MXPA99008302A - Procedure for manufacturing multilobular filaments of crystalline crystalline liquid polymers of high number of deniers, and compositions paralo mi - Google Patents

Abstract

The present invention describes and claims a novel process for the formation of heat-treated multi-lobed filaments, such as yarn and deniers, of a thermotropic liquid crystalline polymer, preferred embodiments include a method for the formation of octalobular monofilaments. heat-treated and as-spun, of a few fully aromatic polyesters and polyesteramides, the process consists of heating a liquid crystalline thermotropic polymer above its melt transition temperature, passing said molten polymer through a an extrusion chamber equipped with an extrusion capillary having a multilobular cross-section to form a multilobular filament, and winding the filament to a suitable stretch, the filaments thus formed are at least 50 deniers per filament, and exhibit essentially uniform molecular orientation at through its section tr In an optional final step, the filaments are heat treated in stages to form filaments exhibiting excellent tensile properties, the heat treated filaments and as they are spun exhibit remarkably good tensile properties comparatively to those of the round filaments most importantly, the multi-lobed filaments of this invention exhibit adhesion properties much superior to those of conventional round filaments

Description

PROCEDURE FOR MANUFACTURING FILAMENTS MU LTILOBU LARES OF HIGH-TERM THERMOTROPIC CRYSTALLINE LIQUID POLYMERS NUMBER OF DENIERS, AND COMPOSITIONS FOR THE SAME BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to methods for forming multi-lobular filaments of a thermotropic liquid crystalline polymer. Specifically, the present invention provides methods for forming multilobal filaments of a high number of deniers, heat treated and as spun, of a variety of fully aromatic thermotropic liquid crystalline polyesteramides and polyesters. This invention also relates to multi-lobed filaments of polyesteramides and thermotropic liquid crystalline polyesters of high denier number, heat treated and as spun.

DESCRIPTION OF THE PREVIOUS TECHNIQUE Thermotropic liquid crystalline polymers (LCPs) are an important group of polymers, which are usually fully aromatic molecules that contain a variety of heteroatom linkages that include ester and / or esteramide linkages. After heating at sufficiently high temperature, the LCPs melt to form a phase of liquid crystalline melt (often referred to as an "anisotropic phase"), rather than an isotropic melt. Generally, LCPs consist of linear molecules ("rigid rod") that can be aligned to produce the order of the desired liquid crystalline material. As a result, the LCPs exhibit low viscosity of the molten material and thus improved performance and process capabilities. Because the LCPs are oriented to form linear "rigid rod" molecules, the LCPs exhibit extremely high mechanical properties. In this way, it is well known in the art that LCPs can be formed into shaped articles, such as films, rods, tubes, fibers, and various other molded articles. Furthermore, it is also known in the art that LCPs, particularly in fiber form, exhibit exceptionally high mechanical properties after a heat treatment process. However, all methods known in the art describe the formation of only fibers of low number of deniers, for example, of about 10 deniers per filament (dpf), which exhibit high mechanical properties in their heat treated forms and such as they are spun Furthermore, there are no reports in the prior art that multi-lobed filaments having multilob cross section can be obtained from LCPs. More important, the multilobal filaments of LCPs do not generally adhere to several other similar or different materials. Thus, an object of the present invention is to provide a method for forming multilobal filaments of LCP of high number of uniformly oriented deniers. A filament with a high number of deniers means a filament of more than 50 dpf. It is also an object of the present invention to provide a method for forming multi-lobulated LCP filaments of more than 50 dpf, which exhibit improved mechanical, thermal and chemical resistance properties in the heat-treated and spun-like form. It is further an object of the present invention to provide a method for forming multi-lob filaments of LCP of high number of deniers, which exhibit properties comparable to those of round filaments of LCP of low number of deniers (ie, filaments of less than 10 dpf ) in their heat-treated states and how they are spun. It is also an object of the present invention to provide multi-lob filaments of LCP of high number of deniers of more than 50 dpf having properties comparable to those of the round filaments of LCP of low number of deniers of less than 10 dpf. Finally, an object of the present invention is to provide multilobal filaments of LCP of high number of deniers exhibiting improved adhesion properties.

There is a great convenience for forming LCP filaments of high number of uniformly oriented deniers, which exhibit improved mechanical, thermal and chemical resistance properties in the heat treated and spun form. For example, LCP filaments with a high number of deniers can replace steel cords in steel belt tires. In addition, since the LCP filaments are of substantially lower density compared to steel cords, it is expected that the LCP filaments exhibit properties superior to those exhibited by the steel cords. Furthermore, the prior art indicates that there is a real need for LCP filaments of high number of deniers that exhibit improved mechanical, thermal and chemical resistance properties.

PREVIOUS TECHNIQUE The following references are described as antecedent prior art. The patent of E.U.A. No. 4,183,895 discloses a process for treating polymeric products that form anisotropic melt material. A heat treatment process allowed to have fibers that have improved mechanical properties, and it was reported that the tenacity of the fiber increased by at least 50% and up to at least 10 grams per denier.

The patent of E.U.A. No. 4,468,364 describes a process for extruding thermotropic liquid crystalline polymers (LCPs). It is claimed that by extruding a LCP through the orifice of a die having a L / D ratio of less than 2 (preferably 0), and at a stretch rate less than 4 (preferably 1), filaments can be obtained which show high mechanical properties The patent of E.U.A. No. 4,910,057 discloses a highly elongated member of substantially uniform cross-sectional configuration, which is capable of providing enhanced service as a reinforcement support in a fiber optic cable. The patent of E.U.A. No. 5,246,776 discloses an aramid monofilament and a method for obtaining same. The patent of E.U.A. No. 5,427,165 discloses a reinforcing assembly formed at least in part from continuous monofilaments of liquid crystalline organic polymer (s). The polymers used therein are mainly aramides. Japanese Patent Laid-open No. 4-333616 discloses a method for making filaments from 50 to 2000 dpf from molten liquid crystalline polymers. The mechanical properties of these heat-treated filaments were significantly lower than the properties reported for filaments of 5 to 10 dpf with fewer corresponding deniers.

Reference J. Rheology 1992, Vol. 36 (p.1057-1078) reports a study of the rheology and orientation behavior of a thermotropic liquid crystalline polyester using capillary dies of different aspect ratios. The reference J. Appl. Polym. Sci. 1995, Vol 55 (p.1489-1493) reports the distribution in rod orientation exempted from thermotropic liquid crystalline polyesters. The orientation function increases with the increasing apparent shear rate of 166 to 270 sec "1, but decreases with the apparent apparent shear rate of 566 to 780 sec" 1 All references described herein are incorporated in their entirety in it as a reference.

BRIEF DESCRIPTION OF THE INVENTION It has now been unexpectedly and surprisingly found that multilobal filaments of high denier number, heat treated and as spun, of at least 50 denier per filament can be obtained which exhibit essentially uniform molecular orientation through its cross section. In addition, these high denier filaments show remarkably good tensile properties which retain at least 80 to 90% of the expected properties of the filaments of low number of conventional deniers, ie, 5 to 10 dpf, which was up to now unreachable by any of the known references of the prior art, as briefly described above. Thus, in accordance with this invention, a method is provided for forming a multi-lobe filament of a thermotropic liquid crystalline polymer having the following properties: (i) deniers of at least about 50 deniers per filament; (I) tenacity of at least about 8 grams per denier; (iii) module of at least about 450 grams per denier; and (iv) elongation of at least about 2%. The process of the present invention is formed of the following steps: (a) heating a thermotropic liquid crystalline polymer at a temperature of at least about 15 ° C above its transition to melting to form a fluid stream of said thermotropic polymer; (b) passing said current through a heated extrusion chamber, wherein said chamber is disposed with a suitable cylindrical orifice having a multilobal cross-section to form the multi-lobe filament of said polymer, and (c) winding said filament to a winding speed of at least about 200 meters per minute and a stretch (D / D) suitable to form the filament of essentially uniform molecular orientation through its cross section, and having a denier value of at least about 50 Deniers per filament. In another aspect of the invention, there is also provided a method for forming a multi-lobed heat-treated filament of a thermotropic liquid crystalline polymer having the following properties: (i) deniers of at least about 50 denier per filament; (ii) tenacity of at least about 20 grams per denier; (iii) module of at least about 600 grams per denier; and (iv) elongation of at least about 3%. Thus, in accordance with this aspect of the present invention, the method is comprised of the following steps: (a) heating a thermotropic liquid crystalline polymer at a temperature of about 15 ° C to about 50 ° C above its transition to the melt to form a fluid stream of said polymer; (b) extruding said polymer stream through a heated cylindrical spinner having at least one extrusion capillary of multilob cross section to form a multilobular filament; (c) winding said filament at a winding speed of at least about 200 meters per minute and a suitable stretch to form a filament of essentially uniform molecular orientation through its cross section, and having a value in deniers in the scale of about 50 to about 1000 deniers per filament; Y(d) heat treating said filament at suitable conditions of temperature and pressure for a sufficient period, optionally in the presence of an inert atmosphere, to form the heat treated multi-lobed filament. In yet another aspect of this invention, a multi-lobed filament such as is spun, of a thermotropic liquid crystalline polymer is also provided. In a further aspect of this invention, there is also provided a heat-treated multi-lobed filament of a thermotropic liquid crystalline polymer. Other aspects and advantages of the present invention are further described in the following detailed description of the preferred embodiments thereof.

DETAILED DESCRIPTION OF THE INVENTION In accordance with this invention, there is provided a method for forming a multilobular filament of a thermotropic liquid crystalline polymer having the following properties: (i) deniers of at least about 50 deniers per filament; (ii) tenacity of at least about 8 grams per denier; (Ii) module of at least about 450 grams per denier; and (iv) elongation of at least about 2%. The process of the present invention is formed of the following steps: (a) heating a thermotropic liquid crystalline polymer at a temperature of at least about 15 ° C above its transition to melting to form a fluid stream of said thermotropic polymer; (b) passing said current through a heated extrusion chamber, wherein said chamber is disposed with a suitable cylindrical orifice having a multilobal cross-section to form the multi-lobe filament of said polymer, and (c) winding said filament to a winding speed of at least about 200 meters per minute and a stretch (D / D) suitable to form the filament of essentially uniform molecular orientation through its cross section, and having a denier value of at least about 50 Deniers per filament. In accordance with the process of the present invention, the preferred polymers are thermotropic liquid crystalline polymers. Thermotropic liquid crystalline polymers are polymers that are crystalline and liquid (ie, anisotropic) in the phase of molten material. Thermotropic liquid crystalline polymers include fully aromatic polyesters, aromatic-aliphatic polyesters, aromatic polyazomethines, aromatic polyesteramides, aromatic polyamides and aromatic polyester carbonates. The aromatic polyesters are considered to be "fully" aromatic in the sense that each portion present in the polyester contributes at least one aromatic ring to the base structure of the polymer. Specific examples of suitable aromatic-aliphatic polyesters are copolymers of polyethylene terephthalate and hydroxybenzoic acid, as described in Polyester X7G-A Self Reinforced Thermoplastic, by WJ Jackson son, HF Kuhfuss and TF Gray son, 30th Anniversary Technical Conference, 1975 Reinforced Plastics / Composites Institute, The Society of the Plastics Industry, Inc., Section 17-D, p. 1-4. A further description of said copolymer can be found in "Liquid Crystal Polymers: I. Preparation and Properties of p-Hydroxybenzoic Acid Copoiymers", Journal of Polymer Science, Polymer Chemistry Edition, Vol 14, pp. 2043-58 (1976), by W. J. Jackson Jr. and H. F. Kuhfuss. The references cited above are incorporated herein by reference in their entirety. Aromatic polyazomethines and processes for preparing them are described in the patents of E.U.A. Nos. 3,493,522; 3,493,524; 3,503,739; 3,516,970; 3,516,971; 3,526,611; 4,048,148 and 4,122,070. Each of these patents is hereby incorporated by reference in its entirety. Specific examples of such polymers include poly (nitrile-2-methyl-1,4-phenylene-nitriloethyl-1,4-phenylene-ethylidene); poly (nitriyl-2-methyl-1,4-phenylene-nitrilomethylidino-1,4-phenylene-methyl-dine); and poly (nitrile-2-chloro-1,4-phenylene-nitrilomethylidino-1,4-phenylene-methylidene). Aromatic polyesteramides are described in the patents of E.U.A. Nos. 5,204,443, 4,330,457, 4,966,956, 4,355,132, 4,339,375, 4,351, 917 and 4,351, 918. Each of these patents is hereby incorporated by reference in its entirety. Specific examples of such polymers include polymers formed from the monomers comprising 4-hydroxybenzoic acid, 2,6-hydroxynaphthoic acid, terephthalic acid, 4,4'-biphenol and 4-aminophenol; and polymers formed from the monomers comprising 4-hydroxybenzoic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, hydroquinone and 4-aminophenol. Preferred aromatic polyamides are those which are processable molten material and form thermotropic melt phase, as described above. Specific examples of such polymers include polymers formed from monomers comprising terephthalic acid, isophthalic acid and 2,2'-bis (4-aminophenyl) propane. Aromatic polyester carbonates are described in the U.S.A. No. 4,107,143, which is incorporated herein by reference in its entirety. Examples of such polymers include those consisting essentially of hydroxybenzoic acid units, hydroquinone units, carbonate units and aromatic carboxylic acid units. Preferred liquid crystalline polymers for use in the process of the present invention are fully aromatic thermotropic polyesters. Specific examples of said polymers can be found in the patents of E.U.A. Nos. 3,991,013; 3,991, 014; 4,057,597; 4,066,620; 4,075,262; 4,118,372; 4,146,702; 4,153,779; 4,156,070; 4,159,365; 4,169,933; 4,181, 792; and 4,188,476, and UK application No. 2,002,404. Each of these patents is hereby incorporated by reference in its entirety. The fully aromatic polyesters that are preferred for use in the present invention are described in the U.S. Patents. commonly assigned Nos. 4,067,852; 4,083,829; 4,130,545; 4,161, 470; 4,184,996; 4,238,599; 4,238,598; 4,230,817; 4,224,433; 4,219,461; and 4,256,624. The descriptions of all patents and applications of E.U.A. commonly assigned identifiers, are hereby incorporated by reference in their entirety. The fully aromatic polyesters described herein are typically capable of forming an anisotropic melt phase at a temperature of less than about 350 ° C. Fully aromatic polyesters which are suitable for use in the process of the present invention can be formed by various ester formation techniques, whereby organic monomeric compounds having functional groups which after condensation form the required recurring portions are reacted. For example, the functional groups of the organic monomeric compounds can be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, etc. The organic monomeric compounds can be reacted in the absence of a heat exchange fluid by a process of acidolysis of molten material. Accordingly, they can be initially heated to form a solution of molten material from the reactants, the reaction continuing as the solid polymer particles are suspended therein. A vacuum can be applied to facilitate the removal of volatile compounds formed during the final stage of condensation (eg, acetic acid or water). In the patent of E.U.A. commonly assigned No. 4,083,829, entitled "Melt Processable Thermotropic Wholly Aromatic Polyester", describes a suspension polymerization process, which can be used to form the fully aromatic polyesters that are preferred for use in the present invention. In accordance with said process, the solid product is suspended in a heat exchange medium. The description of this patent has previously been incorporated herein in its entirety as a reference.

When the process of acidolysis of molten material or the suspension procedure of the patent of E.U.A. No. 4,083,829, the organic monomer reagents from which the fully aromatic polyesters are derived may be initially provided in a modified form, whereby the usual hydroxy groups of said monomers are esterified (ie, provided as lower acyl esters) ). The lower acyl groups preferably have from about two to about four carbon atoms. Preferably, the acetate esters of organic monomer reagents are provided. Representative catalysts which may optionally be used in the process of acidolysis of molten material or in the suspension process of the patent of E.U.A. No. 4,083,829, include dialkyl tin oxide (eg, dibutyl tin oxide), diaryl tin oxide, titanium dioxide, antimony trioxide, alkoxy titanium silicates, titanium alkoxides, alkali metal and metal salts alkaline earth of carboxylic acids (e.g., zinc acetate), gaseous acid catalysts such as Lewis acids (e.g., BF3), hydrogen halides (e.g., HCl), and similar catalysts known to those skilled in the art . The amount of catalyst used is typically from about 0.001 to about 1% by weight based on the total weight of the monomer, and more commonly from about 0.01 to about 0.2% by weight.

The fully aromatic polyesters which are preferred for use in the present invention, commonly show a weight average molecular weight of from about 10,000 to about 200,000, and preferably from about 20,000 to about 50,000 (eg, about 30,000 to about 40,000). ). Said molecular weight can be determined by commonly used techniques, such as measurements of gel permeation chromatography or solution viscosity.

Other methods include determination of the end group by infrared spectroscopy on compression molded films or spectroscopic measurements of nuclear magnetic resonance (NMR) of polymer solutions, or solid phase NMR of powder or polymer films. Alternatively, light scattering techniques can be employed in a solution of pentafluorophenol (or solvent mixture of equal volume of pentafluorophenol and hexafluoroisopropanol) to determine molecular weight. The fully aromatic polyesters or polyesteramides additionally commonly exhibit an inherent viscosity (ie, I.V.) of at least about 2.0 dL / g; for example, about 2.0 to about 10.0 dL / g, when dissolved at a concentration of 0.1% by weight in a 1: 1 solvent mixture of hexafluoroisopropanol (HFIP) / pentafluorophenol (PFP) (v / v) at 25 ° C . Especially preferred polymers for the process of the present invention are fully aromatic polyesters and polyesteramides.

In preferred embodiments of the present invention, the specifically preferred polyesters are listed below: a) The fully aromatic polyester capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consists essentially of the recurring portions I and II, where: I is is The fully aromatic polyester, as described above, is described in the U.S.A. No. 4,161, 470. The polyester comprises from about 10 to about 90 mole percent of a portion I, and from about 10 to about 90 mole percent of the portion II. In one embodiment, portion II is present at a concentration of about 65 to about 85 mole percent, and preferably at a concentration of about 70 to about 80 mole percent; for example, approximately 75 mole percent. In another embodiment, portion II is present at a minor proportion of about 15 to about 35 mole%, and preferably at a concentration of about 20 to about 30 mole percent, b) The fully aromatic polyester capable of forming an anisotropic molten material phase at a temperature below 400 ° C, consists essentially of the recurring portions I, II, III and IV, wherein: is is I I I is I saw him The polyester comprises from about 40 to about 60 mole percent of the portion I, from about 2 to about 30 mole percent of the portion II, and from about 19 to about 29 mole percent of each of portions III and VII. In one of the preferred embodime the polyester comprises from about 60 to about 70 mole percent of the portion I, from about 3 to about 5 mole percent of the portion II, and from about 12.5 to about 18.5 percent in moles of each of portions III and VII. Preferred polyesteramides of the process of the present invention are summarized below: a) The fully aromatic polyesteramide capable of forming an anisotropic melt phase at a temperature below about 360 ° C, consists essentially of the recurring portions II, and VI, where: I I is I is and V I is The fully aromatic polyesteramide, as described above, is described in the U.S. patent. No. 4,330,457, which is hereby incorporated by reference in its entirety. The polyesteramide comprises from about 25 to about 75 mole percent of portion 11, and about 37.5 to about 12.5 mole percent of each of portions I and VI. The polyesteramide preferably comprises from about 40 to about 70 mole percent of portion II, and from about 15 to about 30 mole percent of each of portions I and VI. In one of the preferred embodimeof the invention, the polyesteramide comprises from about 60 to about 65 mole percent of the portion II, and from about 17.5 to about 20 mole percent of each of the portions I and VI . b) The fully aromatic polyesteramide capable of forming an anisotropic melt phase at a temperature below about 380 ° C, consists essentially of the recurring portions I, ll, III, VII and VI, wherein: is I I is l l l is I saw him V I is \ The fully aromatic polyesteramide, as described above, is described in the U.S. patent. No. 5,204,443, which is incorporated herein by reference in its entirety. The polyesteramide comprises from about 40 to about 70 mole percent of portion I, from about 1 to about 20 mole percent of portion II, from about 14.5 to about 30 mole percent of portion III. , from about 7 to about 27.5 mole percent of the VII portion, and from about 2.5 to about 7.5 mole percent of the VI portion. c) The fully aromatic polyesteramide capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consists essentially of the recurring portions I, II, III, IV, V and VI, wherein: I is I is is IV is You see V I is The polyesteramide, as described above, comprises from about 40 to about 70 mole percent of the portion I, from about 10 to about 20 mole percent of the portion II, from about 2.5 to about 20 percent in moles of the portion III, from about 0 to about 3 mole percent of the IV portion, from about 12.5 to about 27.5 mole percent of the V portion, and from about 2.5 to about 7.5 percent in the moles of portion VI.

In accordance with the process of the present invention, a fluid stream of liquid crystalline polymer is provided to any conventional extrusion apparatus, provided that it contains an extrusion orifice having a multilobal cross-section. The foregoing is achieved by heating the thermotropic liquid crystalline polymer of the present invention to form a molten material. Any of the known methods for heating the polymer to form a molten material, it can be used in this invention. The particular apparatus used is not critical to the operation of the method of the present invention, and any suitable apparatus can be used herein. Once it has been discovered that said apparatus is suitable for use with thermotropic liquid crystalline polymers, a contact fusion method is employed so that the residence time of the molten material can be kept brief and constant. The apparatus includes a heated surface against which a molded liquid crystalline polymer rod is pressed. The fluid stream of the molten polymer is then introduced into the extrusion chamber within which are arranged a filter pack and an orifice having a multilob cross section. After having passed through the filter pack, the molten polymer material is extruded through the hole to form a multilobular filament. In this way, a plurality of said holes can be arranged in an extrusion chamber if it is desired to form multi-lobed multifilaments.

In a preferred embodiment, the extrusion chamber is formed of a single orifice multi-lobe chamber, in which the polymer is heated to a temperature in the range of about 20 ° C to about 50 ° C above its transition to the fusion. After the fluid stream of the liquid crystalline polymer is extruded through the orifice, the polymer forms an elongated shaped article having the polymer molecules oriented substantially parallel to the direction of flow. The orientation of the polymer molecules can be confirmed by determining the orientation angle by X-ray analysis. The extruded articles configured in the form of filaments are then stretched and wound on a filament spool. In accordance with the method of this invention, it is critical that the proper stretch ratio be utilized to exploit the maximum benefit of the practice of the present invention. Therefore, in a preferred embodiment, the draw ratio of about 4 to about 20 is used. In a more preferred embodiment, the draw ratio is used on the scale of about 4 to about 15. Stretch ratio (DD) as used herein, is defined as the cross-sectional area ratio of the hole (Ai): the cross-sectional area of the filament (A2). This relationship is also often expressed as the winding speed ratio of the filament (V2): the extrusion rate of the filament (Vi). In this way, the stretch ratio, DD, can be expressed in terms of the following equation: Therefore, in accordance with the process of the present invention, thermophotic liquid crystalline polymer multilobar filaments having essentially uniform molecular orientation can be made that show unusually superior mechanical properties. For example, by the proper practice of the method of the present invention, it is now possible to obtain a filament with a high number of deniers having hitherto unattainable properties. More specifically, it has now been discovered that multi-lobular filaments having a number of deniers in the range of about 100 to about 1000 denier per filament (dpf) can be easily made following the method of this invention. In a preferred embodiment, multi-lobe filaments having a number of deniers on the scale of about 150 to about 500 dpf can be easily made. In another preferred embodiment, filaments having a number of deniers on the scale of about 180 to about 300 dpf can easily be made. The denier as used herein, is defined as a weight in grams of 9,000 meters of filament. The dpf as used herein, is the denier of a single continuous filament. The conditions of temperature and pressure under which the liquid crystalline polymer can be extruded, are not critical to the process of the present invention, and can be readily determined by the person skilled in the art. Typically, the thermotropic polymers are extruded at a temperature from about 280 ° C to about 400 ° C, and at a pressure of about 7.03 kg / cm2 to about 351.5 kg / cm2. As described hereinabove, liquid crystalline polymers They have very rigid molecules similar to a rod. In the resting state, the polymer molecules are aligned in local regions, thus forming ordered arrays or domains. The existence of the domain texture within the microstructure of a liquid crystalline polymer can be confirmed by conventional polarized light techniques, where a polarization microscope using crossed polarizers is used. The mechanical properties of the multilobal filaments produced in accordance with the method of the present invention, they can be further improved by subjecting the articles to heat treatment after extrusion. The articles can be heat treated in an inert atmosphere (eg, nitrogen, argon, helium). For example, as the article can be brought to a temperature of about 10 ° C to about 30 ° C below the melting temperature of the liquid crystalline polymer, temperature at which the filament remains as a solid object. The periods of heat treatment commonly vary from a few minutes to several days, for example, from 0.5 to 200 hours, or more. Preferably, the heat treatment is carried out for a period of from about 1 to about 48 hours (eg, from about 24 hours to about 30 hours). The heat treatment improves the properties of the filament by increasing the molecular weight of the liquid crystalline polymer and increasing the degree of crystallinity. Therefore, in accordance with one of the preferred embodiments of the present invention, there is also provided a method for forming a heat-treated multi-lobed filament of a thermotropic liquid crystalline polymer having the following properties: (i) denier of less approximately 50 deniers per filament; (ii) tenacity of at least about 20 g per denier; (iii) module of at least about 600 g per denier; (iv) elongation of at least about 3%. The process for forming said filament is formed by the following steps: a) heating a thermotropic liquid crystalline polymer at a temperature from about 15 ° C to about 50 ° C above its transition to melting to form a fluid stream of said polymer; b) extruding said polymer stream through a heated cylindrical spinner having at least one extrusion capillary having a multi-looped cross-section; c) winding said filament at a winding speed of at least about 200 meters per minute and at a stretch ratio of about 5 to about 40, so that a multilobal filament of essentially uniform molecular orientation is formed through its section transverse, and have a denier on the scale of about 50 to about 1000 deniers per filament; and d) heat treating said filament at suitable temperature and pressure conditions for a sufficient period, optionally in the presence of an inert atmosphere, to form the heat treated filament. Any of the preferred thermotropic polyesters or polyesteramides described above, can be used in this preferred embodiment. In addition, as described herein, the heat treatment can be carried out in stages at a final temperature of about ° C below the transition to melting of the thermotropic polymer. In a preferred embodiment of the present invention, there is also provided a filament such as spun, of a thermotropic liquid crystalline polymer having the following properties: (a) denier of at least about 50 deniers per filament; (b) tenacity of at least about 8 grams per denier; (c) module of at least about 450 grams per denier; and (d) elongation of at least about 2%.

In a particularly preferred embodiment of the present invention, the denier of multi-lobed filaments as they are spun, is on the scale of about 100 to about 1000 dpf. In a more particularly preferred embodiment of the invention, the denier of multi-lobed filaments as they are spun is on the scale of about 150 to about 500 dpf. In a very particularly preferred embodiment of the present invention, the denier of multi-lobed filaments as they are spun, is on the scale of about 180 to about 300 dpf. In yet another preferred embodiment of the present invention, there is also provided a heat treated multi-lobe filament of a thermotropic liquid crystalline polymer having the following properties: (a) denier of at least about 50 deniers per filament; (b) tenacity of at least about 20 grams per denier; (c) module of at least about 600 grams per denier; and (d) elongation of at least about 3%. The present invention is further illustrated by the following examples, which are provided for purposes of illustration and not to limit the scope of the present invention.

EXAMPLES (GENERAL) The following abbreviations are used in the examples: HBA = 4-hydroxybenzoic acid HNA = 2,6-hydroxynaphthoic acid TA = terephthalic acid IA = isophthalic acid NDA = 2,6-naphthalenedicarboxylic acid BP = 4,4'-biphenol HQ = Hydroquinone AA = 1-acetoxy-4-acetamidobenzene IV = inherent viscosity dL / g = Deciliters per gram; a unit of measurement of IV% by weight = Percent by weight; generally used to represent the concentration of a solution to measure IV = average grams of polymer in 100 ml of a mixture of solvents. MV = Viscosity of the melted material DSC = Differential Scanning Calorimetry T = Tenacity M = Module E = Lengthening gpd = Grams per denier General analytical techniques used for polymer characterization: A variety of analytical techniques were used to characterize the polymer (s) (s) used and the filaments formed in accordance with the present invention, which include the following:] V: the viscosity of the solution of the polymer samples, IV, was measured at 25 ° C at a concentration of 0.1% by weight of solution in equal parts by volume of pentafluorophenol and hexafluoroisopropanol. MV: The MV of the polymer samples was measured using a model 2052 Kayeness melt rheometer equipped with a Hastalloy barrel and a plunger tip. The radius of the die hole was 0.0381 cm, and the length was 2.54 cm. For the purpose of determining the viscosity of the molten material, a viscosity versus shear velocity plot was made by measuring the viscosities at shear rates of 56, 166, 944, 2388 and 8333 sec "1, and interpolated the viscosities at 100 and 1000 sec'1 DSC: the DSC of the polymer samples was carried out in a Perkin Elmer 7700 Thermal Analysis System. In all the runs the samples, sealed in aluminum trays, were heated or cooled at a rate of 20 ° C / min under a nitrogen atmosphere DSC curves obtained from the second heating run were taken for analysis Optical microscopy: Samples were prepared for microscopic analysis by fine sectioning using a knife microtome. The sections were examined by polarized light microscopy to observe the morphological behavior at room temperature.

EXAMPLE 1 This example demonstrates that the mechanical properties of a high-denier multi-lobed filament, such as spun, of a fully aromatic liquid crystalline polyester produced in accordance with the present invention, are comparable to those of the round filament obtained by a conventional process. The multilobal filaments were formed from a fully aromatic liquid crystalline polyester comprising HBA units and HNA units (Vectra ™ A, commercially available from HNA Holdings, Inc., Charlotte, NC). This polymer had a melting temperature of 280 ° C and an inherent viscosity of 6.30 dL / g when measured at a solution concentration of 0.1 weight percent in equal parts by volume of pentafluorophenol and hexafluoroisopropanol at 25 ° C. A sample of the polymer was dried overnight at 130 ° C under vacuum. The polymer was melted in an extruder with a diameter of 2.54 cm, and the extruded material was metered using a conventional polymer metering pump into the spin pack, where it was filtered through 50/80 chipped metal. The molten material was then extruded through a single hole spinner of octalobular cross section. Cross flow extinction was applied to the emerging octalobular filament to provide temperature drop and a stable spinning environment. The extinction was applied 4 cm below the surface of the spinner, which was 120 cm long by 15 cm wide. The rate of extinction flow in the highest part was 30 mpm (O.dmps). The 220 denier octalobular monofilament was coated with water or a spin finish before going around a pulley system that controlled winding speed. This finally wound up on a Sahm reel winder. The mechanical properties of the monofilaments produced according to Example 1 were measured in accordance with D3822 of the ASTM, and the results are given in Table I. For comparison purposes, round monofilaments were also extruded in the manner described above, using a cylindrical spinner. The mechanical properties of round and octalobular filaments are given in Table I.

TABLE I EXAMPLE 2 Octalobular monofilaments of 220 deniers produced according to Example 1 were subjected to heat treatment in stages in the following manner. Heat treatment of short stretches of the monofilament was carried out on racks under zero stress in a flow of dry nitrogen using a programmed temperature profile. The programmed temperature profiles of each of the heat treatments of the octalobular monofilaments are given in Table II. The heat-treated octalobular monofilamette was tested at a gauge length of 25.4 cm; 20% deformation rate and filament breaking 10. After heat treatment, the mechanical properties of the octalobular monofilaments were measured, which are listed in Table II. For comparative purposes, the mechanical properties of round filaments produced under similar conditions are also given in Table II. The measurements were made using the same tests as in example 1. The data demonstrate the increase in properties, which is obtained by subjecting the octalobular monofilaments to gradual conditions of heat treatment.

TABLE II The results shown in Table II clearly demonstrate that octalobular filaments of properties comparable to those of round filaments can easily be obtained following the conditions of the process of the present invention.

EXAMPLE 3 Examples 1 and 2 were repeated in this example, except that Vectra A polymer filaments of high denier number were formed. Table III summarizes the properties of heat-treated octablobular filaments and how they are spun.

TABLE Heat treatment properties for Vectra A octalobular monofilaments with a high number of deniers EXAMPLE 4 Example 4 demonstrates that the octalobular filaments produced in accordance with Example 1 generally exhibit superior finish pick-up when compared to the round filaments produced by conventional methods. Octalobular filaments of about 200 dpf were produced in accordance with Example 1, and were coated with various finishing levels. In all cases, the finish was applied during spinning as described in example 1. The finish was applied in solvent of sodium propanol (IPA). After the filaments were dried, the amount of finish pick-up on the filaments was measured by an extraction method. The extraction results are given in table IV.

TABLE IV Finishing capture for LCP monofilaments as they are spun 200 dpf * FOF = Percent (by weight) of finish on the filaments, measured by the extraction method.

Target FOF = Quantity of finish applied during spinning using a solution comprising about 10% by weight of finish and about 90% by weight of IPA. The results shown in Table IV clearly demonstrate that the octalobular filaments produced in accordance with the process of the present invention exhibit markedly superior retention of the finish than the round filaments produced by conventional methods.

EXAMPLE 5 Example 5 demonstrates that the octalobular filaments produced in accordance with the process of the present invention exhibit superior adhesion properties with respect to round filaments produced by conventional methods. Octalobular filaments of about 200 dpf were produced according to example 4, and were further treated with two pre-dip compositions based on epoxy resin and two resorcinol-formaldehyde latex adhesive (RFL) formulas, by methods known to the skilled artisan. in the technique. The pre-dipping composition A was 4.0% by weight epoxy resin. The pre-dip composition B was composed of 1.6% by weight of epoxy resin and 4.1% by weight of block isocyanurate. The RFL compositions were the following: for RFL-1, the molar ratio of formaldehyde: resorcinol (F / R) was 1.7, and the weight ratio of resin: latex (R / L) was 0.22. For RFL-2, the molar ratio of formaldehyde: resorcinol (F / R) was 2.0, and the weight ratio of resin: latex (R / L) was 0.17. RFL-2 also contained 10% by weight of block isocyanurate in its composition. The adhesion of filaments treated with RFL to rubber was measured by an H test (maximum value). The results are given in Table V. For RFL-1, the molar ratio of formaldehyde: resorcinol (F / R) was 1.7, and the weight ratio of resin: latex (R / L) was 0.22. For RFL-2, the molar ratio of formaldehyde: resorcinol (F / R) was 2.0, and the weight ratio of resin: latex (R / L) was 0.17. RFL-2 also contained about 10% by weight of block isocyanurate.

The adhesion of filaments treated with RFL to rubber was measured by an H test (maximum value). The results are given in table V.

TABLE V Data of adhesion to rubber for monofilaments of LCP of 200 dpf RFL = resorcinol-formaldehyde latex R1: F / R = ratio in moles of 1.7; R / L = weight ratio of 0.22 (where F = formaldehyde and R = resorcinol) R2: R / L = 2.0 mole ratio; R / L = weight ratio of 0.17; Block isocyanurate = 10% by weight (where R = resin and L = latex). The data shown in Table V clearly show that the octalobular filaments exhibit very superior adhesion properties compared to round filaments. Although the invention has been illustrated herein by some of the above examples, it should not be considered to be limited thereto but, rather, the invention encompasses the generic area as described above. Various modifications and modalities can be made without departing from the spirit and scope of the invention.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for forming a multilobular filament of a thermotropic liquid crystalline polymer, having the following properties: (i) denier of at least about 50 deniers per filament; (I) tenacity of at least about 8 grams per denier; (iii) module of at least about 450 grams per denier; and (iv) elongation of approximately 2%; characterized in that said method comprises the steps of: (a) heating a thermotropic liquid crystalline polymer at a temperature of at least about 15 ° C above its transition to melting to form a fluid stream of said thermotropic polymer; (b) passing said current through a heated extrusion chamber, wherein said chamber is disposed with a suitable orifice having a multilobal cross-section to form the multi-lobe filament of said polymer, and (c) winding said filament to a winding speed of at least about 200 meters per minute and a suitable stretch to form the multilobal filament of essentially uniform molecular orientation through its cross section, and having a denier value of at least about 50 denier per filament.

2. The process according to claim 1, further characterized in that said thermotropic liquid crystalline polymer is selected from the group consisting of fully aromatic polyesters, aromatic-aliphatic polyesters, aromatic polyazomethines, aromatic polyesteramides, aromatic polyamides and aromatic polyester carbonates.

3. The process according to claim 1, further characterized in that said thermotropic liquid crystalline polymer is a fully aromatic polyester.

4. The process according to claim 3, further characterized in that said polyester comprises a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of recurring portions I and II, where: I is wherein said polyester comprises from about 10 to about 90 mole percent of portion I, and from about 10 to about 90 mole% of portion II.

5. The process according to claim 3, further characterized in that said polyester comprises a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 400 ° C, consisting essentially of recurring portions I, II, III and VII, where: I is l l l is I saw him wherein said polyester comprises from about 40 to about 70 mole percent of portion I, from about 1 to about 20 mole percent of portion II, and from about 14.5 to about 30 mole percent of each of the portions III and VII.

6. The process according to claim 1, further characterized in that said thermotropic liquid crystalline polymer is a fully aromatic polyesteramide.

7. The process according to claim 6, further characterized in that said polyesteramide comprises a fully aromatic polyesteramide processable by melting capable of forming an anisotropic melt phase at a temperature below about 360 ° C, consisting essentially of recurring portions II, III and VI, where: II is l l l is V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion II, and from about 15 to about 30 mole percent of each of portions III and VI.

8. The process according to claim 6, further characterized in that said polyesteramide comprises a fully aromatic polyesteramide processable by melting capable of forming an anisotropic melt phase at a temperature below about 380 ° C, consisting essentially of the recurring portions I, II, III, VII and VI, where: I is he is I I is I saw him V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of portion I, from about 1 to about 20 mole percent of portion II, from about 14. 5 to about 30 mole percent of portion III, from about 7 to about 27.5 mole percent of portion VII, and from about 2.5 to about 7.5 mole percent of portion VI.

9. The process according to claim 6, further characterized in that said polyesteramide comprises a fully aromatic polyesteramide processable by melting capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I, II, III, IV, V and VI, where: I is I I is l l l is IV is You see V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion I, from about 10 to about 20 mole percent of the portion II, from about 2.5 to about 20 mole percent of the portion III, from about 0 to about 3 mole percent of the IV portion, from about 12.5 to about 27.5 mole% of the V portion, and from about 2.5 to about 7.5 mole percent of the VI portion .

10. The process according to claim 1, further characterized in that said thermotropic liquid crystalline polymer is heated to a temperature of about 20 ° C to about 50 ° C above its transition to melting. 11. The method according to claim 1, further characterized in that said orifice has a multilobal cross section of at least six. 12. The method according to claim 1, further characterized in that said orifice has a multilobular cross section. 13. The method according to claim 1, further characterized in that said stretch ratio is from about 4 to about 20. 14. The method according to claim 1, further characterized in that said stretch ratio is around from 4 to about 15. 15. The method according to claim 1, further characterized in that said multilobal filaments are a multilobular monofilament. 16. The method according to claim 15, further characterized in that the denier of said filament is from about 100 to about 1000 denier per filament. 17. The method according to claim 15, further characterized in that the denier of said filament is from about 150 to about 500 denier per filament. 18. - The method according to claim 15, further characterized in that the denier of said filament is from about 180 to about 300 denier per filament. 19. The product produced by the process according to claim 1. 20. The product produced by the process according to claim 4. 21. The product produced by the process according to claim 5. 22. - The product produced by the process according to claim 7. 23. The product produced by the process according to claim 8. 24.- The product produced by the process according to claim 9. 25.- The product produced by the process according to claim 17. 26.- The product produced by the process according to claim 18. 27.- A process for forming a multilobar filament treated with heat, of a thermotropic liquid crystalline polymer having the following properties: (i) denier of at least about 50 deniers per filament; (ii) tenacity of at least about 20 grams per denier; (iii) module of at least about 600 grams per denier; and (iv) elongation of about 3%; said method comprising the steps of: (a) heating the thermotropic liquid crystalline polymer at a temperature from about 15 ° C to about 50 ° C above its melting transition, to form a fluid stream of said polymer; (b) extruding said polymer stream through a heated cylindrical spinner having at least one extrusion capillary of multilob cross-section, to form a filament; (c) winding said multilobular filament at a winding speed of at least about 200 meters per minute and a suitable stretch ratio to form a filament of essentially uniform molecular orientation across the cross section, and having a denier on the scale from about 50 to about 1000 denier per filament; and (d) heat treating said multilobular filament at suitable pressure and temperature conditions and for a sufficient period, optionally in the presence of an inert atmosphere, to form the heat treated filament. 28. The process according to claim 27, further characterized in that said thermotropic liquid crystalline polymer is selected from the group consisting of: (i) a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I and II, wherein: I is wherein said polyester comprises from about 10 to about 90 mole percent of portion I; and from about 10 to about 90 mole percent of portion II; (ii) a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 400 ° C, consisting essentially of the recurring portions I, II, III and VII, wherein: I is is is I saw him wherein said polyester comprises from about 40 to about 70 mole percent of portion I, from about 1 to about 20 mole percent of portion II, and from about 14.5 to about 30 mole percent of each of the portions III and VII; (ni) a fully aromatic polyester amide processable by melting capable of forming an anisotropic melt phase at a temperature below about 360 ° C, consisting essentially of the recurring portions II, I and VI, wherein: is V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of portion II, from about 15 to about 30 mole percent of each of portions I and VI; (iv) a fully aromatic polyesteramide processable by melting capable of forming an anisotropic melt phase at a temperature below about 380 ° C, consisting essentially of the recurring portions I, II, III, VII and VI, wherein: is II is lll is Vil is and V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion I, from about 1 to about 20 mole percent of the portion II, from about 14.5 to about 30 mole percent of the lil portion, from about 7 to about 27.5 mole percent of the portion VII, and from about 2.5 to about 7.5 mole percent of the portion VI; and (v) a fully aromatic, melt-processable polyesteramide capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I, II, III; IV, V and VI, where: is

11 is lll 10 IV is 15 V is and VI is 20 ? -O- ^ wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion I, from about 10 to about 20 mole percent of the portion II, from about 2.5 to about 20 percent percent of the portion III, from about 0 to about 3 mole percent of the IV portion, from about 12.5 to about 27.5 mole percent of the V portion, and from about 2.5 to about 7.5 mole percent of the VI portion. 29. The method according to claim 27, further characterized in that said orifice has an octalobular cross section. The method according to claim 27, further characterized in that said heat treatment in step (d) is carried out in stages at a final temperature of about 15 ° C below the transition to melting said thermotropic liquid crystalline polymer. 31. The method according to claim 27, further characterized in that the denier of said filament is from about 150 to about 500 denier per filament. 32. The method according to claim 27, further characterized in that the denier of said filament is from about 180 to about 300 deniers per filament. 33.- The product produced by the procedure according to claim 27. 34. - The product produced by the process according to claim 28. 35.- The product produced by the process according to claim 29. 36.- The product produced by the process according to claim 30. 37.- The product produced by the process according to claim 30. product produced by the process according to claim 31. 38. A multi-lobed filament, such as is spun, of a thermotropic liquid crystalline polymer having the following properties: (a) denier of at least about 50 denier per filament; (b) tenacity of at least about 8 grams per denier; (c) module of approximately 450 grams per denier; and (d) elongation of at least about 2 percent. 39.- The filament according to claim 38, further characterized in that said thermotropic liquid crystalline polymer is selected from the group consisting of: (i) a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I and II, where: wherein said polyester comprises from about 10 to about 90 mole percent of the portion I, and from about 10 to about 90 mole percent of the portion II; (ii) a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 400 ° C, consisting essentially of the recurring portions I, II, III, and VII, wherein: is is I saw him wherein said polyester comprises from about 40 to about 70 mole percent of portion I, from about 1 to about 20 mole percent of portion II, and from about 14.5 to about 30 mole percent of each of the portions III and VII; (iii) a fully aromatic polyester amide processable by melting capable of forming an anisotropic melt phase at a temperature below about 360 ° C, consisting essentially of the recurring portions II, I and VI, wherein: I I is is V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of portion II, and from about 15 to about 30 mole percent of each of portions I and VI; (iv) a fully aromatic, melt-processable polyesteramide capable of forming an anisotropic melt phase at a temperature below about 380 ° C, consisting essentially of the recurring portions I, II, III, VII and VI, wherein: is II is lll is Vil is 20 and VI is wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion I, from about 1 to about 20 mole percent of the portion II, from about 14.5 to about 30 mole percent of the portion III, from about 7 to about 27.5 mole percent of the VII portion, and from about 2.5 to about 7.5 mole percent of the VI portion; and (v) a fully aromatic, melt-processable polyesteramide capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I, II, III, IV, V and VI, where: he is is is IV e You see You see wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion I, from about 10 to about 20 mole percent of the portion II, from about 2.5 to about 20 mole percent of the portion III, from about 0 to about 3 mole percent of the IV portion, from about

12. 5 to about 27.5 mole percent of the V portion, and from about 2.5 to about 7.5 mole of the VI portion. 40. The filament according to claim 38, further characterized in that the denier of said filament is from about 100 to about 1000 denier per filament. 41. The filament according to claim 38, further characterized in that the denier of said filament is from about 150 to about 500 denier per filament. 42. The filament according to claim 38, further characterized in that the denier of said filament is from about 180 to about 300 deniers per filament. 43.- A heat-treated multi-lobed filament of a thermotropic liquid crystalline polymer that has the following properties: (a) denies at least about 50 deniers per filament; (b) tenacity of at least about 20 grams per denier; (c) module of at least about 600 grams per denier; and (d) elongation of at least about 3 percent. 44. The filament according to claim 43, further characterized in that said thermotropic liquid crystalline polymer is selected from the group consisting of: (i) a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I and II, wherein: I is wherein said polyester comprises from about 10 to about 90 mole percent of the portion I, and from about 10 to about 90 mole percent of the portion II; (ii) a fully aromatic polyester processable by melting capable of forming an anisotropic melt phase at a temperature below about 400 ° C, consisting essentially of the recurring portions I, II, III and VII, wherein: is \ I I is l l l is I saw him wherein said polyester comprises from about 40 to about 70 mole percent of portion I, from about 1 to about 20 mole percent of portion II, and from about 14.5 to about 30 mole percent of each of the portions III and VII; (Ii) a fully aromatic, melt-processable polyesteramide capable of forming an anisotropic melt phase at a temperature below about 360 ° C, consisting essentially of the recurring portions II, I and VI, wherein: is V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of portion II, from about 15 to about 30 mole percent of each of portions I and VI; (iv) a fully aromatic, melt-processable polyesteramide capable of forming an anisotropic melt phase at a temperature below about 380 ° C, consisting essentially of the recurring portions I, II, III, VII and VI, wherein: is 11 is 10 lll is 15 Vil is and V I is wherein said polyesteramide comprises from about 40 to about 70 mole percent of portion 1, from about 1 to about 20 mole percent of portion II, from about 14.5 to about 30 mole percent of the portion III, from about 7 to about 27.5 mole percent of the VII portion, and from about 2.5 to about 7.5 mole percent of the VI portion; and (v) a fully aromatic, melt-processable polyesteramide capable of forming an anisotropic melt phase at a temperature below about 350 ° C, consisting essentially of the recurring portions I, II, III; IV, V and VI, where: I is II is IV is 15 V is 20 VI is wherein said polyesteramide comprises from about 40 to about 70 mole percent of the portion I, from about 10 to about 20 mole percent of the portion II, from about 2.5 to about 20 percent of the portion lll , from about 0 to about 3 mole percent of the IV portion, from about 12.5 to about 27.5 mole percent of the V portion, and from about 2.5 to about 7.5 mole percent of the VI portion. 45. The filament according to claim 43, fer characterized in that the denier of said filament is from about 100 to about 1000 denier per filament. 46. The filament according to claim 43, fer characterized in that the denier of said filament is from about 150 to about 500 denier per filament. 47. The filament according to claim 43, fer characterized in that the denier of said filament is around * 180 to approximately 300 deniers per filament.