EP1025294B1 - Procede de fabrication de spandex et spandex obtenu par ce procede - Google Patents

Procede de fabrication de spandex et spandex obtenu par ce procede Download PDF

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EP1025294B1
EP1025294B1 EP98959369A EP98959369A EP1025294B1 EP 1025294 B1 EP1025294 B1 EP 1025294B1 EP 98959369 A EP98959369 A EP 98959369A EP 98959369 A EP98959369 A EP 98959369A EP 1025294 B1 EP1025294 B1 EP 1025294B1
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spandex
pvp
solution
glycol
polyurethane
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EP1025294A1 (fr
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Shingo Ito
Toshikazu Matsuda
Masao Umezawa
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Du Pont Toray Co Ltd
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Du Pont Toray Co Ltd
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    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • 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 is related to a process for making a dry-spun spandex and, more particularly, to the use of poly(N-vinyl-2-pyrrolidone) with elastomeric segmented polyurethanes for the dry-spinning process.
  • spandex Because of its excellent stretch characteristics, spandex is extensively used in garments such as legwear, innerwear, and sportswear. Reliable fiber spinning is economically advantageous during manufacture of the fiber because waste is reduced.
  • Japanese Published Patent Application 48-80150 discloses the use of poly(N-vinyl-2-pyrrolidone) in making wet-spun polyurethane- and polyurethaneurea-based spandex to improve whiteness retention.
  • the process of this invention for preparing spandex comprises the steps of:
  • Figure 1 illustrates a typical spinning cell, feed (godet) rolls, and windup in schematic form.
  • spandex 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.
  • "Coalesced multifilament” means a fiber (or yarn) composed of a plurality of individual spandex filaments that have been adhered together, for example by having been passed through a coalescence jet.
  • the fiber-forming polymers used in the process of the present invention are polyurethanes.
  • Polyurethane solutions can make spandex of marginal quality or can even be unspinnable in a dry-spinning process, especially when multiple filaments are combined to make higher decitex spandex.
  • a sensitive measure of spinnability can be inadequate for use in apparel applications such as hosiery.
  • the dry-spinnability and along-end uniformity of polyurethane-based spandex can be improved by adding poly(N-vinyl-2-pyrrolidone) and copolymers thereof to a dry-spinning solution. Such an effect is not observed with polyurethaneurea-based spandex.
  • the polyurethane polymers of this invention are prepared from a polymeric glycol, a diisocyanate, and a low-molecular weight diol chain extender.
  • the polymers can be based on polyether glycols, polyester glycols, polycarbonate diols, and the like.
  • Polyether glycols are preferred. More preferred are poly(tetra-methyleneether) glycol (hereinafter abbreviated as PO4G) and a modified PO4G which is a copolymer of tetrahydrofuran and 3-methyltetrahydro-furan (poly(tetramethyleneether-co-3-methyltetramethyleneether) glycol), hereinafter abbreviated as 3MePO4G.
  • PO4G When used in the process of the present invention, it generally has a number average molecular weight in the range of about 1000-3000.
  • 3MePO4G used in the present invention generally has a number average molecular weight of at least about 1500 but not more than about 8000, preferably at least about 2500 but not higher than about 6000, and more preferably of about 3000-4000.
  • the 3MePO4G has a 3-methyltetramethyleneether moiety content of about 4-20 mole percent.
  • the diisocyanates used in this invention can be aromatic diisocyanates such as 1,1'-methylenebis(4-isocyanatobenzene) (hereafter abbreviated as MDI).
  • MDI is used in a molar ratio of diisocyanate to homopolyether glycol (the "capping ratio") of about 1.5-4.0; the capping ratio when copolyether glycol is used is about 2.4-4.5, preferably about 3.0-4.0.
  • the low molecular weight diol chain extender is ethylene glycol, 1,3-propanediol, 1,4-butanediol (abbreviated hereinafter as "2G”, "3G", and “4G” respectively), and mixtures thereof.
  • Attaining the desired properties in the spandex can be accomplished by adjusting the composition and ratios of the polymeric glycol, diisocyanate, and chain extender. For example, if the molecular weight of the polymeric glycol is high, the relative amount of diisocyanate (that is, the capping ratio) should be high. Similarly, if the chain extender has a high molecular weight, the relative amount of chain extender should be low.
  • a polyurethane is prepared in the melt, dissolved in a solvent to obtain a polyurethane solution, and then dry spun. This is the "melt polymerization-and-dissolution” method.
  • a polyurethane is synthesized directly in a solvent. As it is formed, the polyurethane dissolves in the solvent to form a solution that is then dry spun. This is the “solution polymerization” method.
  • solution polymerization There are variants to each general method.
  • the polyurethane can be produced by first reacting a polyether glycol with a diisocyanate to form an isocyanate-terminated glycol which is then reacted with a diol in the absence of a solvent to effect chain extension (the "two-step melt” method).
  • a suitable polyether glycol, a suitable diisocyanate, and a suitable diol chain extender can be reacted at substantially the same time in the absence of solvent to synthesize the polyurethane (the "one-step melt” method).
  • the melt-prepared polyurethane used in making fibers of the invention can then be dissolved in the solvent by conventional techniques. Typical methods include mixing and dissolution by stirring, ultrasound, high speed shearing and the like. When necessary, a dissolution adjuvant also may be used.
  • a polyurethane in the form of a powder or small chips facilitates dissolution of the polyurethane.
  • the polyether glycol and the diisocyanate can be mixed and reacted to form an isocyanate-terminated prepolymer.
  • the methods used for this reaction include ordinary stirring, subjecting the solution to ultrasound during stirring, and/or using a homogenizing mixer, a static mixer, a biaxial extruder, a kneader or the like.
  • the isocyanate-terminated ("capped") glycol can then be dissolved in a solvent. It is convenient if the solvent for the capped polyol is the same solvent as will be used for making the polyurethane solution that is to be dry spun. A diol can then be added to effect chain extension.
  • the process of forming the polyurethane directly in a solvent may also be performed in one step, for example by dissolving the polymeric glycol and diol in a solvent and then adding diisocyanate to effect polymerization. This is the "one-step solution polymerization method”.
  • Typical useful amine catalysts include, for example, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethyl-ethylene diamine, N,N,N',N'-tetramethyl-1,3-propane diamine, N,N,N',N'-tetramethylhexane diamine, bis-2-dimethyl amino ethyl ether, N,N,N',N',N'-pentamethyl-diethylene triamine, tetramethylguanidine, triethylene diamine, N,N'-dimethylpiperizine, N-methyl-N'-dimethyl aminoeth
  • the solvent composition should include at least one solvent selected from the group consisting of dimethylacetamide (“DMAc”), dimethylformamide (“DMF”), and dimethylsulfoxide (“DMSO”).
  • DMAc is preferred, both for the processes in which the polyurethane is first polymerized and then dissolved in a solvent, and for the processes in which the polyurethane is polymerized in a solvent.
  • DMAc dimethylacetamide
  • DMF dimethylformamide
  • DMSO dimethylsulfoxide
  • additives for specific purposes optionally can be added to the solution, so long as the additives do not interfere with the effects of the invention.
  • additives include benzotriazole-based stabilizers, ultraviolet light absorbers, other light resistance agents, antioxidants, anti-tack agents, lubricants such as mineral oil and silicone oils, antistatic agents and the like.
  • additives include hindered phenolic stabilizers such as 2,6-di-t-butyl-4-methylphenol as a light stabilizer, an antioxidant such as "Sumilizer” GA-80 (made by Sumitomo Kagaku Kogyo KK), benzotriazoles including a variety of "Tinuvin” stabilizers (sold by Ciba Specialties), phosphorus chemicals such as “Sumilizer” P-16 (also made by Sumitomo), a nitrogen oxide trap such as HN-150 (manufactured by Nippon Hydrazine), a light stabilizer such as "Sumisorb” 300#622 (manufactured by Sumitomo), hindered amine stabilizers including various "Tinuvin” types, inorganic pigments such as titanium oxide, zinc oxide, carbon black and the like, metal salts such as magnesium stearate and barium sulfate, bacteriocides containing silver, zinc, or compounds thereof, deodorants,
  • poly(N-vinyl-2-pyrrolidone) hereinafter "PVP"
  • PVP poly(N-vinyl-2-pyrrolidone)
  • copolymers of vinyl-2-pyrrolidone are added to the polyurethane solution, so that the final spandex has a PVP or PVP copolymer content in the range of about 1-10 weight percent (preferably about 1.5-7 weight percent), based on the weight of the total polymer solids content (spandex).
  • suitable comonomers that can be polymerized with N-vinyl-2-pyrrolidone to make PVP copolymers useful in the process of the invention include vinyl acetate and N-but-1-enyl-2-pyrrolidone.
  • Any suitable method can be used for adding PVP or copolymers thereof to the polyurethane solution.
  • Representative methods include using a static mixer, stirring, and the like. It is advantageous to add the PVP as a solution because doing so makes it easier to add and mix it uniformly into the polyurethane solution.
  • the addition to the polyurethane solution can also be carried out with a simultaneous addition of the aforementioned chemicals such as a light stabilizer, an antioxidant, a pigment, or the like, for example as a slurry.
  • the "K value" of the PVP polymers used in this invention is 20-70 (preferably in 26-34) for best spinnability of polyurethane-based spandex.
  • the molecular weight of PVP is too low, the viscosity of the spinning solution may be excessively reduced, and threadline continuity may be lost during spinning.
  • the molecular weight of the PVP is too high, the spinning solution viscosity can become too high to spin.
  • K value and its relationship to PVP molecular weight see "PVP - A Critical Review of the Kinetics and Toxicology of Polyvinylpyrrolidone (Povidone)", B. V. Robinson, et al., Lewis Publishers, 1990.
  • PVP is preferably synthesized in isopropyl alcohol solvent for improved PVP purity.
  • the spinning solution containing the polyurethane and PVP is dry-spun to form the spandex and then wound up.
  • the polyurethane spinning solution is extruded from a spinneret assembly 10 mounted in or on the dry-spinning cell 12.
  • a co-current stream of hot, inert gas the "aspiration" gas
  • the solvent of the spinning solution is evaporated into the hot, inert gas, thereby converting the several streams of spinning solution into continuous spandex filaments 16 as they proceed down the cell.
  • a countercurrent stream of inert gas may also be introduced at the bottom of the cell through inlet 18.
  • the two streams of inert gas, now containing evaporated solvent are drawn off through an aspiration device 20 near the bottom of the cell.
  • the filament bundle exits through a hole 30 in the bottom of the cell and passes through an optional coalescence jet 22 to a first feed (godet) roll 28.
  • the jet 22 is supplied with a flow of gas through inlet 24.
  • the spandex then passes over optional finish roll 32 for optional application of a lubricant from optional reservoir 33, thence to a second feed (godet) roll 34, and thence to a windup apparatus comprising a traverse guide 36, optional drive roll 38, and cylindrical core or bobbin 40, onto which the spandex is wound.
  • Seven filaments 16 are illustrated in Figure 1, but fewer (including two filaments) or more (including 3, 5, 12, 24, 48, or even more) filaments can be prepared and joined into a chosen number of coalesced multifilaments by passing them through a conventional coalescence jet. Monofilaments can also be produced by the process of the present invention. Geometries of spinning cells and arrangements of rolls other than those shown in Figure 1 can be used.
  • the ratio of the speeds of the second godet roll (feed roll) to that of the windup roll is referred to herein as the "windup stretch ratio" of the spandex.
  • the windup stretch ratio is in the range of about 1.15 to 1.65.
  • the process of the present invention provides an improvement in spinning continuity of polyurethane-based spandex, due to reduced breaks, lower twinning frequency of monofilaments, and less yarn migration (that is, less drift of the fibers into the aspiration gas removal system of the dry-spinning cell and less incorporation into adjacent coalesced multifilaments).
  • the effect is more pronounced in coalesced multifilaments than in monofilaments, though some improvement is seen with monofilaments, too.
  • Coalesced multifilaments usually have higher decitex, so that the effect can be more apparent at higher yarn decitex, that is, above 20 decitex, for example at 50 decitex, 77 decitex, and higher.
  • the improvement can also be more marked when more filament ends are being spun, for example 24 ends versus 12 ends.
  • CDV Coefficient of Denier Variability
  • polyurethaneureas which are a particular sub-group of polyurethanes in which the chain extension is effected by a low-molecular weight diamine such as ethylene diamine (hereinafter "EDA"), does not benefit from the addition of PVP.
  • EDA ethylene diamine
  • the polyurethane/DMAc solution viscosity was determined in accordance with the general method of ASTM D1343-69 with a Model DV-8 Falling Ball Viscometer, (sold by Duratech Corp., Waynesboro, VA), operated at 40°C.
  • the spandex 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 polyurethane fiber was stretched to 50% elongation across the tensiometer.
  • the tensiometer measured the tension as the multifilament was fed through the rolls.
  • the average tension, variance, standard deviation, and coefficient of variance were calculated, and the coefficient of variance was reported as CDV, since the denier is directly proportional to the measured tension.
  • a low CDV indicates high fiber uniformity and is a sensitive measure of spinning quality, since fiber non-uniformities arise during spinning.
  • Stabilizing additives were incorporated into the spandex of the Examples and the Comparison Examples by conventional slurry addition and mixing during dry-spinning so that the fiber contained 2.0 wt% Methacrol( 2462B (a polymer of bis(4-isocyanatocyclohexyl)-methane) and 3-t-butyl-3-aza-1,5-pentanediol, made by DuPont), 1.2 wt% Methacrol( 2390D (a condensation polymer of p-cresol and divinyl benzene, made by DuPont) and a small amount of silicone oil. Spinning speeds were measured at the windup roll.
  • decitex spandex was a monofilament
  • 50 decitex spandex was comprised of three coalesced filaments
  • 44 decitex spandex had four coalesced filaments
  • 77 decitex spandex was comprised of five filaments.
  • PVP utilized K-value of 30 (available from International Specialty Products, Japan, or Kanto Kagaku, Japan or BASF, Germany).
  • glycol refers to the polymeric glycol used
  • Comp indicates a Comparison Example
  • V means Very
  • n.m means not measured
  • Co-PVP indicates that a copolymer comprising N-vinyl-2-pyrrolidone was used
  • C.E. refers to the chain extender used.
  • the CDV of 20 decitex monofilament spandex in the Examples is about 9 to 10 without PVP and 6 to 8 with levels of PVP within this invention.
  • a spinning solution was prepared by adding 61.8g of a DMAc solution of PVP (made by Kanto Kagaku, 40% PVP concentration by weight) and the additive slurry to 2000g of the polyurethane/DMAc solution and stirring the mixture for 2 hours.
  • the spinning solution was dry spun at a speed of 540m/minute with a ratio in rotational speeds between the second godet roll and the windup roll (the "windup stretch ratio") of 1.40 to give 20 decitex spandex containing 2.7wt% PVP.
  • a spinning solution was obtained by adding 19.9g of a DMAc solution (40% concentration by weight) of PVP (Kanto Kagaku) to 1967g of the same polyurethane solution as in Example 1, followed by stirring for 2 hours.
  • 20 decitex spandex containing 0.8wt% PVP was obtained by dry spinning the resulting spinning solution at a speed of 540m/minute and a windup stretch ratio of 1.40.
  • CDV Code Division Multiple Access
  • a spinning solution was obtained by adding 63.0g of a DMAc solution (40% concentration by weight) of PVP ("Rubiskol", made by BASF) to 1983g of a polyurethane solution substantially the same as that of Example 1, followed by stirring for 2 hours. Spandex was dry-spun as in Example 2.
  • EXAMPLE 1 Comp. 1A 2 Comp. 1B GLYCOL PO4G PO4G PO4G POG C.E. 2G 2G 2G 2G PVP, wt% 2.7 0.8 3.0 0 Decitex 20 20 20 20 20 20 20 Spinnability V.Good Good Good V.Good Good Good
  • a 40wt% solution of PVP in DMAc was added to a polyurethane solution as described in Example 1 and stirred for 2 hours.
  • the spinning solution was dry-spun at 540 m/min, using an aspiration gas temperature of 390(C and a windup stretch ratio of 1.32.
  • the resulting 50 decitex coalesced multifilament spandex contained 2.0wt% PVP and had a desirably low CDV of 14.
  • Example 4 was repeated, but no PVP was added to the spinning solution.
  • the CDV was higher at 22.
  • a polyurethane was prepared in DMAc solution as in Example 1; the solution was 39wt% solids.
  • a 40wt% solution of PVP (Kanto Kagaku) in DMAc was added to the polyurethane solution and stirred for 2 hours.
  • the spinning solution was dry-spun to give a 77 decitex coalesced multifilament spandex which had a PVP content of 2.0wt%.
  • the aspiration gas temperature was 420(C, the windup stretch ratio was 1.32, and the spinning speed was 540m/min.
  • a spinning solution was obtained by adding the additive slurry and 62.2g of a DMAc solution (40% PVP concentration by weight) of "Rubiskol" PVP to 2011g of the polyurethane/DMAc solution.
  • the spinning solution was dry spun at a speed of 540m/min and a windup stretch ratio of 1.40.
  • a polyurethane/DMAc spinning solution prepared as in Example 6 into which the additive slurry had been mixed but to which no PVP was added, was dry spun at a windup stretch ratio of 1.40 at a speed of 540m/minute.
  • EXAMPLE 5 Comp. 4 GLYCOL PO4G PO4G C.E. 4G 4G PVP, wt% 2.9 0.0 Decitex 20 20 Spinnability V.Good Good
  • Table III shows that the dry-spinnability of a 1,4-butanediol-chain extended polyurethane was also improved when PVP was added to the polyurethane solution, even when 20 decitex monofilament was being spun.
  • a spinning solution was prepared by adding the stabilizer additive slurry and 55.4g of a DMAc solution (40% PVP concentration by weight) of "Rubiskol" PVP to 1792g of the polyurethane/DMAc solution, followed by stirring for 2 hours.
  • the resultant solution was dry spun at a speed of 540m/minute and a windup stretch ratio of 1.40.
  • Example 6 To the polyurethane/DMAc solution (40% polymer concentration by weight) of Example 6 was added the additive slurry but no PVP, and the resulting spinning solution was dry spun at a ratio in speeds between the second godet roll and the windup roll of 1.40 at a speed of 540m/minute.
  • a polyurethane-based spandex was prepared in a manner substantially the same as that of Example 6 except that the capping ratio was 3.0, the chain extender was ethylene glycol, and the level of PVP in the dry-spun spandex was 3.0 weight percent.
  • Example 7 The polyurethane solution of Example 7 was dry-spun but without adding PVP.
  • EXAMPLE 6 Comp. 5 7 Comp. 6 GLYCOL 3MePO4G 3MePO4G 3MePO4G 3MePO4G C.E. 4G 4G 2G 2G PVP, wt% 2.9 0.0 3.0 0.0 Decitex 20 20 20 20 Spinnability V.Good Good V.Good Good
  • a 40wt% solution of Ganex P-904 (a vinyl pyrrolidone/1-butenyl pyrrolidone 90/10 copolymer, International Specialty Products, Tokyo) in DMAc was added to the same polyurethane solution as in Example 1 and stirred for 2 hours.
  • the spinning solution was dry-spun at 540m/min with a windup stretch ratio of 1.40 to give a monofilament spandex of 20 decitex. Spinnability was very good.
  • the spandex contained 2.6wt% of the PVP copolymer.
  • Table V shows that copolymers of PVP also have a beneficial effect on the dry-spinnability of polyurethanes.
  • PO4G having a molecular weight of 1800 (9,000 g) and MDI (200 g) were mixed together (capping ratio 1.58), heated to 90°C, and stirred for two hours to prepare an isocyanate-terminated prepolymer.
  • the prepolymer was cooled to room temperature.
  • a 500 g portion of the prepolymer was dissolved in 1000 g of DMAc. 7.8 g of ethylene diamine and 1.17 g of diethylamine were dissolved in 80.7 g of DMAc, and the resulting solution was added with rapid mixing to the prepolymer solution.
  • the resulting polyurethaneurea solution contained 33wt% solids.
  • a 33wt% PVP solution in DMAc (98 g) was added to the polyurethaneurea solution.
  • the spinning solution was dry-spun with an aspiration gas temperature of 420°C, a spinning speed of 670 m/min, and a windup stretch ratio of 1.21 to form a four-filament, 44 decitex coalesced spandex which contained 6.0wt% PVP.
  • CDV was 22.
  • Table VI shows that the presence of PVP in the dry-spinning solution of a polyurethaneurea had a deleterious effect even for a coalesced multifilament, which is contrary to what was observed with polyurethanes.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)

Claims (9)

  1. Procédé de préparation de spandex comprenant les étapes de :
    A. préparation d'une solution de polymère d'un polyuréthanne élastomère segmenté, à base de 1,1'-méthylènebis(4-isocyanatobenzène), d'un polyétherglycol choisi parmi le groupe constitué du poly(tétraméthylèneéther)glycol et du poly(tétra-méthylèneéther-co-3-méthyltétraméthylèneéther)glycol et d'un diol choisi parmi le groupe constitué de l'éthylèneglycol, du 1,3-propanediol et du 1,4-butanediol ;
    B. addition à la solution préparée dans l'étape A de 1-10% en poids de la teneur totale en solides de polymère d'un polymère choisi parmi le groupe constitué de la poly(N-vinyl-2-pyrrolidone) et de copolymères de PVP ;
    C. filage à sec de la solution préparée dans l'étape B pour former le spandex ; et
    D. renvidage du spandex.
  2. Procédé selon la revendication 1 dans lequel le spandex est un multifilament fondu.
  3. Procédé selon la revendication 2 dans lequel le polymère de PVP est ajouté de sorte que le spandex ait une teneur en polymère de PVP de 1,5-7%, par rapport au poids du spandex, et que le spandex ait un décitex d'au moins environ 40.
  4. Procédé selon la revendication 3 dans lequel le polymère de PVP a une valeur K de 20-70 et le spandex est renvidé à un rapport d'étirage d'enroulement de 1,15-1,65.
  5. Procédé selon la revendication 3 dans lequel le polyétherglycol est le poly(tétraméthylèneéther-co-3-méthyltétraméthylèneéther)glycol et le diol est choisi parmi le groupe constitué de l'éthylèneglycol et du 1,4-butanediol.
  6. Procédé selon la revendication 5 dans lequel le polyétherglycol a une teneur de la partie 3-méthyltétraméthylèneéther dans l'intervalle de 4-20% en mole et un poids moléculaire moyen en nombre de 2500-6000.
  7. Procédé selon la revendication 3 dans lequel le polyétherglycol est le poly(tétraméthylène-éther)glycol et le diol est choisi parmi le groupe constitué de l'éthylèneglycol et du 1,4-butanediol.
  8. Spandex préparé par le procédé selon la revendication 1.
  9. Spandex préparé par le procédé selon la revendication 6.
EP98959369A 1997-10-21 1998-10-21 Procede de fabrication de spandex et spandex obtenu par ce procede Expired - Lifetime EP1025294B1 (fr)

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JP30787497 1997-10-21
JP30787497 1997-10-21
PCT/US1998/022271 WO1999020818A1 (fr) 1997-10-21 1998-10-21 Procede de fabrication de spandex ® et spandex ® obtenu par ce procede

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DE (1) DE69805318T2 (fr)
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DE102005054653B4 (de) * 2005-11-11 2009-09-10 Uhde Inventa-Fischer Gmbh & Co. Kg Vorrichtung und Verfahren zur Herstellung schmelzgesponnener Filamente

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US3287441A (en) * 1959-04-07 1966-11-22 Du Pont Melt-spinnable composition of a poly (nu-vinyl amide) and a polymer from the class consisting of polyamides, polyureas, and polyurethanes
JPS4880150A (fr) * 1972-01-31 1973-10-26
KR100226239B1 (ko) * 1994-03-04 1999-10-15 요시다 다까시 내구성 폴리우레탄 섬유 및 그의 제조 방법

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WO1999020818A1 (fr) 1999-04-29
DE69805318T2 (de) 2002-12-19
TW454052B (en) 2001-09-11
KR20010031244A (ko) 2001-04-16
BR9815229A (pt) 2000-11-21
BR9815229B1 (pt) 2009-05-05
KR100507822B1 (ko) 2005-08-10
EP1025294A1 (fr) 2000-08-09
DE69805318D1 (de) 2002-06-13

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