example) is also synthesized. After polymerization, the polymer is shaped into granules. These. are washed for removal of residual caprolactam: for this, the granules are immersed in an excess of water at 90 ⁰ C for a few hours. The granules are then dried under primary vacuum (<0.5 mbar) for 16 hours at 110 ^° C. Traction tests are carried out on extruded rods and conditioned for 30 days at 50% relative humidity and at 23 ^° C. ⁰ C. The diameter of the rods is between 0.5 mm and 1 mm. An INSTRON ^® 1185 pulling machine is used with a force sensor of 100 N capacity at a traverse speed of 50 mm / minute. The nominal stress (ratio of the measured force to the measured section s by Palmer diameter measurement) is plotted as a function of the relative strain applied. The results are reported in Table 1.

- Table 1 -

IO

A polyamide-based composition is obtained whose elongation at break is greater than that of a polyamide which does not comprise the mineral compound, and whose modulus is improved. s [0071] It obs _J _CN erve the transmission electron microscope (TEM) of the compositions obtained as above comprising PA 6 and 2% by weight of compound based on zirconium phosphate, on an average thickness cuts 0 , 1 μm. The presence of very numerous dispersed mineral lamellae of nanometric thickness and width 50 to 100 nm is observed. 0

Example 3 Mechanical properties of the yarns obtained according to the process of the invention.

1) In tension: elongation and tensile strength

Spinning tests were conducted with a polyamide 6 loaded particles of α-ZrP intercalated HMD, as prepared in Example 2 above, so as to obtain son consisting of 10 filaments. The extrusion speeds are set at 12 m. min ^"1. The call speeds vary from 650 m.min ^{" 1} to 1100 m. min ^"1. A post stretching at 14O ⁰ C is applied. The draw ratio applied between heated rolls for each yarn tested is shown in Table 2 below. The tensile properties are shown in Table 3. These properties are measured with a force cell with a capacity of 10 N, for a gauge length of 200 mm, at 200 mm / min, at 23 ^° C. and RH 50%.

- Table 2 - Characteristics of the wires

Rate Rate at Call Rate Stretching Load Rate strand (dtex) (m / min) lamellar (%)

Thread 1 2 2,, 1 166 9.7 800 0

Wire 2 2,, 55 8.4 800 0.2

Thread 3 2 2,, 0 044 10.3 800 0.5 Table 3-Mechanical properties of the yarns

Elongation at break (%) Breaking stress (23 ⁰ C, 50% RH) (cN / tex)

Wire 1 79, 6 ± 8.3 29.7 + 2.2

Yarn 2 83, 7 + 11, 5 28.3 + 2.7

Thread 3 73, 7 ± 7.4 32.3 ± 2.0

2) In compression: transverse modulus and transverse plastic threshold stress [0073] The transverse filament compression test is a small-scale transposition of a conventional mechanical engineering test, the principle of which is the following: a fiber diameter D, or a single filament extracted from a wire, is placed between two surfaces. The axes of said fiber and said surfaces are parallel. One of the two surfaces is movable and compresses the fiber over a length L with a force F. The result of the test is a conventional force / displacement type curve. Figure 1 shows an example of such a curve. This curve is used to determine on the one hand the transverse modulus (E) and on the other hand the transverse threshold of plasticity (R _y ).

The module is determined from the initial linear zone. An assumption of calculation must be made: the Poisson's ratio is fixed at 0.4, whereas it can vary from 0.3 to 0.5. The impact on the calculation of the module is very small. The equation used for the calculation is as follows:

2F (3 + v)

F _ LD ^' π

ΔD '

Where F is the force ΔD is the measured displacement, and v is the Poisson's ratio. The other determined quantity is the transverse plasticity threshold stress R _y . This magnitude is determined at the center of the fiber. At this location Constraints coexist in two orthogonal directions. A criterion of plasticity, the Von Mises criterion, is therefore used to evaluate the stress at the plasticity threshold. Given the state of stress, the threshold R _y is expressed by the following equation:

This test is of interest for understanding the behavior of the fibers in a number of applications: carpets and carpets, and felt used in stationery in particular.

The variations in the transverse plasticity threshold of the yarns are presented in Table 4, as a function of the stretching ratio and the lamellar charge ratio. The properties are globally improved in the presence of ¹ α-ZrP.

- Table 4 -

Mechanical properties in transverse compression of a filament extracted from the fit

Constraint at the Module Threshold Rate _ Velocity ^l at αe cross-sectional plasticity * * * * of the call ^C. Transverse R _y E (MPa) ^{dd *} (m / min ¹ )?

(MPa)

FiH 35.4 ± 2.7 500 ± 30 2.16 800 0

Wire 2 48.4 ± 6.0 480 ± 80 2.5 800 0.2

FH 3 49.1 ± 1, 8 650 ± 30 2.04 800 0.5

Claims

A yarn, fiber or filament comprising a polyamide matrix in which are dispersed between 0.01% and 5% by weight, preferably between 0.02% and 3% by weight, more preferably between 0.05% and 2% by weight. weight of nanometric particles, and having a transverse plasticity threshold stress of between 40 and 150 MPa, preferably between 45 and 95 MPa, with a degree of elongation at break of between 20% and 140%, advantageously between 40% and 100%.

2. The yarn, fiber or filament according to claim 1, in which the matrix is a polyamide chosen from polyamide 6 (PA 6), polyamide 6.6 (PA 6.6) and copolymer PA 6 / 6.6, alone or in mixtures in all proportions of two or more of them.

3. Yarn, fiber or filament according to claim 1 or claim 2, having a strand of between 1, 9 and 130 dtex, preferably between 1, 9 and 100 dtex, more preferably between 1, 9 and 66 dtex.

4. The yarn, fiber or filament according to any one of claims 1 to 3, wherein the nanometric particles are lamellar fillers with a form factor equal to or greater than 3, preferably between 4 and 1000, inclusive, preferably still between 5 and 500 inclusive.

The yarn, fiber or filament according to any one of claims 1 to 4, wherein the smallest particle size is in the nanometer range to a few tens of nanometers.

The yarn, fiber or filament according to any one of claims 1 to 4, wherein the nanometric particles dispersed in the polyamide matrix have a form factor between 4 and 1000 inclusive, and the smallest particle size is less than or equal to 100 nm, preferably less than or equal to 75 nm, preferably less than or equal to 50 nm.

7. Yarns, fibers and filaments according to any one of the preceding claims, in which the nanometric particles are chosen from phyllosilicates of the mica type and oxides, sulphides or exfoliable phosphates from metals or non-metals.

8. Yarns, fibers and filaments according to any one of the preceding claims, in which the nanometric particles are chosen from clays and zirconium phosphate, advantageously in its alpha crystalline form ("α-ZrP").

9. Yarns, fibers and filaments according to any one of the preceding claims, comprising a polyamide matrix in which are dispersed between 0.01% and 1% by weight, preferably between 0.01% and 0.5% by weight, of nanoparticles of zirconium phosphate in α crystalline form ("α-ZrP").

Process for preparing yarns, fibers or filaments by melt spinning a filled composition comprising at least one polyamide matrix in which are dispersed between 0.01% and 5% by weight, preferably between 0.02% and 3% by weight. % by weight, more preferably between 0.05% and 2% by weight of nanoscale particles, said method being characterized in that the ratio of call rate / extrusion rate is between 20 and 300, preferably between 30 and 200, more preferably between 40 and 180, for example between 50 and 90.

11. The method of claim 10, characterized in that the calling speed is between 150 m / min and 2000 m / minute, preferably between 200 m / min and 1500 m / minute. ^•

12. The method of claim 10 or claim 11, characterized in that the extrusion rate is between 5 and 25 m / minute.

13. Method according to any one of claims 10 to 12, characterized in that it is implemented with a call speed set to

800 m / minute for an extrusion speed of 10, 12 or 15 m / minute.

An article comprising yarns, fibers and / or filaments according to any one of claims 1 to 9, or obtained according to the process of any one of claims 10 to 13.

15. Article according to claim 14, characterized in that it is a felt machine for paper.

16. Article according to claim 14, characterized in that it is a carpet, a mat or a carpet.

17. Article according to claim 14, characterized in that it is a rope or a belt.

18. Article according to claim 14, characterized in that it is a fabric for printing transfer or for filtration.

19. Article according to claim 14, characterized in that it is a net.