CN105696101A - 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 PDFInfo
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- CN105696101A CN105696101A CN201610074529.7A CN201610074529A CN105696101A CN 105696101 A CN105696101 A CN 105696101A CN 201610074529 A CN201610074529 A CN 201610074529A CN 105696101 A CN105696101 A CN 105696101A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—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
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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)
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
Technical field
The application is the divisional application of Chinese patent application 201080027998.4。The present invention relates to the high strength fabric being made up of Thin Specs constant compression (thingaugeconstantcompression) elastic fiber。The clothing being made up of this constant compression elastic fiber have the sensation making wearer as snug as a bug in a rug。In addition these clothing tolerate the diapirism caused by the high strength fabric made with this elastic fiber。
Background technology
In recent years, due to the life style of the change of global range, surmount basic isolation features and except being substantially isolated function, the demand of the higher function of fabric is constantly in high level。A kind of demand to above-mentioned functions is have Thin Specs but does not sacrifice the intensity of fabric and the fabric of globality。This external visibility reducing and being not transmitted through for underwear coat allowing less packing volume, " bulk " sense compared with the fabric of Thin Specs。
Synthesis elastic fiber (SEF) generally is made up to produce elasticity of the polymer with soft chain segment and hard segment。The polymer with hard segment and soft chain segment is poly-(ether-amide) typically, such asOr copolyesters, such asOr thermoplastic polyurethane, such asBut, the SEF of significantly high percentage elongation typically uses the polymer with hard segment and soft chain segment, for instance dry-spinning polyurethaneOr melt spinning thermoplastic's polyurethaneAlthough the elongation at break of these SEF is different from low-level to high level, but all can normally be described as having the modulus (strain) increased and exponentially increase along with percentage elongation (stress)。
Melt spinning TPU fibers provides some advantages compared with dry-spinning polyurethane fiber, because not using solvent in melt spinning process, and in dry spinning process, polymer is dissolved in a solvent and carries out spinning。Then make this solvent divide from described fiber middles to be evaporated。It is difficult to from described dry-spinning fiber, completely remove all solvents。In order to promote to remove described solvent from dry-spinning fiber, typically these fibers are made small size and makes it become bundled together to produce multifilament (multi-filament) (banding) fiber。Compared with melt spun fibre, for given danier, this can cause bigger physical size。These physical characteristics cause that more bulk in fabric and described multifilament bundled person's character promotes the loss of comfortableness。
Melt spinning TPU fibers manufactures by TPU polymer is carried out melt spinning。TPU polymer is prepared by the reaction of following three kinds of components: the intermediate that namely (a) is hydroxy-end capped, its polyethers hydroxy-end capped typically or polyester；(b) polyisocyanates, such as diisocyanate；(c) chain extender of short-chain hydroxyl end-blocking。Described hydroxy-end capped intermediate forms the soft chain segment of TPU polymer and described polyisocyanates and chain extender form the hard segment of TPU polymer。The combination of described soft chain segment and hard segment gives TPU polymer elasticity。TPU polymer is also lightly crosslinked to provide the performance strengthened frequently by the polyisocyanate blocked prepolymer of use。This crosslinking material is added in melted TPU polymer during the melt spinning of fiber。
Wish obtain the TPU elastic fiber of relative constancy compression (relativelyconstantcompression) that there is percentage elongation between zero-sum 250% and wish to prepare the constant compression clothing comprising described TPU fiber and/or fabric。It is also desirable to these constant compression fabrics are Thin Specs and have high puncture resistance (punctureresistance)。The clothing manufactured by above-mentioned fabrics can provide higher comfort and confidence for wearer。
Accompanying drawing explanation
Fig. 1 is the microphotograph of 70 denier multifilament yarn of commercially available dry-spinning polyurethane fiber。
Fig. 2 is the microphotograph of 70 daniers of the constant compression thermoplastic polyurethane fibers of the melt spinning of the present invention。
Fig. 3 is the curve of the Y-axis of square (square micron) that show the X-axis vs. fiber width as danier。The fiber of the present invention is compared with commercially available dry-spinning fiber。
Summary of the invention
It is an object of the present invention to provide high strength fibre Thin Specs, constant compression, its have at least 400% ultimate elongation and have load period and in the zero load cycle between 100% to 200% percentage elongation opposing straight and/or constant modulus。This straight and/or constant modulus by load period stress under 100% percentage elongation less than the 0.023 every danier of fors, under 150% percentage elongation less than the 0.023 every danier of fors, under 200% percentage elongation less than the 0.053 every danier of fors；With by stress in the zero load cycle under 200% percentage elongation less than the 0.027 every danier of fors, under 150% percentage elongation less than the 0.018 every danier of fors, confirmed less than the 0.015 every danier of fors under 100% percentage elongation。
A kind of exemplary fiber is by manufacturing thermoplastic polyurethane polymer, preferred polyester-polyurethane polymer melt spinning。Described fiber is by lightly crosslinked to described polymer melt interpolation cross-linking agent (preferred 5-20 weight %) during melt spinning process。
A kind of method preparing described fiber includes melt spinning process, forms described fiber from there through making polymer melt through spinneret。Fiber leaves the speed of this spinneret and fiber is wound into the speed of bobbin and is relatively close to。That is, this fiber should with leave more than fiber the speed of spinneret at most 50%, the speed of preferably 20%, more preferably 10% be wound into bobbin。
It is a further object of this invention to manufacture fabric with described Thin Specs, constant compression fiber。In exemplary embodiment, manufacture described fabric by the hard fibre of described elastic fiber with such as nylon and/or polyester fiber etc being combined (such as by knitting (knit) or tatting (weave))。With the fabric of the fiber manufacture of described novelty, also there is high bursting strength (burststrength)。
Clothing garment, such as underwear are manufactured by described elastic fiber。Described clothing provide good comfort for wearer。
The invention still further relates to following embodiment:
1. an elastic fiber for Thin Specs, constant compression, high bursting strength, its have at least 400% ultimate elongation and have load period and in the zero load cycle between 100% to 200% percentage elongation the modulus of opposing straight。
2. the fiber of embodiment 1, wherein the monfil of 40 daniers has the width less than 100 microns。
3. the fiber of embodiment 1, wherein when the fiber of described 70 daniers is made into fabric and measures the puncture strength of described fabric according to ASTMD751, described fabric has the fracture load more than 6 pounds。
4. the fiber of embodiment 1, wherein said fiber is thermoplastic polyurethane fibers。
5. the fiber of embodiment 4, wherein said fiber is polyester thermoplastic's polyurethane。
6. the fiber of embodiment 5, wherein said fiber polyether crosslinking agent cross-links。
7. the fiber of embodiment 5, the weight average molecular weight of wherein said polyester thermoplastic's polyurethane is 200,000-700,000 dalton。
8. the fiber of embodiment 6, wherein said cross-linking agent is the 5-20 weight % of the total weight of described polyester thermoplastic's polyurethane and described cross-linking agent。
9. the fiber of embodiment 8, wherein said cross-linking agent is the 8-12 weight % of the total weight of described polyester thermoplastic's polyurethane and described cross-linking agent。
10. the fabric comprising at least two difference fiber, the at least one that at least one in wherein said fiber is in thermoplastic polyurethane fibers and described fiber is hard fibre, and wherein said thermoplastic polyurethane's fiber has the load-deformation curve of opposing straight between 100% to 200% percentage elongation。
11. the fabric of embodiment 10, wherein said fabric is made up of two bundle thermoplastic polyurethane fibers of relatively every a branch of hard fibre。
12. the fabric of embodiment 10, wherein said thermoplastic polyurethane fibers has 20-600 danier。
13. the fabric of embodiment 12, wherein said thermoplastic polyurethane fibers has 70-360 danier。
14. the fabric of embodiment 10, wherein said hard fibre is selected from nylon and polyester。
15. the fabric of embodiment 14, wherein said hard fibre has about 70 daniers and described thermoplastic polyurethane fibers has about 140 danier。
16. clothing item, it comprises the fabric of embodiment 10。
17. the clothing item of embodiment 16, wherein said goods are underwears。
18. the clothing item of embodiment 17, wherein said goods are medicated bras。
19. the method preparing elastic fiber, this elastic fiber have load period and in the zero load cycle between 100% to 200% percentage elongation the modulus of opposing straight, described method includes:
A thermoplastic elastomer polymer melt spinning is passed through spinneret by ()；With
B this elastic fiber is wound into bobbin with the winding speed being not more than the speed 50% that polymer melt leaves described spinneret by ()。
20. the method for embodiment 19, wherein said winding speed is not more than 20% that polymer melt leaves the speed of described spinneret。
21. the method for embodiment 20, wherein said winding speed is not more than 10% that polymer melt leaves the speed of described spinneret。
22. the method for embodiment 19, wherein said thermoplastic elastomer polymer is thermoplastic polyurethane。
Detailed Description Of The Invention
The fiber of the present invention is prepared by thermoplastic elastomer (TPE)。Preferred thermoplastic elastomer (TPE) is thermoplastic polyurethane polymer (TPU)。The present invention is described use TPU, it should be appreciated that simply a kind of embodiment and those skilled in the art can use other thermoplastic elastomer (TPE) for these。
TPU polymer type for the present invention can be this area and the TPU polymer of any routine of known in the literature, as long as this TPU polymer has enough molecular weight。Described TPU polymer reacts typically via the polyisocyanates polyester such as hydroxy-end capped with intermediate, hydroxy-end capped polyethers, hydroxy-end capped Merlon or its mixture and one or more chain extenders and prepares, and all these are well-known to those skilled in the art。
Described hydroxy-end capped intermediate polyester is usually number-average molecular weight (Mn) for about 500 to about 10,000, hopefully about 700 to about 5,000, preferably about 700 being generally less than 1.3 to about 4,000 and acid number, being preferably smaller than the linear polyesters of 0.8。Molecular weight is determined by analyzing functional end-group and relates to number-average molecular weight。Described polymer is prepared in the following way: the esterification of (1) one or more glycol and one or more dicarboxylic acids or anhydride or (2) by ester exchange reaction, that is, the reaction of one or more glycol and dicarboxylic ester。The preferably relatively sour generally excessive mol ratio more than a diol, to obtain the dominant linear chain of terminal hydroxyl。Suitable intermediate polyester also includes multiple lactone, for instance polycaprolactone, and it is typically prepared by 6-caprolactone and bifunctional initiator such as diethylene glycol。The dicarboxylic acids of desired polyester can be aliphatic, alicyclic, aromatics or its combination。Can individually or the suitable dicarboxylic acids used by mixture generally there is 4-15 carbon atom including altogether: succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, p-phthalic acid, cyclohexane dicarboxylic acid etc.。The anhydride of above-mentioned dicarboxylic acids can also be used, such as phthalic anhydride, tetrahydrophthalic anhydride etc.。Adipic acid is preferred acid。Can be aliphatic, aromatics or its combination for reacting the glycol forming desired intermediate polyester, and there is 2-12 carbon atom altogether, it include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-HD, 2,2-dimethyl-1, ammediol, 1,4-cyclohexanedimethanol, 1,10-decanediol, 1,12-dodecanediol etc.。1,4-butanediol is preferred glycol。
Hydroxy-end capped polyether intermediate is polyether polyol, it is derived from the glycol with 2-15 carbon atom altogether or polyhydric alcohol, preferred alkyl diol (diolorglycol), and the ether of described alcohol and the alkylene oxide (typically oxirane or expoxy propane or its mixture) including having 2-6 carbon atom reacts。Such as, it is possible to by first make propylene glycol and propylene oxide reaction followed by with reacting ethylene oxide and prepare the polyethers of hydroxyl-functional。The primary hydroxyl produced by oxirane is more more reactive than secondary hydroxyl and be therefore preferred。Available commercially available polyether polyol includes: the PEG comprising the oxirane with glycol reaction, poly-(propylene glycol) that comprise expoxy propane react with propylene glycol, comprise the water that reacts with oxolane (PTMEG) gather (oxygen tetramethylene glycol)。PEO macromonomer (PTMEG) is preferred polyether intermediate。Polyether polyol farther includes the polyamide adducts of alkylene oxide and can include, such as, comprise the ethylenediamine adduct of the product of ethylenediamine and expoxy propane, comprise diethylenetriamines and the diethylenetriamines adduct of the product of expoxy propane and similar polyamide type polyether polyhydric alcohol。Copolyether can also be used in the present invention。Typical copolyether includes the product of THF and oxirane or the product of THF and expoxy propane。These can be buied from BASF as PolyTHFB (block copolymer) and PolyTHFR (random copolymer)。Different polyether intermediate generally has the number-average molecular weight (Mn) determined by analyzing functional end-group, and its mean molecule quantity is more than about 700, and such as about 700 to about 10,000, hopefully about 1000 to about 5,000, it is preferable that about 1000 to about 2500。A kind of concrete desired polyether intermediate is the blend of the PTMEG of the blend of polyethers of two or more different molecular weights, such as 2000Mn and 1000Mn。
The most preferred embodiment of the present invention uses the intermediate polyester reacted and prepare by 50/50 blend of adipic acid with 1,4-butanediol and 1,6-HD。
The Merlon of the present invention-based polyurethanes resin is reacted by the blend of diisocyanate with hydroxy-end capped Merlon and chain extender and prepares。Described hydroxy-end capped Merlon can be prepared by glycol and carbonate reaction。
US Patent No. 4,131,731 is incorporated herein by about the disclosure of hydroxy-end capped Merlon and their preparation。Above-mentioned Merlon is line style and has terminal hydroxyl and substantially get rid of other end group。Fundamental reaction thing is glycol and carbonic ester。Suitable glycol is selected from comprising 4-40, the alicyclic diol of preferred 4-12 carbon atom and aliphatic diol and being selected from the polyether polyols that per molecule comprises 2-20 alkoxyl and each alkoxyl comprises 2-4 carbon atom。The glycol being suitable for the present invention includes comprising the aliphatic diol of 4-12 carbon atom, such as butanediol-1,4, pentanediol-1,4, neopentyl glycol, hexanediol-1,6,2,2,4-trimethyl hexanediol-l, 6, decanediol-1,10, hydrogenate two Caulis et Folium Lini base glycol (hydrogenateddilinoleylglycol), hydrogenate two oil base glycol (hydrogenateddioleylglycol)；And alicyclic diol such as cyclohexanediol-1,3, hydroxymethyl-cyclohexane-1,4, cyclohexane diol-1,4, hydroxymethyl-cyclohexane-1,3,1,4-endo-methylene group-2-hydroxyl-5-methylol hexamethylene, poly alkylene glycol。Glycol for this reaction can be single glycol or diol mixture, and this depends on the character desired by finished product。
Hydroxy-end capped intermediate polycarbonate be usually this area and known in the literature those。Suitable carbonic ester is selected from the alkylene carbonates being made up of 5 to 7 rings with below general formula:
Wherein R is the saturated divalent group comprising 2-6 carbons。Suitable carbonic ester used in this application includes 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, what be suitable for the application is dialkyl carbonate, carbonic acid alicyclic ester and diaryl carbonate。Described dialkyl carbonate can comprise 2-5 carbon atom in each alkyl and its instantiation is diethyl carbonate and carbonic acid dipropyl。Carbonic acid alicyclic ester, particularly carbonic acid two alicyclic ester can comprise 4-7 carbon atom in each circulus, and can there are the one in described structure or two kinds。When a group is alicyclic, another can be alkyl or aryl。On the other hand, if a group is aryl, another can be alkyl or alicyclic。The preferred embodiment of the diaryl carbonate that can comprise 6-20 carbon atom in each aryl is dipheryl carbonate base ester, carboxylol base ester and carbonic acid dinaphthyl ester。
By at the temperature of 100 DEG C-300 DEG C and the pressure of 0.1-300mmHg, when existing or being absent from ester exchange catalyst, glycol is made to react with carbonic ester, preferred as alkylene carbonates by 10:1-1:10 but the molar range of preferred 3:1-1:3 and carry out described reaction, simultaneously by low boiling glycol is distilled off。
More particularly, it is seen that hydroxy-end capped Merlon was prepared with two stages。In the first phase, glycol and alkylene carbonates react to form the Merlon of low-molecular-weight hydroxyl end-blocking。By at 100 DEG C-300 DEG C, preferably 150 DEG C-250 DEG C 10-30mmHg, the reduction of preferred 50-200mmHg pressure under distillation and remove more lower boiling glycol。Fractionating column is used to be separated from reactant mixture by this by-product glycol。Described by-product glycol is taken out from the top of described tower and unreacted alkylene carbonates and diol reactant are back to reaction vessel as backflow。Inert gas flow or atent solvent stream can be used to promote the removing of by-product glycol when formed。When the degree of polymerization of the bright hydroxy-end capped Merlon of the scale of the by-product glycol obtained is 2-10, described pressure is gradually decrease to 0.1-10mmHg and removes unreacted glycol and alkylene carbonates。The beginning of second stage of this mark reaction, period by under the pressure of 100 DEG C-300 DEG C, preferably 150 DEG C-250 DEG C and 0.1-10mmHg, distill out glycol when formed and the Merlon of condensation low-molecular-weight hydroxyl end-blocking until the hope molecular weight of the hydroxy-end capped Merlon of acquisition。The molecular weight (Mn) of hydroxy-end capped Merlon can be about 500 to about 10,000, but in a preferred embodiment, it will for 500-2500。
Second neccessary composition of the TPU polymer of the preparation present invention is polyisocyanates。
The polyisocyanates of the present invention generally has formula R (NCO)n, wherein n is generally 2-4, and owing to composition is thermoplastic be very preferably 2。Therefore, owing to they cause crosslinking only with considerably less amount, such as based on the gross weight of all polyisocyanates less than 5 weight %, hopefully less than the 2 weight % polyisocyanates using degrees of functionality to be 3 or 4。R generally has the aromatics of about 20 carbon atoms of 2-altogether, alicyclic and aliphatic or their combination。The example of suitable aromatic diisocyanates includes diphenyl methane-4,4 '-diisocyanate (MDI), H12MDI, meta-xylene diisocyanate (XDI), m-tetramethylene xylene diisocyanate (TMXDI), phenylene-1,4-diisocyanate (PPDI), 1,5-naphthalene two Carbimide. (NDI) and diphenyl methane-3,3 '-dimethoxy-4 ', 4 '-diisocyanate (TODI)。The example of suitable aliphatic vulcabond include isoflurane chalcone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), 1,6-cyclohexane diisocyanate (HDI), 1,6-bis-isocyanate group-2,2,4,4-tetramethyl hexane (TMDI), 1,10-decane diisocyanate and trans-dicyclohexyl methyl hydride diisocyanate (HMDI)。It is a kind of diisocyanate very preferably containing the o-MDI to (2,4) isomer less than approximately 3 weight %。
3rd neccessary composition of the TPU polymer manufacturing the present invention is chain extender。Suitable chain extender is lower aliphatic or the short-chain diol with about 10 carbon atoms of about 2-, and including such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2,2'-ethylenedioxybis(ethanol)., the cis-trans-isomer of cyclohexyl dihydroxymethyl, neopentyl glycol, 1,4-butanediol, 1,6-hexylene glycol, 1,3-butanediol and 1,5-pentanediol。In addition aromatic diol can be used as chain extender, and for high heat application (highheatapplication) prioritizing selection aromatic diol。Benzenediol (HQEE) and Xylene glycol are the suitable chain extenders of the TPU for manufacturing the present invention。Xylene glycol is 1,4-bis-(methylol) benzene and the mixture of 1,2-bis-(methylol) benzene。Benzenediol is preferred aromatic chain extender and specifically includes hydroquinone, that is, also referred to as double; two (beta-hydroxy ethyl) ethers of 1,4-bis-(2-hydroxyl-oxethyl) benzene；Resorcinol, that is, also referred to double; two (beta-hydroxy ethyl) ethers of 1,3-bis-(2-hydroxyethyl) benzene；Catechol, that is, also referred to double; two (beta-hydroxy ethyl) ethers of 1,2-bis-(2-hydroxyl-oxethyl) benzene)；With its combination。A kind of preferred chain extender is 1,4-butanediol。
Above-mentioned three kinds of neccessary compositions (hydroxy-end capped intermediate, polyisocyanates and chain extender) preferably react in the presence of a catalyst。
Usually, it is possible to use any conventional catalyst is so that diisocyanate reacts with hydroxy-end capped intermediate or chain extender and described catalyst is usually well known in the art and literature。The example of suitable catalyst includes various alkyl ethers or the alkyl sulfide alcohol ether of bismuth or stannum, and wherein moieties has about 20 carbon atoms of 1-, and instantiation includes Bismuth Octoate, lauric acid bismuth etc.。Preferred catalyst includes various tin catalyst, such as stannous octoate, two sad dibutyl tins, dibutyl tin laurate etc.。The amount of described catalyst is generally on a small quantity, such as, be about 20ppm-based on the gross weight of polyurethane formation monomer and be about 200ppm。
The TPU polymer of the present invention can pass through any typical polymerization methods manufacture of well known in the art and literature。
The thermoplastic polyurethane of the present invention is prepared preferably via " step (oneshot) " method, all components is wherein simultaneously or substantially added simultaneously to heated extruder together and makes it react the described polyurethane of formation。The equivalent proportion of the total yield of diisocyanate and hydroxy-end capped intermediate and diol chain-extension agent is typically about 0.95-about 1.10, it is desirable to ground about 0.97-about 1.03, it is preferable that about 0.97-about 1.00。The Xiao A hardness of the TPU formed should be about 85A for 65A-95A, preferably about 75A-, to obtain the most desirable end product properties。The reaction temperature adopting urethane catalyst is usually about 175 DEG C of-Yue 245 DEG C, preferably about 180 DEG C of-Yue 220 DEG C。The molecular weight (Mw) of thermoplastic polyurethane is usually about 100,000-about 800,000, hopefully about 150,000-about 400,000, preferably about 150,000-about 350,000, and it is by the gpc measurement relative to polystyrene standards。
Described thermoplastic polyurethane can also utilize prepolymer process to prepare。In prepolymer approach, react one or more excessive with usually equivalent for hydroxy-end capped intermediate polyisocyanates to form the pre-polymer solution wherein with free or unreacted polyisocyanates。Reaction is typically under suitable urethane catalyst exists to carry out at about 80 DEG C of-Yue 220 DEG C, preferred about 150 DEG C of-Yue 200 DEG C。Subsequently, the chain extender of selectivity type as noted above adds by the equivalent being generally equivalent to terminal isocyanate groups and any free or unreacted diisocyanate cpd。Thus diisocyanate total amount is about 0.95-about 1.10 relative to the total yield ratio of hydroxy-end capped intermediate and the total yield of chain extender, it is desirable to ground about 0.98-about 1.05, it is preferable that about 0.99-about 1.03。Regulate hydroxy-end capped intermediate relative to the equivalent proportion of chain extender to produce 65A-95A, preferred 75A-85A Shore hardness。Chain extending reaction temperature is typically about 180 DEG C of-Yue 250 DEG C, it is preferable that about 200 DEG C of-Yue 240 DEG C。Typically, prepolymer approach can carry out in any conventional equipment, and described device is preferably extruder。Therefore, the di-isocyanate reaction excessive with equivalent in the Part I of extruder of hydroxy-end capped intermediate is to form pre-polymer solution and added by chain extender in downstream part subsequently and react with this pre-polymer solution。Can using various conventional extruders, extruder is equipped with the separating screw rod that draw ratio is at least 20, preferably at least 25。
Can using available additive with suitable amount, described additive includes opaque pigment, coloring agent, mineral filler, stabilizer, lubricant, UV absorbent, processing aid and other desired additive。Available opaque pigment includes titanium dioxide, zinc oxide and titan yellow (titanateyellow), and available coloring pigment includes white carbon black, oxide yellow thing (yellowoxides), brown oxide (brownoxides), the metal-oxide of natural and calcine loess or umber, chrome oxide green, cadmium pigment, chromium pigment and other mixing and organic pigment。Available filler includes kieselguhr (superfloss) clay, silicon dioxide, Talcum, Muscovitum, wollastonite (wallostonite), barium sulfate and calcium carbonate。If desired, it is possible to use the useful stabilizer of such as antioxidant etc, it includes phenol antioxidant, and available light stabilizer includes organophosphorus ester and organo-tin mercaptide (mercaptides)。Available lubricant includes metallic stearate, paraffin oil and amide waxe。Available UV absorbent includes 2-(2'-hydroxyl phenol) benzotriazole and 2-Viosorb 110。
Plasticiser additive can also be advantageously used not affect character to reduce hardness。
During melt spinning process, TPU polymer as above can use cross-linking agent lightly crosslinked。Described cross-linking agent is the prepolymer of the hydroxy-end capped intermediate of Wei the polyethers, polyester, Merlon, polycaprolactone or its mixture that react with polyisocyanates。Polyester or polyethers are the preferably hydroxy-end capped intermediate for manufacturing cross-linking agent, and when using with polyester TPU combination, polyethers is most preferred。Described cross-linking agent prepolymer has more than about 1.0, the isocyanate functionality of preferably about 1.0-about 3.0, more preferably about 1.8-about 2.2。If the two ends of especially preferred hydroxy-end capped intermediate are all with isocyanate-terminated, then therefore there is the isocyanate functionality of 2.0。
For manufacturing the polyisocyanates of cross-linking agent and identical in manufacturing TPU polymer mentioned above。The diisocyanate of such as MDI etc is preferred diisocyanate。
The number-average molecular weight (Mn) of described cross-linking agent is about 1,000-about 10,000 dalton, it is preferable that about 1,200-about 4,000, more preferably from about 1,500-about 2,800。There is the cross-linking agent higher than about 1500Mn and produce good permanent deformation character (setproperties)。
Percentage by weight for the cross-linking agent of TPU polymer is about 2.0%-about 20%, preferably about 8.0%-about 15%, it is more preferable to about 10%-about 13%。The percentage ratio of cross-linking agent used is based on the percentage by weight of the gross weight of TPU polymer and cross-linking agent。
Preferred melt spinning process for manufacturing the TPU fiber of the present invention includes preformed TPU polymer is supplied to extruder, so that TPU polymer melt leaving the downstream of extruder position or adding cross-linking agent after TPU melt leaves extruder continuously near TPU melt。Before melt leaves extruder or after melt leaves extruder, described cross-linking agent can be added in extruder。If added after melt leaves extruder, then described cross-linking agent needs to utilize either statically or dynamically blender to make itself and TPU melt mixed to guarantee that cross-linking agent is suitably mixed in TPU polymer melt。After the extruder, melted TPU polymer flows into spinning manifold together with cross-linking agent。Melt material flow is divided into different streams by spinning manifold, and wherein each stream is conducted to multiple spinneret。Typically, the presence of the Melt Pump being used for each the different streams flowed out from spinning manifold, each of which Melt Pump is to some spinneret feed。Described spinneret has aperture, and melt is forced through described aperture and leaves described spinneret with the form of monfil。The size in the hole in spinneret will depend upon which desired fiber size (danier)。
Described TPU polymer melt can be made by spinning pack (spinpackassembly) and to leave this spinning pack as fiber。Preferred spinning pack used is that of the slug flow of the generation TPU polymer by this assembly。Most preferred spinning pack is that described in PCT Patent application WO2007/076380, and it is merged in the application in full。
Once this fiber leaves spinneret, it is cooled before being wound up on bobbin。This fiber, through the first godet, applies oil preparation, and described fiber advances to the second godet。It is the relative speed that fiber is wound into bobbin for manufacturing an importance of the technique of the fiber of the present invention。With regard to relative speed, it refers to that melt leaves the speed (meltflow ability) of spinneret for winding speed。In normal prior art TPU melt spinning process, fiber is wound with the speed of 4-6 times of meltflow ability。So draw or stretch described fiber。For the unique fiber of the present invention, it is not desired to this extension traction (extensivedrawing)。Described fiber must to wind at least equal to the speed of meltflow ability to implement described technique。For the fiber of the present invention, it is necessary to exceeding meltflow ability and be not more than 50%, be preferably no greater than 20%, speed more preferably no more than 10% winds described fiber, the situation being not more than 5% produces fabulous result。It is believed that the winding speed equal with meltflow ability can be desirable, but must take to wind speed slightly faster to implement described technique。For example, fiber leaves spinneret with the speed of 300 meters per minute, it is most preferred that wind with the speed of 300-315 rice per minute。
The fiber of the present invention can be made with multiple danier numeral system。Danier is the term showing fiber size in this area。Danier is the weight of the grams in 9000 meters of fibre lengths。The fiber of the present invention is typically fabricated the size into 20-600 danier, preferred 40-400, more preferably 70-360 danier。
When being manufactured fiber by the method for the present invention, usually after cooling or period and just be wound enter bobbin before the release additives (one example is silicone oil) of such as oil preparation etc added to the surface of fiber。
One importance of melt spinning process is the mixing of TPU polymer melt and cross-linking agent。Suitable Homogeneous phase mixing is for obtaining consistent fibre property and realize the long running time when not producing fibrous fracture be important。The mixing of TPU melt and cross-linking agent should be the method obtaining slug flow, i.e. first in first out。Dynamic mixer or static mixer can be utilized to realize suitable mixing。Static mixer is more difficult to cleaning；Therefore, dynamic mixer is preferred。The dynamic mixer with feed worm and batch mixing pin is preferred blender。The US Patent No. 6,709,147 being incorporated herein by discloses this blender and has rotatable batch mixing pin。Batch mixing pin is also in fixed position, such as, be connected on the cylinder of blender and extend towards the centrage of feed worm。Mixed feeding screw rod can invest the end of extruder screw by screw thread, and the shell of blender can be bolt-connected on extruder。The feed worm of dynamic mixer should be following design, and it is when almost without back-mixing, makes polymer melt move in the way of being progressively advanced thus obtaining the slug flow of melt。The L/D of mixing screw should more than 3 and less than 30, preferably about 7 to about 20, it is more preferable to about 10 to about 12。
Temperature in the mixed zone that TPU polymer melt mixes with cross-linking agent wherein is about 200 DEG C of-Yue 240 DEG C, it is preferable that about 210 DEG C of-Yue 225 DEG C。These temperature are necessarily used for obtaining described reaction and do not degrade described polymer simultaneously。
It is about 200,000-about 800,000, preferably about 250,000-about 500,000 that the TPU formed and cross-linking agent react the molecular weight (Mw) to obtain the TPU in final fibers form during melt spinning process, it is more preferable to about 300,000-about 450,000。
Spinning temperature (temperature of spinneret interpolymer melt) should be above the fusing point of polymer, it is preferable that higher than about 10 DEG C of-Yue of melting point polymer 20 DEG C。Operable spinning temperature is more high, and spinning effect is more good。However, when spinning temperature is too high, polymer can be degraded。Therefore, higher than about 10 DEG C of-Yue of the fusing point of TPU polymer 20 DEG C for realize be best when non-polymer is degraded the balance of good spinning。If spinning temperature is too low, polymer is likely in spinneret solidify and cause fibrous fracture。
The unique fiber of the present invention have load period and in the zero load cycle between 100% to 200% percentage elongation opposing straight and/or constant modulus。This constant modulus by stress in load period under 100% percentage elongation less than the 0.023 every danier of fors, under 150% percentage elongation less than the 0.036 every danier of fors, confirmed less than the 0.053 every danier of fors under 200% percentage elongation；And by stress in the zero load cycle under 200% percentage elongation less than the 0.027 every danier of fors, under 150% percentage elongation less than the 0.018 every danier of fors, confirmed less than the 0.015 every danier of fors under 100% percentage elongation, this data of all of which are collected by 360 denier fibers。
In addition, this constant modulus by stress in load period under 100% percentage elongation less than the 0.158 every danier of fors, under 150% percentage elongation less than the 0.207 every danier of fors, confirmed less than the 0.265 every danier of fors under 200% percentage elongation；And by stress in the zero load cycle under 200% percentage elongation less than the 0.021 every danier of fors, under 150% percentage elongation less than the 0.012 every danier of fors, confirmed less than the 0.008 every danier of fors under 100% percentage elongation, this data of all of which are collected by 360 denier fibers。
It is the one developed for elastomeric yarn by DuPont for obtaining the code test code of above modulus values。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)。% permanent deformation is measured after the 5th circulates。Then, make this fiber samples by circulating and be stretched to fracture for the 6th time。Instrument record load under each elongation, maximum load before breaking, and the fracture load that unit is the every danier of fors (breakingload) and elongation at break at maximum load and percentage elongation。This test generally at room temperature carries out (23 DEG C ± 2 DEG C；With 50% ± 5% humidity)。
The fiber of the present invention has the elongation at break of at least 400%, preferably about 450 to 500%。This fiber is circular monofilaments。With reference to Fig. 2, it is seen that 70 Denier monofilament fibers are substantially circular in transverse shape。Fig. 1 shows 70 Denier monofilament dry-spinning fibers, and it has bigger cross-sectional width。
Fig. 3 shows the curve compared by the melt spun fibre of dry-spinning fiber Yu the present invention。This curve describes the relation of square (square micron) of danier (X-axis) vs. fiber width。The melt spun fibre of this curve display present invention has the constant-slope on this curve, and described dry-spinning fiber has the slope exponentially increased。Result is that the fabric prepared with the fiber of the present invention is thinner and thus make wearer more comfortable。
Another key character of the fiber of the present invention is that it demonstrates the bursting strength of improvement in fabric compared with dry-spinning fiber。
Can by using 1 inch diameter ball enforcement BallBurstPunctureStrengthTest to show this feature according to ASTMD751。This test simulation finger is through this fabric until forming hole。Very surprisingly the relative dry-spinning polyurethane fiber of the fiber of the present invention demonstrates the improvement of about 50-75% in bursting strength。Even if the hot strength of fiber is almost identical, there is also the improvement of described bursting strength。
In addition the fiber of the present invention has higher thermal capacitance。The combination of straight modulus curve, higher thermal capacitance and thinner specification causes that the fabric prepared with fiber of the present invention makes garment wearer be comfortable on。
The fabric prepared with fiber of the present invention can by knitting or tatting manufacture。Often preferably manufacture fabric with other fiber together with this TPU fiber。Especially preferred use hard fibre is together with the elastic fiber of the present invention。Preferred hard fibre, such as nylon and/or polyester。This hard fibre improves the anti-snagging of fabric for 100% elastic fiber fabric。A kind of preferred fabric is with knitting that of alternating strands, alternating strands such as a branch of 140 danier TPU/70 Denier nylon and a branch of 140 danier TPU alternately (being called 1-1 fabric) or then 2 bundle 140 danier TPU (being called 1-2 fabric) after a branch of 140 danier TPU/70 Denier nylon。
The fabric that can use the present invention manufactures clothing。Due to the comfortableness that this fiber provides, the most preferred use of described fabric is to manufacture underwear or fitted garment。The underwear of such as medicated bra etc and T-shirt and such as run for campaign item, ski, the sportswear of bicycle or other motion can benefit from the character of these fibers。The straight modulus of these fibers benefited from by the clothing worn next to the skin, because once described fiber reaches body temperature, then this modulus is even lower。The clothing of sensation close-fitting vest 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 the fiber of the present invention and fabric can be used to manufacture any clothing。Exemplary embodiment can be the Shoulder belt of brassiere manufactured by woven fabric and the cup cover of medicated bra manufactured by knitted fabric, and wherein said woven fabric and knitting fabric both of which comprise the melt spinning TPU fibers of the present invention。Described bra belt does not need adjustable button, because this fabric is elastic。
It is better understood with the present invention by reference following example。
Embodiment
The intermediate (polyhydric alcohol) terminated by polyester hydroxyl for the TPU polymer of embodiment is reacted with 1,4-chain expansion of succinic acid agent and MDI and prepares。This PEPA is prepared by 50/50 mixture reaction of adipic acid and 1,4-butanediol and 1,6-HD。This polyhydric alcohol has the Mn of 2500。This TPU is prepared by a step process。The cross-linking agent being added in TPU during spinning technique is to produce isocyanate-terminated polyethers and prepared polyether prepolymer by 1000MnPTMEG and MDI reaction。The consumption of this cross-linking agent is the TPU 10 weight % adding the total weight of cross-linking agent。Melt spinning fibers is used for the 40 of embodiment, 70,140 and 360 denier fibers to manufacture。
Embodiment 1
Provide this embodiment to illustrate compared with the melt spinning TPU fibers of prior art (40 danier) and commercially available dry-spinning fiber (70 danier), the modulus curve of the opposing straight of fiber of the present invention (70 danier)。
The testing regulations used is as above with regard to described by testing elastic character。Use Instron model 5564 tonometer with Merlin software。This experimental condition is 23 DEG C ± 2 DEG C and 50% ± 5% humidity。The fibre length of test specimen is 50.0mm。Test four samples and result is the meansigma methods of 4 test specimens。Result is shown in Table I。
Table I
Above-mentioned all data are the meansigma methodss of 4 test specimens。
From the data above, it is seen that the melt spun fibre of the present invention has the modulus curve of opposing straight during the 5th test cycle。First time circulation is typically ignored because this is to alleviate the stress in fiber。
Embodiment 2
Provide this embodiment so that the width of the melt spun fibre of the present invention compared with commercially available dry-spinning fiber to be described。Described width is measured by SEM。Result shows in table ii。
Table II
As can be seen, dry-spinning fiber has much bigger width and this difference increases with danier number and becomes much larger。
Embodiment 3
Provide this embodiment so that the bursting strength of the improvement of the melt spinning TPU fibers of the present invention compared with commercially available dry-spinning urethane fibers to be described。70 denier fibers are used to be prepared single jersey (signelJersey) knitting fabric by each types of fibers。The bursting puncture strength of fabric is measured according to ASTMD751。Result is shown in Table III。This result is the meansigma methods of 5 test specimens。
Table III
| Test | Dry-spinning | Melt-spun |
| Fracture load (load at failure, lbs) | 5.78 | 9.03 |
| Fault 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 |
The melt spun fibre of the surprising present invention of being that while does not have higher hot strength compared with dry-spinning fiber, but the bursting strength of described melt spun fibre is higher。
Although according to patent statute, having elaborated best mode and preferred embodiment, but the scope of the present invention be not limited to this, but limited by the scope of the appended claims。
Claims (10)
1. an elastic fiber for Thin Specs, constant compression, high bursting strength, its have at least 400% ultimate elongation and have load period and in the zero load cycle between 100% to 200% percentage elongation the modulus of opposing straight。
2. the fiber of claim 1, wherein the monfil of 40 daniers has the width less than 100 microns。
3. the fiber of claim 1, wherein when the fiber of described 70 daniers is made into fabric and measures the puncture strength of described fabric according to ASTMD751, described fabric has the fracture load more than 6 pounds。
4. the fiber of claim 1, wherein said fiber is thermoplastic polyurethane fibers。
5. the fiber of claim 4, wherein said fiber is polyester thermoplastic's polyurethane。
6. the fiber of claim 5, wherein said fiber polyether crosslinking agent cross-links。
7. the fiber of claim 5, the weight average molecular weight of wherein said polyester thermoplastic's polyurethane is 200,000-700,000 dalton。
8. the fiber of claim 6, wherein said cross-linking agent is the 5-20 weight % of the total weight of described polyester thermoplastic's polyurethane and described cross-linking agent。
9. the fiber of claim 8, wherein said cross-linking agent is the 8-12 weight % of the total weight of described polyester thermoplastic's polyurethane and described cross-linking agent。
10. the fabric comprising at least two difference fiber, the at least one that at least one in wherein said fiber is in thermoplastic polyurethane fibers and described fiber is hard fibre, and wherein said thermoplastic polyurethane's fiber has the load-deformation curve of opposing straight between 100% to 200% percentage elongation。
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| CN201080027998.4A Active CN102803586B (en) | 2009-06-25 | 2010-06-24 | The high strength fabric be made up of Thin Specs constant compression elastomer |
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| 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 |
| EP3072913A1 (en) * | 2010-12-21 | 2016-09-28 | Lubrizol Advanced Materials, Inc. | Elastomer resins, fibers and fabrics thereof, and uses thereof |
| US20130255103A1 (en) | 2012-04-03 | 2013-10-03 | Nike, Inc. | Apparel And Other Products Incorporating A Thermoplastic Polymer Material |
| BR112015015762B1 (en) * | 2012-12-28 | 2022-02-01 | Invista Technologies S.A.R.L. | Garment article including a stretch fabric composite |
| 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 |
| BR112017011558B1 (en) * | 2014-12-04 | 2021-11-09 | Zhengzhou Zhongyuan Spandex Engineering Technology Co., Ltd | DRY WIRING COMPONENT OF ELASTIC FIBERS AND DRY WIRING PART OF ELASTIC FIBER |
| US9883702B2 (en) | 2015-10-07 | 2018-02-06 | Mast Industries (Far East) Limited | Portion of bra and bra having zones of varying elastic moduli |
| EP4241601A3 (en) | 2019-08-02 | 2023-10-25 | NIKE Innovate C.V. | An upper for an article of footwear |
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| 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 |
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