EP2920343A1 - Fibre à deux composants, son processus de préparation et son utilisation, et tissu comprenant cette fibre - Google Patents

Fibre à deux composants, son processus de préparation et son utilisation, et tissu comprenant cette fibre

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Publication number
EP2920343A1
EP2920343A1 EP13791774.6A EP13791774A EP2920343A1 EP 2920343 A1 EP2920343 A1 EP 2920343A1 EP 13791774 A EP13791774 A EP 13791774A EP 2920343 A1 EP2920343 A1 EP 2920343A1
Authority
EP
European Patent Office
Prior art keywords
polymer
fiber
bicomponent fiber
component
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13791774.6A
Other languages
German (de)
English (en)
Other versions
EP2920343B1 (fr
Inventor
DeHui YIN
Akira Nomura
Wei Zhuang
Etsuhiro YAMAMOTO
Bin-Erik CHEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP2920343A1 publication Critical patent/EP2920343A1/fr
Application granted granted Critical
Publication of EP2920343B1 publication Critical patent/EP2920343B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, 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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Definitions

  • the present invention relates to a bicomponent fiber, the preparation process and the use thereof, and the fabrics comprising the same.
  • Multi-component fibers displaying various properties, undergo much development and find wide use.
  • An important use of them is in knitting or woven fabrics. Knitting or woven fabrics, as opposed to nonwoven fabrics, have relatively high elasticity and recovery property so that the final product is durable and easily conforms to the subject using or wearing these products.
  • multi-component or bicomponent fibers are usually made by solution spinning process.
  • This process leads to inclusion in the final fibers of impurities, such as solvents, monomers and oligomers, which negatively affect the mechanical property or durability of the fiber or human health.
  • impurities such as solvents, monomers and oligomers
  • DMF dimethylformide
  • Melt-spinning process is commonly used in preparing polyester, nylon and polyolefin fibers which may find use in garment production, but is seldom used for preparing fibers made of thermoplastic polyurethanes.
  • With the increasing demands for diversified knitting or woven products there is a constant need to develop highly elastic fibers for making knitting or woven articles, such as lady underwear and pantyhose, with zero content of solvents and low contents of monomers and oligomers.
  • US2011/0275262 discloses a bicomponent spandex which comprises polyurethane-urea compositions in at least one region of the cross-section. It finds use in products such as garments, swimwear and hosiery.
  • the bicomponent spandex disclosed therein is prepared by solution spinning techniques.
  • US 6, 773, 810 B2 discloses elastic bicomponent fibers having a core/sheath construction, especially a fiber in which the polymer that forms the sheath has a lower melting point than the polymer that forms the core. It also discloses that the core comprises the thermoplastic elastomer, preferably a thermoplastic polyurethane (TPU), and the sheath comprises homogeneously branched polyolefins.
  • TPU thermoplastic polyurethane
  • US 7, 740, 777 B2 discloses a method and apparatus for producing polymer fibers and non-woven fabrics including multiple polymer components.
  • EP 1,944, 396 Al discloses an elastomeric core-sheath conjugate fiber by melt-spinning process for stretchable clothing, in which the materials for both the core and the sheath can be TPU. However, it does not disclose using cross-linkers in preparing the fiber.
  • thermoplastic polyurethane (TPU) components and being at least partly cross-linked by thermoplastic urethane prepolymers, said fiber being superior in high recovery, heat-bonding behavior, dyeability and chemical-resistance.
  • the bicomponent fiber according to the invention comprises
  • thermoplastic polyurethane component i) a first thermoplastic polyurethane component
  • thermoplastic polyurethane component which may be the same as or different from component i),
  • the fiber size is between 8 denier and 300 denier, more preferably between 10 denier and 100 denier.
  • component i) is the same as component ii).
  • the bicomponent fiber is prepared by a melt-spinning process, in which a cross-linker is added separately to either or both of the melt of TPU components i) and ii).
  • a cross-linker is added separately to either or both of the melt of TPU components i) and ii).
  • knitting or woven fabrics with excellent elastic extensibility made by using the bicomponent fiber of the present invention, thus providing materials for stylish, stretchable clothing of high supportability, such as lady underwear, stocking and pantyhose.
  • a further aspect of the invention relates to the use of the fiber of the present invention in producing knitting or woven fabrics.
  • FIG 1 is a schematic view showing one embodiment of the process according to the invention.
  • FIG. 2a is a schematic view of a core-sheath bicomponent fiber according to one embodiment of the invention, in which polymer i) is for the core and polymer ii) is for the sheath.
  • FIG. 2b is a schematic view of a side-by-side bicomponent fiber according to one embodiment of the invention.
  • FIG. 3 is a micrograph of a core-sheath (50%/50%) bicomponent fiber according to one embodiment of the invention.
  • the fiber size is 30 denier.
  • the present invention provides a bicomponent fiber, which comprises i) a first thermoplastic polyurethane component; and
  • thermoplastic polyurethane component which may be the same as or different from component i),
  • At least one of components i) and ii) is crosslinked by a crosslinker to form at least one polymer of polymer i) and polymer ii), of which polymer i) has a melting point higher than that of polymer ii) by at least 10°C, and
  • the fiber size is between 8 denier and 300 denier, more preferably between 10 denier and 100 denier.
  • bicomponent fiber means a fiber comprising at least two components, i.e., having at least two distinct polymeric regions.
  • inventive bicomponent fibers may be depicted as a core/sheath structure; however, the fiber can also have a structure of any one of the configurations such as symmetrical (concentric) core/sheath, asymmetrical (eccentric) core/sheath, side-by-side, pie sections, crescent moon and the like.
  • the bicomponent fiber of the present invention consists of two polymers that are each derived from the same or different TPU components which have been at least partly crosslinked by the same or different crosslinkers, with the proviso that the polymers have a melting temperature difference of at least 10°C.
  • the melting temperature difference is at least 15°C.
  • the TPU component i) and TPU component ii) may be the same or different, which are prepared by reaction of (a) isocyanates with (b) compounds which are reactive toward isocyanates and have a number average molecular weight of from 400 g/mol to 8000 g/mol, and (c) chain extenders having a number average molecular weight of from 50 g/mol to 500 g/mol, optionally in the presence of (d) catalyst and/or (e) customary auxiliaries and/or (f) additives.
  • Organic isocyanates (a) which may be used are generally known aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates, preferably diisocyanates, for example tri-, terra-, penta-, hexa-, hepta- and/or octa-methylenediisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1 ,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1 ,4-diisocyanate, 1 -isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • IPDI isophoronediisocyanate
  • HDI 1,6-Hexamethylendiisocyanat
  • TXDI Tetramethylenxylendiisocyant
  • HXDI 1,4- and/or l,3-bis(isocyanatomethyl)cyclohexane
  • cyclohexane 1 ,4-diisocyanate 2.4- Tetramethylenxylendiisocyant (TMXDI), 1,4- and/or l,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1 ,4-diisocyanate
  • NDI diisocyanate
  • TDI 2,4- and/or 2,6-diisocyanate
  • 3,3'-dimethyldiphenyl diisocyanate 1,2-diphenylethane diisocyanate and/or phenylenediisocyanate, or mixtures thereof.
  • the organic isocyanate is an isocyanate which comprises at least 90% by weight, more preferably at least 95% by weight, particularly preferably at least 99% by weight, of diphenylmethanediisocyanate (MDI).
  • MDI diphenylmethanediisocyanate
  • polyhydroxy compounds for example polyesterols, polyetherols and/or polycarbonatediols, which are usually also summarized under the term "polyols (bl)", having number average molecular weights of from 400 to 8000 g/mol, preferably from 500 g/mol to 6000 g/mol, in particular from 1000 g/mol to 4000 g/mol, and preferably an average functionality of from 1.8 to 2.3, preferably from 1.9 to 2.2, in particular 2. It is also possible to use mixtures of polyols (bl).
  • polyols (bl) are commonly known in the art, and has been described in "Polyurethane Handbook, 2 nd Edit. Giinter Oertel", Carl Hanser Verlag, Kunststoff 1994 in chapter 3.1.
  • Chain extenders (c) which may be used are generally known aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds having a molecular weight of from 50 to 500, preferably difunctional compounds, for example diamines and/or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular 1 ,4-butanediol, 1,6-hexanediol, and/or di-, tri-, terra-, penta-, hexa-, hepta-, octa-, nona- and/or decaalkylene glycols having 3 to 8 carbon atoms, preferably corresponding oligo- and/or polypropylene glycols, it also being possible to use mixtures of chain extenders. Particularly preferred chain extender is 1 ,4-butanediol.
  • Suitable catalysts (d) which accelerate in particular the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl and/or amino groups of the components (b) and (c) are the customary tertiary amines known according to the prior art, such as, for example, triethylamine, dimethylcyclohexylamine, N-methyl-morpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo-(2,2,2)octane and the like, and metal compounds, such as titanic acid esters, iron compounds, e.g. iron(III) acetylacetonate, tin compounds, e.g.
  • the catalysts are usually used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of polyhydroxy compound (b).
  • customary auxiliaries (e) and/or additives (f) can also be added to the components (a) to (c), including surface-active substances, inorganic and/or organic fillers, reinforcing agents, plasticizers, flame proofing agents, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments, if appropriate further stabilizers in addition to the stabilizer mixture according to the invention, e.g. hydrolysis, light or heat stabilizers or stabilizers to prevent discoloration.
  • the component (e) also includes hydrolysis stabilizers, such as, for example, polymeric and low molecular weight carbodiimides.
  • Component (f) may include other thermoplastics, such as polycarbonate (PC), polyvinylchloride (PVC), polymethylmethacrylate (PMMA), polyamide (PA), polybutylene terephthalate (PBT), polystyrene (PS), thermoplastic polyester elastomers (TPEE), etc.
  • PC polycarbonate
  • PVC polyvinylchloride
  • PMMA polymethylmethacrylate
  • PA polyamide
  • PBT polybutylene terephthalate
  • PS polystyrene
  • thermoplastic polyester elastomers thermoplastic polyester elastomers
  • chain regulators usually having a molecular weight of from 31 to 499, may also be used.
  • chain regulators are compounds which have only one functional group reactive toward isocyanates, such as, for example, mono functional alcohols, mono functional amines and/or mono functional polyols.
  • Chain regulators can be used in general in an amount of from 0 to 5 parts by weight, preferably from 0.1 to 1 part by weight, based on 100 parts by weight of component b) and by definition are included under the component c).
  • the preparation process for the TPU used in the present invention may be found in EP1078944B1.
  • the TPU used may have a weight average molecular weight of 20,000 to 1,000,000, preferably 40,000 to 500,000, and more preferably 50,000 to 300,000.
  • TPUs with the trademark of Elastollan ® from BASE Most preferably, Elastollan ® 2200, 1100 or 600 series from BASF are used.
  • the TPU used in the present invention preferably has, independent of one another, a Shore A hardness measured in accordance with DIN 53505 of from 65 Shore A to 98 Shore A, more preferably from 70 Shore A to 95 Shore A, even more preferably from 75 Shore A to 90 Shore A, which may be different or the same for the two TPU components. If the hardness is too low, the fiber will have very low strength; on the other hand, if the hardness is too high, the fiber will have very low elasticity.
  • a crosslinker is added into at least one of the TPUs to improve mechanical properties of the bicomponent fibers.
  • a crosslinker is only added into the TPU component i), which may form the polymer i) for providing high recovery in the bicomponent fiber.
  • one or more crosslinkers are added to both TPU components i) and ii), producing polymer i) and polymer ii) respectively.
  • polymer i) having a higher melting point is for core and polymer ii) having a lower melting point is for sheath, such as one shown in Fig 2(a).
  • polymer i) having a higher melting point may provide the fiber with crimping property and polymer ii) having a lower melting point provide the fiber with heat bonding property.
  • crosslinker as defined below is added to either or both of the melted components i) and ii).
  • the crosslinkers are added in an amount of from about 0% to about 15%, preferably 1% to 10%, more preferably 2% to 8% by weight of the TPU for polymer ii), and in an amount of from about 5% to 25%, preferably 8% to 20%), and more preferably 10% to 15% by weight of the TPU for polymer i).
  • the crosslinker used in the present invention is a NCO-terminated prepolymer with a functionality of 1.5 to 3, preferably 1.5 to 2.5, and more preferably 1.6 to 2.1.
  • the crosslinkers used is a prepolymer having a NCO content of 3% to 20% by weight, preferably 4% to 10% by weight, and more preferably 5% to 8%) by weight.
  • the crosslinker can be prepared by reaction of isocyanates with compounds which are reactive toward isocyanates and have a number average molecular weight of from 200 g/mol to 10000 g/mol, preferably 250 g/mol to 8000 g/mol, and more preferably 500 g/mol to 6000 g/mol.
  • the crosslinkers are added into the melt of the TPU components. In some other embodiments, the crosslinkers are added into the TPU components before melting. There is no restriction as to the time for adding the prepolymers, and it can be determined by a person skilled in the art according to actual process.
  • the crosslinkers can be either in a solid or in a liquid state.
  • crosslinkers and also their production and processing are described in, for example, EP2139934A1.
  • the crosslinkers may be based on aliphatic and/or aromatic isocyanates, preferably on aromatic isocyanates.
  • the crosslinkers used in the present invention can be commercialized products, such as prepolymers with the trademark of Elastollan ® from BASF. Most preferably, type PLP9302 or CR-1 from BASF can be used.
  • polymer i) has a melting point higher than polymer ii) by at least 10°C, preferably by at least 15°C, more preferably by at least 20°C.
  • polymer i) has a melting point higher than polymer ii) by up to 80°C, more preferably by up to 60°C and even more preferably by up to 40°C.
  • polymer ii) such as for sheath, is present in an amount of 5 to 80% by weight, preferably 8% to 50% by weight, more preferably 10% to 40% by weight, based on the total weigh of the bicomponent fiber.
  • the bicomponent fiber may have a cross-section of sheath-core type (concentric or eccentric), or side-by-side type.
  • Sheath-core type (concentric or eccentric) structure is preferred.
  • the fiber contains polymer i) for core and polymer ii) for sheath, in which polymer i) has a higher melting point, such as more than 170°C, and polymer ii) may have a lower melting point such as less than 170°C, more preferably less than 160°C and even more preferably less than 150°C.
  • polymer i) usually has a higher elasticity than polymer ii), resulting in the final fiber having a 300% recovery of more than 80%).
  • the 300%> recovery was tested according to DIN 53835.
  • the fibers have good elasticity and heat bonding property at the same time, which is particularly suitable for producing lady underwear, pantyhose, etc.
  • the fiber may further include additives in one or both of the two components.
  • the sheath includes additives to improve chemical resistance or dyeability of the fiber.
  • the compatibility of the two polymers according to the present invention can be improved as compared with conventional bicomponent fibers made from different types of polymers.
  • the bicomponent fibers according to the present invention still have outstanding recovery, for example, a 300%) recovery of more than 75%, more preferably more than 80%, and even more preferably more than 88%.
  • the bicomponent fiber is made from a process including the following steps:
  • the spin head having two or more nozzles have such configurations that the produced bicomponent fiber has a core/sheath structure, or has a structure of any one of the configurations such as symmetrical (concentric) core/sheath, asymmetrical (eccentric) core/sheath, side-by-side, pie sections, crescent moon and the like.
  • the fiber is wound up in a stretched state through one or more godet rollers, and wound up on a bobbin by the rotation of a winder.
  • a spin oil such as silicone-based oil or mineral oil is applied, preferably sprayed, on to the fibers to facilitate winding.
  • prepolymers as defined above are added to either or both of the melted components i) and ii) as the crosslinker.
  • the prepolymer is added in an amount of from about 0% to about 15%, preferably 1% to 10%, more preferably 2% to 8%) by weight of the TPU for polymer ii), and in an amount of from about 5% to 25%, preferably 8% to 20%, and more preferably 10% to 15% by weight of the TPU for polymer i).
  • the roller for drawing the fiber preferably has a speed of 200 m/min to 800 m/min, and even more preferably 300 m/min to 700 m/min.
  • 2 to 5 godet rollers are used; more preferably, 2 to 4, most preferably 3, godet rollers are used.
  • 2 to 4 godet rollers are used to draw the fiber at a speed of 300 m/min to 700 m/min, thus preparing a fiber with a great balance between appropriate size and high recovery.
  • the bicomponent fibers prepared according to the present invention are for producing woven or knitting fabrics.
  • the sheath polymer having a relatively lower melting temperature has a good bonding ability while the core polymer provides the fiber with high recovery.
  • a further heating step may be applied to the product, rendering the sheath polymer to be partly melted so that binding sites are formed at the place where two fibers connect.
  • Elongation at break is determined according to DIN 53834. 300% recovery
  • 300% recovery is determined according to DIN53835, in which the recovery after 5 successive load-recovery cycles with the elongation of 300%> at a stretching speed of 100 mm/min is tested. The following criteria are provided to assess the result ("+” means good, and "-” means poor).
  • the Flow Beginning Temperature (FBT) tested by a capillary rheometer isregarded as the T m , under the condition of 30 kg force, 1mm die I.D., 10 mm die length, and 3°C/min heating rate. The following criteria are provided to assess the test results("+” means good, and "-" means poor).
  • Fiber size is measured by microscope.
  • Example 1 Two commercialized TPUs El l 80A and E2280A (obtained from BASF, both having a Shore A hardness of 80A; their weight average molecular weight is 130,000 and 210,000, respectively) are used for preparing monocomponent fibers.
  • the commercialized prepolymer PLP9302 (obtained from BASF with a molecular weight of about 2500) is used as the cross-linker (the functionality of PLP9302 is 2.0 and the NCO% is about 5.3).
  • E1180A, E2280A and PLP9302 are also used to prepare bicomponent fibers. Specifically, the fibers are prepared by the following steps: (1) E1180A and E2280A are melted in different extruders at a temperature of 200°C and 210°C respectively,
  • PLP9302 is mixed into melted E1180A and E2280 in an amount of 2% and 10% by weight of respective base TPU, respectively,
  • the fiber after passing through a spray of spin oil obtained from Takemoto Oil & Fat Co., Ltd, is wound up through three godet rollers and wound up at a spinning rate of 300 m/min.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Multicomponent Fibers (AREA)
  • Mechanical Engineering (AREA)
  • Socks And Pantyhose (AREA)
  • Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)
  • Knitting Of Fabric (AREA)
  • Woven Fabrics (AREA)

Abstract

La présente invention concerne une fibre à deux composants, comprenant i) un premier composant thermoplastique en polyuréthane, et ii) un second composant thermoplastique en polyuréthane, lequel peut être identique au composant i) ou différent de celui-ci, au moins un des composants i) et ii) étant réticulé par un agent de réticulation pour former au moins un polymère du polymère i) et du polymère ii), parmi lesquels le polymère i) présente un point de fusion au moins 10 °C plus élevé que celui du polymère ii), et la taille de la fibre étant comprise entre 8 deniers et 300 deniers, de préférence encore entre 10 deniers et 100 deniers. Les fibres à deux composants de la présente invention présentent un meilleur comportement de liaison thermique et une meilleure récupération, peuvent être teintes et sont résistantes aux produits chimiques.
EP13791774.6A 2012-11-16 2013-11-07 Fibre à deux composants, son processus de préparation et son utilisation, et tissu comprenant cette fibre Active EP2920343B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2012084718 2012-11-16
PCT/EP2013/073293 WO2014075987A1 (fr) 2012-11-16 2013-11-07 Fibre à deux composants, son processus de préparation et son utilisation, et tissu comprenant cette fibre

Publications (2)

Publication Number Publication Date
EP2920343A1 true EP2920343A1 (fr) 2015-09-23
EP2920343B1 EP2920343B1 (fr) 2017-01-11

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Country Status (7)

Country Link
EP (1) EP2920343B1 (fr)
JP (1) JP6418610B2 (fr)
KR (1) KR102108988B1 (fr)
CN (1) CN104797749B (fr)
ES (1) ES2622199T3 (fr)
TW (1) TWI646231B (fr)
WO (1) WO2014075987A1 (fr)

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WO2019215104A1 (fr) * 2018-05-11 2019-11-14 Covestro Deutschland Ag Composition de polyuréthane thermoplastique et son utilisation
WO2021003236A1 (fr) * 2019-07-03 2021-01-07 Lubrizol Advanced Materials, Inc. Fibres de polyuréthane thermoplastique à deux constituants et tissus fabriqués à partir de celles-ci

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ES2622199T3 (es) 2017-07-05
CN104797749B (zh) 2017-06-13
JP6418610B2 (ja) 2018-11-07
WO2014075987A1 (fr) 2014-05-22
CN104797749A (zh) 2015-07-22
TW201432107A (zh) 2014-08-16
KR20150086508A (ko) 2015-07-28
JP2016503466A (ja) 2016-02-04
EP2920343B1 (fr) 2017-01-11
TWI646231B (zh) 2019-01-01
KR102108988B1 (ko) 2020-05-11

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