EP0914504B1 - Verwachsenes multifiles spandexgarn und verfahren zu seiner herstellung - Google Patents

Verwachsenes multifiles spandexgarn und verfahren zu seiner herstellung Download PDF

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Publication number
EP0914504B1
EP0914504B1 EP97933567A EP97933567A EP0914504B1 EP 0914504 B1 EP0914504 B1 EP 0914504B1 EP 97933567 A EP97933567 A EP 97933567A EP 97933567 A EP97933567 A EP 97933567A EP 0914504 B1 EP0914504 B1 EP 0914504B1
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EP
European Patent Office
Prior art keywords
multifilament
guide
filaments
spandex
fused
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP97933567A
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English (en)
French (fr)
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EP0914504A1 (de
Inventor
Masao Umezawa
Hideki Nakanishi
Toshikazu Matsuda
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Du Pont Toray Co Ltd
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Du Pont Toray Co Ltd
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes

Definitions

  • the present invention relates to a method of preparing a fused spandex. More particularly, it relates to a method for dry-spinning a solution of a high-melting thermoplastic polyurethane, bundling the resulting spandex, and fusing the resulting bundle to form the fused multifilament spandex by a method which does not employ false-twisting.
  • European published Patent Application Number 756026 discloses a method wherein immediately after dry-spinning of segmented polyurethaneureas which are not thermoplastic, the filaments are slightly bonded by passing them through a "thread control element with comb-like shape" immediately after spinning to form a multifilament which can be readily and easily split into single filaments.
  • Japanese published Patent Application Number 53-139847 describes melt-spinning of a low-melting polyurethane from widely spaced spinneret holes and the bonding of the resulting filaments into a fused multifilament spandex by passing them through a guide placed at a selected distance from the face of the spinneret.
  • Spandex is widely used in various applications such as apparel because it has desirable characteristics including high stretch and recovery. Expanding applications have led to new needs such as high uniformity combined with mechanical properties that are available from, for example, thermoplastic polyurethanes and polyurethaneureas. Spandex with desirable properties such as good heat settability, high elastic recovery, and good resistance to environmental conditions can be prepared by dry-spinning a high-melting thermoplastic polyurethane to make a spandex such as that disclosed in International Patent Application Number WO95/23883. Good heat settability is an advantage, for example, when the spandex is to be used in combination with other fibers such as wool which should not be exposed to the temperatures necessary to heat-set such spandex.
  • spandex uniformity tends to be unsatisfactorily low when filaments of such a polyurethane are dry-spun and fused by the conventional false-twist coalescence method, perhaps due to fluctuations in the twisting force.
  • the combination of good uniformity with the desirable properties of a dry-spun thermoplastic polyurethane is still needed.
  • Subject matter of the present invention is a method for preparing a fused multifilament spandex according to claim 1.
  • a solution of high-melting thermoplastic polyurethane is extruded from a spinneret into a heated atmosphere to produce a plurality of filaments which are then brought into a side-by-side relationship with each other and fused into a fused multifilament by passing the filaments over or through a guide by a method which does not employ false-twisting.
  • polyurethane has its usual meaning, that is, a manufactured fiber in which the fiber-forming substance is a long chain synthetic elastomer comprised of at least 85% by weight of a segmented polyurethane.
  • Thermoplastic polyurethane and “thermoplastic polyurethaneurea” mean a polyurethane and a polyurethaneurea, respectively, with a melting point (“T m ”) in the range of 160°C to 250°C, and preferably in the range of 230°C to 250°C, when measured by differential scanning calorimetry (hereinafter "DSC”), and a DSC-measured glass transition temperature (“T g ”) of no more than O°C, preferably no more than -20°C.
  • DSC differential scanning calorimetry
  • the present invention provides a method for preparing a fused multifilament spandex comprising:
  • the method of the present invention can be applied to filaments comprising primarily polyurethanes, polyurethaneureas, or blends of polyurethanes and polyurethaneureas, so long as the polyurethane, polyurethaneurea or mixture thereof has a T m in the range of about 160-250°C, and most preferably in the range of about 230°C to 250°C, and has a T g of no more than about O°C, preferably no more than about -20°C.
  • T m in the range of about 160-250°C
  • T g of no more than about O°C
  • resulting spandex is best prepared by dry-spinning from solution.
  • polyurethanes with melting points below 160°C or above 250°C should be avoided. If the melting point is too low, the heat resistance is insufficient. If the melting point is too high, the heat settability and fusability by the method of the present invention are insufficient.
  • Spandex can be prepared by reacting a polymeric glycol with a diisocyanate to form a "capped glycol", dissolving the capped glycol in a suitable solvent,.'reacting the dissolved capped glycol with a difunctional chain extender to form the polyurethane or polyurethaneurea in solution, and dry-spinning the solution through a heated spinning column.
  • Suitable solvents include dimethylacetamide (DMAc), dimethyl-formamide, N-methylpyrrolidone, and the like. This "prepolymer method" is preferred when the chain extender is a diamine. Alternatively, when the chain extender is a diol, melt polymerization can also be used.
  • Reaction of all ingredients can also be carried out in solution for diamine- and diol-extended polymers.
  • chain extender is a diol
  • such polymers are polyurethanes
  • chain extender is a diamine
  • polymers are polyurethaneureas.
  • the ingredients can be added sequentially or all at once (the "one shot method").
  • the polymer is dissolved in a suitable solvent by any suitable method prior to dry-spinning.
  • the solution can also be prepared from one type of polyurethane or two or more types of polyurethane.
  • the polymeric glycol can be a polyether diol or a polyester diol.
  • Suitable polyether diols include those derived from butanediol, 3-methyl-1,5-pentanediol, tetrahydrofuran, 3-methyltetrahydrofuran, and copolymers thereof.
  • Preferred polyether diols include polytetramethyleneether glycol (PTMEG) and PTMEG having copolymerized therein minor amounts of 3-methyltetrahydrofuran.
  • Glycol-terminated polyesters which can be used in conjunction with the present invention include the reaction products of ethylene glycol, butanediol, and 2,2-dimethyl-1,3-propane diol with diacids such as adipic acid, succinic acid, and dodecanedioic acid. Copolymers can also be used.
  • Any organic diisocyanate can be used, for example bis(p-isocyanatophenyl)methane (“MDI”), tolylene diisocyanate, bis(4-isocyanatocyclohexyl)methane (“HMDI”), hexamethylene diisocyanate, and 3,3,5-trimethyl-5-methylene-cyclohexyl diisocyanate.
  • MDI bis(p-isocyanatophenyl)methane
  • HMDI bis(4-isocyanatocyclohexyl)methane
  • hexamethylene diisocyanate bis(4-isocyanatocyclohexyl)methane
  • 3,3,5-trimethyl-5-methylene-cyclohexyl diisocyanate 3,3,5-trimethyl-5-methylene-cyclohexyl diisocyanate.
  • Diol chain extenders which can be used include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,2-propanediol, 1,4-cyclohexanediol, 1,4-cyclohexane-dimethanol, 1,4-bis(p-hydroxyethoxy)-benzene, bis( ⁇ -hydroxyethyl)tere-phthalate, and p-xylenediol. Ethylene glycol and 1,3-propanediol are preferred.
  • Examples of useful diamine chain extenders include ethylenediamine, 2-methyl-1,5-pentanediamine, 1,3-diamino-cyclohexane, 1,2-propanediamine, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane.
  • Ethylenediamine is preferred.
  • a small amount of a monofunctional chain terminator such as diethylamine can be added with the chain extender to control molecular weight.
  • the diisocyanate and chain extender should be chosen together in order to maintain the T m and T g in the selected range.
  • a diol chain extender is preferred when an aromatic diisocyanate such as MDI is used.
  • An aliphatic diisocyanate such as HMDI is preferred when the chain extender is a diamine. More preferred combinations are MDI with ethylene glycol and HMDI with ethylenediamine.
  • Mixtures of diol and diamine chain extenders can be used, and polymer blends of polyurethanes and polyurethanureas are also acceptable, provided the T m and T g are in the specified ranges.
  • Stabilizers to provide resistance to light and oxidation include 2,6-di- t -butyl-4-methylphenol (butylated hydroxytoluene or BHT), hindered phenols such as Sumilizer GA-80 (made by Sumitomo Kagaku, Osaka, Japan), benzotriazole and derivatives thereof, phosphorus agents such as Sumilizer P-16 (also made by Sumitomo Kagaku), hindered amine light stabilizers, inorganic pigments such as titanium dioxide and carbon black, metal soaps such as magnesium stearate, bactericides such as silver, zinc, and compounds thereof, deodorizers, lubricants such as various types of silicone and mineral oil, mixtures of huntite and hydromagnesite, barium sulfate, cerium oxide, and various antistatic agents including phosphoric acids
  • a nitrogen oxide resisting agent such as HM-150 made by Japan Hydrazine (Tokyo, Japan)
  • thermal oxidation stabilizers such as Sumilizer GA-80 made by Sumitomo Kagaku
  • photostabilizers such as Sumisorb 300#622, also made by Sumitomo Kagaku.
  • the times and methods of adding these additives can vary.
  • they can be mixed into the polyurethane solution by a conventional method such as with a static mixer.
  • the polymer solution produced in this way is extruded from a spinneret into a heated atmosphere.
  • the heated atmosphere is usually composed primarily of an inert gas such as nitrogen. However, the atmosphere can also contain water vapor and/or steam, as well as other gases. A vacuum can also be applied to the heated atmosphere.
  • the arrangement of holes in the spinneret can vary.
  • the spinneret holes are arranged in groups comprising two, three, four or more holes, and therefore each group can produce a plurality of individual filaments.
  • the distance between the holes within each such group is preferably smaller than the distance between the nearest members of adjacent groups of holes.
  • the extruded solution is made into filaments by drying with heat in a spinning column.
  • These filaments can be paralleled (bundled) by passing them through a first, comb-shaped guide which collects the filaments from each group of spinneret holes so that the filaments are later fused (coalesced) only with other filaments from their own group of spinneret holes.
  • the bundled filaments can then be fused into a coalesced multifilament by passing them over a second guide.
  • the comb guide can be located near the bottom of the spinning column, and the second guide, just outside the bottom of the spinning column, where false-twist jets would normally be in conventional dry-spinning of non-thermoplastic polyurethanes.
  • lubricating agents such as silicone oil not be applied to the as-spun filament before it is thus bundled and coalesced. Contrary to the method ordinarily used in making coalesced multifilaments by dry-spinning, false twisting is not used in the present invention. It was highly unexpected that passing dry-spun filaments over a guide without false-twisting would result in a coalesced multifilament and that this process would give higher quality spandex than using a false-twist coalescence jet.
  • fiber guides that can be used in the method of the present invention to fuse the as-spun filaments.
  • examples include slit guides with V-shaped or U-shaped bottoms, rolls with V- or U-shaped grooves cut into them, closed-ring guides, and pigtail guides, which have the form of a short open-ended helix.
  • Such guides can be ceramic (for example alumina-based) and can be used individually or in combination in the method of the present invention. It is not necessary to heat the guides in the present method.
  • the multifilament After coalescence, the multifilament is wound up on a bobbin or tubecore to form a wound package.
  • the spandex of the present invention can be used alone or with various other types of fibers by knitting, weaving, or stitching it.
  • it can be used appropriately in underwear, stockings, pantyhose, circular knits, tricot knits, bathing suits, ski pants, socks, work clothes, fireproof clothing, western style clothes, men's suits and women's clothes when combined with wool, golf pants, wet suits, brassieres, girdles, gloves, socks, and other various types of control garments, in sanitary products such as disposable diapers, waterproof materials, safety clothing and laboratory wear, hairnets, for wrapping fruits and vegetables, foods, horticulture, electrical insulating materials, cloth wipes, copy cleaners, and gaskets.
  • DSC measurements were made as follows. Polyurethane in DMAc solvent was applied as a coating either to glass or to polyester film backing that was inert to the polyurethane solution. The solvent in the coated film was removed by drying in 15-150°C dry gas, and a small portion of the film was peeled from the backing and prepared for DSC measurement. Only films with a residual solvent content of no more than 2% were used. The DSC measurement was taken on the second heating of the film sample.
  • Coefficient of Denier Variance was used as a measure of the uniformity of the coalesced multifilament.
  • the multifilament was removed from a package using a rolling take-off and fed across a tensiometer comprising a piezoelectric ceramic pin.
  • the take-up roll's circumference was 50% greater than the feed roll's circumference, and the feed and take-up rolls rotated at the same rpm, so that the multifilament was stretched to 50% elongation across the tensiometer.
  • the tensiometer measured the tension as the multifilament was fed through the rolls.
  • Examples 1, 2, 3 and 4 illustrate the method of the present invention and the high quality of the fused spandex so produced.
  • Comparison Example 1 illustrates the poor results obtained when as-spun thermoplastic polyurethane is fused by means of a conventional false-twist jet.
  • Comparison Example 2 shows that polymers having too high a melting point cannot be fused by the method of the present invention.
  • Comparison Example 3 illustrates the use of polymers having a very high melting point (outside the range of the present invention) in making fused multifilaments using conventional coalescence jets.
  • the number average molecular weight of the polyurethane thus obtained was approximately 80,000 as measured by gel permeation chromatography (GPC).
  • the DSC melting point of a film cast from the polyurethane solution was approximately 240°C, and the Tg was -70°C.
  • a spinning solution was produced next by adding 0.8% silicone oil, 0.65% HN-150, 0.33% Sumilizer GA-80, and 0.12% Sumisorb 300#622 as additives.
  • the spinning solution was made into filaments by spinning it into a 380°C nitrogen gas heated atmosphere using a spinneret with two adjacent holes 0.25 mm in diameter.
  • the two as-spun filaments were cohered in a ceramic slit guide with a U-shaped bottom which was provided in front of a godet roll, then moved past the godet roll, oil applied, and the resulting fused multifilament was wound up at 650 m/min.
  • the multifilament thus obtained was 22 denier.
  • the shape of the multifilament was an eyeglass shape of two joined circles.
  • the CDV an indicator of the uniformity of the multifilament, was very good at 11.
  • This multifilament had a strength of 35 g and elongation of 430%. In other words, very high strength spandex was obtained.
  • Example 1 Spinning and processing were conducted by varying only the following parts of Example 1. Specifically, the two strands of the as-spun filament from the spinneret were passed through an air twisting jet in front of the godet roller to cohere them.
  • the coalescence jet was substantially like that described in U.S. Patent No. 3,353,344.
  • the fused multifilament obtained was 22 denier.
  • the shape of the multifilament was the same as in Example 1, having two joined circles.
  • the CDV which is an indicator of the uniformity of the multifilament, was high at 22. The uniformity of the multifilament was therefore low.
  • This multifilament had a strength of 36 g and elongation of 450%. When this yam was covered and made into underwear in the same way as in Example 1, the large amount of knitting mutilation made it impossible to obtain a product.
  • Example 1 The polyurethane solution of Example 1 was made into as-spun filament by spinning it into a 420°C nitrogen gas heated atmosphere using a spinneret that had three adjacent holes 0.25 mm in diameter.
  • the three as-spun filaments were cohered by passage through a U-shaped slit guide provided in front of a godet roller, moved past the godet roller, oil applied, and the resulting fused multifilament was then wound up at 650 m/min.
  • the multifilament obtained was 45 denier.
  • the shape of the multifilament was a deformed triangle in which three circles were joined.
  • the CDV of this multifilament was good at 12.
  • Core spun yam was produced using the above multifilament in combination with wool. Circular knits were then made by using spun yam of this core spun yam and wool. When dyed and heat set at 110°C, the target fabric width was attained and the knit had a good surface.
  • the DSC melting point was approximately 280°C when measured using a film made from the solution.
  • the Tg was -70°C.
  • This solution was spun and processed in the same way as in Example 1.
  • the spandex was composed of two independent round-cross-sectioned fibers.
  • the coalesced multifilament of the present invention was not obtained.
  • the nitrogen gas temperature in the spinning column was raised to add heat to the filaments. Nonetheless, good multifilament of the same cross section as in Example 1 could still not be produced.
  • the melting point was approximately 240°C when measured by DSC using a film formed from the polymer solution.
  • the Tg was -70°C.
  • the spinning solution was made into as-spun filaments by spinning it into a 360°C nitrogen gas heated atmosphere using a spinneret that had two adjacent holes 0.25 mm in diameter.
  • the two as-spun filaments were passed through a U-shaped slit guide provided in front of a godet roller, moved past the godet roller, oil applied, and the resulting fused multifilament was then wound up at 580 m/min.
  • the multifilament so obtained was 20 denier.
  • the shape of the multifilament was eyeglass shaped in the same way as in Example 1, having two joined circles.
  • the CDV was good at 12.
  • This multifilament had a strength of 26 g and an elongation of 440%. In other words, high elongation spandex was obtained.
  • Cohered multifilament was obtained when the solution of Comparison Example 2 was spun and processed in the same way as in Comparison Example 1.
  • the fineness was 20 denier.
  • the shape of this multifilament was the same as in Example 1.
  • the CDV was good at 12.
  • This multifilament had a strength of 20 g and elongation of 510%. In other words, very high elongation polyurethane fibers were obtained.
  • knitting mutilation developed in one area although the cause was uncertain, being due either to low heat settability or the fabric being narrower than the target width. The garments were therefore difficult to wear and gave an overly strong sense of compression when worn.
  • the polyurethane fibers also broke in 4 days in an actual wear test.
  • the number average molecular weight of the polyurethane was approximately 90,000 as measured by GPC.
  • the DSC melting point was approximately 230°C when measured on a film formed from said polymer solution.
  • the Tg was -70°C.
  • Spinning solution was produced by adding 0.8% silicone oil, 0.65% HN-150, 0.33% Sumilizer GA-80, and 0.12% Sumisorb 300#622 to the solution.
  • the spinning solution was spun into filaments by extruding it into a 380°C nitrogen gas heated atmosphere using a spinneret that had two adjacent holes 0.25 mm in diameter.
  • the two as-spun filaments next were cohered by passage through a U-shaped slit guide provided in front of a godet roller, moved past the godet roller, oil applied, and the fused multifilament was then wound up at 670 m/min.
  • the multifilament so obtained was 21 denier.
  • the multifilament was eyeglass-shaped with two joined circles.
  • the CDV was very good at 11.
  • This multifilament had a strength of 35 g and elongation of 430%. In other words, very high strength spandex was obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (6)

  1. Verfahren zum Herstellen eines Spandex aus Schmelz-Mulitfilament, wobei die Verbesserung umfaßt:
    Trockenspinnen eines thermoplastischen Polyurethans mit einem Schmelzpunkt im Bereich von etwa 160°C bis 250°C und einer Glasübergangstemperatur, die nicht höher ist als etwa 0°C, um Filamente wie gesponnen zu bilden;
    Bündeln einer Vielzahl der wie gesponnenen Filamente in einer ersten Führung;
    Leiten der gebündelten Filamente durch eine zweite Führung, um ein Schmelz-Multifilament zu bilden, wobei weder die erste Führung noch die zweite Führung Vordrehungen in den Filamenten verursachen; und
    Aufwickeln des Schmelz-Multifilaments.
  2. Verfahren nach Anspruch 1, wobei das thermoplastische Polyurethan einen Schmelzpunkt im Bereich von etwa 230°C bis 250°C aufweist.
  3. Verfahren nach Anspruch 1, wobei die erste Führung eine Kammführung ist und die zweite Führung eine Sauschwanzführung, eine geschlossene Ringführung oder eine Schlitzführung ist.
  4. Verfahren nach Anspruch 1, wobei das Polyurethan Polyurethanharnstoff ist.
  5. Spandex aus Schmelz-Multifilament, der keine Vordrehungen aufweist, hergestellt nach dem Verfahren von Anspruch 1.
  6. Spandex aus Schmelz-Multifilament, der keine Vordrehungen aufweist, hergestellt nach dem Verfahren von Anspruch 4.
EP97933567A 1996-07-24 1997-07-24 Verwachsenes multifiles spandexgarn und verfahren zu seiner herstellung Expired - Lifetime EP0914504B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP8214218A JPH1046432A (ja) 1996-07-24 1996-07-24 ポリウレタン糸の乾式紡糸法
JP21421896 1996-07-24
JP214218/96 1996-07-24
PCT/US1997/012810 WO1998028471A1 (en) 1996-07-24 1997-07-24 Coalesced multifilament spandex and method for its preparation

Publications (2)

Publication Number Publication Date
EP0914504A1 EP0914504A1 (de) 1999-05-12
EP0914504B1 true EP0914504B1 (de) 2002-01-23

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EP (1) EP0914504B1 (de)
JP (1) JPH1046432A (de)
DE (1) DE69710072T2 (de)
WO (1) WO1998028471A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007533109A (ja) * 2004-04-15 2007-11-15 テクストロニクス， インク． 電気的伝導性エラストマ、それを製造する方法及びそれを含む物品
EP2243498B1 (de) * 2008-02-15 2015-12-02 Toray Opelontex Co., Ltd. Desodorierendes material
TW201331434A (zh) * 2011-12-16 2013-08-01 Sumitomo Chemical Co 纖維及其製造方法
JP2013047409A (ja) * 2012-10-31 2013-03-07 Asahi Kasei Fibers Corp 伸縮性布帛及びその製造方法
EP3122795B1 (de) * 2014-03-25 2022-06-15 Basf Se Tpu pneumatikschlauch
JP2015158038A (ja) * 2015-04-30 2015-09-03 旭化成せんい株式会社 伸縮性布帛及びその製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL280787A (de) * 1961-07-11
US3558757A (en) * 1964-07-02 1971-01-26 Celanese Corp False twisting
US3342027A (en) * 1965-05-04 1967-09-19 Du Pont Coalesced multifilament yarn
US3777470A (en) * 1968-11-19 1973-12-11 Asahi Chemical Ind Method of forming a yarn package
JPS53139847A (en) * 1977-05-13 1978-12-06 Unitika Ltd Polyurethane elastic yarn and method of manufacture thereof
BR8505705A (pt) * 1984-11-15 1986-08-12 Du Pont Fieira
JP2724214B2 (ja) * 1989-07-25 1998-03-09 旭化成工業株式会社 分繊用弾性糸及びその製造方法

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JPH1046432A (ja) 1998-02-17
DE69710072T2 (de) 2002-08-29
DE69710072D1 (de) 2002-03-14
WO1998028471A1 (en) 1998-07-02
EP0914504A1 (de) 1999-05-12

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