CN102803586A - High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers - Google Patents

High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers Download PDF

Info

Publication number
CN102803586A
CN102803586A CN2010800279984A CN201080027998A CN102803586A CN 102803586 A CN102803586 A CN 102803586A CN 2010800279984 A CN2010800279984 A CN 2010800279984A CN 201080027998 A CN201080027998 A CN 201080027998A CN 102803586 A CN102803586 A CN 102803586A
Authority
CN
China
Prior art keywords
fiber
fabric
thermoplastic polyurethane
denier
crosslinking agent
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
CN2010800279984A
Other languages
Chinese (zh)
Other versions
CN102803586B (en
Inventor
R·R·韦杜拉
J·E·小布莱森
M-W·李
D·M·菲舍尔
C·A·斯普瑞格
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.)
Lubrizol Advanced Materials Inc
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=42470526&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN102803586(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Lubrizol Advanced Materials Inc filed Critical Lubrizol Advanced Materials Inc
Priority to CN201510244031.6A priority Critical patent/CN104831377A/en
Priority to CN201610074529.7A priority patent/CN105696101B/en
Publication of CN102803586A publication Critical patent/CN102803586A/en
Application granted granted Critical
Publication of CN102803586B publication Critical patent/CN102803586B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

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

Abstract

Elastic fibers are disclosed which have a relatively flat modulus curve at between 100% and 200% elongation. The fibers can be made into garments having a very comfortable feel. The preferred elastic fibers are made from thermoplastic polyurethane polymers and are made by a unique melt spinning process where the fiber is wound into bobbins at a speed just slightly higher than the melt velocity of the polymer exiting the spinneret.

Description

By approaching the high strength fabric that specification constant compression elastomer constitutes
Technical field
The present invention relates to by approaching the high strength fabric that specification constant compression (thin gauge constant compression) elastomer is processed.The clothes of being processed by this constant compression elastomer have makes wearer's sensation as snug as a bug in a rug.These clothes tolerate the diapirism that is caused by the high strength fabric of processing with this elastomer in addition.
Background technology
In recent years, because the life style of the variation of global range, surmount basic isolation features and except basic isolation features, the demand of the higher function property of fabric is in high level always.To a kind of demand of above-mentioned functions property is to have thin specification but the fabric of not sacrificing the intensity and the globality of fabric.The fabric of this thin specification is allowed the reduction of lower packing volume, " bulk " sense and with regard to underwear, is not seen through the external visibility of coat.
Synthetic elastomer (SEF) is processed to produce elasticity by the polymer with soft chain segment and hard segment usually.Polymer with hard segment and soft chain segment typically is to gather (ether-amide); For example
Figure BDA0000123895260000011
or copolyesters; For example
Figure BDA0000123895260000012
or thermoplastic polyurethane; For example
Figure BDA0000123895260000013
yet; Very the SEF of high elongation rate typically uses the polymer with hard segment and soft chain segment; For example dry-spinning polyurethane
Figure BDA0000123895260000014
or melt-spun thermoplastic polyurethane
Figure BDA0000123895260000015
although the elongation at break of these SEF from low-level to high level and difference, all can normally be described to have along with percentage elongation (stress) increases and press the modulus (strain) of index law increase.
Melt-spun TPU fiber provides some advantages of comparing with the dry-spinning polyurethane fiber, because in melt spinning technology, do not use solvent, and in dry-spinning technology, polymer is dissolved in the solvent and carries out spinning.Make this solvent come out then from said fiber vaporized in part.Be difficult to all solvents are removed from said dry-spinning fiber fully.In order to promote from the dry-spinning fiber, to remove said solvent, typically these fibers are processed small size and make its bunchy together to produce multifilament (multi-filament) (band shape) fiber.Compare with melt-spun fibre, for given DENIER, this can cause bigger physical size.These physical characteristics cause more bulk and person's character said multifilament bundled in the fabric to impel the loss of comfortableness.
Melt-spun TPU fiber is made through the TPU polymer is carried out melt spinning.The TPU polymer is made by the reaction of following three kinds of components: i.e. (a) hydroxy-end capped intermediate, and it typically is hydroxy-end capped polyethers or polyester; (b) polyisocyanates, for example vulcabond; (c) chain extender of short-chain hydroxyl end-blocking.Said hydroxy-end capped intermediate forms soft chain segment and the hard segment of said polyisocyanates and chain extender formation TPU polymer of TPU polymer.TPU is given in the combination of said soft chain segment and hard segment polymer elasticity.The TPU polymer is also often lightly crosslinked so that the performance of enhancing to be provided through using polyisocyanate blocked prepolymer.This cross-linked material is added to during the melt spinning of fiber in the fusion TPU polymer.
Hope to obtain to have the TPU elastomer of the relative constant compression (relatively constant compression) of percentage elongation between zero-sum 250% and hope that preparation comprises the constant compression clothes and/or the fabric of said TPU fiber.Hope in addition these constant compression fabrics be thin specification with have high anti-puncturing property (puncture resistance).Can be the wearer by the clothes of above-mentioned fabrics manufacturing higher comfort and confidence is provided.
Description of drawings
Fig. 1 is the microphoto of 70 DENIER multifilament of commercially available dry-spinning polyurethane fiber.
Fig. 2 is the microphoto of 70 DENIERs of the constant compression thermoplastic polyurethane fibers of melt spinning of the present invention.
Fig. 3 is the curve of demonstration as the Y axle of square (square micron) of the X axle vs. fiber width of DENIER.Fiber of the present invention and commercially available dry-spinning fiber are compared.
Summary of the invention
Target of the present invention provides thin high strength fibre specification, constant compression, and it has at least 400% ultimate elongation and has in load period and straight and/or constant relatively modulus between in 100% to 200% percentage elongation in the zero load cycle.This straight and/or constant modulus through in load period stress under 100% percentage elongation less than the every DENIER of 0.023 fors, under 150% percentage elongation less than the every DENIER of 0.023 fors, under 200% percentage elongation less than the every DENIER of 0.053 fors; With through stress in the zero load cycle under 200% percentage elongation less than the every DENIER of 0.027 fors, under 150% percentage elongation less than the every DENIER of 0.018 fors, under 100% percentage elongation, be able to confirm less than the every DENIER of 0.015 fors.
A kind of exemplary fiber is through making thermoplastic polyurethane polymer, preferred polyester polyether polyols with reduced unsaturation melt spinning.Said fiber is through adding crosslinking agent (preferred 5-20 weight %) and lightly crosslinked to said polymer melt during melt spinning technology.
A kind of method for preparing said fiber comprises melt spinning technology, forms said fiber through making polymer melt pass spinnerets thus.Fiber leaves the speed of this spinnerets and speed that fiber roll moves into into bobbin is approaching relatively.That is to say, this fiber should with the speed of leaving spinnerets greater than fiber at the most 50%, preferred 20%, more preferably 10% speed reels and gets into bobbin.
Another target of the present invention is to make fabric with said thin specification, constant compression fiber.In exemplary embodiment, through combining (for example through knitting (knit) or tatting (weave)) to make said fabric with hard fibre such as nylon and/or polyester fiber said elastomer.Fabric with the fiber manufacturing of said novelty also has high bursting strength (burst strength).
Clothes clothes, for example underwear are by said elastomer manufacturing.Said clothes provide good comfort for the wearer.
Detailed Description Of The Invention
Fiber of the present invention is by thermoplastic elastomer.Preferred thermoplastic elastomer (TPE) is thermoplastic polyurethane polymer (TPU).To use TPU to describe the present invention, but be to be understood that this is that a kind of embodiment and those skilled in the art can use other thermoplastic elastomer (TPE).
Be used for the TPU polymer that TPU polymer type of the present invention can be the known any routine of this area and document, as long as this TPU polymer has enough molecular weight.Said TPU polymer generally prepares through the for example hydroxy-end capped polyester of polyisocyanates and intermediate, hydroxy-end capped polyethers, hydroxy-end capped Merlon or its mixture and the reaction of one or more chain extenders, and all these are well-known to those skilled in the art.
Said hydroxy-end capped intermediate polyester generally be number-average molecular weight (Mn) for about 500 to about 10,000, hope ground about 700 to about 5,000, preferably about 700 to about 4,000 and acid number be generally less than 1.3, preferably less than 0.8 linear polyesters.Molecular weight is through analyzing functional end-group and confirm and relating to number-average molecular weight.Said polymer prepares through following mode: the esterification of (1) one or more glycol and one or more dicarboxylic acids or acid anhydrides perhaps (2) is passed through ester exchange reaction, that is, and and the reaction of one or more glycol and dicarboxylic ester.The general excessive mol ratio greater than one mole of glycol of preferred acid relatively is to obtain the dominant linear chain of terminal hydroxyl.Suitable intermediate polyester also comprises multiple lactone, polycaprolactone for example, and it is typically by 6-caprolactone and for example diethylene glycol (DEG) preparation of bifunctional initiator.The dicarboxylic acids of desirable polyester can be aliphatic, alicyclic, aromatics or its combination.Can be separately or generally have altogether 4-15 carbon atom and comprise: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, terephthalic acid (TPA), cyclohexane dicarboxylic acid or the like by the suitable dicarboxylic acids that mixture uses.Can also use the acid anhydrides of above-mentioned dicarboxylic acids, for example phthalic anhydride, tetrahydrophthalic anhydride etc.Hexanedioic acid is preferred acid.Being used to react the glycol that forms the intermediate polyester of hoping can be aliphatic, aromatics or its combination, and has 2-12 carbon atom altogether, and it comprises ethylene glycol, 1,2-propylene glycol, 1; Ammediol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1; 6-hexylene glycol, 2,2-dimethyl-1, ammediol, 1; 4-cyclohexanedimethanol, 1,10-decanediol, 1,12-dodecanediol or the like.1, the 4-butanediol is preferred glycol.
Hydroxy-end capped polyether intermediate is a PPG; It is derived from glycol with 2-15 carbon atom altogether or polyalcohol, preferred alkyl glycol (diol or glycol), and said alcohol reacts with the ether that comprises the alkylene oxide (typically oxirane or expoxy propane or its mixture) with 2-6 carbon atom.For example, can then prepare the polyethers of hydroxyl-functional subsequently with reacting ethylene oxide through at first making propylene glycol and propylene oxide reaction.The primary hydroxyl that is produced by oxirane has more reactive than secondary hydroxyl and is preferred therefore.Available commercially available PPG comprises: comprise and the gathering (ethylene glycol), comprise and the gathering (propylene glycol), comprise gather (the oxygen tetramethylene glycol) of the water that reacts with oxolane (PTMEG) of the expoxy propane of propylene glycol reaction of the oxirane of glycol reaction.Polyoxy tetramethylene glycol (PTMEG) is preferred polyether intermediate.PPG further comprises the polyamide adducts of alkylene oxide and can comprise; For example; The ethylenediamine adduct that comprises the product of ethylenediamine and expoxy propane comprises the diethylenetriamines adduct and the similar polyamide based PPG of the product of diethylenetriamines and expoxy propane.Also can use copolyether in the present invention.Typical copolyether comprises the product of THF and oxirane or the product of THF and expoxy propane.These can be buied as Poly THF B (block copolymer) and Poly THF R (random copolymer) from BASF.Different polyether intermediate generally has definite number-average molecular weight (Mn) through analyzing functional end-group, and its mean molecule quantity be greater than about 700, for example about 700 to about 10,000, hope about 1000 to about 5,000, preferably about 1000 to about 2500.A kind of concrete desirable polyether intermediate is the blend of PTMEG of blend, for example 2000Mn and 1000Mn of the polyethers of two kinds or more kinds of different molecular weights.
Most preferred embodiment of the present invention is used by adipic acid and 1,4-butanediol and 1, and 50/50 blend of 6-hexylene glycol reacts and the intermediate polyester of preparation.
Merlon of the present invention-based polyurethanes resin prepares through the blend reaction of vulcabond and hydroxy-end capped Merlon and chain extender.Said hydroxy-end capped Merlon can prepare through glycol and carbonate reaction.
U.S. Pat 4,131, the relevant hydroxy-end capped Merlon and the disclosure of their preparation are incorporated this paper by reference in 731.Above-mentioned Merlon be line style and have terminal hydroxyl and get rid of other end group basically.The fundamental reaction thing is two pure and mild carbonic acid esters.Suitable glycol is selected from alicyclic diol and the aliphatic diol that comprises 4-40, preferred 4-12 carbon atom and is selected from per molecule and comprises the polyether polyols that 2-20 alkoxyl and each alkoxyl comprise 2-4 carbon atom.Be suitable for glycol of the present invention and comprise the aliphatic diol that comprises 4-12 carbon atom, for example butanediol-1,4, pentanediol-1; 4, neopentyl glycol, hexylene glycol-1; 6,2,2,4-trimethyl hexylene glycol-1; 6, decanediol-1,10, hydrogenation two flax base glycol (hydrogenated dilinoleylglycol), hydrogenation two oil base glycol (hydrogenated dioleylglycol); And alicyclic diol for example cyclohexanediol-1,3, hydroxymethyl-cyclohexane-1,4, cyclohexane diol-1,4, hydroxymethyl-cyclohexane-1,3,1,4-endo-methylene group-2-hydroxyl-5-methylol cyclohexane, PAG.The glycol that is used for this reaction can be single glycol or diol mixture, and this depends on the desirable character of finished product.
Hydroxy-end capped intermediate polycarbonate generally is known those in this area and the document.Suitable carbonic acid ester be selected from have following general formula by 5 to 7 yuan of alkylene carbonates of forming of ring:
Figure BDA0000123895260000061
Wherein R is the saturated divalent group that comprises 2-6 straight chain carbon atom.The suitable carbonic acid ester that the application uses comprises carbonic acid ethylidene ester, carbonic acid 1,3-propylidene ester, carbonic acid 1,4-butylidene ester, carbonic acid 1; 2-propylidene ester, carbonic acid 1,2-butylidene ester, carbonic acid 2,3-butylidene ester, carbonic acid 1; 2-ethylidene ester, carbonic acid 1,3-pentylidene ester, carbonic acid 1,4-pentylidene ester, carbonic acid 2; 3-pentylidene ester and carbonic acid 2,4-pentylidene ester.
In addition, suitable the application's is dialkyl carbonate, carbonic acid alicyclic ester and diaryl carbonate.Said dialkyl carbonate can in each alkyl, comprise the 2-5 carbon atom and its instantiation is carbonic acid diethyl ester and carbonic acid dipropyl.Carbonic acid alicyclic ester, particularly carbonic acid two alicyclic esters can comprise 4-7 carbon atom in each circulus, and can have a kind of in the said structure or two kinds.When a group when being alicyclic, another can be an alkyl or aryl.On the other hand, if a group is an aryl, another can be an alkyl or alicyclic.The preferred embodiment that can in each aryl, comprise the diaryl carbonate of 6-20 carbon atom is dipheryl carbonate base ester, carboxylol base ester and carbonic acid dinaphthyl ester.
Through under the pressure of 100 ℃-300 ℃ temperature and 0.1-300mm Hg; Exist or do not exist under the situation of ester exchange catalyst; Make glycol and carbonic acid ester, preferred as alkylene carbonates by 10: 1-1: 10 but preferred 3: 1-1: 3 molar range reaction and carry out said reaction, remove the low boiling glycol through distillation simultaneously.
More specifically, said hydroxy-end capped Merlon prepared with two stages.In the phase I, glycol and alkylene carbonates reaction are to form the Merlon of low-molecular-weight hydroxyl end-blocking.Through removing more lower boiling glycol distilling down at the pressure of the reduction of 10-30mmHg, preferred 50-200mm Hg under 100 ℃-300 ℃, preferred 150 ℃-250 ℃.Use fractionating column that this accessory substance glycol is separated from reactant mixture.Said accessory substance glycol is back to reaction vessel from the top taking-up of said tower and with unreacted alkylene carbonates and diol reactant as backflow.Can use inert gas flow or atent solvent to flow to promote removing of when forming accessory substance glycol.When the degree of polymerization of the bright hydroxy-end capped Merlon of the scale of the accessory substance glycol that obtains is 2-10, said pressure is reduced to 0.1-10mm Hg gradually and removes unreacted two pure and mild alkylene carbonates.The beginning of the second stage of this sign reaction, during through when forming, under 100 ℃-300 ℃, the pressure of preferred 150 ℃-250 ℃ and 0.1-10mmHg, distilling out glycol the Merlon of condensation low-molecular-weight hydroxyl end-blocking up to the hope molecular weight of the hydroxy-end capped Merlon of acquisition.The molecular weight of hydroxy-end capped Merlon (Mn) can be for about 500 to about 10,000, but in a preferred embodiment, it will be 500-2500.
Second neccessary composition for preparing TPU polymer of the present invention is a polyisocyanates.
Polyisocyanates of the present invention generally has formula R (NCO) n, wherein n is generally 2-4, and because composition is thermoplastic and be preferably very much 2.Therefore because they cause crosslinked and only with considerably less amount, for example based on the gross weight of all polyisocyanates less than 5 weight %, hope that it is 3 or 4 polyisocyanates that ground uses degree of functionality less than 2 weight %.R can be the aromatics that generally has about 20 carbon atoms of 2-altogether, alicyclic and aliphatic or their combination.The instance of suitable aromatic diisocyanates comprise diphenyl methane-4,4 '-vulcabond (MDI), H 12MDI ,-XDI (XDI) ,-tetramethylene XDI (TMXDI), phenylene-1; 4-vulcabond (PPDI), 1; 5-naphthalene two isocyanic acids (NDI) and diphenyl methane-3,3 '-dimethoxy-4 ', 4 '-vulcabond (TODI).The instance of suitable aliphatic vulcabond comprises isoflurane chalcone diisocyanate (IPDI), 1; 4-cyclohexane diisocyanate (CHDI), 1,6-cyclohexane diisocyanate (HDI), 1,6-two isocyanate groups-2; 2; 4,4-tetramethyl hexane (TMDI), 1,10-decane vulcabond and trans-dicyclohexyl methyl hydride diisocyanate (HMDI).Containing neighbour less than about 3 weight %-to the MDI of (2,4) isomers is a kind of vulcabond very preferably.
The 3rd neccessary composition of making TPU polymer of the present invention is a chain extender.Suitable chain extender is lower aliphatic or the short-chain diol with about 10 carbon atoms of about 2-; And comprise for example cis-trans-isomer, the neopentyl glycol, 1 of ethylene glycol, diethylene glycol (DEG), propylene glycol, DPG, tripropylene glycol, triethylene glycol, cyclohexyl dihydroxymethyl; 4-butanediol, 1; 6-hexylene glycol, 1,3 butylene glycol and 1, the 5-pentanediol.Can use aromatic diol as chain extender in addition, and use (high heat application) for high heat and preferentially select aromatic diol.Benzenediol (HQEE) and Xylene glycol are the suitable chain extenders that is used to make TPU of the present invention.Xylene glycol is 1,4-two (methylol) benzene and 1, the mixture of 2-two (methylol) benzene.Benzenediol is preferred aromatic chain extender and comprises hydroquinones particularly,, is also referred to as 1 that is, two (beta-hydroxy ethyl) ethers of 4-two (2-hydroxyl-oxethyl) benzene; Resorcinol promptly, also is called 1, two (beta-hydroxy ethyl) ethers of 3-two (2-hydroxyethyl) benzene; Catechol promptly, also is called 1, two (beta-hydroxy ethyl) ethers of 2-two (2-hydroxyl-oxethyl) benzene); With its combination.A kind of preferred chain extender is 1, the 4-butanediol.
Preferably reaction in the presence of catalyst of above-mentioned three kinds of neccessary compositions (hydroxy-end capped intermediate, polyisocyanates and chain extender).
Usually, can use any conventional catalyst so that vulcabond and hydroxy-end capped intermediate or chain extender reaction and said catalyst are normally known in this area and the document.The instance of appropriate catalyst comprises the various alkyl ethers or the alkyl sulfide alcohol ether of bismuth or tin, and wherein moieties has about 20 carbon atoms of 1-, and instantiation comprises Bismuth Octoate, laurate bismuth etc.Preferred catalyst comprises various tin catalysts, for example stannous octoate, two sad dibutyl tins, dibutyl tin laurate etc.The amount of said catalyst is generally on a small quantity, for example forms the about 200ppm of the about 20ppm-of gross weight of monomer based on polyurethane.
TPU polymer of the present invention can be through known any conventional polymerization manufacturing in this area and the document.
Thermoplastic polyurethane of the present invention wherein perhaps is added into all components simultaneously heated extruder basically simultaneously together and makes its reaction form said polyurethane preferably via " step (one shot) " method preparation.It is about 1.10 that the equivalent proportion of the total yield of vulcabond and hydroxy-end capped intermediate and diol chain-extension agent is generally about 0.95-, hopes that the about 0.97-in ground is about 1.03, preferably about 0.97-about 1.00.The Xiao A hardness of formed TPU should be 65A-95A, the about 85A of about 75A-preferably, to obtain the most desirable finished product character.Adopting the reaction temperature of urethane catalyst generally is about 175 ℃-Yue 245 ℃, preferably about 180 ℃-Yue 220 ℃.The molecular weight of thermoplastic polyurethane (Mw) generally is about 100, and 000-is about 800,000, hope that ground is about 150, and 000-is about 400,000, preferably about 150, and 000-is about 350,000, and it is through the gpc measurement with respect to polystyrene standards.
Said thermoplastic polyurethane can also utilize the prepolymer process preparation.In the prepolymer approach, hydroxy-end capped intermediate and one or more excessive polyisocyanates reactions of equivalent usually wherein had the free perhaps pre-polymer solution of unreacted polyisocyanates to form.Reaction is generally being carried out under about 80 ℃-Yue 220 ℃, preferred about 150 ℃-Yue 200 ℃ in the presence of the suitable urethane catalyst.Subsequently, the chain extender of selectivity type as noted above adds by the equivalent that generally equals terminal isocyanate groups and any free perhaps unreacted diisocyanate cpd.Thus the vulcabond total amount with respect to the total yield of the total yield of hydroxy-end capped intermediate and chain extender than for about 0.95-is about 1.10, hope about 0.98-about 1.05, preferably about 0.99-about 1.03.Regulate hydroxy-end capped intermediate with respect to the equivalent proportion of chain extender to produce 65A-95A, preferred 75A-85A Shore hardness.The chain extending reaction temperature is generally about 180 ℃-Yue 250 ℃, preferably about 200 ℃-Yue 240 ℃.Typically, the prepolymer approach can carry out in any conventional equipment, and said device is preferably extruder.Therefore, hydroxy-end capped intermediate in the first of extruder with the excessive di-isocyanate reaction of equivalent with form pre-polymer solution and subsequently downstream part divide with chain extender add and with this pre-polymer solution reaction.Can use various conventional extruders, extruder is equipped with that draw ratio is at least 20, preferred at least 25 divergence type screw rod.
Can use available additive with suitable amount, said additive comprises the additive of opaque pigment, colouring agent, mineral filler, stabilizing agent, lubricant, UV absorbent, processing aid and other hope.Available opaque pigment comprises titanium dioxide, zinc oxide and titan yellow (titahate yellow), and available coloring pigment comprises carbon black, oxide yellow thing (yellow oxides), brown oxide (brown oxides), natural and forge the metal oxide and the organic pigment of manufacture-yellow soil or umber, chrome oxide green, cadmium pigment, chromium pigment and other mixing.Available filler comprises diatomite (superfloss) clay, silica, talcum, mica, wollastonite (wallostonite), barium sulfate and calcium carbonate.If desired, can use the useful stabilizing agent such as anti-oxidant, it comprises phenol antioxidant, and available light stabilizer comprises organophosphorus ester and organo-tin mercaptide (mercaptides).Available lubricant comprises metallic stearate, paraffin oil and amide waxe.Available UV absorbent comprises 2-(2 '-hydroxyl phenol) BTA and 2-Viosorb 110.
Can also advantageously use plasticiser additive not influence character to reduce hardness.
During melt spinning technology, aforesaid TPU polymer can use crosslinking agent lightly crosslinked.Said crosslinking agent is the prepolymer with the hydroxy-end capped intermediate that can be polyethers, polyester, Merlon, polycaprolactone or its mixture of polyisocyanates reaction.Polyester or polyethers are the preferred hydroxy-end capped intermediates that is used to make crosslinking agent, and polyethers is most preferred when using with polyester TPU combination.Said crosslinking agent prepolymer has greater than about 1.0, about 3.0, the isocyanate functionality of about 1.8-about 2.2 more preferably of about 1.0-preferably.If especially the two ends of preferred hydroxy-end capped intermediate are all with isocyanate-terminated, then therefore has 2.0 isocyanate functionality.
The polyisocyanates that is used for making crosslinking agent is being made the identical of TPU polymer with mentioned above.Vulcabond such as MDI is preferred vulcabond.
The number-average molecular weight of said crosslinking agent (Mn) is about 1, and about 10,000 dalton of 000-are preferred about 1, and 200-is about 4,000, more preferably from about 1, and 500-about 2,800.Have the crosslinking agent that is higher than about 1500Mn and produce permanent deformation character preferably (set properties).
The percentage by weight of crosslinking agent that is used for the TPU polymer is about 20% for about 2.0%-, and preferably about 8.0%-is about 15%, and more preferably from about 10%-about 13%.The percentage of used crosslinking agent is based on the percentage by weight of the gross weight of TPU polymer and crosslinking agent.
The preferred melt spinning technology that is used to make TPU fiber of the present invention comprises preformed TPU polymer is conducted to extruder, so that TPU polymer melt and interpolation crosslinking agent continuously in the downstream of leaving the extruder position near the TPU melt or the TPU melt leaves extruder after.Can or after melt leaves extruder, said crosslinking agent be added in the extruder before melt leaves extruder.If after melt leaves extruder, add, then said crosslinking agent need utilize static state or dynamic mixer that itself and TPU melt mixed suitably are mixed in the TPU polymer melt to guarantee crosslinking agent.After leaving extruder, fusion TPU polymer flows into spinning manifold with crosslinking agent.Spinning manifold is divided into different materials flows with melt material flow, and wherein each materials flow is conducted to a plurality of spinneretss.Usually, have the Melt Pump that is used for from each different materials flows of spinning manifold outflow, wherein each Melt Pump is to some spinnerets feed.Said spinnerets has aperture, and melt is forced through said aperture and leaves said spinnerets with the form of monfil.The size in the hole in the spinnerets will depend on desirable fiber size (DENIER).
Can make said TPU polymer melt through spinning pack (spin pack assembly) and leave this spinning pack as fiber.Used preferred spinning pack is slug flow the sort of that produces the TPU polymer through this assembly.Most preferred spinning pack is in PCT patent application wO 2007/076380, describe the sort of, and it is merged in the application in full.
In case this fiber leaves spinnerets, it was cooled before being wound up on the bobbin.This fiber applies finish through first godet roller, and said fiber advances to second godet roller.An importance that is used to make the technology of fiber of the present invention is that fiber roll moves into the relative speed into bobbin.With regard to relative speed, it is meant that for coiling speed melt leaves the speed (melt speed) of spinnerets.In normal prior art TPU melt spinning technology, fiber is reeled with the speed of 4-6 times of melt speed.Said fiber like this draws or stretches.For unique fiber of the present invention, do not hope this extension traction (extensive drawing).Said fiber must be reeled to implement said technology with the speed that equals melt speed at least.For fiber of the present invention, must be not more than 50% to surpass melt speed, preferably be not more than 20%, more preferably no more than 10% the speed said fiber of reeling, 5% the situation of being not more than produces fabulous result.According to thinking that the coiling speed that equates with melt speed can be desirable, the speed of still must taking to reel is slightly faster implemented said technology.For instance, fiber leaves spinnerets with the speed of 300 meters of per minutes, most preferably reels with the speed of per minute 300-315 rice.
Fiber of the present invention can be with multiple denier manufacturing.DENIER is the term that shows fiber size in this area.DENIER is the weight in the gram number of 9000 meters fibre lengths.Fiber of the present invention generally is manufactured to 20-600 DENIER, preferred 40-400, the more preferably size of 70-360 DENIER.
When making fiber by method of the present invention, usually after cooling or during and got into the surface that bobbin before will the release additives (the one of which instance is a silicone oil) such as finish adds fiber to by reeling just.
An importance of melt spinning technology is the TPU polymer melt and the mixing of crosslinking agent.Suitable even mixing is to obtaining consistent fibre property and realizing that under the situation that does not produce fibrous fracture the long running time is important.The mixing of TPU melt and crosslinking agent should be the method that obtains slug flow, i.e. first in first out.Can utilize dynamic mixer or static mixer to realize suitable mixing.Static mixer more is difficult to cleaning; Therefore, dynamic mixer is preferred.Dynamic mixer with feed worm and batch mixing pin is preferred blender.The U.S. Pat 6,709,147 of incorporating this paper by reference into discloses this blender and has had rotatable batch mixing pin.Batch mixing pin can also be in a fixed position, and for example is connected on the cylindrical shell of blender and extends towards the center line of feed worm.The mixed feeding screw rod can invest the end of extruder screw through screw thread, and the shell of blender can be connected on the extruder through bolt.The feed worm of dynamic mixer should be following design, its under the situation that does not almost have back-mixing, thereby make polymer melt move the slug flow that obtains melt with the mode of progressively advancing.The L/D of mixing screw should be greater than 3 and less than 30, and preferred about 7 to about 20, and more preferably from about 10 to about 12.
The TPU polymer melt is about 200 ℃-Yue 240 ℃ with temperature in the mixed zone that crosslinking agent mixes therein, preferred about 210 ℃-Yue 225 ℃.These temperature must be used to obtain the said reaction said polymer of not degrading simultaneously.
Formed TPU and crosslinking agent react during melt spinning technology with the molecular weight (Mw) that obtains the TPU in the final fibers form for about 200, and 000-is about 800,000, and be preferred about 250, and 000-is about 500,000, and more preferably from about 300,000-about 450,000.
Spinning temperature (temperature of spinnerets interpolymer melt) should be higher than the fusing point of polymer, preferably is higher than about 10 ℃-Yue 20 ℃ of melting point polymers.Operable spinning temperature is high more, and spinning effect is good more.Yet if spinning temperature is too high, polymer can be degraded.Therefore, about 10 ℃ of the fusing point-Yue 20 ℃ of balances for good spinning under the situation that is implemented in no depolymerization that are higher than the TPU polymer are best.If spinning temperature is too low, polymer possibly solidify and cause fibrous fracture in spinnerets.
Unique fiber of the present invention has in load period and straight and/or constant relatively modulus between in 100% to 200% percentage elongation in the zero load cycle.This constant modulus through stress in load period under 100% percentage elongation less than the every DENIER of 0.023 fors, under 150% percentage elongation less than the every DENIER of 0.036 fors, under 200% percentage elongation, be able to confirm less than the every DENIER of 0.053 fors; And through stress in the zero load cycle under 200% percentage elongation less than the every DENIER of 0.027 fors, under 150% percentage elongation less than the every DENIER of 0.018 fors, under 100% percentage elongation, be able to confirm that wherein all this data are collected by 360 denier fibers less than the every DENIER of 0.015 fors.
In addition, this constant modulus through stress in load period under 100% percentage elongation less than the every DENIER of 0.158 fors, under 150% percentage elongation less than the every DENIER of 0.207 fors, under 200% percentage elongation, be able to confirm less than the every DENIER of 0.265 fors; And through stress in the zero load cycle under 200% percentage elongation less than the every DENIER of 0.021 fors, under 150% percentage elongation less than the every DENIER of 0.012 fors, under 100% percentage elongation, be able to confirm that wherein all this data are collected by 360 denier fibers less than the every DENIER of 0.008 fors.
The code test rules that are used to obtain above modulus numerical value be by DuPont to elastomeric yarn develop a kind of.This test makes fiber stand a series of 5 circulations.In each circulation, fiber is stretched to 300% percentage elongation, and adopts constant stretch speed to make its loose (between original measuring length and 300% percentage elongation).Measure the % permanent deformation in the 5th circulation back.Then, this fiber sample is circulated through the 6th time and be stretched to fracture.The load of instrument record under each elongation, the maximum load before fracture, and unit is fracture load (breaking load) and the elongation at break under peak load and the percentage elongation of the every DENIER of fors.This test is at room temperature carried out (23 ℃ ± 2 ℃ usually; With 50% ± 5% humidity).
Fiber of the present invention has at least 400%, preferred about elongation at break of 450 to 500%.This fiber is a circular monofilaments.With reference to Fig. 2, visible 70 denier monofilament fibers are circular basically in transverse shape.Fig. 1 shows 70 denier monofilament dry-spinning fibers, and it has bigger cross-sectional width.
Fig. 3 shows the curve that dry-spinning fiber and melt-spun fibre of the present invention are compared.This curve is described the relation of square (square micron) of DENIER (X axle) vs. fiber width.This curve shows that melt-spun fibre of the present invention has the constant-slope on this curve, and said dry-spinning fiber has the slope that increases by index law.The result is thinner and thereby make the wearer more comfortable with the fabric of fiber production of the present invention.
Another key character of fiber of the present invention is to compare it demonstrates improvement in fabric bursting strength with the dry-spinning fiber.
Can show this characteristic through use 1 inch diameter ball to implement Ball Burst Puncture Strength Test according to ASTM D751.This test simulation finger passes this fabric until forming the hole.Very surprised is the relative dry-spinning polyurethane fiber of fiber of the present invention demonstrates about 50-75% aspect bursting strength improvement.Even the TENSILE STRENGTH of fiber much at one, also there is the improvement of said bursting strength.
Fiber of the present invention in addition has higher thermal capacitance.Straight modulus curve, higher thermal capacitance and more the combination of thin specification cause making garment wearer feel comfortable with the fabric of fiber production of the present invention.
Fabric with fiber production of the present invention can be through knitting or tatting manufacturing.Often preferably make fabric with this TPU fiber with other fiber.Especially preferably use hard fibre with elastomer of the present invention.Preferred hard fibre, for example nylon and/or polyester.This hard fibre has improved the anti-snag property of fabric for 100% elastic fiber fabric.A kind of preferred fabric is fiber knitted the sort of with replacing, and alternately the for example a branch of 140 DENIER TPU/70 denier nylon of fiber and a branch of 140 DENIER TPU alternately then 2 restraint 140 DENIER TPU (being called the 1-2 fabric) after (being called the 1-1 fabric) or a branch of 140 DENIER TPU/70 denier nylon.
Can use fabric of the present invention to make clothes.Because the comfortableness that this fiber provides, the most preferred use of said fabric are to make underwear or fitted garment.Underwear such as brassiere and T-shirt and be used for campaign item such as running, skiing, bicycle or the sportswear of other motion can be benefited from the character of these fibers.The clothes that wear next to the skin are benefited from the straight modulus of these fibers, because in case said fiber reaches body temperature, this modulus even lower then.The close-fitting clothes of sensation will become more comfortable in about 30 seconds to 5 minutes after this fiber reaches body temperature.It will be appreciated by those skilled in the art that and to use fiber of the present invention and fabric to make any clothes.Exemplary embodiment can be the cup cover of the Shoulder belt of brassiere made by woven fabric and the brassiere made by knitted fabric, and wherein said woven fabric and knit goods all comprise melt-spun TPU fiber of the present invention.Said bra belt does not need adjustable button, because this fabric is flexible.
Through understanding the present invention better with reference to following examples.
Embodiment
The TPU polymer that is used for embodiment is through the hydroxy-end capped intermediate (polyalcohol) and 1 of polyester, and agent of 4-chain expansion of succinic acid and MDI react and make.This PEPA is through adipic acid and 1,4-butanediol and 1,50/50 mixture reaction of 6-hexylene glycol and making.This polyalcohol has 2500 Mn.This TPU is made by a step process.The crosslinking agent that during spinning technique, is added among the TPU is the polyether prepolymer that is made to produce isocyanate-terminated polyethers by 1000Mn PTMEG and MDI reaction.The consumption of this crosslinking agent is 10 weight % of the TPU total weight that adds crosslinking agent.40,70,140 and 360 denier fibers that the fiber melt spinning are used for embodiment with manufacturing.
Embodiment 1
Provide this embodiment and compare the straight relatively modulus curve of fiber of the present invention (70 DENIER) with commercially available dry-spinning fiber (70 DENIER) with the melt-spun TPU fiber (40 DENIER) of prior art with explanation.
Employed testing regulations such as preceding text are described with regard to testing elastic character.Use has Instron model 5564 tensometers of Merlin software.This experimental condition is 23 ℃ ± 2 ℃ and 50% ± 5% humidity.The fibre length of test specimen is 50.0mm.Testing four samples and result is the mean value of 4 test specimens.The result is shown in Table I.
Table I
Figure BDA0000123895260000161
Above-mentioned all data are the mean value of 4 test specimens.
From above data, visible melt-spun fibre of the present invention has straight relatively modulus curve during the 5th testing cycle.Circulation for the first time is left in the basket because this is the stress that alleviates in the fiber usually.
Embodiment 2
Provide this embodiment compares melt-spun fibre of the present invention with commercially available dry-spinning fiber with explanation width.Measure said width through SEM.The result is presented in the Table II.
Table II
Figure BDA0000123895260000171
As seeing, the dry-spinning fiber has much bigger width and this difference becomes bigger with the denier increase.
Embodiment 3
Provide this embodiment compares the improvement of melt-spun TPU fiber of the present invention with commercially available dry-spinning urethane fibers with explanation bursting strength.Use 70 denier fibers to prepare single jersey (signel Jersey) knit goods by each types of fibers.Measure the bursting puncture intensity of fabric according to ASTM D751.The result is shown in Table III.This result is the mean value of 5 test specimens.
Table III
Test Dry-spinning Melt-spun
Fracture load (load at failure, lbs) 5.78 9.03
The fracture displacement (displacement at failure, in.) 8.7 10.6
Fracture load/thickness (lbf/in.) 705 1250
Energy to fracture (lbf-in) 23.0 40.8
Do not have higher TENSILE STRENGTH although melt-spun fibre surprisingly of the present invention is compared with the dry-spinning fiber, the bursting strength of said melt-spun fibre is higher.
Though according to patent statute, set forth best mode and preferred embodiment, scope of the present invention is not limited thereto, but limits through the scope of appended claims.

Claims (22)

1. the elastomer of a thin specification, constant compression, high bursting strength, it has at least 400% ultimate elongation and has in load period and straight relatively modulus between in 100% to 200% percentage elongation in the zero load cycle.
2. the fiber of claim 1, wherein the monfil of 40 DENIERs has the width less than 100 microns.
3. the fiber of claim 1, wherein said fabric has the fracture load greater than 6 pounds when the fiber of said 70 DENIERs is made into fabric and measures the puncture intensity of said fabric according to ASTM D751.
4. the fiber of claim 1, wherein said fiber is a thermoplastic polyurethane fibers.
5. the fiber of claim 4, wherein said fiber is the polyester thermoplastic polyurethane.
6. the fiber of claim 5, wherein said fiber is crosslinked with polyether crosslinking agent.
7. the fiber of claim 5, the weight average molecular weight of wherein said polyester thermoplastic polyurethane is 200,000-700,000 dalton.
8. the fiber of claim 6, wherein said crosslinking agent is the 5-20 weight % of the total weight of said polyester thermoplastic polyurethane and said crosslinking agent.
9. the fiber of claim 8, wherein said crosslinking agent is the 8-12 weight % of the total weight of said polyester thermoplastic polyurethane and said crosslinking agent.
10. fabric that comprises at least two kinds of different fibers; At least a in the wherein said fiber is that at least a in thermoplastic polyurethane fibers and the said fiber is hard fibre, and wherein said thermoplastic polyurethane's fiber has straight relatively load-deformation curve between in 100% to 200% percentage elongation.
11. the fabric of claim 10, wherein said fabric is processed by two bundle thermoplastic polyurethane fibers of relative each bundle hard fibre.
12. the fabric of claim 10, wherein said thermoplastic polyurethane fibers has the 20-600 DENIER.
13. the fabric of claim 12, wherein said thermoplastic polyurethane fibers has the 70-360 DENIER.
14. the fabric of claim 10, wherein said hard fibre is selected from nylon and polyester.
15. the fabric of claim 14, wherein said hard fibre have about 70 DENIERs and said thermoplastic polyurethane fibers has about 140 DENIERs.
16. clothing item, it comprises the fabric of claim 10.
17. the clothing item of claim 16, wherein said goods are underwears.
18. the clothing item of claim 17, wherein said goods are brassieres.
19. a method for preparing elastomer, this elastomer have in load period and straight relatively modulus between in 100% to 200% percentage elongation in the zero load cycle, said method comprises:
(a) the thermoplastic elastomer polymer melt spinning is passed through spinnerets; With
(b) this elastomer reel is got into bobbin with the coiling speed that is not more than polymer melt and leaves the speed 50% of said spinnerets.
20. the method for claim 19, wherein said coiling speed be not more than polymer melt leave said spinnerets speed 20%.
21. the method for claim 20, wherein said coiling speed be not more than polymer melt leave said spinnerets speed 10%.
22. the method for claim 19, wherein said thermoplastic elastomer polymer is a thermoplastic polyurethane.
CN201080027998.4A 2009-06-25 2010-06-24 The high strength fabric be made up of Thin Specs constant compression elastomer Active CN102803586B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510244031.6A CN104831377A (en) 2009-06-25 2010-06-24 High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers
CN201610074529.7A CN105696101B (en) 2009-06-25 2010-06-24 The high strength fabric being made of thin gauge constant compression elastomer

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US22035709P 2009-06-25 2009-06-25
US61/220,357 2009-06-25
PCT/US2010/039773 WO2010151633A1 (en) 2009-06-25 2010-06-24 High strength fabrics consisting of thin gauge constant compression elastic fibers

Related Child Applications (2)

Application Number Title Priority Date Filing Date
CN201610074529.7A Division CN105696101B (en) 2009-06-25 2010-06-24 The high strength fabric being made of thin gauge constant compression elastomer
CN201510244031.6A Division CN104831377A (en) 2009-06-25 2010-06-24 High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers

Publications (2)

Publication Number Publication Date
CN102803586A true CN102803586A (en) 2012-11-28
CN102803586B CN102803586B (en) 2016-02-17

Family

ID=42470526

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201080027998.4A Active CN102803586B (en) 2009-06-25 2010-06-24 The high strength fabric be made up of Thin Specs constant compression elastomer
CN201610074529.7A Active CN105696101B (en) 2009-06-25 2010-06-24 The high strength fabric being made of thin gauge constant compression elastomer
CN201510244031.6A Pending CN104831377A (en) 2009-06-25 2010-06-24 High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers

Family Applications After (2)

Application Number Title Priority Date Filing Date
CN201610074529.7A Active CN105696101B (en) 2009-06-25 2010-06-24 The high strength fabric being made of thin gauge constant compression elastomer
CN201510244031.6A Pending CN104831377A (en) 2009-06-25 2010-06-24 High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers

Country Status (13)

Country Link
US (2) US20100325782A1 (en)
EP (3) EP2883983A1 (en)
JP (4) JP5717733B2 (en)
KR (2) KR101799924B1 (en)
CN (3) CN102803586B (en)
AU (2) AU2010264444B2 (en)
BR (1) BRPI1015425B1 (en)
CA (1) CA2765405C (en)
MX (1) MX2011014050A (en)
MY (2) MY154572A (en)
SG (2) SG176815A1 (en)
TW (2) TWI523980B (en)
WO (1) WO2010151633A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103354817A (en) * 2010-12-21 2013-10-16 路博润高级材料公司 Elastomer resins, fibers and fabrics thereof, and uses thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2582863A1 (en) * 2010-06-15 2013-04-24 Lubrizol Advanced Materials, Inc. Melt spun elastic fibers having flat modulus
US20120028542A1 (en) * 2010-07-30 2012-02-02 Krishan Weerawansa Self-Adjusting Bra Strap
US20130255103A1 (en) 2012-04-03 2013-10-03 Nike, Inc. Apparel And Other Products Incorporating A Thermoplastic Polymer Material
US20150351474A1 (en) * 2012-12-28 2015-12-10 Douglas K. Farmer Garments including elastic composite fabric
US9565877B2 (en) 2013-10-18 2017-02-14 Mast Industries (Far East) Limited Garment that clings to a wearer's skin and method of manufacture thereof
US9883702B2 (en) 2015-10-07 2018-02-06 Mast Industries (Far East) Limited Portion of bra and bra having zones of varying elastic moduli
CN114451633A (en) 2019-08-02 2022-05-10 耐克创新有限合伙公司 Upper for an article of footwear
CN112725927B (en) * 2020-12-31 2022-04-15 江苏恒科新材料有限公司 Super-soft and thick dyed nylon-like polyester fiber and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040092696A1 (en) * 2002-11-08 2004-05-13 Vedula Ravi Ram Heat resistant high moisture vapor transmission thermoplastic polyurethane
US20040266301A1 (en) * 2003-06-30 2004-12-30 Vedula Ravi R. Melt spun polyether TPU fibers having mixed polyols and process
WO2005005697A1 (en) * 2003-06-30 2005-01-20 Noveon Ip Holdings Corp. Melt spun monofilament or elastic tape and process

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2435863C3 (en) * 1974-07-25 1983-02-24 Dynamit Nobel Ag, 5210 Troisdorf Linear, saturated, semi-crystalline copolyesters
US3981310A (en) * 1975-01-22 1976-09-21 International Playtex, Inc. Molded brassiere cups
GB1562711A (en) * 1976-06-16 1980-03-12 Fisher M Brassiere
US4131731A (en) 1976-11-08 1978-12-26 Beatrice Foods Company Process for preparing polycarbonates
US4393186A (en) * 1979-06-19 1983-07-12 Lord Corporation Thermoplastic polyurethanes prepared by reacting polyisocyanate, polyester polyol, cycloaliphatic diol and a monofunctional chain-terminating compound
US4727094A (en) * 1983-09-27 1988-02-23 Union Carbide Corporation Method for producing polyurethanes
JPS61185520A (en) * 1985-02-12 1986-08-19 Kuraray Co Ltd Production of polyester polyurethane
US4877856A (en) * 1987-08-31 1989-10-31 The Bf Goodrich Company Soft thermoplastic polyurethane for blown film application
JPH0465521A (en) * 1990-07-05 1992-03-02 Toray Ind Inc Production of polyphenylene sulfide monofilament
DE4319953A1 (en) * 1993-06-16 1994-12-22 Basf Ag Non-tacky, highly elastic mono- and multifilament polyester-polyurethane elastomer threads, processes for their production by melt spinning and their use
JP3422857B2 (en) * 1994-04-04 2003-06-30 保土谷化学工業株式会社 Thermoplastic polyurethane resin having a wide rubber region and method for producing the same
DE4414327A1 (en) * 1994-04-25 1995-10-26 Bayer Ag Process for the production of elastane threads
KR100212616B1 (en) * 1996-12-26 1999-08-02 전원중 Polyurethane elastic yarn full support stocking
JP4132244B2 (en) * 1998-07-06 2008-08-13 株式会社クラレ Polyurethane elastic fiber comprising thermoplastic polyurethane and method for producing the same
JP2000109534A (en) * 1998-10-05 2000-04-18 Toyobo Co Ltd Polyurethane and elastic fiber
KR100307214B1 (en) * 1998-11-06 2001-11-30 조민호 Melt-spinnable thermoplastic linear polyurethan-urea resin
JP3255615B2 (en) * 1999-02-24 2002-02-12 カネボウ株式会社 Polyurethane elastic fiber nonwoven fabric, method for producing the same, and synthetic leather using the polyurethane elastic fiber nonwoven fabric
GB0030310D0 (en) * 2000-12-13 2001-01-24 Medical Res Council Apparatus and method for imaging a histological sample
US6911502B2 (en) * 2001-02-23 2005-06-28 Noveon Ip Holdings Corp. Polyurethane elastomeric fiber and process for making the fiber
CN1170017C (en) * 2001-10-09 2004-10-06 江苏南黄海实业股份有限公司 Preparation method of melt spinning polyurethane fiber thin denier filament
US6995231B2 (en) * 2001-12-21 2006-02-07 Noveon Ip Holdings, Corp. Extrudable highly crystalline thermoplastic polyurethanes
US6709147B1 (en) * 2002-12-05 2004-03-23 Rauwendaal Extrusion Engineering, Inc. Intermeshing element mixer
US7357889B2 (en) * 2003-04-09 2008-04-15 Lubrizol Advanced Materials, Inc. Melt spun TPU fibers and process
KR100524323B1 (en) * 2003-09-01 2005-10-26 주식회사 효성 Process for preparing Elastic Fiber having High modulus, Alkali-resistance and Heat-resistance
DE102005028056A1 (en) * 2005-06-16 2006-12-21 Basf Ag Thermoplastic polyurethane containing isocyanate
US7300331B2 (en) * 2005-10-11 2007-11-27 Invista North America S.Ar.L. Brassiere construction using multiple layers of fabric
ES2330794T3 (en) 2005-12-22 2009-12-15 Lubrizol Advanced Materials, Inc. SET OF THREAD PACKAGING.
CN101535538A (en) * 2006-11-10 2009-09-16 巴斯夫欧洲公司 Fibers, particularly nonwoven fabric based on thermoplastic polyurethane
EP2203492B1 (en) * 2007-10-22 2015-12-23 Lubrizol Advanced Materials, Inc. Soft, elastic, plasticizer-free thermoplastic polyurethane and process to synthesize the same
CN101457018A (en) * 2007-12-14 2009-06-17 烟台万华新材料科技有限公司 Thermoplastic polyurethane elastomer with hydrolytic stability and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040092696A1 (en) * 2002-11-08 2004-05-13 Vedula Ravi Ram Heat resistant high moisture vapor transmission thermoplastic polyurethane
US20040266301A1 (en) * 2003-06-30 2004-12-30 Vedula Ravi R. Melt spun polyether TPU fibers having mixed polyols and process
WO2005005697A1 (en) * 2003-06-30 2005-01-20 Noveon Ip Holdings Corp. Melt spun monofilament or elastic tape and process
US20080193733A1 (en) * 2003-06-30 2008-08-14 Lubrizol Advanced Materials, Inc. Melt Spun Elastic Tape And Process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103354817A (en) * 2010-12-21 2013-10-16 路博润高级材料公司 Elastomer resins, fibers and fabrics thereof, and uses thereof

Also Published As

Publication number Publication date
CA2765405C (en) 2018-06-19
AU2010264444A1 (en) 2011-12-22
AU2010264444B2 (en) 2017-03-16
AU2017201591B2 (en) 2018-08-09
BRPI1015425A2 (en) 2016-04-19
TWI591221B (en) 2017-07-11
JP2015025235A (en) 2015-02-05
EP2446073B1 (en) 2013-12-18
MY154572A (en) 2015-06-30
JP2018024973A (en) 2018-02-15
CA2765405A1 (en) 2010-12-29
EP2446073A1 (en) 2012-05-02
CN102803586B (en) 2016-02-17
WO2010151633A1 (en) 2010-12-29
JP5717733B2 (en) 2015-05-13
US20170029982A1 (en) 2017-02-02
CN104831377A (en) 2015-08-12
TW201114959A (en) 2011-05-01
MY179095A (en) 2020-10-27
KR20160110560A (en) 2016-09-21
TW201632664A (en) 2016-09-16
EP2594667A1 (en) 2013-05-22
MX2011014050A (en) 2012-04-20
JP2016113741A (en) 2016-06-23
JP2012531533A (en) 2012-12-10
TWI523980B (en) 2016-03-01
CN105696101A (en) 2016-06-22
SG10201402444YA (en) 2014-10-30
KR101799924B1 (en) 2017-11-21
AU2017201591A1 (en) 2017-03-30
KR101733649B1 (en) 2017-05-24
SG176815A1 (en) 2012-01-30
EP2594667B1 (en) 2015-01-14
US20100325782A1 (en) 2010-12-30
CN105696101B (en) 2019-07-16
KR20120102578A (en) 2012-09-18
EP2883983A1 (en) 2015-06-17
BRPI1015425B1 (en) 2020-10-27

Similar Documents

Publication Publication Date Title
CN102803586B (en) The high strength fabric be made up of Thin Specs constant compression elastomer
CN100523322C (en) Melt spun monofilament or elastic tape and process
CN102257194A (en) Bicomponent spandex
US20160053408A1 (en) High strength constant compression elastic fibers and fabrics thereof
CN111575817A (en) Method for manufacturing thermoplastic polyurethane fiber
CN107849746A (en) Polyurethane fiber including copolymer polyols

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant