WO2021003236A1 - Bicomponent thermoplastic polyurethane fibers and fabrics made therfrom - Google Patents

Bicomponent thermoplastic polyurethane fibers and fabrics made therfrom Download PDF

Info

Publication number
WO2021003236A1
WO2021003236A1 PCT/US2020/040447 US2020040447W WO2021003236A1 WO 2021003236 A1 WO2021003236 A1 WO 2021003236A1 US 2020040447 W US2020040447 W US 2020040447W WO 2021003236 A1 WO2021003236 A1 WO 2021003236A1
Authority
WO
WIPO (PCT)
Prior art keywords
fabric
thermoplastic polyurethane
bicomponent fiber
astm
core
Prior art date
Application number
PCT/US2020/040447
Other languages
French (fr)
Inventor
Lalith B. SURAGANI VENU
Jr. Joseph J. Vontorcik
Original Assignee
Lubrizol Advanced Materials, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lubrizol Advanced Materials, Inc. filed Critical Lubrizol Advanced Materials, Inc.
Priority to CN202080052026.4A priority Critical patent/CN114127345B/en
Priority to JP2021578016A priority patent/JP2022538459A/en
Priority to US17/623,955 priority patent/US20220411970A1/en
Priority to EP20743924.1A priority patent/EP3994299A1/en
Priority to KR1020227001797A priority patent/KR20220027161A/en
Publication of WO2021003236A1 publication Critical patent/WO2021003236A1/en

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/28Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30Conjugate filaments; Spinnerette packs therefor
    • D01D5/34Core-skin structure; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/292Conjugate, i.e. bi- or multicomponent, fibres or filaments
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/56Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads elastic
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04BKNITTING
    • D04B1/00Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/18Other fabrics or articles characterised primarily by the use of particular thread materials elastic threads
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326Condensation or reaction polymers
    • D04H1/4358Polyurethanes
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825Composite fibres
    • D04H1/43828Composite fibres sheath-core
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005Synthetic yarns or filaments
    • D04H3/009Condensation or reaction polymers
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/10Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes

Definitions

  • the present technology relates to bicomponent fibers and fabrics made therefrom, in particular, core-sheath fibers, made from two different thermoplastic polyurethanes to provide a fiber having unique properties.
  • the present invention relates to a bicomponent fiber, wherein the bicomponent fiber has a core and sheath structure, wherein the bicomponent fiber comprises (a) a core comprising a first polyester thermoplastic polyurethane which has a melting enthalpy of at least 50 J/g measured according to ASTM D3418 and (b) a sheath comprising a second pol yester thermoplastic polyurethane which has a melting enthalpy of 5 J/g or less measured according to ASTM D3418.
  • the present invention also relates to fabrics made from the bicomponent fibers of the present invention.
  • bicomponent fiber refers to a conjugated product of at least two melt-spinnable components, wherein the conjugated product has at least two different longitudinally coextensive polymeric segments.
  • the bicomponent fiber of the present invention comprises two different polymer materials intimately adhered to each other along the length of the fiber, so that the fiber cross-section is for example, a core-sheath arrangement.
  • the bicomponent fiber of the present invention is made from two different polyester thermoplastic polyurethanes.
  • a thermoplastic polyurethane is generally prepared by reacting a polyisocyanate with a polyol intermediate, and optionally a chain extender all of which are well known to those skilled in the art.
  • the bicomponent fiber of the present invention uses two different thermoplastic polyurethane materials, each based on a different polyester polyol intermediate.
  • Hydroxyl ter minated polyester intermediates are generally a linear polyesters having a number average molecular weight (Mn) of from about 500 to about 10,000, desirably from about 700 to about 5,000, and preferably from about 700 to about 4,000, an acid number generally less than 1.3 and preferably less than 0.8.
  • Mn number average molecular weight
  • the molecular weight is determined by assay of the terminal functional groups and is related to the number average molecular weight.
  • polyester pol yols are produced by (1) an esterification reaction of one or more glycols with one or more di carboxylic acids or anhydrides or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a preponderance of terminal hydroxyl groups. Suitable polyester intermediates also include various lactones such as polycaprolactone typically made from e-caprolactone and a bifunctional initiator such as di ethylene glycol.
  • the dicarboxylic acids of the desired polyester can be aliphatic, cycloal iphatic, aromatic, or combinations thereof.
  • Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cy clohexane dicarboxylic, and the like.
  • Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used.
  • the glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of from 2 to 12 carbon atoms, and include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 2, 2-dimethyl-l, 3 -propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like.
  • the fiber of the present invention includes a first thermoplastic polyurethane based on the butanediol succinate and a second thermoplastic polyurethane based on butanediol adipate.
  • Thermoplastic polyurethanes used in the present invention are made using a polyisocyanate component.
  • the polyisocyanate component includes one or more diisocyanates.
  • Useful polyisocyanates may be selected from aromatic polyisocyanates or aliphatic polyisocyanates or combinations thereof.
  • polyisocyanates examples include, but are not limited to aromatic diisocyanates such as 4,4 ' -methylenebis(phenyl isocya nate) (MDI), w-xylene diisocyanate (XDI), phenylene-1, 4-diisocyanate, 3,3’-dimethyl-4,4’- biphenylene diisocyanate (TODI), 1,5 -naphthalene diisocyanate (NDI), and toluene diisocya nate (TDI), as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,6- hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane- 1, 10-diiso cyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohex
  • the polyisocyanate component comprises or consists of one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is es sentially free of, or even completely free of, aliphatic diisocyanates.
  • thermoplastic polyurethane compositions described herein are optionally made using a chain extender component.
  • Chain extenders include may include diols, diamines, and combination thereof.
  • Suitable chain extenders include relatively small polyhydroxy compounds, for ex ample lower aliphatic or short chain glycols having from 2 to 20, or 2 to 12, or 2 to 10 carbon atoms.
  • Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, di propylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pen- tanediol, neopentylglycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyeth- oxy) phenyljpropane (HEPP), hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3- methyl-l,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine,
  • any conventional catalyst can be utilized to react the diisocyanate with the hydroxyl terminated intermediate or the chain extender and the same is well known to the art and to the literature.
  • suitable catalysts include the various alkyl ethers or alkyl thiol ethers of bismuth or tin wherein the alkyl portion has from 1 to about 20 carbon atoms with specific examples including bismuth octoate, bismuth laurate, and the like.
  • Pre ferred catalysts include the various tin catalysts such as stannous octoate, dibutyltin dioc-leader, dibutyltin dilaurate, and the like. The amount of such catalyst is generally small such as from about 20 to about 200 parts per million based upon the total weight of the polyure thane forming monomers.
  • thermoplastic polyurethanes of this invention can be made by any of the con ventional polymerization methods well known in the art and literature.
  • Thermoplastic polyurethanes of the present invention are preferably made via a "one shot” process wherein all the components are added together simultaneously or substantially simultaneously to a heated extruder and reacted to form the polyurethane.
  • the equivalent ratio of the diisocyanate to the total equivalents of the hydroxyl terminated inter mediate and the diol chain extender is generally from about 0.95 to about 1.10, desirably from about 0.97 to about 1.03, and preferably from about 0.97 to about 1.00.
  • the molecular weight (Mw) of thermoplastic polyurethanes useful in the present invention may be from about 50,000 Daltons to about 300,000 Daltons, for example, 50,000 Daltons to about 100,000 Daltons as measured by GPC relative to polystyrene standards.
  • the thermoplastic polyurethane used for the sheath in the bicomponent fiber of the present invention has a molecular weight of about 50,000 Daltons to 75,000 Daltons.
  • the thermoplastic polyurethane used for the core in the bicomponent fiber of the present invention has a molecular weight of about 80,000 Daltons to about 100,000 Daltons.
  • thermoplastic polyurethanes can also be prepared utilizing a pre-polymer process.
  • the hydroxyl terminated intermediate is reacted with generally an equivalent excess of one or more polyisocyanates to form a pre-polymer solution having free or unreacted polyisocyanate therein.
  • a selective type of chain extender as noted above is added in an equivalent amount generally equal to the isocyanate end groups as well as to any free or unreacted diisocyanate compounds.
  • the overall equivalent ratio of the total diisocyanate to the total equivalent of the hydroxyl terminated intermediate and the chain extender is thus from about 0.95 to about 1.10, desirably from about 0.98 to about 1.05 and preferably from about 0.99 to about 1.03.
  • the pre-polymer route can be carried out in any conventional device with an extruder being preferred.
  • the hydroxyl termi nated intermediate is reacted with an equivalent excess of a diisocyanate in a first portion of the extruder to form a pre-polymer solution and subsequently the chain extender is added at a downstream portion and reacted with the pre-polymer solution.
  • Any conventional extruder can be utilized, with extruders equipped with barrier screws having a length to diameter ratio of at least 20 and preferably at least 25.
  • Useful additives can be utilized in suitable amounts and include opacifying pigments, colorants, mineral fillers, stabilizers, lubricants, UV absorbers, processing aids, and other additives as desired.
  • Useful opacifying pigments include titanium dioxide, zinc oxide, and titanate yellow
  • useful tinting pigments include carbon black, yellow oxides, brown oxides, raw and burnt sienna or umber, chromium oxide green, cadmium pigments, chromium pigments, and other mixed metal oxide and organic pigments.
  • Useful fillers in clude diatomaceous earth (superfloss) clay, silica, talc, mica, wollastonite, barium sulfate, and calcium carbonate.
  • useful stabilizers such as antioxidants can be used and include phenolic antioxidants, while useful photostabilizers include organic phosphates, and organotin thiolates (mercaptides).
  • useful lubricants include metal stearates, paraffin oils and amide waxes.
  • Useful UV absorbers include 2-(2'-hydroxyphenol) benzotriazoles and 2-hy- droxybenzophenones.
  • Plasticizer additives can also be utilized advantageously to reduce hardness with out affecting properties.
  • Bicomponent continuous filaments of the present invention can be made using a melt-spinning process.
  • Figure 1 illustrates the typical bicomponent melt spinning technique with a pair of extruders.
  • the steps for making the bicomponent fibers include vacuum batch drying at 80°C for 12 hours, feeding of dried thermoplastic polyurethane polymers into ex truder from a hopper, melting the first and second thermoplastic polyurethane compositions in respective extruders with 1.24 inch single screw and an L/D of 24, and extruding the melts using two feeding systems/conduits by a melt pump and then to a spinneret or die.
  • the back pressure at the extruder outlet was kept constant with a loop control.
  • the extruder had four heating zones that were maintained between 180°C - 220°C.
  • the basic system consists of two feeding systems, two polymers to the spin packs and a distribution system to meter both polymers to the die.
  • spinneret for producing bicomponent or multicomponent filaments is known in the industry. Such a pro cess is described in US Patent No. 5, 162,074, which is incorporated herein by reference.
  • spinneret includes a casing containing spin packs, plurality of plates to create a pattern for polymer to flow.
  • the bicomponent continuous filament spinnerets may also be configured for extrudate to have desired cross-sections such as symmetrical (concentric) core/sheath, asymmetrical core/sheath, side-by-side, crescent shaped and the like. Addition ally, multiple extruders can be added to increase the number of components. [0020] Once the fiber exits the spinneret, it is cooled before winding onto bobbins. The fiber is passed over a set of godets, finish oil is applied, and the fiber proceeds to another set of godets.
  • the thermoplastic polyu rethane described above may be crosslinked with a crosslinking agent.
  • Crosslinking agents are generally a pre-polymer of a hydroxyl terminated intermediate that is a polyether, poly ester, polycarbonate, polycaprolactone, or mixture thereof reacted with a polyisocyanate.
  • Crosslinking agents also referred to as pre-polymers in some cases, often will have an iso cyanate functionality of greater than about 1.0, preferably from about 1.0 to about 3.0, and more preferably from about 1.8 to about 2.2.
  • bicomponent fiber is formed without the use of crosslinking agents.
  • both the core thermoplastic polyurethane and the sheath thermoplastic polyurethane are free of crosslinking.
  • the bicomponent fibers of this invention can be made in a variety of denier. Denier is a term in the art designating the fiber size. Denier is the weight in grams of 9000 meters of fiber length.
  • the bicomponent fibers of this invention are typically made in sizes ranging from, 20 to 2500 denier, for example 20 to 600 denier, further for example 40 to 400 denier.
  • anti-tack additives such as finish oils, an example of which are silicone oils, are usually added to the surface of the fibers after or during cooling and just prior to being wound into bobbins.
  • a bicomponent fiber in accordance with the present invention has a core and sheath structure, wherein the bicomponent fiber has a core comprising a first polyester ther moplastic polyurethane, wherein the first polyester thermoplastic polyurethane has a melting enthalpy of at least about 50 J/g, for example, about 60 J/g, measured according to ASTM D3418 (DSC, second heat cycle) and a sheath comprising a second polyester thermoplastic polyurethane, wherein the second polyester thermoplastic polyurethane has a melting en thalpy of about 5 J/g or less measured according to ASTM D3418 (DSC, second heat cycle).
  • the first polyester thermoplastic polyurethane has a contact clarity of 4% or less as measured according to ASTM D1003.
  • the second polyester thermoplastic polyurethane has a contact clarity of at least 12% measured according to ASTM D1003.
  • the bicomponent fiber of the present invention contains a core thermoplastic pol yurethane and a sheath thermoplastic polyurethane, where the core and the sheath thermo plastic polyurethane materials are different from each other.
  • the core thermoplastic polyurethane comprises the reaction product of butanediol succinate and an aromatic diisocyanate while the sheath thermoplastic polyurethane comprises the reaction product of butanediol adipate, an aromatic diisocyanate, and at least one chain extender glycol.
  • the bicomponent fiber comprises about 10% to about 35% by weight of the core thermoplastic polyurethane composition and about 65% to about 90% by weight of the second thermoplastic polyurethane.
  • the final bicomponent fiber has low shrinkage and good clarity.
  • the present inven tion provides these properties surprisingly by combining two different thermoplastic polyu rethane materials having different shrinkage and clarity properties.
  • the core comprises a thermoplastic polyurethane composition having a melting enthalpy of at least 50J/g measured according to ASTM D3418 and a contact clarity of about 4% or less as measured according to ASTM D1003 and the sheath comprises a thermoplastic polyurethane composition having a melting enthalpy of about 5 I/g or less measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of at least 12% measured according to ASTM D1003.
  • the core thermoplastic polyurethane has a shrinkage of less than about 10% after 90 seconds exposure at 70 °C, while the sheath thermoplastic polyurethane has a shrinkage of about 40% to about 60% after 90 seconds exposure at 70 °C.
  • the present invention also includes a fabric comprising the bicomponent fiber of the present invention.
  • the fabric comprises a bicomponent fiber, wherein the bicomponent fiber has a core and sheath structure, wherein the core comprises a thermo plastic polyurethane composition having a melting enthalpy of at least about 50 J/g, for ex ample about 60 J/g, measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of 4% or less as measured according to ASTM D1003 and the sheath com prises a thermoplastic polyurethane composition having a melting enthalpy of about 5 J/g or less measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of at least about 12% measured according to ASTM D1003.
  • the core comprises a thermo plastic polyurethane composition having a melting enthalpy of at least about 50 J/g, for ex ample about 60 J/g, measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of 4% or less as measured according to ASTM D1003
  • the core thermoplastic polyurethane composition has a shrinkage of less than about 10% after 90 seconds exposure at 70 °C and the sheath thermoplastic polyurethane composition has a shrinkage of about 40% to about 60% after 90 seconds exposure at 70 °C.
  • the bicomponent fiber comprises a core to sheath ratio of 10:90 to 35:65. 5.
  • the fabric of the present invention comprises a bicompo nent fiber that has a shrinkage after 90 seconds of exposure at 70 °C of less than about 20% and a contact clarity measured according to ASTM D1003 of greater than about 13%.
  • the bicomponent fiber used in the fabric may also have a melting range of 100 °C to 120 °C measured by DSC.
  • Fabric made using the fibers of this invention can be made by knitting or weaving.
  • fabrics can be made by using the bicomponent fibers of the present invention with other fibers, such as nylon and/or polyester.
  • the fabrics of the present inven tion may be used to make garments, such as for sports apparel applications.
  • the enhanced clarity of the fibers of the present invention also provides benefits for applications where graphics are applied to the fabrics.
  • TPU 1 is a polyester thermoplastic polyurethane comprising the reaction product of bu- tanediol succinate and an aromatic diisocyanate having a melt enthalpy measured by DSC, second heat cycle of 60 J/g.
  • TPU 2 is a polyester thermoplastic polyurethane comprising the reaction product of butanediol adipate, an aromatic diisocyanate, and a chain extender diol having a melt enthalpy measured by DSC, second heat cycle of 5 J/g.
  • Comparative Examples Cl - C9 were made from either 100% of one TPU material or blends of pellets of TPU 1 and TPU 2 to form a mono-component filament.
  • Inventive Examples 1-4 are bicomponent fibers having a core-sheath cross section. When fibers were able to be successfully made, these were tested for shrinkage using a one meter length of fiber that was measured before and after exposure to a temperature of 70 °C for 90 seconds.
  • transitional term“comprising,” which is synonymous with “including,”“containing,” or“characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases“consisting essentially of’ and“consisting of,” where“consisting of’ excludes any element or step not specified and“consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Multicomponent Fibers (AREA)
  • Knitting Of Fabric (AREA)
  • Woven Fabrics (AREA)

Abstract

The present invention relates to a bicomponent fiber, wherein the fiber has a core and sheath structure. The bicomponent fiber is made from two different polyester thermo-plastic polyurethanes to provide a fiber with enhanced clarity and low shrinkage.

Description

BICOMPONENT THERMOPLASTIC POLYURETHANE FIBERS AND FABRICS
MADE THERFROM
TECHNICAL FIELD
[0001] The present technology relates to bicomponent fibers and fabrics made therefrom, in particular, core-sheath fibers, made from two different thermoplastic polyurethanes to provide a fiber having unique properties.
SUMMARY OF THE INVENTION
[0002] The present invention relates to a bicomponent fiber, wherein the bicomponent fiber has a core and sheath structure, wherein the bicomponent fiber comprises (a) a core comprising a first polyester thermoplastic polyurethane which has a melting enthalpy of at least 50 J/g measured according to ASTM D3418 and (b) a sheath comprising a second pol yester thermoplastic polyurethane which has a melting enthalpy of 5 J/g or less measured according to ASTM D3418.
[0003] The present invention also relates to fabrics made from the bicomponent fibers of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0004] The term“bicomponent fiber” as used herein, refers to a conjugated product of at least two melt-spinnable components, wherein the conjugated product has at least two different longitudinally coextensive polymeric segments. In one embodiment, the bicomponent fiber of the present invention comprises two different polymer materials intimately adhered to each other along the length of the fiber, so that the fiber cross-section is for example, a core-sheath arrangement.
[0005] The bicomponent fiber of the present invention is made from two different polyester thermoplastic polyurethanes. A thermoplastic polyurethane is generally prepared by reacting a polyisocyanate with a polyol intermediate, and optionally a chain extender all of which are well known to those skilled in the art.
[0006] The bicomponent fiber of the present invention uses two different thermoplastic polyurethane materials, each based on a different polyester polyol intermediate. Hydroxyl ter minated polyester intermediates are generally a linear polyesters having a number average molecular weight (Mn) of from about 500 to about 10,000, desirably from about 700 to about 5,000, and preferably from about 700 to about 4,000, an acid number generally less than 1.3 and preferably less than 0.8. The molecular weight is determined by assay of the terminal functional groups and is related to the number average molecular weight. These polyester pol yols are produced by (1) an esterification reaction of one or more glycols with one or more di carboxylic acids or anhydrides or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a preponderance of terminal hydroxyl groups. Suitable polyester intermediates also include various lactones such as polycaprolactone typically made from e-caprolactone and a bifunctional initiator such as di ethylene glycol. The dicarboxylic acids of the desired polyester can be aliphatic, cycloal iphatic, aromatic, or combinations thereof. Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 4 to 15 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cy clohexane dicarboxylic, and the like. Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used. The glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, and have a total of from 2 to 12 carbon atoms, and include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- hexanediol, 2, 2-dimethyl-l, 3 -propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and the like.
[0007] In one embodiment, the fiber of the present invention includes a first thermoplastic polyurethane based on the butanediol succinate and a second thermoplastic polyurethane based on butanediol adipate.
[0008] Thermoplastic polyurethanes used in the present invention are made using a polyisocyanate component. In some embodiments, the polyisocyanate component includes one or more diisocyanates. Useful polyisocyanates may be selected from aromatic polyisocyanates or aliphatic polyisocyanates or combinations thereof. Examples of useful polyisocyanates in clude, but are not limited to aromatic diisocyanates such as 4,4'-methylenebis(phenyl isocya nate) (MDI), w-xylene diisocyanate (XDI), phenylene-1, 4-diisocyanate, 3,3’-dimethyl-4,4’- biphenylene diisocyanate (TODI), 1,5 -naphthalene diisocyanate (NDI), and toluene diisocya nate (TDI), as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,6- hexamethylene diisocyanate (HDI), 1,4-cyclohexyl diisocyanate (CHDI), decane- 1, 10-diiso cyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohexylmethane- 4,4'-diisocyanate (H12MDI). In some embodiments, mixtures of two or more polyisocyanates may be used.
[0009] In some embodiments, the polyisocyanate component comprises or consists of one or more aromatic diisocyanates. In some embodiments, the polyisocyanate component is es sentially free of, or even completely free of, aliphatic diisocyanates.
[0010] The thermoplastic polyurethane compositions described herein are optionally made using a chain extender component. Chain extenders include may include diols, diamines, and combination thereof.
[0011] Suitable chain extenders include relatively small polyhydroxy compounds, for ex ample lower aliphatic or short chain glycols having from 2 to 20, or 2 to 12, or 2 to 10 carbon atoms. Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, di propylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pen- tanediol, neopentylglycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hydroxyeth- oxy) phenyljpropane (HEPP), hexamethylenediol, heptanediol, nonanediol, dodecanediol, 3- methyl-l,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, and hy- droxyethyl resorcinol (HER), and the like, as well as mixtures thereof.
[0012] The above three necessary ingredients (hydroxyl terminated intermediate, polyisocyanate, and chain extender) are preferably reacted in the presence of a catalyst.
[0013] Generally, any conventional catalyst can be utilized to react the diisocyanate with the hydroxyl terminated intermediate or the chain extender and the same is well known to the art and to the literature. Examples of suitable catalysts include the various alkyl ethers or alkyl thiol ethers of bismuth or tin wherein the alkyl portion has from 1 to about 20 carbon atoms with specific examples including bismuth octoate, bismuth laurate, and the like. Pre ferred catalysts include the various tin catalysts such as stannous octoate, dibutyltin dioc- toate, dibutyltin dilaurate, and the like. The amount of such catalyst is generally small such as from about 20 to about 200 parts per million based upon the total weight of the polyure thane forming monomers.
[0014] The thermoplastic polyurethanes of this invention can be made by any of the con ventional polymerization methods well known in the art and literature. [0015] Thermoplastic polyurethanes of the present invention are preferably made via a "one shot" process wherein all the components are added together simultaneously or substantially simultaneously to a heated extruder and reacted to form the polyurethane. The equivalent ratio of the diisocyanate to the total equivalents of the hydroxyl terminated inter mediate and the diol chain extender is generally from about 0.95 to about 1.10, desirably from about 0.97 to about 1.03, and preferably from about 0.97 to about 1.00. The molecular weight (Mw) of thermoplastic polyurethanes useful in the present invention may be from about 50,000 Daltons to about 300,000 Daltons, for example, 50,000 Daltons to about 100,000 Daltons as measured by GPC relative to polystyrene standards. In one embodiment, the thermoplastic polyurethane used for the sheath in the bicomponent fiber of the present invention has a molecular weight of about 50,000 Daltons to 75,000 Daltons. In one embod iment, the thermoplastic polyurethane used for the core in the bicomponent fiber of the present invention has a molecular weight of about 80,000 Daltons to about 100,000 Daltons.
[0016] The thermoplastic polyurethanes can also be prepared utilizing a pre-polymer process. In the pre-polymer route, the hydroxyl terminated intermediate is reacted with generally an equivalent excess of one or more polyisocyanates to form a pre-polymer solution having free or unreacted polyisocyanate therein. Subsequently, a selective type of chain extender as noted above is added in an equivalent amount generally equal to the isocyanate end groups as well as to any free or unreacted diisocyanate compounds. The overall equivalent ratio of the total diisocyanate to the total equivalent of the hydroxyl terminated intermediate and the chain extender is thus from about 0.95 to about 1.10, desirably from about 0.98 to about 1.05 and preferably from about 0.99 to about 1.03. Typically, the pre-polymer route can be carried out in any conventional device with an extruder being preferred. Thus, the hydroxyl termi nated intermediate is reacted with an equivalent excess of a diisocyanate in a first portion of the extruder to form a pre-polymer solution and subsequently the chain extender is added at a downstream portion and reacted with the pre-polymer solution. Any conventional extruder can be utilized, with extruders equipped with barrier screws having a length to diameter ratio of at least 20 and preferably at least 25.
[0017] Useful additives can be utilized in suitable amounts and include opacifying pigments, colorants, mineral fillers, stabilizers, lubricants, UV absorbers, processing aids, and other additives as desired. Useful opacifying pigments include titanium dioxide, zinc oxide, and titanate yellow, while useful tinting pigments include carbon black, yellow oxides, brown oxides, raw and burnt sienna or umber, chromium oxide green, cadmium pigments, chromium pigments, and other mixed metal oxide and organic pigments. Useful fillers in clude diatomaceous earth (superfloss) clay, silica, talc, mica, wollastonite, barium sulfate, and calcium carbonate. If desired, useful stabilizers such as antioxidants can be used and include phenolic antioxidants, while useful photostabilizers include organic phosphates, and organotin thiolates (mercaptides). Useful lubricants include metal stearates, paraffin oils and amide waxes. Useful UV absorbers include 2-(2'-hydroxyphenol) benzotriazoles and 2-hy- droxybenzophenones.
[0018] Plasticizer additives can also be utilized advantageously to reduce hardness with out affecting properties.
[0019] Bicomponent continuous filaments of the present invention can be made using a melt-spinning process. Figure 1 illustrates the typical bicomponent melt spinning technique with a pair of extruders. The steps for making the bicomponent fibers include vacuum batch drying at 80°C for 12 hours, feeding of dried thermoplastic polyurethane polymers into ex truder from a hopper, melting the first and second thermoplastic polyurethane compositions in respective extruders with 1.24 inch single screw and an L/D of 24, and extruding the melts using two feeding systems/conduits by a melt pump and then to a spinneret or die. The back pressure at the extruder outlet was kept constant with a loop control. The extruder had four heating zones that were maintained between 180°C - 220°C. The basic system consists of two feeding systems, two polymers to the spin packs and a distribution system to meter both polymers to the die. It should be understood by those skilled in the art that the spinneret for producing bicomponent or multicomponent filaments is known in the industry. Such a pro cess is described in US Patent No. 5, 162,074, which is incorporated herein by reference. Typically, spinneret includes a casing containing spin packs, plurality of plates to create a pattern for polymer to flow. The bicomponent continuous filament spinnerets may also be configured for extrudate to have desired cross-sections such as symmetrical (concentric) core/sheath, asymmetrical core/sheath, side-by-side, crescent shaped and the like. Addition ally, multiple extruders can be added to increase the number of components. [0020] Once the fiber exits the spinneret, it is cooled before winding onto bobbins. The fiber is passed over a set of godets, finish oil is applied, and the fiber proceeds to another set of godets.
[0021] In some embodiments, during the melt spinning process, the thermoplastic polyu rethane described above may be crosslinked with a crosslinking agent. Crosslinking agents are generally a pre-polymer of a hydroxyl terminated intermediate that is a polyether, poly ester, polycarbonate, polycaprolactone, or mixture thereof reacted with a polyisocyanate. Crosslinking agents (also referred to as pre-polymers in some cases), often will have an iso cyanate functionality of greater than about 1.0, preferably from about 1.0 to about 3.0, and more preferably from about 1.8 to about 2.2.
[0022] In one embodiment of the present invention, bicomponent fiber is formed without the use of crosslinking agents. In this embodiment, both the core thermoplastic polyurethane and the sheath thermoplastic polyurethane are free of crosslinking.
[0023] The bicomponent fibers of this invention can be made in a variety of denier. Denier is a term in the art designating the fiber size. Denier is the weight in grams of 9000 meters of fiber length. The bicomponent fibers of this invention are typically made in sizes ranging from, 20 to 2500 denier, for example 20 to 600 denier, further for example 40 to 400 denier.
[0024] When bicomponent fibers are made by the process of this invention, anti-tack additives such as finish oils, an example of which are silicone oils, are usually added to the surface of the fibers after or during cooling and just prior to being wound into bobbins.
[0025] A bicomponent fiber in accordance with the present invention has a core and sheath structure, wherein the bicomponent fiber has a core comprising a first polyester ther moplastic polyurethane, wherein the first polyester thermoplastic polyurethane has a melting enthalpy of at least about 50 J/g, for example, about 60 J/g, measured according to ASTM D3418 (DSC, second heat cycle) and a sheath comprising a second polyester thermoplastic polyurethane, wherein the second polyester thermoplastic polyurethane has a melting en thalpy of about 5 J/g or less measured according to ASTM D3418 (DSC, second heat cycle). In one embodiment of this bicomponent fiber, the first polyester thermoplastic polyurethane has a contact clarity of 4% or less as measured according to ASTM D1003. In another em bodiment of this bicomponent fiber, the second polyester thermoplastic polyurethane has a contact clarity of at least 12% measured according to ASTM D1003.
[0026] The bicomponent fiber of the present invention contains a core thermoplastic pol yurethane and a sheath thermoplastic polyurethane, where the core and the sheath thermo plastic polyurethane materials are different from each other. In one embodiment, the core thermoplastic polyurethane comprises the reaction product of butanediol succinate and an aromatic diisocyanate while the sheath thermoplastic polyurethane comprises the reaction product of butanediol adipate, an aromatic diisocyanate, and at least one chain extender glycol.
[0027] In the present invention, the bicomponent fiber comprises about 10% to about 35% by weight of the core thermoplastic polyurethane composition and about 65% to about 90% by weight of the second thermoplastic polyurethane.
[0028] In one embodiment of the present invention, the final bicomponent fiber has low shrinkage and good clarity. For some applications, it is desired to have a bicomponent fiber having a shrinkage after 90 seconds of exposure at 70 °C of less than about 20% and a contact clarity measured according to ASTM D1003 of greater than about 13%. The present inven tion provides these properties surprisingly by combining two different thermoplastic polyu rethane materials having different shrinkage and clarity properties. In one embodiment, the core comprises a thermoplastic polyurethane composition having a melting enthalpy of at least 50J/g measured according to ASTM D3418 and a contact clarity of about 4% or less as measured according to ASTM D1003 and the sheath comprises a thermoplastic polyurethane composition having a melting enthalpy of about 5 I/g or less measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of at least 12% measured according to ASTM D1003. In another embodiment, the core thermoplastic polyurethane has a shrinkage of less than about 10% after 90 seconds exposure at 70 °C, while the sheath thermoplastic polyurethane has a shrinkage of about 40% to about 60% after 90 seconds exposure at 70 °C. Shrinkage is measured by using a one meter long length of the fiber and measuring it before and after exposure to the elevated temperature. The difference between the two measurements is the shrinkage. [0029] The present invention also includes a fabric comprising the bicomponent fiber of the present invention. In one embodiment, the fabric comprises a bicomponent fiber, wherein the bicomponent fiber has a core and sheath structure, wherein the core comprises a thermo plastic polyurethane composition having a melting enthalpy of at least about 50 J/g, for ex ample about 60 J/g, measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of 4% or less as measured according to ASTM D1003 and the sheath com prises a thermoplastic polyurethane composition having a melting enthalpy of about 5 J/g or less measured according to ASTM D3418 (DSC, second heat cycle) and a contact clarity of at least about 12% measured according to ASTM D1003. In one embodiment, the core thermoplastic polyurethane composition has a shrinkage of less than about 10% after 90 seconds exposure at 70 °C and the sheath thermoplastic polyurethane composition has a shrinkage of about 40% to about 60% after 90 seconds exposure at 70 °C. In the fabric in accordance with the present invention, the bicomponent fiber comprises a core to sheath ratio of 10:90 to 35:65. 5.
[0030] In another embodiment, the fabric of the present invention comprises a bicompo nent fiber that has a shrinkage after 90 seconds of exposure at 70 °C of less than about 20% and a contact clarity measured according to ASTM D1003 of greater than about 13%. The bicomponent fiber used in the fabric may also have a melting range of 100 °C to 120 °C measured by DSC.
[0031] Fabric made using the fibers of this invention can be made by knitting or weaving. In some embodiments, fabrics can be made by using the bicomponent fibers of the present invention with other fibers, such as nylon and/or polyester. The fabrics of the present inven tion may be used to make garments, such as for sports apparel applications. The enhanced clarity of the fibers of the present invention also provides benefits for applications where graphics are applied to the fabrics.
[0032] The invention will be better understood by reference to the following examples.
[0033] Filaments were prepared based on the thermoplastic polyurethanes listed in Table 1. TPU 1 is a polyester thermoplastic polyurethane comprising the reaction product of bu- tanediol succinate and an aromatic diisocyanate having a melt enthalpy measured by DSC, second heat cycle of 60 J/g. TPU 2 is a polyester thermoplastic polyurethane comprising the reaction product of butanediol adipate, an aromatic diisocyanate, and a chain extender diol having a melt enthalpy measured by DSC, second heat cycle of 5 J/g. Comparative Examples Cl - C9 were made from either 100% of one TPU material or blends of pellets of TPU 1 and TPU 2 to form a mono-component filament. Inventive Examples 1-4 are bicomponent fibers having a core-sheath cross section. When fibers were able to be successfully made, these were tested for shrinkage using a one meter length of fiber that was measured before and after exposure to a temperature of 70 °C for 90 seconds.
Table 1
Figure imgf000011_0001
1 Filaments were spun and knitted into a fabric. Heat was applied to fuse the fibers in the fabric. The fabric shrunk and deformed such that a clarity measurement could not be ob tained.
2 A continuous filament could not be made with these blends. Incompatibility (immiscibil- ity non-miscibility) between the two TPU materials caused the blend to have insufficient melt strength to make a continuous filament.
[0034] As shown by the data above, blends of two incompatible thermoplastic polyure thanes could not form a continuous filament with both acceptable shrinkage and clarity. However, bicomponent fibers of the same two thermoplastic polyurethane compositions un expectedly provided both high clarity and low shrinkage. [0035] Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about.” It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.
[0036] As used herein, the transitional term“comprising,” which is synonymous with “including,”“containing,” or“characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alternative embodiments, the phrases“consisting essentially of’ and“consisting of,” where“consisting of’ excludes any element or step not specified and“consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.
[0037] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

1. A fabric comprising:
a bicomponent fiber, wherein the bicomponent fiber has a core and sheath structure, wherein the core comprises a thermoplastic polyurethane composition having a melting enthalpy of at least about 50 J/g measured according to ASTM D3418 and a contact clarity of 4% or less as measured according to ASTM D1003 and the sheath comprises a thermoplastic polyurethane composition having a melting enthalpy of about 5 J/g or less measured according to ASTM D3418 and a con tact clarity of at least 12% measured according to ASTM D1003.
2. The fabric of claim 1, wherein the core thermoplastic polyurethane composition has a shrinkage of less than 10% after 90 seconds exposure at 70 °C.
3. The fabric of claim 1 or 2, wherein the sheath thermoplastic polyurethane composition has a shrinkage of 40% to 60% after 90 seconds exposure at 70 °C.
4. The fabric of any of claims 1 to 3, wherein the bicomponent fiber comprises a core to sheath ratio of 10:90 to 35:65.
5. The fabric of any of claims 1 to 4, wherein the bicomponent fiber has a shrinkage after 90 seconds of exposure at 70 °C of less than 20% and a contact clarity measured ac cording to ASTM D1003 of greater than 13%.
6. The fabric of any of claims 1 to 5, wherein the bicomponent fiber has a melting range of 100 °C to 120 °C measured by DSC.
7. The fabric of any of claims 1 to 6, wherein the core comprises a polyester thermo plastic polyurethane.
8. The fabric of any of claims 1 to 7, wherein the sheath comprises a polyester thermo plastic polyurethane that is different from the core thermoplastic polyurethane.
9. The fabric of any of claims 1 to 8, wherein the core comprises a thermoplastic polyurethane comprising the reaction product of butanediol succinate and an aromatic diisocya nate.
10. The fabric of claim 9, wherein the core comprises a thermoplastic polyurethane con sisting of the reaction product of butanediol succinate and aromatic diisocyanate.
11. The fabric of any of claims 1 to 10, wherein the sheath comprises a thermoplastic polyurethane comprising the reaction product of butanediol adipate, an aromatic diisocya nate, and a chain extender.
12. The fabric of claim 11, wherein the sheath comprises a thermoplastic polyurethane consisting of the reaction product of butanediol adipate, an aromatic diisocyanate, and a chain extender.
13. The fabric of any of claims 1 to 11, wherein both the core thermoplastic polyure thane and the sheath thermoplastic polyurethane are free of crosslinking.
14. The fabric of any of claims 1 to 13, wherein the core comprises a thermoplastic pol yurethane having a melting enthalpy of about 60 J/g.
15. The fabric of any of claims 1 to 14, wherein the sheath comprises a thermoplastic polyurethane having a melting enthalpy of 5 J/g.
16. A bicomponent fiber having a core and sheath structure, wherein the bicomponent fiber comprises:
(a) a core comprising a first polyester thermoplastic polyurethane; wherein the first polyester thermoplastic polyurethane has a melting enthalpy of at least 50 J/g measured according to ASTM D3418. (b) a sheath comprising a second polyester thermoplastic polyurethane, wherein the second polyester thermoplastic polyurethane has a melting enthalpy of 5 J/g or less measured according to ASTM D3418.
17. The bicomponent fiber of claim 16, wherein the first polyester thermoplastic polyu rethane has a contact clarity of 4% or less as measured according to ASTM D1003.
18. The bicomponent fiber of claims 16 or 17, wherein the second polyester thermo plastic polyurethane has a contact clarity of at least 12% measured according to ASTM D1003.
19. The bicomponent fiber of any of claims 16 to 18, wherein the first polyester thermoplastic polyurethane comprises the reaction product of butanediol succinate and an aro matic diisocyanate.
20. The bicomponent fiber of any of claims 16 to 19, wherein the second polyester ther moplastic polyurethane comprises the reaction product of butanediol adipate, an aromatic diisocyanate, and a chain extender.
21. The bicomponent fiber of any of claims 16 to 20, wherein the bicomponent fiber comprises 65% to 90% by weight of the second thermoplastic polyurethane.
22. The bicomponent fiber of any of claims 16 to 21, wherein the bicomponent fiber comprises 10% to 35% by weight of the core thermoplastic polyurethane composition.
23. The bicomponent fiber of any of claims 16 to 22, wherein the first thermoplastic polyurethane has a shrinkage of less than 10% after 90 seconds exposure at 70 °C .
24. The bicomponent fiber of any of claims 16 to 23, wherein the second thermoplastic polyurethane has a shrinkage of 40% to 60% after 90 seconds exposure at 70 °C.
25. The bicomponent fiber of any of claims 16 to 24, wherein the first polyester thermo plastic polyurethane has a melting enthalpy of 60 J/g measured according to ASTM D3418.
26. The bicomponent fiber of any of claims 16 to 25, wherein the second polyester ther moplastic polyurethane has a melting enthalpy of 5 J/g measured according to ASTM D3418.
27. The bicomponent fiber of any of claims 16 to 26, wherein both the first and second thermoplastic polyurethanes are free of crosslinking.
28. A fabric comprising:
a bicomponent fiber, wherein the bicomponent fiber has a core and sheath structure, wherein the core comprises a polyester thermoplastic polyurethane com prising the reaction product of butanediol succinate and an aromatic diisocyanate and has a melting enthalpy of at least 50J/g measured according to ASTM D3418 and a contact clarity of 4% or less as measured according to ASTM D1003 and the sheath comprises a polyester thermoplastic polyurethane comprising the reaction product of butanediol adipate, an aromatic diisocyanate, and a chain extender and has a melting enthalpy of 5 J/g or less measured according to ASTM D3418 and a contact clarity of at least 12% measured according to ASTM D1003, wherein both the core thermoplastic polyurethane and the sheath thermoplastic polyurethane are free of crosslinking.
29. The fabric of claim 28, wherein the fabric is a knitted fabric.
30. The fabric of claim 28, wherein the fabric is a woven fabric.
31. The fabric of claim 28, wherein the fabric is a non-woven fabric.
PCT/US2020/040447 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therfrom WO2021003236A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202080052026.4A CN114127345B (en) 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therefrom
JP2021578016A JP2022538459A (en) 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therefrom
US17/623,955 US20220411970A1 (en) 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therefrom
EP20743924.1A EP3994299A1 (en) 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therfrom
KR1020227001797A KR20220027161A (en) 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962870356P 2019-07-03 2019-07-03
US62/870,356 2019-07-03

Publications (1)

Publication Number Publication Date
WO2021003236A1 true WO2021003236A1 (en) 2021-01-07

Family

ID=71738300

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/040447 WO2021003236A1 (en) 2019-07-03 2020-07-01 Bicomponent thermoplastic polyurethane fibers and fabrics made therfrom

Country Status (7)

Country Link
US (1) US20220411970A1 (en)
EP (1) EP3994299A1 (en)
JP (1) JP2022538459A (en)
KR (1) KR20220027161A (en)
CN (1) CN114127345B (en)
TW (1) TW202111175A (en)
WO (1) WO2021003236A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114457490A (en) * 2022-03-23 2022-05-10 合肥工业大学 Waterproof breathable polylactic acid fiber fabric with core-shell structure

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162074A (en) 1987-10-02 1992-11-10 Basf Corporation Method of making plural component fibers
JPH055217A (en) * 1991-06-24 1993-01-14 Kuraray Co Ltd Polyurethane conjugate elastic fiber
EP2920343A1 (en) * 2012-11-16 2015-09-23 Basf Se A bicomponent fiber, the preparation process and the use thereof, and the fabrics comprising the same
CN104911747B (en) * 2015-06-03 2017-06-06 东华大学 A kind of elastic energy storage phase change fiber and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69228606T2 (en) * 1991-07-03 1999-06-24 Kanebo Ltd METHOD AND DEVICE FOR PRODUCING A THERMOPLASTIC POLYURETHANE ELASTOMER
US20050245157A1 (en) * 2004-04-30 2005-11-03 Kimberly-Clark Worldwide, Inc. Nonwoven fabrics comprising strata with differing levels or combinations of additives and process of making the same
JP6515031B2 (en) * 2012-10-23 2019-05-15 ルブリゾル アドバンスド マテリアルズ, インコーポレイテッド Dyeable and flame retardant thermoplastic polyurethane fibers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5162074A (en) 1987-10-02 1992-11-10 Basf Corporation Method of making plural component fibers
JPH055217A (en) * 1991-06-24 1993-01-14 Kuraray Co Ltd Polyurethane conjugate elastic fiber
EP2920343A1 (en) * 2012-11-16 2015-09-23 Basf Se A bicomponent fiber, the preparation process and the use thereof, and the fabrics comprising the same
CN104911747B (en) * 2015-06-03 2017-06-06 东华大学 A kind of elastic energy storage phase change fiber and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ASTM ASTM: "ASTM D1003 - 13", TEST METHOD FOR HAZE AND LUMINOUS TRANSMITTANCE OF TRANSPARENT PLASTICS, 30 November 2013 (2013-11-30), West Conshohocken, PA, XP055574175, Retrieved from the Internet <URL:http://www.astm.org/cgi-bin/resolver.cgi?D1003-13> [retrieved on 20190326], DOI: 10.1520/D1003-13 *
ASTM ASTM: "ASTM D3418-15", TEST METHOD FOR TRANSITION TEMPERATURES AND ENTHALPIES OF FUSION AND CRYSTALLIZATION OF POLYMERS BY DIFFERENTIAL SCANNING CALORIMETRY, 30 June 2015 (2015-06-30), West Conshohocken, PA, XP055609589, Retrieved from the Internet <URL:http://www.astm.org/cgi-bin/resolver.cgi?D3418-15> [retrieved on 20190730], DOI: 10.1520/D3418-15 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114457490A (en) * 2022-03-23 2022-05-10 合肥工业大学 Waterproof breathable polylactic acid fiber fabric with core-shell structure
CN114457490B (en) * 2022-03-23 2023-09-26 合肥工业大学 Waterproof breathable polylactic acid fiber fabric with core-shell structure

Also Published As

Publication number Publication date
US20220411970A1 (en) 2022-12-29
EP3994299A1 (en) 2022-05-11
CN114127345B (en) 2024-05-31
KR20220027161A (en) 2022-03-07
JP2022538459A (en) 2022-09-02
TW202111175A (en) 2021-03-16
CN114127345A (en) 2022-03-01

Similar Documents

Publication Publication Date Title
US7763351B2 (en) Melt spun elastic tape and process
EP0974608B1 (en) Thermoplastic polyurethanes, elastic fibers therefrom, and method for producing the fibers
JP4926696B2 (en) Melt spun TPU fiber and process
JP5717733B2 (en) High-strength fabric made of thin gauge constant compression elastic fiber
EP0449036B1 (en) Polyurethane, elastic polyurethane fiber and polyesterpolycarbonate diol used for the same
JPH0742610B2 (en) Polyurethane elastic fiber
US20220411970A1 (en) Bicomponent thermoplastic polyurethane fibers and fabrics made therefrom
US11136431B2 (en) Crystalline thermoplastic polyurethane article
US20210395434A1 (en) Crystalline thermoplastic polyurethane article
JP7237326B2 (en) Elastic fiber and its manufacturing method
JPH07258914A (en) Production of heat-resistant urethane yarn
JP2008111133A (en) Thermoplastic polyurethane

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20743924

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021578016

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20227001797

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2020743924

Country of ref document: EP

Effective date: 20220203