JP2010512465A - Melt-spun elastester multifilament yarn - Google Patents

Abstract

  The present invention relates to a process for producing an elastomeric ester multifilament yarn by melt spinning a polyetherester thermoplastic elastomer under commercially feasible conditions, wherein the polyetherester thermoplastic elastomer is polytrimethylene ether dicarboxyl. It relates to a process which is a polytrimethylene ether ester comprising a rate ester soft segment and a hard segment selected from trimethylene dicarboxylate ester hard segment and / or tetramethylene dicarboxylate ester hard segment.

Description

  The present invention relates to a process for producing an elastomeric ester multifilament yarn by melt spinning a polyetherester thermoplastic elastomer under commercially viable conditions, wherein the polyetherester thermoplastic elastomer is a polytrimethylene ether. It relates to a process which is a polytrimethylene ether ester comprising a dicarboxylate ester soft segment and a hard segment selected from trimethylene dicarboxylate ester hard segment and / or tetramethylene dicarboxylate ester hard segment.

  The name “elastoester” is a common expression in the United States in the context of fibers containing at least 50% by weight aliphatic polyether and at least 35% by weight polyester. Elastoester is elastic like spandex, can be easily washed, and can withstand high temperatures when wet. Elastoester retains dye better than fabrics made from nylon and spandex, and is less likely to be discolored or adversely affected by chlorine, an important property for clothing such as swimwear It is said.

  US Pat. No. 6,562,457 discloses a polyetherester thermoplastic elastomer comprising a polytrimethylene ether ester soft segment and a tetramethylene ester hard segment. US Pat. No. 6,599,625 discloses a polyetherester thermoplastic elastomer comprising a polytrimethylene ether ester soft segment and a trimethylene ester hard segment. U.S. Pat. No. 6,905,765 discloses a polyetherester elastomer comprising a poly (trimethylene-ethylene ether) ester soft segment and an alkylene ester hard segment.

  The above publications show that the polyetheresters disclosed in the publication are useful in producing fibers, whether continuous filaments or staple fibers, and are used to prepare woven, knitted and non-woven fabrics. It shows that fibers can be used. The disclosed fibers are stretchable, have good chlorine resistance, can be dyed under standard polyester dyeing conditions, have excellent strength and elongation recovery properties, particularly improved unloading power and Has excellent physical properties including stress relaxation.

  US Pat. No. 6,562,457 and US Pat. No. 6,599,625 are capable of melt spinning fibers from the disclosed polymers at a speed of about 1200 m / min or less and about 6 times or less. It further shows that it can be stretched. The ability to melt spin under these conditions would be commercially advantageous over solution spinning used for manufactured synthetic fibers containing spandex or elastane; at least 85% segmented polyurethane.

  In spite of the general disclosure described above, only US Pat. No. 6,562,457 and US Pat. No. 6,599,625 only have a speed of about 160 m / min with a stretch ratio of 4 times. 1 illustrates the melt spinning of monofilaments. These spinning conditions are too slow for practical commercialization of the fiber. Successful commercialization generally requires spinning speeds greater than about 1200 m / min and draw ratios as high as 5 times, and further requires that the fibers take the form of multifilaments.

  It has now been found that certain polyetherester thermoplastic elastomers can be melt spun at spinning speeds greater than about 1200 m / min and under other commercially viable conditions to produce multifilaments (multifilament yarns). It was. Accordingly, the present invention melts an elastomeric ester fiber comprising a polytrimethylene ether dicarboxylate ester soft segment and a polytrimethylene ether ester polymer containing a trimethylene dicarboxylate ester hard segment or a tetramethylene dicarboxylate ester hard segment. Provides commercially viable conditions for spinning.

According to the present invention,
(A) about 80 to about 40% by weight of a polytrimethylene ether dicarboxylate ester soft segment based on the combined weight of the hard segment and the soft segment, trimethylene dicarboxylate ester, tetramethylene dicarboxylate ester and their Providing a polyetherester thermoplastic elastomer comprising about 20 to about 60% by weight of a hard segment selected from the group consisting of a mixture;
(B) melt spinning the elastomer by extruding the elastomer through one or more spinnerets to form at least two filaments;
(C) A method of preparing an elastester multifilament yarn comprising the step of processing the filament into a multifilament yarn, wherein the melt spinning is performed at a spinning speed higher than about 1200 meters / minute.

  The method of the present invention may further comprise the step of cutting the multifilament yarn into staple fibers.

  The present invention also relates to multifilament yarns prepared by the above method and fabrics comprising multifilament yarns thus prepared.

  The resulting multifilament yarn is preferably an elastomeric ester yarn having an elongation of about 100 to about 600% and a strength of about 0.5 to about 2.5 grams / denier, and about 0.5 to about 20 denier. / Filament (dpf).

  In a preferred embodiment of the present invention, the multifilament yarn is a spun drawn yarn, and the process is processed at a draw speed of about 1250 to about 5000 meters / minute as measured with a roller at the end of the draw process. The process of extending | stretching is included. Preferably, the step of processing into a spun drawn multifilament includes filament drawing, annealing, entanglement and winding steps.

  In another preferred embodiment, the multifilament yarn is a partially drawn yarn and the spinning speed is preferably greater than about 1500 meters / minute.

  The multifilament textured yarn includes (a) a step of preparing a package of partially drawn multifilament yarn, (b) a step of unwinding the yarn from the package, and (c) a step of drawing the filament to form a drawn yarn. And (d) a false twisted texture of the drawn yarn to form a textured yarn, and (e) a step of winding the yarn on a package, and may be prepared from the partially drawn yarn.

  All publications, patent applications, patents and other references mentioned herein are hereby incorporated by reference for all purposes as if fully set forth unless otherwise indicated. The

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

  Trademarks are shown in capital letters unless explicitly noted.

  Unless otherwise specified, all percentages, parts, ratios, etc. are by weight.

  When an amount, concentration or other value or parameter is given as either a range, a preferred range or a list of preferred upper and preferred lower values, this is regardless of whether the range is disclosed separately, It should be understood that all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value are specifically disclosed. Where numerical ranges are listed herein, unless otherwise specified, the ranges are intended to include the endpoints and all integers and fractions within the range. It is not intended to limit the scope of the invention to the specific values recited when defining a range.

  When the term “about” is used in describing a range of values or endpoints, the disclosure should be understood to include the associated specific value or endpoint.

  As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having” Or any variations thereof are intended to cover non-exclusive inclusions. For example, a process, method, article or device that includes a list of elements is not necessarily limited to only those elements, and other elements not explicitly described in such processes, methods, articles or devices are not unique. It may also contain elements. Further, unless expressly stated to the contrary, “or” means non-exclusive “or” and does not mean exclusive “or”. For example, the condition A or B is satisfied by any one of the following. A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present) and both A and B are true (or present).

  The use of the singular ("a" or "an") is used to describe elements and components of the invention. This is only used for convenience and to give a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

  The materials, methods, and examples herein are illustrative only and not intended to be limiting except as described herein. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

Polyetherester thermoplastic elastomer The polyetherester thermoplastic elastomer for use in the present invention is preferably
About 80 to about 40 wt%, more preferably about 75 to about 50 wt%, even more preferably about 70 to about 60 wt% polytrimethylene ether ester soft segment, based on the combined weight of the hard and soft segments And about 20 to about 60% by weight, more preferably about 25 to about 50% by weight, even more preferably about 30 to about 40% by weight of hard segments (polytrimethylene ester and / or polytetramethylene ester) .

  The polyetherester thermoplastic elastomer is preferably at least about 0.8 dl / g, more preferably at least about 1.2 dl / g and preferably no more than about 2.0 dl / g, more preferably no more than about 1.6 dl / g. Has intrinsic viscosity.

  “Polytrimethylene ether ester soft segment” and “soft segment” are used in conjunction with the present invention to mean the reaction product of a polymeric ether glycol and a “dicarboxylic acid equivalent” via an ester linkage, Here, at least about 50%, more preferably at least about 85%, and even more preferably about 95-100% by weight of the polymeric ether glycol used to form the soft segment is polytrimethylene ether glycol ( PO3G).

  "Polytrimethylene ester hard segment", "polytetramethylene ester hard segment" and "hard segment" are 1,3-propanediol (trimethylene glycol) or 1,4-butanediol ( Used in conjunction with the present invention to mean the reaction product of one or more of tetramethylene glycol) and one or more dicarboxylic acid equivalents, wherein about 50 moles of diol used to form the hard segment %, More preferably at least about 75 mol%, even more preferably at least about 85 mol%, even more preferably about 95-100 mol% in 1,3-propanediol and / or 1,4-butanediol is there.

  A “dicarboxylic acid equivalent”, as is generally recognized by those skilled in the art, is a dicarboxylic acid equivalent that is a compound that functions substantially like a dicarboxylic acid in the reaction of a dicarboxylic acid with a polymeric glycol and a polymeric diol. Means. In addition to dicarboxylic acids, dicarboxylic acid equivalents for purposes of the present invention include diester forming properties such as, for example, monoesters and diesters of dicarboxylic acids, and acid halides (eg, acid chlorides) and acid anhydrides. Derivatives.

Polymeric ether glycol for the soft segment PO3G for the purposes of the present invention is an oligomeric ether glycol and / or a polymer ether glycol in which at least 50% of the repeating units are trimethylene ether units. More preferably from about 75% to 100%, even more preferably from about 90 to 100%, even more preferably from about 99% to 100% of the repeating units are trimethylene ether units.

PO3G is preferably a polymer or copolymer prepared by polycondensation of monomers comprising 1,3-propanediol and thus containing — (CH ₂ CH ₂ CH ₂ O) -linkages (eg trimethylene ether repeat units) Bring.

  In addition to the trimethylene ether units, there may be lesser amounts of other units such as other polyalkylene ether repeating units. In the context of this disclosure, the term “polytrimethylene ether glycol” refers to oligomers and polymers containing essentially pure 1,3-propanediol and up to 50% by weight of comonomer (the oligomers described below and Including PO3G made from polymers).

  The 1,3-propanediol used to prepare PO3G may be obtained by any of a variety of well-known chemical pathways or biochemical transformation pathways. Preferred routes are, for example, US Pat. No. 5,015,789, US Pat. No. 5,276,201, US Pat. No. 5,284,979, US Pat. No. 5,334,778. No., US Pat. No. 5,364,984, US Pat. No. 5,364,987, US Pat. No. 5,633,362, US Pat. No. 5,686,276 US Pat. No. 5,821,092, US Pat. No. 5,962,745, US Pat. No. 6,140,543, US Pat. No. 6,232,511, US Pat. No. 6,235,948, US Pat. No. 6,277,289, US Pat. No. 6,297,408, US Pat. No. 6,331,264, US Pat. No. 6,342,646 U.S. Pat. No. 7,038,092, U.S. Patent Application Publication No. 2004 / 0225161A1, U.S. Patent Application Publication No. 2004 / 0260125A1, U.S. Patent Application Publication No. 2004 / 0225162A1, and U.S. Pat. This is described in Japanese Patent Application Publication No. 2005 / 0069997A1.

  Preferably, 1,3-propanediol is obtained biochemically from a renewable source (“bioderivative”) 1,3-propanediol).

  A particularly preferred 1,3-propanediol source is via a fermentation process using a renewable biological source. As an illustrative example of a starting material from a renewable source, the biochemical pathway to 1,3-propanediol (POD) is described using raw materials produced from biological and renewable resources such as corn raw materials. ing. For example, strains capable of converting glycerol to 1,3-propanediol have been found in the species: Klebsiella, Citrobacter, Clostridium and Lactobacillus. This technique in several publications including the previously cited US Pat. No. 5,633,362, US Pat. No. 5,686,276 and US Pat. No. 5,821,092. Is disclosed. US Pat. No. 5,821,092 discloses a process for the biological production of 1,3-propanediol from glycerol, particularly using recombinant organisms. This method introduces E. coli transformed with a heterologous pdudiol dehydratase gene with specificity for 1,2-propanediol. The transformed E. coli is grown in the presence of glycerol as a carbon source and 1,3-propanediol is isolated from the grown medium. Since both fungi and yeast can convert glucose (eg, corn sugar) or other sugars to glycerol, the methods disclosed in these publications are 1,3-propanediol which is fast, inexpensive and environmentally responsible. Provide a monomer source.

  Biologically derived 1,3-propanediol as produced by the method described and referenced above is carbon from atmospheric carbon dioxide introduced by the plant that constitutes the feedstock for the production of 1,3-propanediol. Containing. Thus, the preferred bioderived 1,3-propanediol for use in connection with the present invention contains only renewable carbon and no fossil fuel-based or petroleum-based carbon. Therefore, PO3G using bio-derived 1,3-propanediol, and elastomers based thereon, do not deplete fossil fuels where 1,3-propanediol used in the composition continues to decrease, and once used again by plants As a result, carbon is released and returned to the atmosphere, so it has less impact on the environment. Thus, the compositions of the present invention can be characterized as being more natural and having less environmental impact than similar compositions containing petroleum glycols.

Biologically derived 1,3-propanediol, PO3G and elastomers based thereon may be distinguished by double carbon isotope characterization methods from analogous compounds made from petroleum sources or fossil fuel carbon. This method usually distinguishes chemically identical materials and assigns the carbon in the copolymer according to the source (and possibly the year) of growth of the biosphere (plant) component. The isotopes ¹⁴ C and ¹³ C provide additional information for this problem. Radiocarbon dating isotopes ( ¹⁴ C) can clearly allocate sample carbon between fossil (“dead”) and biosphere (“live”) sources due to their nuclear half-life of 5730 to (Currie, L.A. "Source Apportionment of Atmospheric Particles", Characterization of Environmental Particles, J.Buffle and H.P.van Leeuwen, Eds., 1 of Vol.1 of the IUPAC Environmental Analytical Chemistry Series (Lewis (Publishers, Inc.) (1992) 3-74). The basic assumption of radiocarbon dating is that the continuity of the ^14C concentration in the atmosphere leads to the continuity of ^{14C in the} organism. When dealing with isolated samples, relate the age of the sample:
t = (− 5730 / 0.693) ln (A / A ₀ )
Can be derived roughly by
In the formula, t = age, 5730 is the half-life of radioactive carbon. A and A ₀ are the ¹⁴ C specific activity of the sample and the modern standard, respectively (Hsien, Y., Soil Sci. Soc. Am J., 56, 460, (1992)). However, because of atmospheric nuclear testing since 1950 and the burning of fossil fuels since 1850, ¹⁴ C has acquired a second geochemical time characteristic. The ¹⁴ C concentration in atmospheric CO _{2 and} thus in the living biosphere approximately doubled at the peak of the nuclear test in the mid 1960s. ^{The 14} C concentration has since gradually increased to a steady-state cosmic ray (atmosphere) baseline isotope ratio ( ¹⁴ C / ¹² C) of approximately 1.2 × 10 ⁻¹² with an approximate relaxation “half-life” of 7-10 years. do not have (this latter half-life receive literally back to. Rather, be used more atmospheric nuclear-on / decay function to trace the variation of atmospheric ¹⁴ C and biospheric ¹⁴ C since the onset of the nuclear age. Must). The support of annual dating of recent biospheric carbon is biospheric ¹⁴ C time characteristic of the latter. ¹⁴ C can be measured by accelerator mass spectrometry (AMS), and the results are given in units of “modern carbon content” (f _M ). f _M is defined by National Institute of Standards and Technology (NIST) standard reference materials (SRMs) 4990B and 4990C, known as oxalic acid standards HOxl and HOxl, respectively. The basic definition relates to 0.95 times the ¹⁴ C / ¹² C isotope ratio of HOxl (related to AD 1950). This is almost equal to pre-industrial timber, which correlates with decay. For the current living biosphere (plant material), f _M ≈1.1.

Stable carbon isotope ratio ( ¹³ C / ¹² C) provides a supplementary route to source identification and designation. ¹³ C / ¹² C ratio in a given biological source material is the result of ¹³ C / ¹² C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C ₃ plants (hardwood), C ₄ plants (grass) and marine carbonate all show significant differences in ¹³ C / ¹² C values and corresponding δ ¹³ C values. Furthermore, C ₃ and C ₄ plant lipid substances degrade differently than materials derived from carbohydrate components of the same plant as a result of metabolic pathways. Within the accuracy of the measurement, ¹³ C shows a large variation due to the isotope fractionation effect. Most notable with respect to the present invention is the photosynthesis mechanism. The main cause of the difference in the carbon isotope ratio in plants, photosynthetic carbon metabolism in plants, reaction especially occurring during primary carboxylation, i.e., closely related to the differences in the path of the initial fixation of atmospheric CO _2. Two major types of planting are those that introduce a “C ₃ ” (or Calvin-Benson) photosynthetic cycle and those that introduce a “C ₄ ” (or Hatch-Sack) photosynthetic cycle. C ₃ plants, such as hardwoods and conifers, are dominant in the area of mild climate. In C ₃ plants, the primary CO ₂ fixation or carboxylation reaction involves the enzyme Riburoze-1,5-diphosphate carboxylase and the first stable product is a 3-carbon compound. On the other hand, C ₄ plants include tropical grasses, plants such as corn and sugar cane. In C ₄ plants, another enzyme, an additional carboxylation reaction involving a phosphodiester-pyruvate carboxylase, is the primary carboxylation reaction. The first stable carbon compound is a 4-carbon acid, which is later decarboxylated. The CO ₂ thus released is fixed again by the C ₃ cycle.

ＰＤＢ標準材料（ＲＭ）が枯渇してきたので、一連の代替ＲＭは、ＩＡＥＡ、ＵＳＧＳ、ＮＩＳＴおよび選択された他の国際同位体試験所と協力して開発されてきた。ＰＤＢからのパーミル偏差のための表記法はδ¹³Ｃである。測定は、質量４４、４５および４６の分子イオンに関する高精度安定比質量分析法（ＩＲＭＳ）によってＣＯ₂に関して行われる。 Both C ₄ and C ₃ plants show a range of ¹³ C / ¹² C isotope ratios, but typical values are about −10 to −14 / mil (C ₄ ) and −21 to −26. / Mil (C ₃ ) (Weber et al., J. Agric. Food Chem., 45, 2942 (1997)). Coal and oil generally fall within this latter range. ^{The 13} C measurement scale is originally defined by a zero set by PDB Yalime (PDB) limestone. Here, the value is given in parts per thousand deviation from this material. The “δ ¹³ C” value is parts per thousand (per mil) abbreviated as% ₀ and is calculated as follows:

As PDB standard materials (RM) have been depleted, a series of alternative RMs have been developed in cooperation with IAEA, USGS, NIST and other selected international isotope laboratories. The notation for permill deviation from the PDB is δ ¹³ C. Measurements are made on CO ₂ by high precision stable ratio mass spectrometry (IRMS) on molecular ions of mass 44, 45 and 46.

Thus, bio-derived 1,3-propanediol and compositions comprising bio-derived 1,3-propanediol are subject to ¹⁴ C (f _M ) and double carbon isotope characterization methods that demonstrate the novelty of the composition. It can be completely distinguished from petroleum derived equivalents. The ability to distinguish between these products is beneficial in tracking these materials for commercial purposes. For example, a product that includes both a “new” carbon isotope distribution and an “old” carbon isotope distribution can be distinguished from a product made from only “old” materials. Therefore, if this material is tracked for commercial purposes to determine shelf life, and in particular to assess environmental impacts, based on the unique distribution of this material and for purposes of determining competition There is.

  The 1,3-propanediol used as a reactant or as a component of the reactant preferably has a purity of greater than about 99 wt%, more preferably greater than about 99.9 wt%, as determined by gas chromatographic analysis. . U.S. Patent No. 7,038,092, cited above, U.S. Patent Application Publication No. 2004 / 0260125A1, U.S. Patent Application Publication No. 2004 / 0225161A1, and U.S. Patent Application Publication No. 2005 / 0069997A1. Particularly preferred is the purified 1,3-propanediol disclosed in US Pat. No. 5,047,086 and PO3G produced from purified 1,3-propanediol disclosed in US 2005/0020805 A1.

The purified 1,3-propanediol preferably has the following characteristics.
(1) UV absorption at 220 nm of less than about 0.200, UV absorption at 250 nm of less than about 0.075 and UV absorption at 275 nm of less than about 0.075, and / or (2) less than about 0.15 L ^* a ^* b ^* "b ^* " brightness (ASTM D6290) and a composition having an absorbance at 270 nm of less than about 0.075, and / or (3) a peroxide composition of less than about 10 ppm, and / or ( 4) A concentration of total organic impurities (organic compounds other than 1,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and even more preferably less than about 150 ppm as measured by gas chromatography.

  The starting materials for making PO3G will depend on the desired PO3G, availability of starting materials, catalysts, equipment, etc. and include “1,3-propanediol reactant”. “1,3-propanediol reactant” means 1,3-propanediol, and oligomers and prepolymers of 1,3-propanediol and preferably mixtures thereof having a degree of polymerization of preferably 2-9. In some cases, it may be desirable to use 10% or less of low molecular weight oligomers where they are available. Accordingly, the starting material preferably comprises 1,3-propanediol and its dimers and trimers. The starting material is particularly preferably composed of about 90% by weight or more of 1,3-propanediol, more preferably 99% by weight or more of 1,3-propanediol, based on the weight of the 1,3-propanediol reactant. .

  PO3G can be manufactured via a number of processes known in the art as disclosed in US Pat. No. 6,977,291 and US Pat. No. 6,720,459. It is. A preferred process is as described in the previously cited US Patent Application Publication No. 2005 / 0020805A1.

As indicated above, PO3G may contain smaller amounts of other polyalkylene ether repeating units in addition to trimethylene ether units. Thus, the monomer for use in preparing the polytrimethylene ether glycol is about 50 wt% or less (preferably about 20 wt% or less, more preferably about 10 wt%) in addition to the 1,3-propanediol reactant. % Or less, and still more preferably about 2% or less by weight) comonomer polyol. Suitable comonomer polyols include aliphatic diols such as ethylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol. 1,12-dodecanediol, 3,3,4,4,5,5-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1 , 6-hexanediol and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol; fat Cyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and isosorbide; and polyhydroxy compounds such as glycerol, trimethylo Propane and pentaerythritol. A preferred group of comonomer diols is ethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl 2- (hydroxymethyl) -1,3-propanediol, C ₆ -C ₁₀ diol (1,6-hexanediol, 1,8-octane diol, and 1,10-decanediol) and isosorbide, and their Selected from the group consisting of mixtures. Particularly preferred diols other than 1,3-propanediol include ethylene glycol, 2-methyl-1,3-propanediol and C ₆ -C ₁₀ diol.

  One preferred PO3G-containing comonomer is poly (trimethylene-ethylene ether) glycol as described in US Patent Application Publication No. 20040030095A1. Preferred poly (trimethylene-ethylene ether) glycols are greater than 50 to about 99 mole percent (preferably about 60 to about 98 mole percent, more preferably about 70 to about 98 mole percent) 1,3-propanediol and up to 50 To about 1 mol% (preferably about 40 to about 2 mol%, more preferably about 30 to about 2 mol%) of ethylene glycol.

Preferably, the purified PO3G is essentially free of acid-catalyzed end groups, but very low levels of unsaturated end groups in the range of about 0.003 to about 0.03 meq / g, mainly Allyl end groups may be contained. Such PO3G has the following formula (II) HO - a ((CH _{2) 3} -O) compounds with _{m CH 2 CH = CH 2 -} ((CH 2) 3 O) m -H and formula (III) HO It can be thought of as comprising (consisting essentially of a compound).
Wherein m is in a range such that Mn (number average molecular weight) is in the range of about 200 to about 5000. The compound of formula (III) is present in an amount such that allyl end groups (preferably all unsaturated ends or end groups) are present in the range of about 0.003 to about 0.03 meq / g. . While a small number of allyl end groups in PO3G are useful for controlling the molecular weight of the elastomer, for example, the number of allyl end groups is excessive so that a composition ideally suited for fiber end use can be prepared. Not limited to.

  Preferred PO3G for use in the present invention has a Mn of at least about 750, more preferably at least about 1000, and even more preferably at least about 2000. Mn is preferably less than about 5000, more preferably less than about 4000, and even more preferably less than about 3500. A blend of PO3G can also be used. For example, PO3G can include a blend of higher molecular weight PO3G and lower molecular weight PO3G. Here, preferably, the higher molecular weight PO3G has a number average molecular weight of about 1000 to about 5,000, and the lower molecular weight PO3G has a number average molecular weight of about 200 to about 950. The Mn of the blended PO3G is preferably still in the range described above.

  Preferred PO3G for use herein is preferably from about 1.0 to about 2.2, more preferably from about 1.2 to about 2.2, and even more preferably from about 1.5 to about 2.1. Typically a polydisperse polymer with polydispersity (ie Mw / Mn). Polydispersity can be adjusted by using a blend of PO3G.

  PO3G for use in the present invention preferably has a brightness of less than about 100 APHA, more preferably less than about 50 APHA.

式中、Ｒはジカルボン酸等価物からカルボキシル官能基を除去後に残る二価基を表し、ｘはＰＯ３Ｇ中のトリメチレンエーテル単位の数を表す整数である。 When using PO3G substantially based on 1,3-propanediol to form the soft segment, it is possible to represent the soft segment as containing units represented by the following structure.

In the formula, R represents a divalent group remaining after removal of the carboxyl functional group from the dicarboxylic acid equivalent, and x is an integer representing the number of trimethylene ether units in PO3G.

  The polymer ether glycol used to prepare the polytrimethylene ether ester soft segment of the polyether ester may also contain 50% by weight or less of polymer ether glycol other than PO3G. Such preferred other polymeric ether glycols include, for example, polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, copolymers of tetrahydrofuran and 3-alkyltetrahydrofuran, and mixtures thereof.

式中、ｎは３（トリメチレン）または４（テトラメチレン）であり、Ｒ’はジカルボン酸等価物からカルボキシル官能基を除去後に残る二価基を表す。殆どの場合、本発明において用いられるポリエーテルエステルエラストマーの軟セグメントおよび硬セグメントを調製するために用いられるジカルボン酸等価物は同じである。 Diols for hard segments When trimethylene glycol / tetramethylene glycol is used to form hard segments, it is possible to represent hard segments as containing units having the following structure:

In the formula, n is 3 (trimethylene) or 4 (tetramethylene), and R ′ represents a divalent group remaining after removing the carboxyl functional group from the dicarboxylic acid equivalent. In most cases, the dicarboxylic acid equivalents used to prepare the soft and hard segments of the polyetherester elastomer used in the present invention are the same.

  The hard segment may also be prepared with less than 50 mol% (preferably less than about 25 mol%, more preferably less than about 15 mol%) of diols having a molecular weight of less than about 400, preferably other than trimethylene glycol or tetramethylene glycol. Is possible. The other diol is preferably an aliphatic diol and can be acyclic or cyclic. Ethylene glycol, isobutylene glycol, butylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, 2-methyltrimethylene glycol, hexamethylene glycol and decamethylene glycol, dihydroxycyclohexane, cyclohexanedimethanol, hydroquinone bis (2-hydroxy Diols having up to about 15 carbon atoms such as ethyl) ether are preferred. Aliphatic diols containing 2 to 8 carbon atoms are particularly preferred. Ethylene glycol is most preferred. Two or more other diols can be used.

Dicarboxylic acid equivalents The dicarboxylic acid equivalents can be aromatic, aliphatic or alicyclic. In this regard, an “aromatic dicarboxylic acid equivalent” is a dicarboxylic acid equivalent in which each carboxyl group is bonded to a carbon atom in the benzene ring system, such as the dicarboxylic acid equivalents described below. An “aliphatic dicarboxylic acid equivalent” is a dicarboxylic acid equivalent in which each carboxyl group is bonded to a fully saturated carbon atom or to a carbon atom that is part of an olefinic double bond. When a carbon atom is in the ring, the equivalent is “alicyclic”. The dicarboxylic acid equivalent can contain any substituents or combinations thereof as long as the substituents do not interfere with the polymerization reaction or do not adversely affect the properties of the polyetherester product.

  Preferred are dicarboxylic acid equivalents selected from the group consisting of dicarboxylic acids and diesters of dicarboxylic acids. More preferred are dimethyl esters of dicarboxylic acids.

  Aromatic or alicyclic dicarboxylic acids or diesters, alone or in small amounts, are preferred. Particularly preferred are dimethyl esters of aromatic dicarboxylic acids.

Representative aromatic dicarboxylic acids useful in the present invention include terephthalic acid, isophthalic acid, dibenzoic acid, naphthalic acid; bis (p-carboxyphenyl) methane, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalene. Substituted dicarboxylic acid compounds having a benzene nucleus such as dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-sulfonyldibenzoic acid; and C ₁ -C ₁₀ alkyl substitutions such as halo derivatives, alkoxy derivatives or aryl derivatives Derivatives and other ring-substituted derivatives. Hydroxy acids such as p- (hydroxyethoxy) benzoic acid can also be used as long as aromatic dicarboxylic acids are also present. Representative aliphatic and alicyclic dicarboxylic acids useful in the present invention are sebacic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid, adipic acid, dodecanedioic acid, glutaric acid, succinic acid. Acid, oxalic acid, azelaic acid, diethylmalonic acid, fumaric acid, citraconic acid, allylmalonic acid, 4-cyclohexane-1,2-dicarboxylic acid, pimelic acid, suberic acid, 2,5-diethyladipic acid, 2- Ethylsuberic acid, 2,2,3,3-tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naphthalenedicarboxylic acid or decahydro-2,6-naphthalenedicarboxylic acid, 4,4'-bicyclohexyldicarboxylic acid Acid, 4,4'-methylenebis (cyclohexylcarboxylic acid), 3,4 Flange carboxylate and 1,1-cyclobutane dicarboxylate. Dicarboxylic acid equivalents in the form of the diesters, acid halides and anhydrides of the aliphatic dicarboxylic acids described above are also useful for providing the polyetheresters of the present invention. Representative aromatic diesters include dimethyl terephthalate, bibenzoate, isophthalate, phthalate and naphthalate.

  Of the above, terephthalic acid, dibenzoic acid, isophthalic acid and naphthalic acid; dimethyl terephthalate, bibenzoate, isophthalate, naphthalate and phthalate; and mixtures thereof are preferred. Particularly preferred dicarboxylic acid equivalents are phenylene dicarboxylic acids, in particular phenylene dicarboxylic acids selected from the group consisting of terephthalic acid and isophthalic acid, and diesters of phenylene dicarboxylic acids, in particular dimethyl esters, dimethyl terephthalate and dimethyl isophthalate. In addition, two or more dicarboxylic acid equivalents can be used. For example, terephthalic acid and / or dimethyl terephthalate can be used with small amounts of other dicarboxylic acid equivalents.

  In preferred embodiments, at least about 70 mol% (more preferably at least about 80 mol%, even more preferably at least about 90 mol%, even more preferably about 95-100 mol%) of the dicarboxylic acid equivalent is terephthalic acid and / Or dimethyl terephthalate.

Preparation of Polyether Ester Elastomer The polyether ester for use in the spinning method of the present invention is preferably (a) polytrimethylene ether glycol, (b) trimethylene glycol or tetramethylene glycol or mixtures thereof and (c) Prepared by providing and reacting a dicarboxylic acid, ester, acid chloride or acid anhydride. Other glycols and diols as described above can also be provided and reacted. The procedure for preparing a polyetherester elastomer containing a polytrimethylene ether ester soft segment and a trimethylene ester hard segment is disclosed in detail in US Pat. No. 6,599,625. The procedure for preparing a polyetherester elastomer comprising a polytrimethylene ether ester soft segment and a tetramethylene ester hard segment is disclosed in detail in US Pat. No. 6,562,457.

Additives Polyetherester thermoplastic elastomers are limited to additives selected from the group consisting of matting agents, nucleating agents, thermal stabilizers, thickeners, optical brighteners, pigments and antioxidants in addition to elastomers. Although not, it may take the form of a composition comprising one or more additives containing them. For example, titanium dioxide or other pigments can be added to the polymer or in fiber production.

  It is also possible to make the polyetherester elastomer acid-dyeable using the additives described in US Patent Application Publication No. 2003-0083441 A1 and WO 01/034693. The additive of WO 01/034693 contains a secondary amine or secondary amine salt in an amount effective to promote acid-dyeability of acid-dyeable compositions and acid-dyed compositions. Including. The secondary amine units are preferably present in the polymer composition in an amount of at least about 0.5 mole percent, more preferably at least about 1 mole percent. The secondary amine units are preferably present in the polymer composition in an amount of no more than about 15 mol%, more preferably no more than about 10 mol%, even more preferably no more than about 5 mol%, based on the weight of the composition. . The additive of US 2003-0083441 A1 is a polymeric additive based on tertiary amines. The polymeric additive is prepared from (i) a triamine containing secondary amine units or secondary amine salt units and (ii) one or more other monomer units and / or polymer units. One preferred polymeric additive comprises a polyamide selected from the group consisting of polyiminobisalkylene terephthalamide, polyiminobisalkylene isophthalamide and polyiminobisalkylene-1,6 naphthalamide and salts thereof.

  The polyether ester useful in the present invention is made to be dyeable with a cation using dyeability modifiers such as the dyeability modifiers described in US Pat. No. 6,312,805. It is also possible.

Filament and Yarn Preparation For spinning, the polymer is heated to a temperature above its melting point, after which it is about 175 to about 295 ° C, preferably at least about 200 ° C and about 275 ° C or less, most preferably about 270 ° C or less. Extrude at a temperature through a spinneret, preferably a porous die. Higher temperatures are useful for lower residence times.

  The fiber may be drawn or undrawn. When drawing the fiber, the draw ratio is at least 1.01, preferably about 5 or less, more preferably about 4 or less, and most preferably about 3 or less.

  In a preferred embodiment of the present invention, the method is advantageously used to prepare a spun drawn yarn, also known as a “fully drawn yarn”. The preferred process for producing spun drawn yarns, including filament spinning, drawing, optional annealing, optional entanglement and winding, is similar to the process used to prepare poly (ethylene terephthalate) yarns. Preferably, the spun yarn produced by the method of the present invention is a multifilament yarn.

  An advantage of the present invention is that a spun drawn yarn using a higher draw ratio than disclosed in US Pat. No. 6,562,457 and US Pat. No. 6,599,625 for the same polyether ester. Can be prepared. This can be done by using a spinning speed below the standard and then stretching at the speed previously used. When performing this method, there are fewer breaks than previously occurred.

  The stretching speed (measured with a roll at the end of the stretching process) is greater than about 1200 m / m, preferably at least about 3000 m / m, more preferably at least about 3200 m / m, and preferably no more than about 8000 m / m. More preferably, it is about 7000 m / m or less. Another advantage of the present invention is that the spun drawn yarn can be spun on equipment previously used to spin poly (ethylene terephthalate) spun drawn yarn.

  Spun drawn yarns can usually be wound on a package and used to produce a fabric, or further processed into other types of yarns such as textured yarns.

  Although the method of the present invention is exemplified below for the preparation of spun drawn yarns, the present invention is also useful for preparing partially drawn yarns.

  The basic steps for producing partially drawn yarns including poly (ethylene terephthalate) filament spinning, entanglement and winding are described in US Pat. No. 6,287,688, US Pat. No. 6,333,106 and US Pat. This is described in Japanese Patent Application Publication No. 2001-030378A1. It is possible to practice the present invention using those processes or other processes conventionally used to produce partially oriented polyester yarns.

  The partially drawn yarn is a multifilament yarn. The yarn (also known as “bundle”) preferably comprises at least about 2, more preferably at least about 25 filaments. The yarn typically has a total denier of from about 1 to about 500, preferably at least about 20, more preferably at least about 50, and even more preferably from about 50 to about 300.

  The filament is preferably at least about 0.5 denier / filament (dpf), more preferably at least about 1 dpf, and no more than about 20 dpf, more preferably no more than about 7 dpf. Typical filaments are about 3-7 dpf and fine filaments are about 0.5 to about 2.5 dpf.

  The spinning speed is greater than about 1200 meters / minute ("m / m") and can be greater than or equal to about 5000 meters / minute. The spinning speed is preferably at least about 1500 m / m, more preferably at least about 3000 m / m. Spinning speed is generally defined as the maximum process speed and is considered the draw roll speed for the present invention. Thus, the advantages of the present invention are that the process can be performed at a faster rate than that disclosed in US Pat. No. 6,562,457 and US Pat. No. 6,599,625 for the same polyether ester. It can be implemented.

  An advantage of the present invention is that polyether ester partially drawn yarns can be spun on equipment previously used to spin poly (ethylene terephthalate) partially drawn yarns, and therefore the spinning speed is preferably about 4000 m / s. m or less, more preferably about 3500 m / m or less.

  Partially drawn yarns can usually be wound on a package and used to produce a fabric, or can be further processed into other types of yarns such as textured yarns. Partially drawn yarns can be stored in cans before the fabric is prepared or further processed, or can be used directly without forming packaging or other storage.

  Textured yarns can be prepared from partially drawn yarns or spun drawn yarns. The main difference is that partially drawn yarns usually require drawing, whereas spun drawn yarns are already drawn.

  U.S. Pat. No. 6,287,688, U.S. Pat. No. 6,333,106 and U.S. Patent Application Publication No. 2001-030378A1 all describe the basis for producing textured yarns from partially drawn yarns. The process is described. It is possible to practice the present invention using those processes or other processes conventionally used to produce partially oriented polyester yarns. The basic steps include unwinding the yarn from the package, stretching, twisting, heat setting, untwisting, and winding on the package. In the texturing, crimping is applied by untwisting by a method generally known as twisting, heat setting, and false twisting texturing. False twist texturing is carefully controlled to avoid excessive breakage of the yarn and filament.

  A preferred method for friction false twisting as described in US Pat. No. 6,287,688, US Pat. No. 6,333,106 and US Patent Application Publication No. 2001-030378A is 140. Using the twist insertion device to heat the partially drawn yarn to a temperature between 0 ° C. and 220 ° C., and in the region between the twist insertion device and the heater inlet, the yarn has a twist angle of about 46 degrees to 52 degrees Twisting the yarn and winding the yarn on a winder.

  When prepared from a spun drawn yarn, the method is the same except that the draw is dropped to a very low level (eg, the draw ratio can be as low as 1.01).

  These multifilament yarns (also known as “bundles”) contain the same number of filaments as the partially drawn yarn and the spun drawn yarn that produces the partially drawn yarn. Accordingly, these multifilament yarns preferably comprise at least about 2, even more preferably at least about 25 filaments. Such yarns typically have a total denier of from about 1 to 500, preferably at least about 20, preferably at least about 50, more preferably from about 50 to about 300. The filament is preferably at least about 0.1 dpf, more preferably at least about 0.5 dpf, more preferably at least about 0.8 dpf, and up to about 10 or more dpf, more preferably about 5 dpf or less, most preferably about 3 dpf or less.

  Staple fibers and staple products can be prepared from the polyetheresters of the present invention. One preferred method is (a) about 80 to about 40% by weight of a polytrimethylene ether dicarboxylate ester soft segment and about a hard segment selected from the group consisting of trimethylene dicarboxylate ester and tetramethylene dicarboxylate ester. Providing a polytrimethylene ether ester comprising 20 to about 60% by weight; (b) melt spinning the polytrimethylene ether ester into filaments at a temperature of about 245 ° C to about 285 ° C; Quenching the filament; (d) stretching the quenched filament; and (e) a mechanical crimper at a crimp level of about 8 to about 30 crimps / inch (about 3 to about 12 crimps / cm). Using to crimp the drawn filament; (f) from about 50 to about 120; Relaxing the crimped filaments at a temperature of (g) cutting the relaxed filaments into staple fibers, preferably having a length of about 0.2 to about 6 inches (about 0.5 to about 15 cm). Including. In one preferred embodiment of the method, the drawn filaments are annealed at about 85 ° C. to about 115 ° C. before crimping. Preferably, the annealing is performed under tension using a heated roll. In another preferred embodiment, the drawn filaments are not annealed before crimping.

  Staple fibers are useful in preparing textile yarns and textiles or nonwovens, and can also be used for fiber filler applications and carpet manufacture.

  The spinning method of the present invention can also be used to improve spinning feed in the preparation of bulky continuous filament (“BCF”) yarns. The production of BCF yarn and BCF yarn is described in, for example, US Pat. No. 5,645,782, US Pat. No. 6,109,015, US Pat. No. 6,113,825, US Pat. No. 6,576,340, U.S. Pat. No. 6,723,799, U.S. Pat. No. 6,740,276, and U.S. Patent Application Publication No. 2003-0175522A1. BCF yarns are used to prepare all types of carpets, not just textiles. The composition of the present invention can be used to improve the spinning speed of the preparation of the composition.

  The preferred steps involved in preparing the bulky continuous filament include spinning (eg, extruding, cooling and coating the filament (spin finish)), about 80 to about 200 ° C. and about 1.1 to about 5, preferably Single-stage or multi-stage stretching (preferably with heated roll assistance, heating pin assistance or hot fluid assistance (eg, steam or air)) at a draw ratio of at least about 1.5 and preferably no more than about 4.5, about Annealing, bulking, entanglement at temperatures from 120 to about 200 ° C. (can be done in one step with bulking or in a subsequent separate step), optionally on packaging for relaxation and subsequent use Including winding the filament.

  Bulky continuous filament yarns can be made into carpets using known techniques. Typically, multiple yarns are cable twisted together, heat set, and then tufted into a primary backing in an apparatus such as an autoclave. Thereafter, the latex adhesive and secondary backing are applied.

  Individual filaments can be round, or octalobal, delta, sunburst (also known as sol), scalloped oval, trilobal It can have other shapes such as (trilobal), tetra-channel (also known as quatra-channel), scalloped ribbon, ribbon, star, etc. Individual filaments can be solid, hollow or multi-hollow.

  While it is possible to prepare filaments with yarn bundles having different cross-sectional shapes using a single spinneret, the present invention is preferably practiced by spinning one type of filament cross-section from the spinneret. Is done.

  The following examples are presented for purposes of illustrating the invention. The following examples are not intended to be limiting. All parts, percentages, etc. are by weight unless otherwise indicated.

Intrinsic viscosity Intrinsic viscosity (IV) was measured according to ASTM method 2857-70. Prior to weighing, the polymer sample was dried at 70 ° C. for 3 hours. Samples were run at 30 ° C. with a 0.5% solution in m-cresol. In order to improve efficiency, accuracy and precision, an AUTOVISC® Automatic Measuring System (Cannon Instrument Company, State College, PA., USA) automated viscosity measurement system was used. A high density infrared fiber optic detection system was used instead of an operator, and an air bath was used instead of the oil or water bath normally used to provide constant temperature. AUTOVISC (R) exceeds the accuracy specifications of ASTM D-445 "Standard Test Method for Kinetic Viscosity of Transient and Opaque Liquids".

Number Average Molecular Weight Number average molecular weight was calculated according to ASTM D5296-97 using poly (ethylene terephthalate) and hexafluoroisopropanol solvent with Mw-44,000 calibration standards.

% Hard Segment The% hard segment was determined as described in US Pat. No. 6,562,457.

Fiber Strength and Elongation Tensile strength at break, T-gram / denier (gpd) and% elongation at break E are INSTRON. Measured with RTM. The tester was equipped with a Series 2712 (002) Pneumatic Action Grip wearing an acrylic contact surface. The test was repeated three times. Report the average of the results.

  The average denier for the fibers used in the strength and elongation measurements is reported as “denier 1”.

The average denier for the fiber used in measuring the unload force, stress relaxation and% permanent set of the fiber is reported as “denier 2”.

  The unloading force was measured with dN / texeffx1000. A single filament with a gauge length of 2 inches (5 cm) was used for each measurement. Separate measurements were made using 0-300% elongation cycles. The sample was cycled 5 times at a constant elongation rate of 100% / min and then held at 300% elongation for 0.5 minutes after the 5th elongation before unloading force (ie stress at a specific elongation) was applied. It was measured. While removing the load from this final elongation, the stress, or unload force, was measured at various elongations. Use the general form "UPx / y" where x is the% elongation of the fiber cycled 5 times and y is the% elongation measured stress, i.e. the unload force. The unloading force is reported here.

Stress relaxation was measured as the percent loss of stress on the fiber over 30 seconds with the sample held at 300% elongation at the end of the fifth load cycle.
S = ((FC) ^* 100) / F
Where
S = Stress relaxation,%
F = stress at full elongation C = stress after 30 seconds

  The% permanent set was measured from the stress / strain curve recorded on the chart paper.

Example 1
This example describes the preparation of a polyetherester elastomer having a polytrimethylene ether ester soft segment and a tetramethylene ester hard segment as described in US Pat. No. 6,562,457. The polymer was designed to have a 72/28 weight ratio of soft segment to hard segment. A polymer was prepared from dimethyl terephthalate, 1,4-butanediol and polytrimethylene ether glycol using a batch method.

An autoclave reactor equipped with a stirrer, vacuum jet and distillation can was charged with 8.81 kg of dimethyl terephthalate, 8.94 kg of 1,4-butanediol, 20.2 kg of polytrimethylene ether glycol with a number average molecular weight of 2019, 22 g of tetra An isopropyl titanate polymerization catalyst and 37.5 g of ETHANOX 330 antioxidant (Albemarle Corporation) were charged. The reactor temperature was gradually raised to 210 ° C. and about 2.6 kg of methanol was recovered from the reactor by distillation. The reaction was further continued at 250 ° C. under reduced pressure for an additional 1.5 hours to increase the molecular weight. The resulting polymer was extruded from the reactor and converted to pellets, which were dried overnight at 80-90 ° C. under reduced pressure before subsequent use. The polymer properties were as follows:
Intrinsic viscosity: 1.403 dL / g
Mn: 31400
Mw: 61200
Tg of soft segment: -67 ° C
Tm of hard segment: 170 ° C
% Hard segment: 28%

  The following fiber spinning examples were conducted with the polymer of Example 1.

Spinning Procedure The polymer of Example 1 was extruded through a sand filter spin pack and a porous spinneret maintained at 273 ° C. (holes with a diameter of 0.3 mm and a capillary depth of 0.56 mm, the number of holes shown below in Table 1). . The filament stream exiting the spinneret was quenched with air at 21 ° C. and converged into a bundle. The transfer (feed) rolls having the surface speeds listed in the table below are yarn bundles one after another at the speeds listed in Table 1 below for the draw roll set, the entangled jet, the descending roll set and the winding. Was sent out. The spinning conditions for the yarn are listed in Table 1. The properties of the yarn obtained are listed in Table 2.

  Comparative Examples 1 and 2 present the properties of two different commercial spandex yarns for comparison with the data of Examples 2-9.

Table 1

Table 2

(Table 2 continued)

  The data in Table 1 was used at commercially viable speeds substantially faster than those reported in US Pat. No. 6,562,457 and US Pat. No. 6,599,625. It clearly shows that polyetherester elastomers could be spun into yarns according to the present invention. Furthermore, the comparative data demonstrates that the yarn obtained in the process of the present invention has general elastester properties.

Claims (16)

(A) about 80 to about 40% by weight of polytrimethylene ether dicarboxylate ester soft segment, trimethylene dicarboxylate ester, tetramethylene dicarboxylate ester, and the like based on the combined weight of hard segment and soft segment Providing a polyetherester thermoplastic elastomer comprising about 20 to about 60% by weight of a hard segment selected from the group consisting of:
(B) melt spinning the elastomer by extruding the elastomer through one or more spinnerets to form at least two filaments;
(C) A method of preparing an elastester multifilament yarn including a step of processing the filament into a multifilament yarn, wherein the melt spinning is performed at a spinning speed higher than about 1200 meters / minute.   The method of claim 1, wherein the dicarboxylate comprises terephthalate.   The method of claim 1, wherein the polytrimethylene ether ester comprises from about 80 to about 40% by weight polytrimethylene ether terephthalate soft segment and from about 20 to about 60% by weight trimethylene terephthalate hard segment.   The method of claim 1, wherein the polytrimethylene ether ester comprises from about 80 to about 40 wt% polytrimethylene ether terephthalate soft segment and from about 20 to about 60 wt% tetramethylene terephthalate hard segment.   The method of claim 1, wherein the multifilament yarn comprises a filament having from about 0.5 to about 20 denier / filament.   6. The method of claim 5, wherein the method further comprises entanglement and winding of the filament.   The multifilament yarn is a spun drawn yarn and the processing step comprises drawing the filament at a draw speed of about 1250 to about 5000 meters / minute as measured with a roller at the end of the drawing step. The method described in 1.   The method according to claim 7, wherein the step of processing the span-drawn multifilament includes drawing, annealing, entanglement and winding of the filament.   The method of claim 1, wherein the multifilament yarn is a partially drawn yarn.   The method of claim 1, further comprising cutting the multifilament yarn into staple fibers.   The polyetherester thermoplastic elastomer comprises at least one additive selected from the group consisting of matting agents, nucleating agents, thermal stabilizers, thickeners, optical brighteners, pigments and antioxidants. The method according to 1.   The method of claim 1, wherein the multifilament yarn is an elastomeric ester yarn having an elongation of about 100 to about 600%.   The method of claim 1, wherein the multifilament yarn is an elastomeric ester yarn having a strength of about 0.5 to about 2.5 grams / denier.   About 80 to about 40 weight percent polytrimethylene ether dicarboxylate ester soft segment and about 20 to about 60 weight percent hard segment selected from the group consisting of trimethylene dicarboxylate ester and tetramethylene dicarboxylate ester A method of preparing a multifilament textured yarn comprising filaments of polytrimethylene ether ester comprising: (a) preparing a package of partially drawn multifilament yarn by the method of claim 9; and (b) Unwinding the yarn from the package; (c) stretching the filament to form a stretched yarn; and (d) forming a textured yarn by false twisting the stretched yarn. (E) winding the yarn onto a package.   A multifilament yarn prepared by the method of claim 1.   A fabric comprising the multifilament yarn according to claim 15.