CN102803586B - The high strength fabric be made up of Thin Specs constant compression elastomer - Google Patents
The high strength fabric be made up of Thin Specs constant compression elastomer Download PDFInfo
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- CN102803586B CN102803586B CN201080027998.4A CN201080027998A CN102803586B CN 102803586 B CN102803586 B CN 102803586B CN 201080027998 A CN201080027998 A CN 201080027998A CN 102803586 B CN102803586 B CN 102803586B
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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
Abstract
The invention discloses the elastomer of the modulus curve with opposing straight between 100% to 200% percentage elongation.This fiber can make the clothes with very comfort.Preferred elastomer is made up of thermoplastic polyurethane polymer and is passed through unique melt-spinning method preparation, and described fiber is wound with the speed of the meltflow ability only leaving spinnerets a little more than polymer and enters bobbin in the method.
Description
Technical field
The present invention relates to the high strength fabric be made up of Thin Specs constant compression (thingaugeconstantcompression) elastomer.The clothes be made up of this constant compression elastomer have makes wearer's sensation as snug as a bug in a rug.In addition these clothes tolerate the diapirism caused by the high strength fabric made with this elastomer.
Background technology
In recent years, due to the life style of the change of global range, surmount basic isolation features and except basic isolation features, high level is in the demand of the higher function of fabric always.There is Thin Specs but do not sacrifice the intensity of fabric and the fabric of globality to a kind of demand of above-mentioned functions.This fabric compared with Thin Specs allows lower packing volume, the reduction of " bulk " sense and the external visibility not through coat with regard to underwear.
Synthesis elastomer (SEF) is made up to produce elasticity of the polymer with soft chain segment and hard segment usually.There is the polymer Typical of hard segment and soft chain segment poly-(ether-amide), such as
or copolyesters, such as
or thermoplastic polyurethane, such as
but very the SEF of high elongation rate typically uses the polymer with hard segment and soft chain segment, such as dry-spinning polyurethane
or melt spinning thermoplastic's polyurethane
although the elongation at break of these SEF is different from low-level to high level, all normally can be described to that there is the modulus (strain) exponentially increased along with percentage elongation (stress) increase.
Melt spinning TPU fibers provides some advantages compared with dry-spinning polyurethane fiber, because do not use solvent in melt spinning process, and in dry spinning process, polymer to be dissolved in solvent and to carry out spinning.Then make this solvent divide from described fiber middles to be evaporated.All solvents are difficult to remove completely from described dry-spinning fiber.In order to promote to remove described solvent from dry-spinning fiber, typically these fibers being made small size and making its bunchy together to produce multifilament (multi-filament) (band shape) fiber.Compared with melt-spun fibre, for given DENIER, this can cause larger physical size.These physical characteristics cause more bulk in fabric and person's character that is described multifilament bundled to impel the loss of comfortableness.
Melt spinning TPU fibers manufactures by TPU polymer is carried out melt spinning.TPU polymer is obtained 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 vulcabond; (c) chain extender of short-chain hydroxyl end-blocking.Described hydroxy-end capped intermediate forms the hard segment that the soft chain segment of TPU polymer and described polyisocyanates and chain extender form TPU polymer.TPU polymer elasticity is given in the combination of described soft chain segment and hard segment.TPU polymer is also lightly crosslinked to provide the performance of enhancing frequently by the polyisocyanate blocked prepolymer of use.This cross-linked material is added in melting TPU polymer during the melt spinning of fiber.
Wish to obtain the TPU elastomer with relative constancy compression (relativelyconstantcompression) of percentage elongation between zero-sum 250% also to wish to prepare the constant compression clothes and/or the fabric that comprise described TPU fiber.Wish that these constant compression fabrics are Thin Specs and have high puncture resistance (punctureresistance) in addition.The clothes manufactured by above-mentioned fabrics can be wearer and provide higher comfort and confidence.
Accompanying drawing explanation
Fig. 1 is the microphoto of 70 denier multifilament yarn of commercially available dry-spinning polyurethane fiber.
Fig. 2 is the microphoto of 70 DENIER of the constant compression thermoplastic polyurethane fibers of melt spinning of the present invention.
Fig. 3 is the curve of display as the Y-axis of square (square micron) of the X-axis vs. fiber width of DENIER.Fiber of the present invention is compared with commercially available dry-spinning fiber.
Summary of the invention
Target of the present invention be to provide Thin Specs, the high strength fibre of 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 is less than the every DENIER of 0.023 fors by stress in load period, is less than the every DENIER of 0.023 fors under 150% percentage elongation, under 200% percentage elongation, is less than the every DENIER of 0.053 fors under 100% percentage elongation; Under 200% percentage elongation, be less than the every DENIER of 0.027 fors with by stress in the zero load cycle, under 150% percentage elongation, be less than the every DENIER of 0.018 fors, under 100% percentage elongation, be less than the every DENIER of 0.015 fors confirmed.
A kind of exemplary fiber is by by thermoplastic polyurethane polymer, preferred polyester polyether polyols with reduced unsaturation melt spinning and manufacturing.Described fiber is by lightly crosslinked to described polymer melt interpolation crosslinking agent (preferred 5-20 % by weight) during melt spinning process.
The method preparing described fiber comprises a melt spinning process, forms described fiber thus by making polymer melt pass spinnerets.The speed that the speed that fiber leaves this spinnerets and fiber roll move into into bobbin is relative close.That is, this fiber should be greater than speed that fiber leaves spinnerets at the most 50%, the speed winding of preferably 20%, more preferably 10% enters bobbin.
Another target of the present invention manufactures fabric with described Thin Specs, constant compression fiber.In exemplary embodiment, manufacture described fabric by described elastomer to be combined (such as by knitting (knit) or tatting (weave)) with the hard fibre of such as nylon and/or polyester fiber and so on.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 elastomer.Described clothes provide good comfort for wearer.
Detailed Description Of The Invention
Fiber of the present invention is prepared by thermoplastic elastomer (TPE).Preferred thermoplastic elastomer (TPE) is thermoplastic polyurethane polymer (TPU).Use TPU is described the present invention, but is to be understood that this is a kind of embodiment and those skilled in the art can use other thermoplastic elastomer (TPE).
For the TPU polymer that TPU polymer type of the present invention can be this area and any routine of known in the literature, as long as this TPU polymer has enough molecular weight.Described TPU polymer is generally reacted by polyisocyanates and intermediate e such as hydroxy-end capped polyester, hydroxy-end capped polyethers, hydroxy-end capped Merlon or its mixture and one or more chain extenders and is prepared, and all these are well-known to those skilled in the art.
Described hydroxy-end capped intermediate polyester is generally that number-average molecular weight (Mn) is about 500 to about 10,000, hopefully about 700 to about 5,000, preferably about 700 to about 4,000 and acid number is generally less than 1.3, be preferably less 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 acid anhydrides 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 being greater than a diol, to obtain the dominant linear chain of terminal hydroxyl.Suitable intermediate polyester also comprises multiple lactone, such as polycaprolactone, and it is typically prepared by 6-caprolactone and bifunctional initiator such as diethylene glycol (DEG).The dicarboxylic acids of desired polyester can be aliphatic, alicyclic, aromatics or its combination.Can generally have 4-15 carbon atom comprising altogether separately or by the suitable dicarboxylic acids that mixture uses: 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 etc.The acid anhydrides of above-mentioned dicarboxylic acids can also be used, such as phthalic anhydride, tetrahydrophthalic anhydride etc.Hexanedioic acid is preferred acid.Glycol for the intermediate polyester reacting formation hope can be aliphatic, aromatics or its combination, and has 2-12 carbon atom altogether, and it comprises ethylene glycol, 1,2-propylene glycol, 1,3-PD, 1,3-BDO, 1,4-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, 2,2-dimethyl-1, ammediol, 1,4-cyclohexanedimethanol, 1,10-decanediol, 1,12-dodecanediol etc.BDO is preferred glycol.
Hydroxy-end capped polyether intermediate is polyether polyol, it is derived from the glycol or polyalcohol, preferred alkyl glycol (diolorglycol) with 2-15 carbon atom altogether, and described alcohol reacts with the ether comprising the alkylene oxide (typically oxirane or expoxy propane or its mixture) with 2-6 carbon atom.Such as, can by first to make propylene glycol and propylene oxide reaction then subsequently with reacting ethylene oxide and prepare the polyethers of hydroxyl-functional.The primary hydroxyl produced by oxirane has more reactive than secondary hydroxyl and is therefore preferred.Available commercially available polyether polyol comprises: comprise with the PEG of the oxirane of glycol reaction, comprise poly-(propylene glycol) of the expoxy propane reacted with propylene glycol, comprise poly-(the oxygen tetramethylene glycol) of the water reacted with oxolane (PTMEG).PEO macromonomer (PTMEG) is preferred polyether intermediate.Polyether polyol comprises the polyamide adducts of alkylene oxide further and can comprise, such as, comprise the ethylenediamine adduct of the product of ethylenediamine and expoxy propane, comprise the diethylenetriamines adduct of the product of diethylenetriamines and expoxy propane and similar polyamide type polyether polyalcohol.Also copolyether can be used 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 from BASF as PolyTHFB (block copolymer) and PolyTHFR (random copolymer).Different polyether intermediate generally has by analyzing functional end-group and the number-average molecular weight (Mn) determined, its mean molecule quantity for being greater than about 700, such as about 700 to about 10,000, hopefully about 1000 to about 5,000, preferably about 1000 to about 2500.A kind of desired polyether intermediate is specifically the blend of the blend of the polyethers of two or more different molecular weights, the PTMEG of such as 2000Mn and 1000Mn.
Most preferred embodiment of the present invention uses is reacted by 50/50 blend of adipic acid and BDO and 1,6-hexylene glycol and the intermediate polyester prepared.
Merlon of the present invention-based polyurethanes resin is reacted by the blend of vulcabond and hydroxy-end capped Merlon and chain extender and is prepared.Described hydroxy-end capped Merlon can be prepared by glycol and carbonate reaction.
US Patent No. 4,131, about the disclosure of hydroxy-end capped Merlon and their preparation is incorporated to herein by reference in 731.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 acid ester.Suitable glycol is selected from the alicyclic diol and aliphatic diol that comprise 4-40, preferably 4-12 carbon atom and is selected from per molecule and comprises 2-20 alkoxyl and each alkoxyl comprises the polyether polyols of 2-4 carbon atom.Be suitable for glycol of the present invention and comprise the aliphatic diol comprising 4-12 carbon atom, such as butanediol-1,4, pentanediol-1,4, neopentyl glycol, hexylene glycol-1,6,2,2,4-trimethyl hexylene glycols-1,6, decanediol-1,10, hydrogenation two flax base glycol (hydrogenateddilinoleylglycol), hydrogenation two oil base glycol (hydrogenateddioleylglycol); And alicyclic diol such as cyclohexanediol-1,3, hydroxymethyl-cyclohexane-Isosorbide-5-Nitrae, cyclohexane diol-Isosorbide-5-Nitrae, hydroxymethyl-cyclohexane-1,3, Isosorbide-5-Nitrae-endo-methylene group-2-hydroxyl-5-methylol cyclohexane, 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 generally this area and known in the literature those.Suitable carbonic acid ester is selected from the alkylene carbonates be made up of 5 to 7 rings with following general formula:
Wherein R is the saturated divalent group comprising 2-6 carbons.Suitable carbonic acid ester used in this application 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 Isosorbide-5-Nitrae-pentylidene ester, carbonic acid 2,3-pentylidene ester and carbonic acid 2,4-pentylidene ester.
In addition, what be applicable to 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 the one that can exist 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 that can comprise the diaryl carbonate of 6-20 carbon atom in each aryl is dipheryl carbonate base ester, carboxylol base ester and carbonic acid dinaphthyl ester.
By under the pressure of the temperature of 100 DEG C-300 DEG C and 0.1-300mmHg, in existence or when there is not ester exchange catalyst, make glycol and carbonic acid ester, preferred as alkylene carbonates by 10: 1-1: 10 but preferably the molar range of 3: 1-1: 3 is reacted and carries out described reaction, simultaneously by distillation removing low boiling glycol.
More specifically, described hydroxy-end capped Merlon was prepared with two stages.In the first phase, glycol and alkylene carbonates react the Merlon to form low-molecular-weight hydroxyl end-blocking.By at 100 DEG C-300 DEG C, preferably 150 DEG C-250 DEG C under the pressure of 10-30mmHg, the preferably reduction of 50-200mmHg distillation and the more lower boiling glycol of removing.Fractionating column is used to be separated from reactant mixture by this accessory substance glycol.The top of described accessory substance glycol from described tower is taken out 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 accessory substance glycol when formed.When the degree of polymerization of the bright hydroxy-end capped Merlon of scale of the accessory substance glycol obtained is 2-10, described pressure is reduced to 0.1-10mmHg gradually and removes unreacted glycol and alkylene carbonates.The beginning of second stage of this mark reaction, period by distilling out the Merlon of glycol and condensation low-molecular-weight hydroxyl end-blocking when formed until obtain the hope molecular weight of hydroxy-end capped Merlon under the pressure of 100 DEG C-300 DEG C, preferably 150 DEG C-250 DEG C and 0.1-10mmHg.The molecular weight (Mn) of hydroxy-end capped Merlon can be about 500 to about 10,000, but in a preferred embodiment, it will be 500-2500.
The second neccessary composition preparing TPU polymer of the present invention is polyisocyanates.
Polyisocyanates of the present invention generally has formula R (NCO)
n, wherein n is generally 2-4, and due to composition be thermoplasticly be very preferably 2.Therefore, because they cause crosslinked, only with considerably less amount, such as, gross weight based on all polyisocyanates is less than 5 % by weight, is hopefully less than the polyisocyanates that 2 % by weight use degrees of functionality are 3 or 4.R generally has the aromatics of 2-about 20 carbon atoms altogether, alicyclic and aliphatic or their combination.The example of suitable aromatic diisocyanates comprises diphenyl methane-4,4 '-vulcabond (MDI), H
12mDI, m-Xylene Diisocyanate (XDI), m-tetramethylene xylene vulcabond (TMXDI), phenylene-1,4-vulcabond (PPDI), 1,5-naphthalene two isocyanic acid (NDI) and diphenyl methane-3,3 '-dimethoxy-4 ', 4 '-vulcabond (TODI).The example of suitable aliphatic vulcabond comprises 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).A kind of vulcabond very preferably containing the o-MDI to (2,4) isomers being less than about 3 % by weight.
The 3rd neccessary composition manufacturing TPU polymer of the present invention is chain extender.Suitable chain extender is lower aliphatic or the short-chain diol with about 2-about 10 carbon atoms, and comprise the cis-trans-isomer of such as ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, cyclohexyl dihydroxymethyl, neopentyl glycol, 1,4-butanediol, 1,6-hexylene glycol, 1,3-butanediol and 1,5-PD.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 for the manufacture of TPU of the present invention.Xylene glycol is the mixture of Isosorbide-5-Nitrae-two (methylol) benzene and 1,2-bis-(methylol) benzene.Benzenediol is preferred aromatic chain extender and comprises hydroquinones particularly, that is, also referred to as two (beta-hydroxy ethyl) ethers of Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene; Resorcinol, that is, be also called two (beta-hydroxy ethyl) ethers of 1,3-bis-(2-hydroxyethyl) benzene; Catechol, that is, be also called two (beta-hydroxy ethyl) ethers of 1,2-bis-(2-hydroxyl-oxethyl) benzene); With its combination.A kind of preferred chain extender is BDO.
Above-mentioned three kinds of neccessary compositions (hydroxy-end capped intermediate, polyisocyanates and chain extender) are preferably reacted in the presence of a catalyst.
Usually, any conventional catalyst can be used to make vulcabond and hydroxy-end capped intermediate or chain extender react and described catalyst is normally known in this area and document.The example of suitable catalyst comprises various alkyl ether or the alkyl sulfide alcohol ether of bismuth or tin, and wherein moieties has 1-about 20 carbon atoms, and instantiation comprises Bismuth Octoate, laurate bismuth etc.Preferred catalyst comprises 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, form the gross weight of monomer based on polyurethane and be about 20ppm-and be about 200ppm.
TPU polymer of the present invention can by any typical polymerization methods manufacture known in this area and document.
Thermoplastic polyurethane of the present invention is preferably standby via " step (oneshot) " legal system, wherein by all components together simultaneously or be substantially added into by the extruder that heats simultaneously and make it react and form described polyurethane.The equivalent proportion of the total yield of vulcabond and hydroxy-end capped intermediate and diol chain-extension agent is generally about 0.95-about 1.10, hopefully about 0.97-about 1.03, preferably 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 of urethane catalyst is adopted to be generally 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 generally 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, hydroxy-end capped intermediate and one or more polyisocyanates that usually equivalent is excessive are reacted to form the pre-polymer solution wherein with free or unreacted polyisocyanates.Reaction is generally carried out under suitable urethane catalyst exists 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 selective type as noted above is by generally equaling terminal isocyanate groups and any equivalent that is free or unreacted diisocyanate cpd adds.Thus vulcabond total amount relative to the total yield of the total yield of hydroxy-end capped intermediate and chain extender than being about 0.95-about 1.10, hopefully about 0.98-about 1.05, preferably about 0.99-about 1.03.Regulate hydroxy-end capped intermediate relative to the equivalent proportion of chain extender to produce 65A-95A, preferably 75A-85A Shore hardness.Chain extending reaction temperature is generally about 180 DEG C of-Yue 250 DEG C, preferably 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.Various conventional extruders can be used, extruder is equipped with draw ratio to be at least 20, preferably at least 25 separating screw rod.
Can use available additive with suitable amount, described additive comprises opaque pigment, colouring agent, mineral filler, stabilizing agent, lubricant, UV absorbent, processing aid and other additive of wishing.Available opaque pigment comprises titanium dioxide, zinc oxide and titan yellow (titahateyellow), and available coloring pigment comprise carbon black, oxide yellow thing (yellowoxides), brown oxide (brownoxides), natural and forge manufacture-yellow soil or umber, chrome oxide green, cadmium pigment, chromium pigment and other mixing metal oxide and organic pigment.Available filler comprises diatomite (superfloss) clay, silica, talcum, mica, wollastonite (wallostonite), barium sulfate and calcium carbonate.If desired, can use the useful stabilizing agent of such as antioxidant and so on, 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) 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 be lightly crosslinked with crosslinking agent.Described crosslinking agent is the prepolymer that can be the hydroxy-end capped intermediate of polyethers, polyester, Merlon, polycaprolactone or its mixture reacted with polyisocyanates.Polyester or polyethers are the preferably hydroxy-end capped intermediates for the manufacture of crosslinking agent, and when combinationally using with polyester TPU, polyethers is most preferred.Described crosslinking agent prepolymer have be greater than about 1.0, the isocyanate functionality of preferably about 1.0-about 3.0, more preferably about 1.8-about 2.2.If therefore the two ends of especially preferably hydroxy-end capped intermediate all with isocyanate-terminated, then have the isocyanate functionality of 2.0.
Polyisocyanates for the manufacture of crosslinking agent is identical what manufacture in TPU polymer with mentioned above.The vulcabond of such as MDI and so on is preferred vulcabond.
The number-average molecular weight (Mn) of described crosslinking agent is about 1,000-about 10,000 dalton, preferably about 1,200-about 4,000, more preferably from about 1,500-about 2,800.The crosslinking agent had higher than about 1500Mn produces good permanent deformation character (setproperties).
Percentage by weight for the crosslinking agent of TPU polymer is about 2.0%-about 20%, preferably about 8.0%-about 15%, more preferably from about 10%-about 13%.The percentage of crosslinking agent used is the percentage by weight of the gross weight based on TPU polymer and crosslinking agent.
Preferred melt spinning process for the manufacture of TPU fiber of the present invention comprises preformed TPU polymer is supplied to extruder, to make TPU polymer melting and leaving the downstream of extruder position near TPU melt or add crosslinking agent continuously after TPU melt leaves extruder.Before melt leaves extruder or after melt leaves extruder, described crosslinking agent can be added in extruder.If added after melt leaves extruder, then described crosslinking agent needs to utilize static state or dynamic mixer to make itself and TPU melt mixed to guarantee that crosslinking agent is suitably mixed in TPU polymer melt.After the extruder, melting TPU polymer flows into spinning manifold together with crosslinking agent.Melt material flow is divided into different streams by spinning manifold, and wherein each stream is conducted to multiple spinnerets.Usually, there is the Melt Pump being used for each the different stream flowed out from spinning manifold, wherein each Melt Pump is to some spinnerets feed.Described spinnerets has aperture, and melt is forced through described aperture and leaves described spinnerets with the form of monfil.The size in the hole in spinnerets will depend on desired fiber size (DENIER).
Described TPU polymer melt can be made by spinning pack (spinpackassembly) and leave this spinning pack to be used as fiber.Preferred spinning pack used is that it is that to produce by the slug flow of the TPU polymer of this assembly.Most preferred spinning pack is describe in PCT patent application wO2007/076380 that, and it is merged in the application in full.
Once this fiber leaves spinnerets, it is cooled before being wound up on bobbin.This fiber, through the first godet roller, applies finish, and described fiber advances to the second godet roller.An importance for the manufacture of the technique of fiber of the present invention is the relative speed that fiber roll moves into into bobbin.With regard to relative speed, it refers to that melt leaves the speed (meltflow ability) of spinnerets for winding speed.In normal prior art TPU melt spinning process, fiber is wound with the speed of 4-6 times of meltflow ability.Such traction or the described fiber that stretches.For unique fiber of the present invention, do not wish this extension traction (extensivedrawing).Described fiber must at least to equal the speed winding of meltflow ability to implement described technique.For fiber of the present invention, must be not more than 50% to exceed meltflow ability, preferably be not more than 20%, speed more preferably no more than 10% reels 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 reel speed slightly faster to implement described technique.For example, fiber leaves spinnerets with the speed of 300 meters per minute, most preferably reels with the speed of 300-315 rice per minute.
Fiber of the present invention can be made with multiple DENIER numeral system.DENIER is the term showing fiber size in this area.DENIER is in the weight of the grams of 9000 meters of fibre lengths.Fiber of the present invention is generally manufactured to the size of 20-600 DENIER, preferably 40-400, more preferably 70-360 DENIER.
When manufacturing fiber by method of 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 finish and so on added to the surface of fiber.
An importance of melt spinning process is TPU polymer melt and the mixing of crosslinking agent.Suitable Homogeneous phase mixing is concerning the consistent fibre property of acquisition and realize when not producing fibrous fracture the long running time being important.The mixing of TPU melt and crosslinking 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 clean; Therefore, dynamic mixer is preferred.The dynamic mixer with feed worm and batch mixing pin is preferred blender.Be incorporated to US Patent No. 6,709,147 herein by reference disclose this blender and there is rotatable batch mixing pin.Batch mixing pin can also be in a fixed position, and such as, center line on the cylindrical shell being connected to blender and towards feed worm extends.Mixed feeding screw rod can invest the end of extruder screw by screw thread, and the shell of blender can be bolted on extruder.The feed worm of dynamic mixer should be following design, and it is not when almost having back-mixing, makes polymer melt move in the mode of progressively advancing thus obtain the slug flow of melt.The L/D of mixing screw should be greater than 3 and be less than 30, and preferably about 7 to about 20, more preferably from about 10 to about 12.
Temperature wherein in the mixed zone that mixes with crosslinking agent of TPU polymer melt is about 200 DEG C of-Yue 240 DEG C, preferably about 210 DEG C of-Yue 225 DEG C.These temperature must be used for not degrading the while of obtaining described reaction described polymer.
The molecular weight (Mw) that the TPU formed and crosslinking agent react the TPU obtained in final fibers form during melt spinning process is about 200,000-about 800,000, preferred about 250,000-about 500,000, more preferably from about 300,000-about 450,000.
Spinning temperature (temperature of spinnerets interpolymer melt) should higher than the fusing point of polymer, preferably higher than melting point polymer about 10 DEG C of-Yue 20 DEG C.Operable spinning temperature is higher, and spinning effect is better.But if spinning temperature is too high, polymer can be degraded.Therefore, higher than TPU polymer fusing point about 10 DEG C of-Yue 20 DEG C for realize the good spinning when non-polymer is degraded balance be best.If spinning temperature is too low, polymer may solidify and cause fibrous fracture in spinnerets.
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 is less than the every DENIER of 0.023 fors by stress in load period, is less than the every DENIER of 0.036 fors under 150% percentage elongation, is less than the every DENIER of 0.053 fors is confirmed under 200% percentage elongation under 100% percentage elongation; And under 200% percentage elongation, be less than the every DENIER of 0.027 fors by stress in the zero load cycle, under 150% percentage elongation, be less than the every DENIER of 0.018 fors, under 100% percentage elongation, be less than the every DENIER of 0.015 fors confirmed, wherein all this data are collected by 360 denier fibers.
In addition, this constant modulus is less than the every DENIER of 0.158 fors by stress in load period, is less than the every DENIER of 0.207 fors under 150% percentage elongation, is less than the every DENIER of 0.265 fors is confirmed under 200% percentage elongation under 100% percentage elongation; And under 200% percentage elongation, be less than the every DENIER of 0.021 fors by stress in the zero load cycle, under 150% percentage elongation, be less than the every DENIER of 0.012 fors, under 100% percentage elongation, be less than the every DENIER of 0.008 fors confirmed, wherein all this data are collected by 360 denier fibers.
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 circulation.Then, this fiber sample is made to circulate by the 6th time and be stretched to fracture.The load of instrument record under each extends, maximum load before breaking, and unit is the fracture load (breakingload) of the every DENIER of fors and elongation at break at maximum load and percentage elongation.This test is at room temperature carried out usually (23 DEG C ± 2 DEG C; With 50% ± 5% humidity).
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, visible 70 Denier monofilament fibers are substantially circular in transverse shape.Fig. 1 shows 70 Denier monofilament dry-spinning fibers, and it has larger cross-sectional width.
Fig. 3 shows curve dry-spinning fiber and melt-spun fibre of the present invention compared.This curve describes the relation of square (square micron) of DENIER (X-axis) vs. fiber width.This curve shows melt-spun fibre of the present invention and has the constant-slope on this curve, and described dry-spinning fiber has the slope exponentially increased.Result is that the fabric prepared with fiber of the present invention is thinner and thus make wearer more comfortable.
Another key character of fiber of the present invention is the bursting strength that it demonstrates improvement in fabric compared with dry-spinning fiber.
This feature can be shown by using 1 inch diameter ball to implement BallBurstPunctureStrengthTest according to ASTMD751.This test simulation is pointed through this fabric until form hole.Very surprisingly the relative dry-spinning polyurethane fiber of fiber of the present invention demonstrates the improvement of about 50-75% in bursting strength.Even if the TENSILE STRENGTH of fiber is almost identical, also there is the improvement of described bursting strength.
In addition fiber of the present invention has higher thermal capacitance.The combination of straight modulus curve, higher thermal capacitance and thinner specification causes making garment wearer feel comfortable with fabric prepared by fiber of the present invention.
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 preferably use hard fibre together with elastomer 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 that alternating strands such as a branch of 140 DENIER TPU/70 Denier nylon and a branch of 140 DENIER TPU then 2 restraint 140 DENIER TPU (being called 1-2 fabric) after replacing (being called 1-1 fabric) or a branch of 140 DENIER TPU/70 Denier nylon with alternating strands knitting that.
Clothes can be manufactured with fabric of the present invention.Due to the comfortableness that this fiber provides, the most preferred use of described fabric manufactures underwear or fitted garment.The underwear of such as brassiere and so on 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 clothes worn next to the skin, because once described fiber reaches body temperature, then this modulus is even lower.The clothes 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 can manufacture any clothes with fiber of the present invention and fabric.Exemplary embodiment can be the cup cover of the Shoulder belt of brassiere manufactured by woven fabric and the brassiere manufactured by knitted fabric, and wherein said woven fabric and knit goods all comprise melt spinning TPU fibers of the present invention.Described bra belt does not need adjustable button, because this fabric is flexible.
The present invention will be understood better by reference to following examples.
Embodiment
TPU polymer for embodiment is reacted by the intermediate (polyalcohol) of polyester hydroxyl end-blocking with BDO chain extender and MDI and obtains.This polyester polyol is reacted by 50/50 mixture of adipic acid and BDO and 1,6-hexylene glycol and is obtained.This polyalcohol has the Mn of 2500.This TPU is obtained by a step process.The crosslinking agent be added to during spinning technique in TPU reacts to produce isocyanate-terminated polyethers and obtained polyether prepolymer by 1000MnPTMEG and MDI.The consumption of this crosslinking agent is that TPU adds 10 % by weight of the total weight of crosslinking agent.By melt spinning fibers to manufacture 40,70,140 and 360 denier fibers being used for embodiment.
embodiment 1
Provide this embodiment to compare with commercially available dry-spinning fiber (70 DENIER) with the melt spinning TPU fibers (40 DENIER) of prior art to illustrate, the modulus curve of the opposing straight of fiber of the present invention (70 DENIER).
The testing regulations used is as above with regard to described by testing elastic character.Use Instron model 5564 tensometer 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 mean value of 4 test specimens.The results are shown in Table I.
Table I
Above-mentioned all data are the mean value of 4 test specimens.
From above data, visible melt-spun fibre of the present invention has the modulus curve of opposing straight during the 5th test cycle.First time circulation is left in the basket usually because this is the stress alleviated in fiber.
embodiment 2
Provide this embodiment so that the width of melt-spun fibre of the present invention compared with commercially available dry-spinning fiber to be described.Described width is measured by SEM.Result display in table ii.
Table II
As can be seen, dry-spinning fiber there is much bigger width and this difference with DENIER number increase and become larger.
embodiment 3
Provide this embodiment so that the bursting strength of the improvement of 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 prepare single jersey (signelJersey) knit goods by each types of fibers.The bursting puncture strength of fabric is measured according to ASTMD751.The results are 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 |
| 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 |
Although surprisingly melt-spun fibre of the present invention does not have higher TENSILE STRENGTH compared with dry-spinning fiber, the bursting strength of described melt-spun fibre is higher.
Although according to patent statute, set forth best mode and preferred embodiment, scope of the present invention is not limited thereto, but is limited by the scope of appended claims.
Claims (19)
1., from a melt spun elastic fibers prepared by crosslinked thermoplastic polyurethane, wherein said fiber has the ultimate elongation of at least 400%; The wherein stress value that shows below in load period of this melt spun elastic fibers
I () is less than the every DENIER of 0.023 fors under 100% percentage elongation,
(ii) under 150% percentage elongation, be less than the every DENIER of 0.036 fors, and
(iii) under 200% percentage elongation, be less than the every DENIER of 0.053 fors;
The wherein stress value that shows below in the zero load cycle of this melt spun elastic fibers
I () is less than the every DENIER of 0.027 fors under 200% percentage elongation,
(ii) under 150% percentage elongation, be less than the every DENIER of 0.018 fors, and
(iii) under 100% percentage elongation, be less than the every DENIER of 0.015 fors; And
Wherein said thermoplastic polyurethane is prepared from reactant mixture, and described reactant mixture comprises
A () number-average molecular weight is the linearly hydroxy-end capped polyester of 500 to 10,000,
(b) polyisocyanates, and
C () has the diol chain-extension agent of 2-10 carbon atom.
2. the fiber of claim 1, wherein said fiber is the monfil having 40 DENIER and have the width being less than 100 microns.
3. the fiber of claim 1, wherein when described fiber has 70 DENIER and be made into fabric and measure the puncture strength of described fabric according to ASTMD751, described fabric has the fracture load being greater than 6 pounds.
4. the fiber of claim 1, wherein said fiber polyether crosslinking agent is cross-linked.
5. the fiber of claim 1, the weight average molecular weight of wherein said polyester thermoplastic's polyurethane is 200,000-700,000 dalton.
6. the fiber of claim 4, wherein said crosslinking agent is the 5-20 % by weight of the total weight of described polyester thermoplastic's polyurethane and described crosslinking agent.
7. the fiber of claim 6, wherein said crosslinking agent is the 8-12 % by weight of the total weight of described polyester thermoplastic's polyurethane and described crosslinking agent.
8. one kind comprises the fabric of fiber described in claim 1.
9. the fabric of claim 8, further containing the hard fibre comprising nylon and/or polyester fiber.
10. the fabric of claim 9, wherein said fabric is made up of two bundle thermoplastic polyurethane fibers of relatively every a branch of hard fibre.
The fabric of 11. claims 9, wherein said thermoplastic polyurethane fibers has 20-600 DENIER.
The fabric of 12. claims 11, wherein said thermoplastic polyurethane fibers has 70-360 DENIER.
The fabric of 13. claims 9, wherein said hard fibre has 70 DENIER and described thermoplastic polyurethane fibers has 140 DENIER.
14. clothing items, it comprises the fabric of claim 9.
The clothing item of 15. claims 14, wherein said goods are underwears.
The clothing item of 16. claims 15, wherein said goods are brassieres.
17. 1 kinds of methods preparing elastomer described in claim 1, described method comprises:
A thermoplastic polyurethane melt spinning is passed through spinnerets by (); With
B the winding speed winding that this elastomer is not more than 50% with the speed exceeding polymer melt and leave described spinnerets is entered bobbin by ().
The method of 18. claims 17, wherein said winding speed exceedes the speed that polymer melt leaves described spinnerets and is not more than 20%.
The method of 19. claims 18, wherein said winding speed exceedes the speed that polymer melt leaves described spinnerets and is not more than 10%.
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| 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 |
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| 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 |
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