CN101208464A - Spandex compositions for high speed spinning - Google Patents
Spandex compositions for high speed spinning Download PDFInfo
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- CN101208464A CN101208464A CNA200680015888XA CN200680015888A CN101208464A CN 101208464 A CN101208464 A CN 101208464A CN A200680015888X A CNA200680015888X A CN A200680015888XA CN 200680015888 A CN200680015888 A CN 200680015888A CN 101208464 A CN101208464 A CN 101208464A
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Abstract
A spandex comprising a polyurethane or polyurethaneurea reaction product of at least one diisocyanate compound and a poly(tetramethylene-co-ethyleneether) glycol comprising constituent units derived by copolymerizing tetrahydrofuran and ethylene oxide wherein the percentage of ethylene ether moieties is from about 16 to about 70 mole percent with at least one chain extender selected from the group consisting of diamines and diols and at least one chain terminator wherein the spandex is spun at a speed in excess of about 750 meters per minute.
Description
Background of invention
Invention field
The present invention relates to novel spandex (spandex) composition, it comprises poly-(tetramethylene-copolymerization (co)-ethyleneether) glycol that contains by the formation unit that makes oxolane and oxirane copolymerization generation, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol, and wherein the spandex silk is spun into the high speed usually above 750 meters/minute.
Description of Related Art
Poly-(tetramethylene ether) glycol is also referred to as the homopolymers of PolyTHF or oxolane (THF, tetrahydrofuran), because of its application in the soft chain segment of polyurethane-urea but known.Poly-(tetramethylene ether) glycol is given polyurethane-urea elastomer and fiber excellent dynamic performance.They have low-down glass transition temperature, but have the crystalline melt temperatures that is higher than room temperature.Therefore, they are waxy solid at ambient temperature, and need remain under the elevated temperature preventing and solidify.
Be used to reduce the degree of crystallinity of polytetramethylene ether chains with the copolymerization of cyclic ethers.This polymer melting temperature that has reduced the copolyether glycol has also improved simultaneously and has contained this copolymer some dynamic property as the polyurethane-urea of soft chain segment.The comonomer that is used for this purpose comprises oxirane, and it can be brought down below environment temperature with copolymer melt temperature according to co-monomer content.The use of poly-(tetramethylene-copolymerization-ethyleneether) glycol also can improve some dynamic property of polyurethane-urea, for example breaking extension (elongation at break) and cryogenic property, and this is desirable for some final use.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol is as known in the art.At United States Patent(USP) Nos. 4,139, their preparation has been described in 567 and 4,153,786.This analog copolymer can be by any known methods of cyclic ether polymerization preparation, for example " Polytetrahydrofuran " (Gordon﹠amp of P.Dreyfuss work; Breach, N.Y.1982) described in those.This class polymerization comprises the catalysis with strong proton or lewis acid, heteropoly acid and perfluorinated sulfonic acid or acidic resins.In some cases, use as U.S. Patent No. 4,163, the polymerization accelerant described in 115, for example carboxylic acid anhydrides may be favourable.In these cases, main polymer product is a diester, its need be in step subsequently hydrolysis to obtain required polymer diol.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol provides the advantage that is better than gathering (tetramethylene ether) glycol on some specific physical property.Under the percent ethyleneether content that is higher than 20 moles of %, poly-(tetramethylene-copolymerization-ethyleneether) glycol at room temperature is the liquid of appropriate viscosity and has the poly-lower viscosity of (tetramethylene ether) glycol than same molecular amount under the temperature of the fusing point that is higher than poly-(tetramethylene ether) glycol.Surpass those polyurethane made by poly-(tetramethylene ether) glycol or the character of polyurethane-urea by some physical property of poly-(tetramethylene-copolymerization-ethyleneether) polyurethane that glycol is made or polyurethane-urea.
Spandex based on poly-(tetramethylene-copolymerization-ethyleneether) glycol also is as known in the art.For example, the U.S. Patent No. 4,224,432 of authorizing people such as Pechhold discloses and has used poly-(tetramethylene-copolymerization-ethyleneether) glycol with low cyclic ethers content to prepare spandex and other polyurethane-urea.It is preferred that Pechhold points out to be higher than 30% percent ethyleneether content.Pechhold does not point out the use of auxiliary extender (coextender), although it discloses the mixture that can use amine.
The U.S. Patent No. 4,658,065 of authorizing people such as Aoshima discloses uses heteropolyacid catalyst several THF copolyethers of prepared in reaction via THF and polyalcohol.But Aoshima also discloses the cyclic ethers that can comprise copolymerization in polymerization process with THF, for example oxirane.Aoshima discloses and can use the copolyether glycol to prepare spandex, but does not contain the example of the spandex of being made by poly-(tetramethylene-copolymerization-ethyleneether) glycol.
The U.S. Patent No. 3,425,999 of authorizing people such as Axelrood discloses by poly-(tetramethylene-copolymerization-ethyleneether) glycol and has prepared the EU urea to be used for oil resistivity and good cryogenic property.Poly-(tetramethylene-copolymerization-ethyleneether) glycol has 20 to the 60 weight % percent ethyleneether content of (being equivalent to 29 to 71 moles of %).Axelrood is not disclosed in and uses these polyurethane-ureas in the spandex.Axelrood discloses " the most useful cahin extension agent is the diamines that is selected from primary and secondary diamines and composition thereof among the present invention ".Axelrood discloses further that " preferred diamines is the diamines that is obstructed, for example dichloro-benzidine and di-2-ethylhexylphosphine oxide (2-chloroaniline)." the not openly use of ethylenediamine.
Authorize people's such as Nishikawa U.S. Patent No. 6,639,041 discloses the fiber that has favorable elasticity at low temperatures, and it contains the polyurethane-urea made by polyalcohol (this polyalcohol contains the copolyether of THF, oxirane and/or expoxy propane), vulcabond and diamines and the polymer of solvation in organic solvent.Nishikawa points out that these compositions have the improved cryogenic property that is better than standard homopolymers spandex.Nishikawa points out that also " be higher than under the percent ethyleneether content of about 37 moles of %, the unload forces under the low elongation is unacceptably low, and breaking extension reduces, and the set rising, although very slight in the copolyether glycol." embodiment among the Nishikawa shows that when the molar percentage of ethyleneether part in the copolyether rose to 31 to 37 moles of % from 22 moles of %, breaking extension raise, but after rising to 50 moles of %, breaking extension reduces again.On the contrary, the trend that improves of the spandex of the present invention molar percentage that shows the vinethene part in copolyether breaking extension when 27 moles of % rise to 49 moles of %.All samples in this patent is spun under 650 meters/minute or lower speed.
Any fiber manufacturers is all clear, and the quicker spandex that is spun into makes and produces more multi-fibre and reduce manufacturing cost thus in preset time, but spinning speed is subjected to the restriction to the negative effect of some fibre performance.Well known to a person skilled in the art to be, the spinning speed that improves the spandex composition with reduced its elongation and improved its load force comparing than the identical spandex that is spun under the low velocity.Therefore, the spandex fiber is spun into more soon, and the reduction of elongation and the raising of load force are just many more, thus but the drawdown (draftability) of reduction fiber.But the drawdown that reduces causes using more spandexs and improves the clothes manufacturing cost thus in garment configurations.Therefore, usually practice is to slow down spinning speed with the elongation that improves spandex and reduce its load force, thus improve its at cylinder knitting (circular knitting) but and the drawdown in other spandex process operation.
A kind of method that improves based on the productivity ratio of spining technology is disclosed in the U.S. Patent No. 6,916,896 of authorizing people such as Selling.Selling has described and has used the polyurethaneurea compositions that is mixed with vulcabond to improve polymer solution solubility so that the polyurethane urea solutions of high solids content more can be carried out spinning.Even do not use more high spinning speed, also improved the productivity ratio that the weight by the spandex yarn made in preset time records.The vulcabond that polyurethane-urea of the present invention is not sneaked into also has high solution solubility and has the productivity ratio more much higher than Selling.
In JP2002-155421A " Dry-Spinning Process ", disclose by optimizing the other method that spinning condition is boosted productivity.JP2002-155421A discloses the method for boosting productivity when dry-spinning polyurethane.This method is based on regulate the spinning cabinet condition to avoid dry gas and upwards flow and to avoid strand (threadline) transverse instability in spinning cabinet.Two embodiment of JP2002-155421A all use poly-(tetramethylene ether) glycol-based spandex.JP2002-155421A openly is not fit to spandex type of the present invention.Method of the present invention demonstrates the necessary spinning cabinet condition of suitable dried fibres (for example residual 0 to 0.5% dimethylacetamide solvent in the fiber) of making that exceeds that do not depend on.In addition, additive is unnecessary.
The applicant observes, to have about 16 to about 70 moles of %, poly-(tetramethylene-copolymerization-ethyleneether) glycol that for example surpasses about 37 to about 70 moles of % the formation unit that is derived from oxirane is as soft segment base material and equally at a high speed, and the spandex that is spun under promptly surpassing 750 meters/minute provides the improved physical property that is better than other spandex of being spun under similar high speed.Based on other copolyether glycol, for example poly-(tetramethylene-copolymerization-2-methyl tetramethylene ether) or polyester-diol, ethylene glycol, 1 for example, the spandex of the copolyesters of 4-butanediol and adipic acid also has low load force.But these spandexs also have low toughness and/or low elongation usually, and this has limited them to surpass the ability of 1000 meters/minute speed spinning.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol-based spandex of the present invention has the combination of low load force (load power), high elongation and enough toughness, this can be spun into it with the speed above 1300 meters/minute, but produces the fiber with excellence drawdown in the cylinder knitting operation.In addition, spandex of the present invention shows desirable shrinkage factor reduction in the wet processes in heat with the winding speed spinning above 1000 meters/minute the time.
Summary of the invention
The present invention relates to a kind of spandex, it comprises the polyurethane or the polyurethane-urea product of following ingredients: (a) contain poly-(tetramethylene-copolymerization-ethyleneether) glycol by the formation unit that makes oxolane and oxirane copolymerization generation, the cell mesh that wherein is derived from oxirane in poly-(tetramethylene-copolymerization-ethyleneether) glycol with about 16 to about 70 moles of %, for example exist greater than about 37 to about 70 moles of %, (b) at least a vulcabond, (c) at least a cahin extension agent that is selected from diamines and glycol, wherein this spandex is spun into to surpass about 750 meters/minute speed.In one aspect of the invention, the polyurethane of above-mentioned spandex or polyurethane-urea product comprise one or more polymer diols in addition.
The invention still further relates to the method that is used to prepare above-mentioned spandex, it comprises: poly-(tetramethylene-copolymerization-ethyleneether) glycol is contacted with at least a vulcabond to form capped glycol, the cell mesh that wherein is derived from oxirane in poly-(tetramethylene-copolymerization-ethyleneether) glycol with about 16 to about 70 moles of %, for example exist greater than about 37 to about 70 moles of %, (b) capped glycol is dissolved in the solvent, the solution of the capped glycol of (b) is contacted with at least a diamines or diol chain extender, (d) with the solvent spinning of (c), thereby to surpass about 750 meters/minute speed spinning to form spandex.
Detailed Description Of The Invention
The present invention relates to the novel spandex composition made with high spinning speed, some desirable performances that it has improved the spandex fiber make high speed spinning that the negative effect of other performance is minimized simultaneously.Suppose that all other factorses remain unchanged, because the spinning productivity ratio that improves and the fixed cost of reduction, reduce the manufacturing cost of these fibers pro rata with the raising of spinning speed.Improved performance be the wet creep of retraction force (being higher unload forces), toughness and heat (promptly with hot water treatment time reduce shrinkage factor).Spandex composition of the present invention comprises polyurethane and the polyurethane-urea based on poly-(tetramethylene-copolymerization-ethyleneether) glycol.Poly-(tetramethylene-copolymerization-ethyleneether) glycol is valuable in polyurethane and the polyurethaneurea polymer " soft chain segment ".
Segmented polyurethane of the present invention or polyurethane-urea are made by poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild optional aggregation glycol, at least a vulcabond and difunctional chain extenders.Should poly-(tetramethylene-copolymerization-ethyleneether) glycol or diol mixture at first with at least a di-isocyanate reaction to form the prepolymer (" capped glycol ") of NCO-end-blocking, it is dissolved in suitable solvent subsequently, for example in dimethylacetylamide, dimethyl formamide or the N-Methyl pyrrolidone, react with difunctional chain extenders then.When being glycol, cahin extension agent forms polyurethane.When being diamines, cahin extension agent forms polyurethane-urea (a kind of subclass of polyurethane).In the preparation of the polyurethaneurea polymer that can be spun into spandex, the successive reaction by hydroxyl end groups and vulcabond and one or more diamines prolongs glycol.In each case, glycol must increase chain and have essential attributes to provide, and comprises the polymer of viscosity.If desired, can use dibutyl tin dilaurate, stannous octoate, inorganic acid, tertiary amine (for example triethylamine), N, N '-lupetazin and analog and other known catalysts are with auxiliary termination procedure.
Can be by disclosed method in the U.S. Patent No. 4,139,567 of authorizing Prukmayr, use solid perfluorinated sulfonic resin catalyst is made poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to make polyurethane of the present invention and polyurethane-urea.Perhaps, can use any other acidic cyclic ether polymerization catalyst to make these poly-(tetramethylene-copolymerization-ethyleneether) glycol, for example heteropoly acids.Heteropoly acid and salt thereof available in practice of the present invention can be, for example, as authorizes those the used catalyst in the polymerization of cyclic ethers and copolymerization described in people's such as Aoshima the U.S. Patent No. 4,658,065.These polymerizations can comprise the additional promoter (for example acetic anhydride) of use, maybe can comprise and use the chain terminating agent molecule to regulate molecular weight.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to make polyurethane of the present invention and polyurethane-urea can comprise the formation unit by oxolane and oxirane copolymerization are generated, the cell mesh (ethyleneether part) that wherein is derived from oxirane in poly-(tetramethylene-copolymerization-ethyleneether) glycol with about 16 to about 70 moles of %, for example greater than about 37 to about 70 moles of %, or greater than about 37 to about 55 moles of %, or exist greater than about 37 to about 50 moles of %.Randomly, poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to make polyurethane of the present invention or polyurethane-urea can comprise the formation unit by oxolane and oxirane copolymerization are generated, the cell mesh (ethyleneether part) that wherein is derived from oxirane in poly-(tetramethylene-copolymerization-ethyleneether) glycol with about 40 to about 70 moles of %, or about 40 to 55 moles of %, or about 40 to 50 moles of % exist.The percentage of the ethyleneether part that the percentage of the unit that is derived from oxirane that exists in the glycol is equivalent to exist in the glycol.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to make polyurethane of the present invention and polyurethane-urea can have about 650 dalton to about 4000 daltonian mean molecule quantities.Higher poly-(tetramethylene-copolymerization-ethyleneether) glycol molecular weight is for selected physical property, and for example elongation may be favourable.
Poly-(tetramethylene-copolymerization-ethyleneether) glycol that is used to make polyurethane of the present invention and polyurethane-urea can comprise and is derived from the chain terminating agent glycol molecules on a small quantity, the unit of especially non-cyclisation glycol.Non-cyclisation glycol is meant and is not easy the glycol that cyclisation forms cyclic ethers under reaction condition.These non-cyclisation glycol can comprise ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butynediols, 2,2-dimethyl-1, ammediol and water.
Choose wantonly and comprise at least a annexing ingredient, for example the 3-methyltetrahydrofuran, be derived from 1, the ether of ammediol or also can be used for making polyurethane of the present invention and polyurethane-urea as poly-(tetramethylene-copolymerization-ethyleneether) glycol of other glycol that mixes on a small quantity of molecular weight regulator, and can be included in the term " poly-(tetramethylene-copolymerization-ethyleneether) or poly-(tetramethylene-copolymerization-ethyleneether) glycol ".This at least a annexing ingredient can be the comonomer of polymer diol, or it can be another material that mixes with poly-(tetramethylene-copolymerization-ethyleneether) glycol.This at least a annexing ingredient can exist on the degree aspect useful of the present invention that do not detract.
The polymer diol that can be used for making polyurethane of the present invention or polyurethane-urea can have about 650 dalton to about 4000 daltonian mean molecule quantities.Available polymer diol comprises poly-(tetramethylene ether) glycol, poly-(tetramethylene-copolymerization-2-methyl tetramethylene ether) glycol, poly-(ethyleneether) glycol, poly-(propylidene ether) glycol, PCDL and polyester-diol, or the combination of this type of glycol.Polymer diol can be chosen wantonly and comprise at least a annexing ingredient, another comonomer of polymer diol for example, or it can be another material with the polymer diol blend, and this selection is included in the implication of term " polymer diol ".This at least a annexing ingredient can exist, as long as its useful aspect of the present invention that can not detract.When polymer diol is polyester-diol, polyester-diol is selected from (i) ethylene glycol, propylene glycol, butanediol, 2,2-dimethyl-1, ammediol and composition thereof and the (ii) product of terephthalic acid (TPA), butanedioic acid, adipic acid, azelaic acid, decanedioic acid and dodecanedioic acid and composition thereof.
When poly-(tetramethylene-copolymerization-ethyleneether) glycol when being not the polymer diol blend of poly-(ethyleneether) glycol, poly-(tetramethylene-copolymerization-ethyleneether) the two pure and mild polymer diols that merge can have and are less than or equal to for example about 40 moles of %, or about 35 moles of %, or the percent of total of the unit that is derived from oxirane of about 30 moles of %.When poly-(tetramethylene-copolymerization-ethyleneether) glycol and poly-(ethyleneether) glycol blend, poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild poly-(ethyleneether) glycol that merge have about 35 to about 70 moles of %, for example about 37 to about 70 moles of %, or the percent of total of about 40 to about 65 moles of % the unit that is derived from oxirane.No matter polymer diol is poly-(ethyleneether) glycol or another polymer diol, in this blend, poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild polymer diols exist with at least 10 moles of % of the summation of poly-(tetramethylene-copolymerization-ethyleneether) molal quantity of glycol and the molal quantity of polymer diol separately.
Operable vulcabond comprises, but be not limited to, 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, 1-isocyanato--2-[(4-cyanato-phenyl) methyl] benzene, two (4-isocyanato-cyclohexyl) methane, 5-isocyanato--1-(isocyanato-methyl)-1,3,3-trimethyl-cyclohexane, 1,3-two isocyanato-s-4-methyl-benzene, 2,2 '-toluene di-isocyanate(TDI), 2,4 '-toluene di-isocyanate(TDI) and composition thereof.Particularly preferred vulcabond is 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, 1-isocyanato--2-[(4-cyanato-phenyl) methyl] benzene and composition thereof.Most preferred vulcabond is 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene.
When needs polyurethane, cahin extension agent is a glycol.The example of this type of available glycol includes but not limited to ethylene glycol, 1, ammediol, 1,2-propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1,3-trimethylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1, ammediol, 1, two (hydroxyl-oxethyl) benzene and 1 of 4-, 4-butanediol and composition thereof.
When the needs polyurethane-urea, cahin extension agent is a diamines.This type of available diamines includes but not limited to hydrazine, ethylenediamine, 1, the 2-propane diamine, 1, the 3-propane diamine, 1,2-butanediamine (1, the 2-diaminobutane), 1,3-butanediamine (1, the 3-diaminobutane), 1,4-butanediamine (1, the 4-diaminobutane), 1,3-diaminourea-2,2-dimethylbutane, 4,4 '-methylene-two-cyclohexylamine, 1-amino-3,3,5-trimethyl-5-amino methyl cyclohexane, 1, the 6-hexamethylene diamine, 2,2-dimethyl-1, the 3-diaminopropanes, 2,4-diaminostilbene-hexahydrotoluene, N-methylamino two (3-propylamine), the 2-methyl isophthalic acid, the 5-pentanediamine, 1,5-diaminourea pentane, 1, the 4-cyclohexane diamine, 1,3-diaminourea-4-hexahydrotoluene, 1, the 3-cyclohexane diamine, 1,1-methylene-two (4,4 '-diamino hexane), 3-amino methyl-3,5, the 5-trimethyl-cyclohexane, 1,3-pentanediamine (1,3-diaminourea pentane), MXDP and composition thereof.
Randomly, can use chain terminating agent, for example diethylamine, cyclohexylamine, n-hexylamine or monofunctional alcohol chain terminating agent, butanols for example is with the molecular weight of controlling polymers.In addition, the alcohol of higher functional " chain branching agent ", for example pentaerythrite, or trifunctional " chain branching agent ", for example diethylenetriamines can be used for controlling solution viscosity.
Polyurethane of the present invention and polyurethane-urea can be used in any application of the polyurethane that uses this general type or polyurethane-urea, but have specific benefits when being manufactured in the goods that need high elongation, low modulus or good low temperature properties when using.They are particularly useful for makes spandex, elastomer, flexible and rigid foams, coating (solvent base and water base), dispersion, film, adhesive and moulded products.
Unless indicate separately, term used herein " spandex " is meant the artificial fibre of the long-chain synthetic polymer that the segmented polyurethane of at least 85 weight % or polyurethane-urea constitute that wherein becomes fibrous matter to serve as reasons.Spandex also is known as elastane.
Spandex of the present invention can be used for making knitting and weaving stockinette and comprises the clothes or the textile article of this kind fabric.The example of stockinette comprises cylinder, flat pin and warp-knitted fabric and plain weave, twill and SATIN AND SATEEN CLOTH.Term used herein " clothes " is meant clothes product, for example shirt, trousers, skirt, jacket, overcoat, work shirt, work pants, uniform, coat, sportswear, swimsuit, corselet, socks and underwear, also comprise accessory, for example belt, gloves, mitten, cap, hosiery or footwear.Term used herein " textiles " is meant the goods that comprise fabric; clothes for example, and further comprise the protective sleeve of sheet, pillowcase, bedcover, bed clothes, blanket, quilt, quilt cover, sleeping bag, shower curtain, curtain, fabric, the tablecloth, diaper, wiper, wiping dish cloth and indoor ornament or furniture.
Spandex of the present invention can be separately or is combined with various other fibers and to be used in textiles, weft knitting (comprising flat pin and cylinder knitting) knitted fabric, warp-knitted fabric and personal hygiene fabric, for example in the diaper.Spandex can be expose, match (companion) fiber, for example nylon, polyester, acetic acid esters, cotton and analog covering or with its entanglement.
The fabric that comprises spandex of the present invention also can comprise at least a fiber that is selected from protein, cellulose and synthetic polymeric fibers or these members' combination." protein fibre " used herein is meant the fiber that is made of protein, comprises the animal fiber of the natural generation of this class, for example wool, silk, mohair, cashmere, alpaca, Angora, vicugna, camel hair and other fur fiber." cellulose fibre " used herein is meant the fiber of being made by tree or vegetable material, comprises for example cotton, rayon, acetic acid esters, lyocell, flax, ramie and other string." synthetic polymeric fibers " used herein is meant the artificial fibre of being made by polymer, and this polymer is by comprising that for example the chemical composition or the compound of polyester, polyamide, acrylic acid, spandex, polyolefin and aromatic polyamides constitute.
Also can in spandex of the present invention, use the various additives of effective dose, useful aspect of the present invention as long as they can not detract.Example comprises delustering agent (for example titanium dioxide) and stabilizing agent (for example mixture of hydrotalcite, huntite and hydromagnesite, barium sulfate, hindered phenol and zinc oxide), dyestuff and dye enhancer, bactericide, antitack agent, silicone oil, hindered amine as light stabilizer, ultraviolet screener and analog.
Spandex of the present invention or comprise its fabric can be by normal dyeing and print routine, for example by water soluble dyestuffs liquid by dying (exhaust) method to the greatest extent at 20 ℃ to 130 ℃, by contaminating the material comprise spandex with dye solution, or dye and print by the material that comprises spandex with the dye solution spraying.
When using acid dye, can follow conventional method.For example, dying to the greatest extent in the method, fabric can added during the water soluble dyestuffs with pH value of 3 to 9 bathes, it is being passed through being heated to 40-130 ℃ from about 20 ℃ of stable states in about 10 to 80 minutes then.Dye bath and fabric kept 10 to 60 minutes at 40 to 130 ℃ before cooling subsequently.From fabric, wash loose dyestuff then off.The stretching and the restorability that can keep spandex best by the least possible exposure time under being higher than 100 ℃.When using DISPERSE DYES, also can follow conventional method.
Term used herein " washability " is meant anti-the fading property of fabric in family or commercial laundering process of dying.The shortage of washability may cause fading of not washable goods, is called bleeding sometimes.This can cause the change color in the goods that launder with not washable goods.Client requires fabric and yarn to show washability usually.Washability is relevant with fabric composition, textile dyeing and ornamenting method and laundering condition.Clothes of today need have the spandex of improved washability.
Can use conventional assistant chemical additive to assist and further improve the washability of spandex of the present invention.Can use the anionic syntans to improve washable characteristic, and also can serve as retarding agents and retarding agent when between spandex and pairing (partner) yarn, needing the minimum isolation of dyestuff.Anionic sulfonic acid carburetion be when needing the level dyeing level, be used for spandex or pairing (partner) fiber and anionic dyestuff intercept open this dyestuff is had the more auxiliary additive of strong affinity.Can be used in combination cationic color-fixing agent to help improving washability separately or with the anionic color-fixing agent.
The spandex fiber can be by polyurethane of the present invention or polyurethaneurea polymer solution by the fibre spinning method, and for example dry-spinning or melt-spun form.When the needs spandex, common dry-spinning of polyurethane-urea or wet spinning.When dry-spinning, the polymer solution that will comprise polymer and solvent is metered in the spinning chamber to form long filament by the spinning head aperture.Usually, by with the identical solvent that is used for polymerisation, polyurethaneurea polymer is dry spun into long filament.Make gas pass through this chamber, thereby long filament is solidified with evaporating solvent.Dry-spinning long filament under at least 550 meters/minutes winding speed.Term used herein " spinning speed " is meant winding speed, and it is by drive roll speed decision and identical with it.The good spinnability of spandex long filament is a feature with seldom filament breakage in the spinning cabinet and in reeling.Spandex can be used as monofilament and is spun into maybe and can be merged into polyfilament yarn by conventional art.Each long filament is in fabric dtex (dtex), for every long filament 6 to 25dtex.
Well known to a person skilled in the art to be that the spinning speed that improves the spandex composition can reduce its elongation and improve its load force with comparing than the identical spandex that is spun under the low velocity.Therefore, usually practice is to slow down spinning speed with the elongation that improves spandex and reduce its load force, thereby but improves its drawdown in cylinder knitting and other spandex process operation.But, reduce spinning speed and also reduced manufacturing productivity ratio.
When being spun into the spandex fiber sooner, some desirable physical properties are improved, and other fibre property reduces simultaneously.These performances that reduce comprise the elongation of reduction and the required power (load force or modulus) of drawing of fiber that improves, and their raisings common and spinning speed are proportional.These two kinds of performances have all reduced the value of spandex to the client of fabric factory.But the elongation that reduces and the load force of raising can reduce the drawdown of fiber and improve the required spandex amount of elasticity clothes of making thus.The load force that improves also may cause user's comfortableness of reduction owing to the stretching resistance that improves.Therefore, must improve fibre spinning speed with the manufacturing cost that reduces manufacturer and improve the some fibre performance and make that reduction by other required fibre properties causes for user's value of the product minimization of loss between make balance.
But the drawdown of spandex yarn can be subjected to many effects limit.Drawing-off is subjected to the restriction of yarn elongation, unless it is limited by some other factorses at first.An example of other factors is load force (or modulus).For example, if the knitting needle in the circular cyiinder knitting machine only limits to 5 gram tension force in operation, then the spandex drawing of fiber is subjected to the restriction of the 5 gram drawing-offs that tensile force produced.A favourable aspect of the present invention be poly-(tetramethylene-copolymerization-ethyleneether) but the glycol-based spandex keeps very high drawdown in cylinder knitting, even it also still is higher than poly-(tetramethylene ether) glycol-based spandex of high-quality when spandex of the present invention is reeled than the speed of spandex high 50% with comparison.This is presented in the following table 1.
In most spandex final uses, need lower load force, but not only because its positive effect to the drawdown of raising also changes into improved user's comfortableness usually because of lower load force in the elasticity clothes.Higher elongation is similar desirable, but not only because its positive effect to the drawdown of raising also can change into higher can stretching because of higher elongation in the elasticity clothes in some garment configurations.
A favourable aspect of the present invention is, under similar speed and condition during spinning, have than much higher elongation of poly-(tetramethylene ether) glycol-based spandex and lower load force based on the spandex (wherein percent ethyleneether content is 16 to 70 moles of %) of poly-(tetramethylene-copolymerization-ethyleneether) glycol.Poly-(tetramethylene ether) glycol-based spandex is because the restriction that the elongation of high-modulus and reduction applies, at present can not be with than about 870 meters/minute (m/min) big a lot of speed spinning.Consequently it does not have practical value but the further raising of spinning speed has reduced drawdown and therefore reduced user's evaluation so manyly.But, when poly-(tetramethylene-copolymerization-ethyleneether) glycol-based spandex with up to 1300 meters/minute or during bigger speed spinning, load force improves and elongation reduces, but their value still is better than poly-(tetramethylene ether) glycol-based spandex that is spun under much lower speed.This is presented in following table 2 and 3.For example, even all spandexs of the present invention also have 100%, 200% and 300% time lower load force than gathering to be spun under the much higher speed of (tetramethylene ether) glycol-based spandex (it is spun into 844 meters/minute) in comparison.In addition, even spandex of the present invention is spun into much higher speed, but its elongation still is higher than with poly-(tetramethylene ether) glycol-based spandex of 844 meters/minute contrasts that are spun into.Spandex of the present invention can surpass under 750 meters/minute the speed, or is surpassing under 1000 meters/minute the speed, or is being spun into above under 1100 meters/minute the speed.
Stress or resistance to fracture when another factor of restriction spandex yarn drawing-off is the toughness of yarn or breaking extension.Break limits when knitting in the spandex productivity ratio and improved the clothes manufacturing cost.Therefore, the spandex user payes attention to higher toughness to a certain extent.But, if but another factor is limited drawdown, it is unfavorable then surpassing the more high tenacity avoid processing the required minimum of a value of fracture.The inventor has been found that the more high speed spinning of spandex of the present invention has desirably improved toughness.This is also shown in the following table 3.
The retraction force (unload forces) that improves the spandex fiber is normally desirable, because this just retraction force is moved fabric structure together to and give their required character in the elasticity clothes.The unload forces that improves spandex can make fabric manufacturer use spandex still less to realize spandex manufacturer being spun into required decrement in the fabric with the big spandex silk with low load force comparing the spandex with identical retraction force with thinner dawn number.Thinner dawn number makes it can be used in more final uses, especially has a thin dawn to count in those of hard yarn line.
In the dyeing and ornamenting (finish) process in clothes are made, spandex is exposed in the hot water usually, and this moment, the spandex fiber shrank to a certain extent.When clothes were colored with ornamenting, it was desirable having low spandex filament contraction degree in clothes, can keep final fabric form and size as required like this.This can simulate by measuring " the wet creep of heat " (a kind of test through the contraction of design simulation spandex yarn when dyeing) in the laboratory.As shown in following table 4, spandex of the present invention has " the wet creep of heat " of reduction when spinning speed improves.
The following example is showed the present invention and application power thereof.The present invention can have other different embodiment, its some details can do not depart from the scope of the present invention and the situation of spirit under various obvious aspect in make amendment.Correspondingly, embodiment is regarded as exemplary and nonrestrictive.
Unless indicate separately, term used herein " DMAc " is meant dimethylacetamide solvent, term " %NCO " is meant the percentage by weight of isocyanate end in capped glycol, term " MPMD " is meant the 2-methyl isophthalic acid, the 5-pentanediamine, term " EDA " is meant 1, and 2-ethylenediamine, term " PTMEG " are meant poly-(tetramethylene ether) glycol.
Term used herein " end-blocking ratio " is meant the mol ratio of vulcabond and glycol, and it serves as that the basis is determined with 1.0 moles of glycol.Therefore, the end-blocking ratio is typically expressed as single numeral, the vulcabond molal quantity of every mole of glycol.For polyurethane-urea of the present invention, vulcabond is about 1.2 to about 2.3 with the preferred molar ratio of poly-(tetramethylene-copolymerization-ethyleneether) glycol.For polyurethane of the present invention, the preferred molar ratio of vulcabond and poly-(tetramethylene-copolymerization-ethyleneether) glycol is about 2.3 to about 17, preferably approximately 2.9 to about 5.6.
Material
THF and PTMEG (TERATHANE 1800) can be available from Invista S. à .r.l., Wilmington, Delaware, USA.NAFION perfluorinated sulfonic resin can be available from E.I.Dupont de Nemours and Company, Wilmington, Delaware, USA.
Analytical method
Toughness is the breaking stress in the 6th stretching cycle, or in other words, the fracture resistance of fiber under ultimate elongation.Load force is the stress under the appointment elongation in the first stretching cycle, or in other words, fiber is to being stretched to the drag of higher elongation.Unload forces is to specify stress under the elongation in the cycle at the 5th retraction, or in other words, and fiber has been circulated to after 300% elongation 5 times at the retraction force of specifying under the elongation.
The isocyanates percentage (%NCO) of isocyanates percentage-capped glycol blend is according to the method " Quantitative Organic Analysis via FuctionalGroup " of S.Siggia, the 3rd edition, Wiley ﹠amp; Sons, New York, 559-561 page or leaf (1963) use constant-current titration to measure.
In poly-(tetramethylene-copolymerization-ethyleneether) glycol of percent ethyleneether content-of the present invention percent ethyleneether content by
1H NMR mensuration is measured.The sample dissolution that to gather (tetramethylene-copolymerization-ethyleneether) glycol or blend is at suitable NMR solvent, for example CDCl
3In and obtain
1H NMR collection of illustrative plates.To under 3.7-3.2ppm, merge-OCH
2The integration at peak with merge from 1.8-1.35ppm-C-CH
2CH
2The integration at-C-peak compares.-OCH
2-peak is from oxirane base key (O-CH
2CH
2-O-) with from THF base key (O-CH
2CH
2CH
2CH
2-O-), and-C-CH
2CH
2-C-key is only from THF.In order to find to gather the molar fraction of ethyleneether key in (tetramethylene-copolymerization-ethyleneether) glycol, from merge-OCH
2Deduct in the integration at-peak-C-CH
2CH
2The integration at-C-peak, then with this result divided by-OCH
2The integration at-peak.
Number-average molecular weight-pass through the hydroxyl value method to measure the number-average molecular weight of gathering (tetramethylene-copolymerization-ethyleneether) glycol.
Intensity and elasticity-the measure intensity and the elasticity of spandex according to the conventional method of ASTM D 2731-72.Use Instron (Instron) tension test instrument to measure tensile property.To each measurement, use " former state (as-is) " from coiler, promptly without washing or other processing, in controlled environment at about 70 and 65% relative humidity (+/-2%) three threads after aging 24 hours down, 2 inches (5 centimetres) gauge lengths and 0-300% elongation cycle.The constant rate of elongation of sample with 50 cm per minute circulated 5 times, kept 30 seconds under 300% elongation the 5th elongation back then.
In the period 1 under 100%, 200% or 300% elongation sensing lead power---the stress in the initial elongation process on the spandex, and in table, be expressed as gram/dawn, and mark work " LP1 ", " LP2 " or " LP3 " respectively.
Unload forces, the stress in the 5th unloading cycle under 100% or 200% elongation also is expressed as gram/dawn; It marks work " UP1 " or " UP2 " respectively.Use improved Instron anchor clamps to measure breaking extension percentage (" Elo ") and toughness in the 6th stretching cycle, these anchor clamps link to each other with rubber strip and slide to reduce.
Unless set percentage-indicate is separately also measured set percentage on through the sample of 5 0-300% elongation/relaxation cycle.The following calculating of set percentage (" % set "):
% set=100 (Lf-Lo)/Lo
Wherein Lo and Lf are respectively before 5 elongation/relaxation cycle and afterwards, long filament (yarn) length when no tension force ground keeps straight.
Cylinder knitting (CK) drawing-off-in knitting, spandex when the supply package is transported on the support plate and be sent to knitting needle again because knitting needle uses speed and the difference of supplying the feed rate the package from spandex stretch (drawing-off).Hard yarn line delivery rate (meter/minute) is generally 2.5 to 4 times (2.5x to 4x) greatly with the ratio of spandex delivery rate, and is known as processing drawing-off (machine draft), " MD ".This is equivalent to 150% to 300% or the elongation of bigger spandex.Term used herein " hard yarn line " is meant inelastic relatively yarn, for example polyester, cotton, nylon, rayon, acetic acid esters or wool.
The total draft of spandex yarn is processing drawing-off (MD) and package draft (package draft) product (PD), and the latter is the amount that the spandex yarn has stretched in the supply package.For given dawn number (or dtex), the spandex content and the total draft of fabric are inversely proportional to; Total draft is high more, and spandex content is low more.PR is the character that records that is known as " package relax percentage ", and is meant 100* (length of the length of yarn in the package-lax yarn)/(length of yarn in the package).For the spandex that is made at cylinder, use on the elasticity, single needle woven fabric, PR is measured as 5 to 15 usually.The PR that use records, package draft (PD) is defined as 1/ (1-PR/100).Therefore, total draft (TD) also can be used as MD/ (1-PR/100) calculating.Yarn with 4x processing drawing-off and 5%PR has the total draft of 4.21x, and the yarn with 4x processing drawing-off and 15%PR has the total draft of 4.71x.
For economic reasons, circular cyiinder knitting machine attempts using the minimum spandex content consistent with enough fabric properties and uniformity usually.As mentioned above, improving the spandex drawing-off is a kind of mode that reduces content.The principal element of restriction drawing-off is a breaking extension percentage, and the yarn that therefore has high breaking extension percentage is most important factor.Other factors, for example breaking toughness, frictional force, yarn adherence, dawn are counted uniformity and yarn faults can reduce in fact attainable drawing-off.Knitting machine comes to provide margin of safety (margin) for these limiting factors by the drawing-off that reduces from final drawing-off (the breaking extension percentage that records).They reach unacceptable level by improving drawing-off until knitting fracture usually, and 5 fractures of for example per 1000 rotating the needle looms retreat then until recovering acceptable performance and measure this " drawing-off that can bear ".
Tension force in the knitting needle also is the limiting factor of drawing-off.Feed tension in the spandex yarn is directly related with the total draft of spandex yarn.It also becomes with the intrinsic modulus (load force) of spandex yarn.For under high drawing-off, keep knitting in acceptable low-tension, it is favourable that spandex has low modulus (load force).
But therefore have high breaking extension percentage, low modulus (load force), sufficiently high toughness, low friction and viscosity, even dawn number and low defect level for the desirable yarn of high drawdown.
Because its stress-strain is along with the tension force that is applied on the spandex improves spandex yarn drawing-off more (stretching); On the contrary, spandex is drawing-off more muchly, and the tension force in the yarn is just high more.Typical spandex thread path is as follows in the circular cyiinder knitting machine.The spandex yarn measures the package from supply and provides, and crosses or pass broken end detector, crosses one or more break-in rollers, arrives support plate then, and it is with lead knitting needle and import stitch of spandex.When the spandex yarn is derived from the supply package and is crossed each device or roller, because the frictional force that each device that contacts with spandex or roller produce produces tension buildup in the spandex yarn.The spandex total draft at stitch place is therefore relevant with the tension force total amount of passing whole spandex path.
Residual DMAc percentage uses Duratech DMAc analyzer to measure in the residual DMAc-spandex sample in the spandex.Use the tetrachloro-ethylene (perclene) of known quantity from the spandex of known weight, to extract DMAc.Subsequently the ultraviolet radiation absorption by measuring DMAc and should value and regular curve compare, the DMAc in the quantification tetrachloro-ethylene (perclene) measures.
The wet creep of heat-by measuring the initial length of yarn, L
0, it is stretched to 1.5 times of (1.5L of its initial length
0), it was being flooded 30 minutes in the water-bath of 97 to 100 ℃ of maintenances under extended state, it is taken out from bathe, discharge tension force sample was at room temperature relaxed minimum 60 minutes, measure final lengths L then
f, measure the wet creep (HWC) of heat thus.The wet creep percentage of heat is calculated by following formula:
％HWC＝100×[(L
f-L
0)/L
0]
Fiber with low %HWC provides excellent performance in the wet ornamenting operation of heat (for example dyeing).
Embodiment
Embodiment 1-31 (spandex that contains ethyleneether)
Use the 100ppm inorganic acid as catalyst, random poly-(tetramethylene-copolymerization-ethyleneether) glycol that will have ethyleneether units molar percentage shown in the table 1,2 and 4 and a number-average molecular weight is with 1-isocyanato--4-[(4-isocyanato--phenyl) methyl] benzene is 90 ℃ of end-blockings 120 minutes, thus produce prepolymer with two isocyanos shown in the table/glycol molar ratio (end-blocking ratio).With this capped glycol DMAc solvent dilution, increase chain subsequently, carry out the chain end-blocking to produce the spandex polymer solution with diethylamine with EDA.The amount of used DMAc makes the polyurethane-urea that has the 36-38 weight % that accounts for total solution weight in the final spinning solution.Spinning solution dry-spinning is solidified to the post that provides drying nitrogen, by godet roller, and with listed speed coiling.Regulate the spinning cabinet temperature and suck gas flow rate to produce 0.1 to 0.7% residual solvent levels.Long filament shows better spinnability.Fibre property is listed in table 1 in 4.
Comparative Examples " 1-5 " (PTMEG base spandex)
Poly-(tetramethylene ether) glycol that will have 1800 dalton's mean molecule quantities is with 1-isocyanato--4-[(4-isocyanato--phenyl) methyl] benzene is 90 ℃ of end-blockings 90 minutes, is 1.69 prepolymer thereby produce two isocyanos/glycol mol ratio.Subsequently with this capped glycol DMAc solvent dilution, increase chain with the EDA of 90/10 ratio and the mixture of MPMD, and carry out the chain end-blocking with diethylamine and go up and the similar spandex product of the commercial spandex of high-quality to be created in to form.The amount of used DMAc contains final spinning solution to account for the polyurethane-urea of 35 weight % of total solution weight.Spinning solution dry-spinning is solidified to the post that provides drying nitrogen, by godet roller, and with listed speed coiling.Long filament shows better spinnability.Fibre property is listed in table 1 in 4.
Table 1
| Embodiment | ％EO | The end-blocking ratio | Cahin extension agent | Glycol MW | The long filament number of every strand | Winding speed (rice/minute) | PRM (％) | CK processes drawing-off | Total draft |
| 1 2 3 4 5 6 7 8 | 27 27 27 27 38 38 38 38 | 1.63 1.63 1.63 1.63 1.7 1.7 1.7 1.77 | 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA | 2010 2010 2010 2010 2500 2500 2500 2500 | 3 4 4 4 4 4 4 3 | 844 870 1100 1280 870 1100 1280 844 | 14.7 19.2 19.5 20.4 19.5 21.0 18.7 14.0 | 4.1 4.1 3.8 3.6 4.3 4.1 3.7 4.1 | 4.80 5.08 4.72 4.52 5.34 5.19 4.55 4.77 |
| 9 | 49 | 1.64 | 100％EDA | 2045 | 4 | 870 | 15.8 | 4.5 | 5.34 |
| Comparative Examples 1 Comparative Examples 2 | 0 0 | 1.69 1.69 | 90/10 DA/MPMD 90/10 DA/MPMD | 1800 1800 | 3 4 | 844 1100 | 11.6 16.8 | 3.8 3.4 | 4.30 4.09 |
In the table 1 examination of data shown have different percent ethyleneether content, end-blocking ratio, glycol molecular weight, the long filament number of every strand and several different spandexs of (spinning) speed of coiling, its total cylinder knitting drawing-off degree surpasses the spandex based on poly-(tetramethylene ether) glycol.Embodiment 4 and 7 has the total draft degree above Comparative Examples 1 spandex, even they are reeled with high speed more than 50%.
Table 2
| Embodiment | ％EO | Glycol MW | The end-blocking ratio | Cahin extension agent | Anti-chlorine additive % | Winding speed (rice/minute) | The long filament number of every strand | Residual solvent (%) |
| 10 11 12 13 14 15 16 17 18 19 20 21 | 38 38 38 27 27 27 49 49 37 37 37 37 | 2500 2500 2500 2010 2010 2010 2049 2049 1885 1885 1885 1885 | 1.70 1.70 1.70 1.63 1.63 1.63 1.64 1.64 1.60 1.60 1.60 1.60 | EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ EDA100％ | 4 4 4 4 4 4 4 4 0 0 0 0 | 844 1100 1280 870 1100 1280 870 1100 844 870 1100 1280 | 3 4 4 4 4 4 4 4 3 4 4 4 | 0.17 0.19 0.25 0.18 0.36 0.36 0.23 0.21 0.72 0.74 0.73 0.82 |
| 22 | 37 | 1885 | 1.72 | 90/10 EDA/MPMD | 0 | 844 | 3 | 0.79 |
| 23 | 37 | 1885 | 1.72 | 90/10 EDA/MPMD | 0 | 1100 | 4 | 0.79 |
| Comparative Examples 3 | 0 | 1800 | 1.69 | 90/10 EDA/MPMD | 0 | 870 | 4 | 0.42 |
| Comparative Examples 4 | 0 | 1800 | 1.69 | 90/10 EDA/MPMD | 0 | 1100 | 4 | 0.65 |
| Comparative Examples 5 | 0 | 1800 | 1.69 | 90/10 EDA/MPMD | 0 | 1280 | 4 | 0.48 |
Table 2 has shown the composition details of several different spandexs that the long filament number of percent ethyleneether content, glycol molecular weight, end-blocking ratio, cahin extension agent type, additive capacity, coiling (spinning) speed, every strand is different with residual spin solvent.All these is that 44dtex is spun into fiber.The long filament number influences the rate of drying of fiber; Therefore, provide the residual solvent amount in the fiber after the spinning.With fiber drying to also influencing the gained fibre property than the low-residual solvent levels.Generally speaking, dried fibres can improve retraction force or unload forces more.Therefore, select to have the example of given composition of similar residual solvent to compare by winding speed.
Table 3
| Embodiment | ELO (％) | SET (％) | TEN (g/den) | UP1 (g/den) | UP2 (g/den) | LP1 (g/den) | LP2 (g/den) | LP3 (g/den) |
| 10 | 640 | 22.5 | 0.5384 | 0.0170 | 0.0314 | 0.0530 | 0.0848 | 0.1200 |
| 11 | 632 | 22.5 | 0.6721 | 0.0177 | 0.0336 | 0.0655 | 0.1068 | 0.1567 |
| 12 13 14 15 16 17 18 19 20 21 22 23 Comparative Examples, 3 Comparative Examples, 4 Comparative Examples 5 | 630 634 587 539 630 546 622 721 611 537 584 528 443 411 397 | 22.0 26.5 25.9 24.2 26.6 23.3 31.5 33.3 32.5 29.9 30.5 32.2 27.4 25.2 23.9 | 0.7547 0.6557 0.7001 0.8868 0.5483 0.6097 0.4987 0.5000 0.5443 0.5585 0.5577 0.5755 0.8912 0.8701 1.0288 | 0.0182 0.0158 0.0172 0.0175 0.0169 0.0185 0.0156 0.0160 0.0162 0.0178 0.0162 0.0171 0.0170 0.0174 0.0183 | 0.0349 0.0313 0.0341 0.0357 0.0341 0.0377 0.0328 0.0338 0.0343 0.0374 0.0341 0.0365 0.0281 0.0289 0.0317 | 0.0698 0.0706 0.0846 0.0798 0.0653 0.0657 0.0762 0.0941 0.1010 0.1054 0.0813 O.1082 O.1081 0.1179 0.1134 | 0.1151 0.1149 0.1369 0.1431 O.1028 0.1142 0.1134 0.1306 0.1445 O.1596 0.1230 0.1696 0.2170 0.2429 0.2595 | 0.1705 O.1639 O.1983 0.2268 0.1426 0.1701 0.1521 0.1662 0.1909 0.2240 0.1602 0.2443 0.4049 0.2990 0.5548 |
Table 3 has shown the physical property from the embodiment fiber of table 2.The examination of the data in the table 3 shows, for each embodiment and Comparative Examples composition, higher winding speed improved in the 5th restore cycle the retraction force (UP1 and UP2) under 100% and 200% elongation and in the first elongation cycle load force (except the Comparative Examples 4, it has higher residual solvent levels) under 100%, 200% and 300% elongation.Even with 1280 meters/minute winding speed spinning, embodiments of the invention also have than much lower load force of Comparative Examples 3 spandexs that are spun into 870 meters/minute and the elongation of Geng Gao.Therefore as can be seen, embodiments of the invention are worked as at all these winding speeds, even when being higher than 1000 meters/minute following spinning, further drawing-off in the cylinder knitting operation before tension force that also can be in knitting needle or the drawing-off of elongation restriction spandex.
Table 4
| Embodiment | ％EO | Glycol MW | The end-blocking ratio | Cahin extension agent | Winding speed (rice/minute) | The wet creep of heat |
| 24 25 26 27 28 29 30 31 Comparative Examples 1 | 37 37 37 49 49 27 27 27 0 | 1900 1900 1900 2049 2049 2045 2045 2045 1800 | 1.60 1.60 1.60 1.64 1.64 1.63 1.63 1.63 1.69 | 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 100％EDA 90/10 EDA/MPMD | 870 1100 1280 870 1100 870 1100 1280 844 | 16.5 15.1 13.2 16.5 13.2 13.2 12.9 11.7 15.6 |
The examination of the data in the table 4 shows that the winding speed that improves embodiments of the invention has reduced hot wet creep, and can be used for creep is brought down below the degree of contrast spandex.
Claims (20)
1. spandex, it comprises the polyurethane reaction product of following ingredients:
(a) contain by making poly-(tetramethylene-copolymerization-ethyleneether) glycol of the formation unit that oxolane and oxirane copolymerization generate, the cell mesh that wherein is derived from oxirane with about 16 to about 70 moles of %, is preferably greater than about 37 to about 55 moles of % and exists in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) at least a vulcabond;
(c) at least a cahin extension agent that is selected from diamines and glycol; With
Wherein this spandex preferably surpasses about 1000 meters/minute speed and is spun into to surpass about 750 meters/minute.
2. the spandex of claim 1, wherein vulcabond is selected from 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, 1-isocyanato--2-[(4-isocyanato-phenyl) methyl] benzene and composition thereof.
3. the spandex of claim 1, wherein cahin extension agent is selected from hydrazine, ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, 1,2-diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-amino methyl cyclohexane, 2,2-dimethyl-1,3-diaminopropanes, 1,3-diaminourea-2,2-dimethylbutane, 2,4-diaminostilbene-hexahydrotoluene, 1,3-cyclohexane diamine, 2-methyl isophthalic acid, 5-pentanediamine, 1,3-pentanediamine, 4,4 '-methylene-two-cyclohexylamine, and composition thereof.
4. the spandex of claim 2, wherein poly-(tetramethylene-copolymerization-ethyleneether) glycol has about 650 dalton to about 4000 daltonian number-average molecular weights, and the mol ratio of vulcabond and poly-(tetramethylene-copolymerization-ethyleneether) glycol is about 1.2 to about 2.3.
5. the spandex of claim 1, wherein poly-(tetramethylene-copolymerization-ethyleneether) glycol has about 650 dalton to about 4000 daltonian number-average molecular weights, the cell mesh that is derived from oxirane in poly-(tetramethylene-copolymerization-ethyleneether) glycol to exist greater than about 37 to about 50 moles of %, vulcabond is about 2.3 to about 17 with the mol ratio of poly-(tetramethylene-copolymerization-ethyleneether) glycol, and cahin extension agent is selected from ethylene glycol, 1, ammediol, 1, the 2-propylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,2-dimethyl-1, the 3-trimethylene glycol, 2,2,4-trimethyl-1, the 5-pentanediol, 2-methyl-2-ethyl-1, ammediol, 1, two (hydroxyl-oxethyl) benzene and 1 of 4-, 4-butanediol.
6. the spandex of claim 3, wherein vulcabond is selected from 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, 1-isocyanato--2-[(4-isocyanato-phenyl) methyl] benzene and composition thereof, and the mol ratio of vulcabond and poly-(tetramethylene-copolymerization-ethyleneether) glycol is about 1.2 to about 2.3.
7. the spandex of claim 3, wherein vulcabond is 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, and the cell mesh that is derived from oxirane in poly-(tetramethylene-copolymerization-ethyleneether) glycol to exist greater than about 37 to about 50 moles of %
8. the spandex of claim 1 comprises the polymer diol that is selected from poly-(tetramethylene ether) glycol, poly-(tetramethylene-copolymerization-2-methyl tetramethylene ether) glycol, poly-(ethyleneether) glycol, poly-(propylidene ether) glycol, PCDL, polyester-diol and combination thereof in addition.
9. the spandex of claim 8, wherein poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild polymer diols of combination exist with at least 10 moles of % of the summation of poly-(tetramethylene-copolymerization-ethyleneether) molal quantity of glycol and the molal quantity of polymer diol separately.
10. the spandex of claim 8, wherein polymer diol is poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild poly-(ethyleneether) glycol of poly-(ethyleneether) glycol and wherein combination have about 35 to about 70 moles of % the unit that is derived from oxirane in spandex a percent of total.
11. the spandex of claim 8, wherein polymer diol is selected from poly-(tetramethylene ether) glycol, poly-(tetramethylene-copolymerization-2-methyl tetramethylene ether) glycol, poly-(propylidene ether) glycol, PCDL, polyester-diol or its combination, and poly-(tetramethylene-copolymerization-ethyleneether) two pure and mild polymer diols of wherein combination have the percent of total of the unit that is derived from oxirane that is less than or equal to about 35 moles of %.
12. prepare the method for spandex, it comprises:
(a) poly-(tetramethylene-copolymerization-ethyleneether) glycol is contacted to form capped glycol with at least a vulcabond, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) capped glycol is dissolved in the solvent;
The solution of the capped glycol of (b) is contacted with at least a diamines or diol chain extender; With
(d) with the solvent spinning of (c), thereby to surpass about 750 meters/minute speed spinning to form spandex.
13. the method for claim 12, wherein vulcabond is 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, vulcabond is about 1.2 to about 2.3 with the mol ratio of poly-(tetramethylene-copolymerization-ethyleneether) glycol, and cahin extension agent is selected from hydrazine, ethylenediamine, 1, the 2-propane diamine, 1, the 3-propane diamine, the 2-methyl isophthalic acid, the 5-pentanediamine, 1, the 3-pentanediamine, 1, the 3-cyclohexane diamine, 1, the 2-diaminobutane, 1, the 3-diaminobutane, 1-amino-3,3,5-trimethyl-5-amino methyl cyclohexane, 2,2-dimethyl-1, the 3-diaminopropanes, 1,3-diaminourea-2, the 2-dimethylbutane, 2,4-diaminostilbene-hexahydrotoluene and composition thereof.
14. the method for claim 12, wherein vulcabond is 1-isocyanato--4-[(4-isocyanato-phenyl) methyl] benzene, vulcabond is about 2.3 to about 17 with the mol ratio of poly-(tetramethylene-copolymerization-ethyleneether) glycol, and cahin extension agent is selected from ethylene glycol, 1, ammediol, 1,2-propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1,3-trimethylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-methyl-2-ethyl-1, ammediol, 1, two (hydroxyl-oxethyl) benzene and 1 of 4-, the 4-butanediol.
15. the method for claim 14, wherein spinning is that dry-spinning step and poly-(tetramethylene-copolymerization-ethyleneether) glycol have about 650 to about 4000 daltonian number-average molecular weights with the step that forms spandex.
16. a spandex, it comprises the product of following ingredients:
(a) contain by making poly-(tetramethylene-copolymerization-ethyleneether) glycol of the formation unit that oxolane and oxirane copolymerization generate, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) at least a vulcabond;
(c) at least a cahin extension agent that is selected from diamines and glycol; And
Wherein this spandex has the unload forces under 100% elongation at least 0.018 gram/dawn.
17. a spandex, it comprises the product of following ingredients:
(a) contain by making poly-(tetramethylene-copolymerization-ethyleneether) glycol of the formation unit that oxolane and oxirane copolymerization generate, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) at least a vulcabond;
(c) one or more diamine chain extenders; And
Wherein cahin extension agent comprises one or more diamines, and wherein this spandex have at least 0.017 gram/dawn the retraction force under 100% elongation and less than 0.106 gram/dawn in 100% load force under extending.
18. a spandex, it comprises the product of following ingredients:
(a) contain by making poly-(tetramethylene-copolymerization-ethyleneether) glycol of the formation unit that oxolane and oxirane copolymerization generate, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) at least a vulcabond;
(c) one or more diamine chain extenders; And
Wherein cahin extension agent comprises one or more diamines, and wherein this spandex have at least 0.0341 gram/dawn the retraction force under 200% elongation and less than 0.16 gram/dawn in 200% load force under extending.
19. a spandex, it comprises the product of following ingredients:
(a) contain by making poly-(tetramethylene-copolymerization-ethyleneether) glycol of the formation unit that oxolane and oxirane copolymerization generate, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) at least a vulcabond;
(c) one or more diamine chain extenders; And
Wherein cahin extension agent comprises one or more diamines, and wherein this spandex have at least 0.0341 gram/dawn the retraction force under 200% elongation and less than 0.227 gram/dawn in 300% load force under extending.
20. a spandex, it comprises the product of following ingredients:
(a) contain by making poly-(tetramethylene-copolymerization-ethyleneether) glycol of the formation unit that oxolane and oxirane copolymerization generate, the cell mesh that wherein is derived from oxirane exists with about 16 to about 70 moles of % in poly-(tetramethylene-copolymerization-ethyleneether) glycol;
(b) at least a vulcabond;
(c) one or more diamine chain extenders; And
Wherein cahin extension agent comprises one or more diamines, and wherein this spandex have at least 0.495 gram/dawn toughness and less than 0.16 gram/dawn 200% the elongation under load force.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59481105P | 2005-05-09 | 2005-05-09 | |
| US60/594,811 | 2005-05-09 | ||
| US60/738,734 | 2005-11-22 | ||
| US60/738,733 | 2005-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410054162.3A Division CN103806122A (en) | 2005-05-09 | 2006-05-08 | Spandex compositon for high speed spinning |
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| CN101208464A true CN101208464A (en) | 2008-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800158860A Pending CN101171276A (en) | 2005-05-09 | 2006-05-08 | Spandex from poly(tetramethylene-co-ethyleneether) glycols having high ethyleneether content |
| CNA200680015888XA Pending CN101208464A (en) | 2005-05-09 | 2006-05-08 | Spandex compositions for high speed spinning |
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| CNA2006800158860A Pending CN101171276A (en) | 2005-05-09 | 2006-05-08 | Spandex from poly(tetramethylene-co-ethyleneether) glycols having high ethyleneether content |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710786A (en) * | 2013-12-18 | 2014-04-09 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane raw liquid for high-speed spinning |
| TWI751100B (en) * | 2014-05-05 | 2022-01-01 | 盧森堡商英威達技術有限公司 | Bio-derived polyurethane fiber |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517688B (en) * | 2011-12-08 | 2014-04-16 | 烟台泰和新材料股份有限公司 | Preparation method of polyurethane elastomeric fiber possessing excellent heat setting performance |
| CN110627996A (en) * | 2019-10-08 | 2019-12-31 | 苏州大学 | Polyurethane urea, preparation method thereof and super-tough polyurethane urea based on polyurethane urea |
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2006
- 2006-05-08 CN CNA2006800158860A patent/CN101171276A/en active Pending
- 2006-05-08 CN CNA200680015888XA patent/CN101208464A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710786A (en) * | 2013-12-18 | 2014-04-09 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane raw liquid for high-speed spinning |
| TWI751100B (en) * | 2014-05-05 | 2022-01-01 | 盧森堡商英威達技術有限公司 | Bio-derived polyurethane fiber |
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