EP2594667B1 - Elastische Fasern und Gewebe - Google Patents
Elastische Fasern und Gewebe Download PDFInfo
- Publication number
- EP2594667B1 EP2594667B1 EP20130155264 EP13155264A EP2594667B1 EP 2594667 B1 EP2594667 B1 EP 2594667B1 EP 20130155264 EP20130155264 EP 20130155264 EP 13155264 A EP13155264 A EP 13155264A EP 2594667 B1 EP2594667 B1 EP 2594667B1
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- EP
- European Patent Office
- Prior art keywords
- fiber
- denier
- fabric
- crosslinking agent
- fibers
- 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.)
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Images
Classifications
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
- D03D1/0017—Woven household fabrics
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven 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
- D03D15/56—Woven 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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/02—Underwear
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/298—Physical dimension
Definitions
- the present invention relates to high strength fabrics made from thin gauge constant compression elastic fibers. Garments made with the constant compression elastic fibers have a very comfortable feel to the wearer. The garments are also resistant to puncture due to the high strength fabric made with the elastic fibers.
- Synthetic elastic fibers are normally made from polymers having soft and hard segments to give elasticity.
- Polymers having hard and soft segments are typically poly(ether-amide), such as Pebax ® or copolyesters, such as Hytrel ® or thermoplastic polyurethane, such as Estane ® .
- very high elongation SEF typically utilize hard and soft segmented polymers such as dry spun polyurethane (Lycra ® ) or melt spun thermoplastic polyurethane (Estane ® ). While these SEF vary, from low to very high, in elongation of break, all can be commonly described as having an exponentially increasing modulus (strain) with an increase in elongation (stress).
- Melt spun TPU fibers offer some advantages over dry spun polyurethane fibers in that no solvent is used in the melt spun process, whereas in the dry spinning process, the polymer is dissolved in solvent and spun. The solvent is then partially evaporated out of the fibers. All of the solvent is very difficult to completely remove from the dry spun fibers. To facilitate removing the solvent from dry spun fibers, they are typically made into a small size and bunched together to create a multi-filament (ribbon-like) fiber. This results in a larger physical size for a given denier as compared to a melt spun fiber. These physical characteristics results in more bulk in the fabric and the nature of the multi-filament bundle contributes to a loss of comfort.
- TPU fibers are made by melt spinning a TPU polymer.
- TPU polymers are made from the reaction of three components, i.e., (a) a hydroxyl terminated intermediate, which is typically a polyether or polyester end capped with a hydroxyl group; (b) a polyisocyanate, such as a diisocyanate; and (c) a short chain hydroxyl terminated chain extender.
- the hydroxyl terminated intermediate forms the soft segment of the TPU polymer while the polyisocyanate and the chain extender forms the hard segment of the TPU polymer.
- the combination of soft and hard segments gives the TPU polymer elastic properties.
- the TPU polymer is also frequently lightly crosslinked by using a pre-polymer end capped with a polyisocyanate to give enhanced properties. The crosslinking material is added to the melted TPU polymer during melt spinning of the fiber.
- US-A-2004266301 discloses thermoplastic polyether polyurethane polymers which are mixed with a crosslinking agent to achieve long run times in a melt spinning process to make elastic fibers.
- the crosslinking agent is preferably a polyether or polyester polyol reacted with a diisocyanate.
- WO-A-2005005697 discloses articles such as melt spun elastic tapes and heaving denier monofilament fibers made from thermoplastic polyurethane (TPU) polymers.
- the TPU polymer type used can be any conventional TPU polymer.
- TPU elastic fiber which has a relatively constant compression between zero and 250% elongation and to make constant compression garments and/or fabrics containing such TPU fibers. Also, it would be desirable for these constant compression fabrics to be thin gauge and to have a high puncture resistance. Garments made from such fabrics would offer more comfort and confidence to the wearer.
- This flat and/or constant modulus is evidenced by a stress in the load cycle at 100% elongation of less than 0.023 gram-force per denier, at 150% elongation of less than 0.023 gram-force per denier, at 200% elongation of less than 0.053 gram-force per denier; and as evidenced by a stress in the unload cycle at 200% elongation of less than 0.027 gram-force per denier, at 150% elongation of less than 0.018 gram-force per denier, and at 100% elongation of less than 0.015 gram-force per denier.
- An exemplary fiber is made by melt spinning a thermoplastic polyester polyurethane polymer.
- the fiber is lightly crosslinked by adding a crosslinking agent, preferably 5 to 20 weight percent, to the polymer melt during the melt spinning process.
- a process to produce the fiber involves a melt spinning process whereby the fiber is formed by passing the polymer melt through a spinneret.
- the velocity of the fiber exiting the spinneret and the velocity at which the fiber is wound into bobbins is relatively close. That is, the fibers should be wound into bobbins at a speed no more than 50%, preferably 20%, and more preferably 10%, greater than the speed at which the fiber is exiting the spinneret.
- the fabric is made by combining, such as by knitting or weaving, the elastic fiber with a hard fiber, such as nylon and/or polyester fiber. Fabric made with the novel fiber also has high burst strength.
- Clothing garments such as undergarments, are made from the elastic fiber. Such garments offer very good comfort to the wearer.
- the fiber of this invention is made from a thermoplastic polyurethane polymer (TPU).
- TPU thermoplastic polyurethane polymer
- the TPU polymer is generally prepared by reacting a polyisocyanate with a hydroxyl terminated polyester intermediate, with one or more chain extenders, all of which are well known to those skilled in the art.
- the hydroxyl terminated polyester intermediate is generally a linear polyester having a number average molecular weight (Mn) of from 500 to 10,000, desirably from 700 to 5,000, and preferably from 700 to 4,000, an acid number 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.
- a polyester intermediate made from the reaction of adipic acid with a 50/50 blend of 1,4-butanediol and 1,6-hexanediol is used.
- the second necessary ingredient to make the TPU polymer of this invention is a polyisocyanate.
- the polyisocyanate of the present invention is diphenyl methane-4, 4'-diisocyanate (MDI).
- MDI diphenyl methane-4, 4'-diisocyanate
- a highly preferred diisocyanate is MDI containing less than about 3% by weight of ortho-para (2,4) isomer.
- the third necessary ingredient to make the TPU polymer of this invention is the chain extender, i.e., 1,4-butanediol.
- the above three necessary ingredients are preferably reacted in the presence of a catalyst.
- 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.
- Preferred catalysts include the various tin catalysts such as stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, and the like. The amount of such catalyst is generally small such as from 20 to 200 parts per million based upon the total weight of the polyurethane forming monomers.
- TPU polymers of this invention can be made by any of the conventional 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 intermediate and the diol chain extender is generally from 0.95 to 1.10, desirably from 0.97 to 1.03, and preferably from 0.97 to 1.00.
- the Shore A hardness of the TPU formed should be from 65A to 95A, and preferably from 75A to 85A, to achieve the most desirable properties of the finished article.
- Reaction temperatures utilizing urethane catalyst are generally from 175°C to 245°C and preferably from 180°C to 220°C.
- the molecular weight (Mw) of the thermoplastic polyurethane is generally from 100,000 to 800,000 and desirably from 150,000 to 400,000 and preferably 150,000 to 350,000 as measured by GPC relative to polystyrene standards.
- 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.
- Reaction is generally carried out at temperatures of from 80°C to 220°C and preferably from 150°C to 200°C in the presence of a suitable urethane catalyst.
- 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 0.95 to 1.10, desirably from 0.98 to 1.05 and preferably from 0.99 to 1.03.
- the equivalent ratio of the hydroxyl terminated intermediate to the chain extender is adjusted to give 65A to 95A, preferably 75A to 85A Shore hardness.
- the chain extension reaction temperature is generally from 180°C to 250°C with from 200°C to 240°C being preferred.
- the pre-polymer route can be carried out in any conventional device with an extruder being preferred.
- the hydroxyl terminated 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 include diatomaceous earth (superfloss) clay, silica, talc, mica, wallostonite, 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-hydroxybenzophenones.
- Plasticizer additives can also be utilized advantageously to reduce hardness without affecting properties.
- the TPU polymer described above is crosslinked with a crosslinking agent.
- the crosslinking agent is a pre-polymer of a hydroxyl terminated intermediate that is a polyether.
- the crosslinking agent, pre-polymer will have an isocyanate functionality of greater than 1.0, preferably from 1.0 to 3.0, and more preferably from 1.8 to 2.2. It is particularly preferred if both ends of hydroxyl terminated intermediate is capped with an isocyanate, thus having an isocyanate functionality of 2.0.
- the polyisocyanate used to make the crosslinking agent is the same as described above in making the TPU polymer, namely MDI.
- the crosslinking agents have a number average molecular weight (Mn) of from 1,000 to 10,000 Daltons, preferably from 1,200 to 4,000 and more preferably from 1,500 to 2,800. Crosslinking agents with above 1500 M n give better set properties.
- the weight percent of crosslinking agent used with the TPU polymer is from 2.0% to 20%, preferably 8.0% to 15%, and more preferably from 10% to 13%.
- the percentage of crosslinking agent used is weight percent based upon the total weight of TPU polymer and crosslinking agent.
- the preferred melt spinning process to make TPU fibers of this invention involves feeding a preformed TPU polymer to an extruder, to melt the TPU polymer and the crosslinking agent is added continuously downstream near the point where the TPU melt exits the extruder or after the TPU melt exits the extruder.
- the crosslinking agent can be added to the extruder before the melt exits the extruder or after the melt exits the extruder. If added after the melt exits the extruder, the crosslinking agent needs to be mixed with the TPU melt using static or dynamic mixers to assure proper mixing of the crosslinking agent into the TPU polymer melt. After exiting the extruder, the melted TPU polymer with crosslinking agent flows into a manifold.
- the manifold divides the melt stream into different streams, where each stream is fed to a plurality of spinnerets.
- spinneret usually, there is a melt pump for each different stream flowing from the manifold, with each melt pump feeding several spinnerets.
- the spinneret will have a small hole through which the melt is forced and exits the spinneret in the form of a monofilament fiber. The size of the hole in the spinneret will depend on the desired size (denier) of the fiber.
- the TPU polymer melt may be passed through a spin pack assembly and exits the spin pack assembly used as a fiber.
- the preferred spin pack assembly used is one which gives plug flow of the TPU polymer through the assembly.
- the most preferred spin pack assembly is the one described in PCT patent application WO 2007/076380 .
- the fiber is cooled before winding onto bobbins.
- the fiber is passed over a first godet, finish oil is applied, and the fiber proceeds to a second godet.
- An important aspect of the process to make the fiber of this invention is the relative speed at which the fiber is wound into bobbins.
- relative speed we mean the speed of the melt (melt velocity) exiting the spinneret in relationship to the winding speed.
- the fiber is wound at a speed of 4-6 times the speed of the melt velocity. This draws or stretches the fiber. For the unique fibers of this invention, this extensive drawing is undesirable.
- the fibers must be wound at a speed at least equal to the melt velocity to operate the process.
- the fibers of this invention it is necessary to wind the fibers at a speed no greater than 50% faster than the melt velocity, preferably no greater than 20%, and more preferably no greater than 10%, with no greater than 5% giving excellent results. It is thought that a winding speed that is the same as the melt velocity would be ideal, but it is necessary to have a slightly higher winding speed to operate the process. For example, a fiber exiting the spinneret at a speed of 300 meters per minute, would most preferable be wound at a speed of between 300 and 315 meters per minute.
- the 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 fibers of this invention are typically made in sizes ranging from 20 to 600 denier, preferably 40 to 400, and more preferably 70 to 360 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.
- An important aspect of the melt spinning process is the mixing of the TPU polymer melt with the crosslinking agent. Proper uniform mixing is important to achieve uniform fiber properties and to achieve long run times without experiencing fiber breakage.
- the mixing of the TPU melt and crosslinking agent should be a method which achieves plug-flow, i.e., first in first out.
- the proper mixing can be achieved with a dynamic mixer or a static mixer. Static mixers are more difficult to clean; therefore, a dynamic mixer is preferred.
- a dynamic mixer which has a feed screw and mixing pins is the preferred mixer.
- U.S. Patent 6,709,147 describes such a mixer and has mixing pins which can rotate.
- the mixing pins can also be in a fixed position, such as attached to the barrel of the mixer and extending toward the centerline of the feed screw.
- the mixing feed screw can be attached by threads to the end of the extruder screw and the housing of the mixer can be bolted to the extruder machine.
- the feed screw of the dynamic mixer should be a design which moves the polymer melt in a progressive manner with very little back mixing to achieve plug-flow of the melt.
- the L/D of the mixing screw should be from over 3 to less than 30, preferably from 7 to 20, and more preferably from 10 to 12.
- the temperature in the mixing zone where the TPU polymer melt is mixed with the crosslinking agent is from 200°C to 240°C, preferably from 210°C to 225°C. These temperatures are necessary to get the reaction while not degrading the polymer.
- the TPU formed is reacted with the crosslinking agent during the melt spinning process to give a molecular weight (Mw) of the TPU in final fiber form, of from 200,000 to 800,000, preferably from 250,000 to 500,000, more preferably from 300,000 to 450,000.
- Mw molecular weight
- the spinning temperature (the temperature of the polymer melt in the spinneret) should be higher than the melting point of the polymer, and preferably from 10°C to 20°C above the melting point of the polymer.
- the spinning temperature is too high, the polymer can degrade. Therefore, from 10°C to 20°C above the melting point of the TPU polymer, is the optimum for achieving a balance of good spinning without degradation of the polymer. If the spinning temperature is too low, polymer can solidify in the spinneret and cause fiber breakage.
- the unique fiber of this invention has a relatively flat and/or constant modulus in the load and unload cycle between 100% and 200% elongation.
- This flat modulus is evidenced by a stress in the load cycle at 100% elongation of less than 0.226 mN (0.023 gram-force) per denier, at 150% elongation of less than 0.353 mN (0.036 gram-force) per denier, at 200% elongation of less than 0.520 mN (0.053 gram-force) per denier; and as evidenced by a stress in the unload cycle at 200% elongation of less than 0.265 mN (0.027 gram-force) per denier, at 150% elongation of less than 0.177 mN (0.018 gram-force) per denier, and at 100% elongation of less than 0.147 mN (0.015 gram-force) per denier, where all of this data was collected from a 360 denier fiber.
- This flat modulus is also evidenced by a stress in the load cycle at 100% elongation of less than 1.55 mN (0.158 gram-force) per denier, at 150% elongation of less than 2.03 mN (0.207 gram-force) per denier, at 200% elongation of less than .0260 mN (0.265 gram-force) per denier; and as evidenced by a stress in the unload cycle at 200% elongation of less than 0.206 mN (0.021 gram-force) per denier, at 150% elongation of less than 0.118 mN (0.012 gram-force) per denier, and at 100% elongation of less than 0.0785 mN (0.008 gram-force) per denier, where all of this data was collected from a 70 denier fiber.
- the standard test procedure employed to obtain the modulus values above is one which was developed by DuPont for elastic yarns.
- the test subjects fibers to a series of 5 cycles. In each cycle, the fiber is stretched to 300% elongation, and relaxed using a constant extension rate (between the original gauge length and 300% elongation). The % set is measured after the 5 th cycle. Then, the fiber specimen is taken through a 6 th cycle and stretched to breaking.
- the instrument records the load at each extension, the highest load before breaking, and the breaking load in units of grams-force per denier as well as the breaking elongation and elongation at the maximum load.
- the test is normally conducted at room temperature (23°C ⁇ 2°C; and 50% ⁇ 5% humidity).
- the fiber of this invention has an elongation at break of at least 400%, and preferably 450 to 500%.
- the fiber is a monofilament with a round shape. Referring to FIG. 2 , it can be seen that a 70 denier monofilament fiber is substantially round in cross sectional shape.
- FIG. 1 shows a 70 denier monofilament dry spun fiber which has a larger cross section width.
- FIG. 3 shows a graph comparing a dry spun fiber with the melt spun fiber of this invention.
- the graph plots the denier (X axis) vs. the fiber width squared (square microns).
- the graph shows that the melt spun fiber of this invention has a constant slope on the graph, whereas the dry spun fiber has an expotentially increasing slope. The result is that fabric can be made with the fiber of this invention which is thinner and thus more comfortable for the wearer.
- Another important feature of the fiber of this invention is that it exhibits improved burst strength in fabric compared to dry spun fibers.
- the fiber of this invention also has higher heat capacity.
- the combination of flat modulus curve, higher heat capacity, and thinner gauge results in fabric made with the fibers of this invention feeling comfortable to the wearer of garments.
- Fabric made using the fibers of this invention can be made by knitting or weaving. Often it is preferred to make fabric using other fibers with the TPU fibers. Particularly preferred is to use a hard fiber with the elastic fibers of this invention. Hard fibers, such as nylon and/or polyester are preferred. The hard fibers improve the snag resistance of the fabric over a 100% elastic fiber fabric.
- a preferred fabric is one knitted using alternating fibers, such as a strand of 140 denier TPU/70 denier nylon alternating with a strand of 140 denier TPU (referred to as a 1-1 fabric) or a strand of 140 denier TPU/70 denier nylon followed by 2 strands of 140 denier TPU (referred to as 1-2 fabric).
- Garments can be made with the fabric of this invention.
- the most preferred use of the fabric is in making undergarments or tight fitting garments because of the comfort provided by the fiber.
- Undergarments such as bras and T-shirts as well as sport garments used for activities such as running, skiing, cycling or other sports, can benefit from the properties of these fibers.
- Garments worn next to the body benefit from the flat modulus of these fibers, because the modulus is even lower once the fibers reach body temperature.
- a garment that feels tight will become more comfortable in about 30 seconds to 5 minutes after the fibers reach body temperature. It will be understood by those skilled in the art that any garment can be made from the fabric and fibers of this invention.
- An exemplary embodiment would be a bra shoulder strap made from woven fabric and the wings of the bra made from knitted fabric, with both the woven and the knitted fabric containing the melt spun TPU fibers of this invention.
- the bra strap would not require an adjustable clasp because the fabric is elastic.
- the TPU polymer used in the Examples was made by reacting a polyester hydroxyl terminated intermediate (polyol) with 1,4-butanediol chain extender and MDI.
- the polyester polyol was made by reacting adipic acid with a 50/50 mixture of 1,4-butanediol and 1,6-hexanediol.
- the polyol had a Mn of 2500.
- the TPU was made by the one-shot process.
- the crosslinking agent added to the TPU during the spinning process was a polyether pre-polymer made by reacting 1000 Mn PTMEG with MDI to create a polyether end capped with isocyanate.
- the crosslinking agent was used at a level of 10 wt.% of the combined weight of TPU plus crosslinking agent. Fiber were melt spun to make 40, 70, 140 and 360 denier fibers used in the Examples.
- This Example is presented to show the relative flat modulus curve of the fiber (70 denier) of this invention as compared to an existing prior art melt spun TPU fiber (40 denier) and a commercial dry spun fiber (70 denier).
- test procedure used was that described above for testing elastic properties.
- An Instron Model 5564 tensiometer with Merlin Software was used.
- the test conditions were at 23°C ⁇ 2°C and 50% ⁇ 5% humidity.
- Fiber length of test specimens were 50.0 mm.
- Four specimens were tested and the results are the mean value of the 4 specimens tested. The results are shown in Table I.
- melt spun fibers of this invention have a relative flat modulus curve during the 5 th testing cycle.
- the first cycle is usually disregarded as this is relieving stress in the fiber.
- the dry spun fiber has a much higher width and the difference becomes larger as the denier increases.
- This Example is presented to show the improved burst strength of the melt spun TPU fiber of this invention as compared to a commercial dry spun polyurethane fiber.
- 70 denier fibers were used to prepare a signel Jersey knit fabric from each type of fiber. The fabric was tested for burst puncture strength according to ASTM D751. The results are shown in Table III. The results are a mean of 5 samples tested.
- melt spun fibers of this invention did not have higher tensile strength than the dry spun fibers, the burst strength of the melt spun fibers were higher.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
- Nonwoven Fabrics (AREA)
- Knitting Of Fabric (AREA)
- Undergarments, Swaddling Clothes, Handkerchiefs Or Underwear Materials (AREA)
- Corsets Or Brassieres (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Claims (11)
- Schmelzgesponnene elastische Faser, hergestellt aus einem Polyesterthermoplastischen-Polyurethan, das aus einem Reaktionsgemisch hergestellt ist, welches ein Polyisocyanat, ein lineares hydroxyterminiertes Polyester-Zwischenprodukt, einen oder mehrere Kettenverlängerer und ein Vernetzungsmittel umfasst;
wobei das Polyisocyanat Diphenylmethan-4,4'-diisocyanat umfasst;
wobei das lineare hydroxyterminierte Polyester-Zwischenprodukt das Reaktionsprodukt von Adipinsäure mit einem 50/50-Gemisch aus 1,4-Butandiol und 1,6-Hexandiol umfasst und wobei das Zwischenprodukt ein Zahlenmittel des Molekulargewichts (Mn) von 500 bis 10 000 und eine Säurezahl von weniger als 1,3 aufweist;
wobei der eine oder die mehreren Kettenverlängerer 1,4-Butandiol umfassen; und
wobei das Vernetzungsmittel ein Polyether-Vernetzungsmittel umfasst. - Faser gemäß Anspruch 1, wobei das Polyester-thermoplastische-Polyurethan ein Gewichtsmittel des Molekulargewichts von 200000 bis 700 000 Dalton aufweist.
- Faser gemäß Anspruch 1, wobei das Vernetzungsmittel 5 bis 20 Gewichtsprozent des kombinierten Gewichts des Polyester-thermoplastischen-Polyurethans und des Vernetzungsmittels ausmacht.
- Faser gemäß Anspruch 1, wobei das Vernetzungsmittel 8 bis 12 Gewichtsprozent des kombinierten Gewichts des Polyester-thermoplastischen-Polyurethans und des Vernetzungsmittels ausmacht.
- Textilstoff, der wenigstens zwei verschiedene Fasern umfasst, wobei wenigstens eine der Fasern der Faser von Anspruch 1 entspricht und wenigstens eine der Fasern eine harte Faser ist.
- Textilstoff gemäß Anspruch 5, wobei der Textilstoff aus zwei Strängen der der Faser von Anspruch 1 pro Strang harter Faser besteht.
- Textilstoff gemäß Anspruch 5, wobei die Faser von Anspruch 1 einen Titer von 20 bis 600 Denier aufweist.
- Textilstoff gemäß Anspruch 5, wobei die harte Faser aus der Gruppe ausgewählt ist, die aus Nylon und Polyester besteht.
- Textilstoff gemäß Anspruch 8, wobei die harte Faser einen Titer von etwa 70 Denier aufweist und die thermoplastische Polyurethanfaser einen Titer von etwa 140 Denier aufweist.
- Bekleidungsartikel, der den Textilstoff gemäß Anspruch 5 umfasst.
- Bekleidungsartikel gemäß Anspruch 10, wobei es sich bei dem Artikel um Unterwäsche oder ein eng anliegendes Kleidungsstück handelt.
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US22035709P | 2009-06-25 | 2009-06-25 | |
EP10729020.7A EP2446073B1 (de) | 2009-06-25 | 2010-06-24 | Hochfeste stoffe aus dünnen elastischen fasern mit konstanter kompression |
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EP10729020.7A Active EP2446073B1 (de) | 2009-06-25 | 2010-06-24 | Hochfeste stoffe aus dünnen elastischen fasern mit konstanter kompression |
EP20130155264 Active EP2594667B1 (de) | 2009-06-25 | 2010-06-24 | Elastische Fasern und Gewebe |
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EP10729020.7A Active EP2446073B1 (de) | 2009-06-25 | 2010-06-24 | Hochfeste stoffe aus dünnen elastischen fasern mit konstanter kompression |
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US (2) | US20100325782A1 (de) |
EP (3) | EP2883983A1 (de) |
JP (4) | JP5717733B2 (de) |
KR (2) | KR101733649B1 (de) |
CN (3) | CN104831377A (de) |
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CA (1) | CA2765405C (de) |
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MY (2) | MY154572A (de) |
SG (2) | SG176815A1 (de) |
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DE102005028056A1 (de) * | 2005-06-16 | 2006-12-21 | Basf Ag | Thermoplastisches Polyurethan enthaltend Isocyanat |
US7300331B2 (en) * | 2005-10-11 | 2007-11-27 | Invista North America S.Ar.L. | Brassiere construction using multiple layers of fabric |
WO2007076380A2 (en) | 2005-12-22 | 2007-07-05 | Lubrizol Advanced Materials, Inc. | Spin pack assembly |
JP2010509512A (ja) * | 2006-11-10 | 2010-03-25 | ビーエーエスエフ ソシエタス・ヨーロピア | 熱可塑性ポリウレタンに基づく繊維、特に不織布 |
WO2009055361A1 (en) * | 2007-10-22 | 2009-04-30 | Lubrizol Advanced Materials, Inc. | Soft, elastic, plasticizer-free thermoplastic polyurethane and process to synthesize the same |
CN101457018A (zh) * | 2007-12-14 | 2009-06-17 | 烟台万华新材料科技有限公司 | 具有水解稳定性的热塑性聚氨酯弹性体及其制备方法 |
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