EP0046346B1 - Latent schrumpfbare Elastomere, daraus zusammengesetzte Garne und Verfahren zu deren Herstellung und Anwendung - Google Patents

Latent schrumpfbare Elastomere, daraus zusammengesetzte Garne und Verfahren zu deren Herstellung und Anwendung Download PDF

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Publication number
EP0046346B1
EP0046346B1 EP19810303473 EP81303473A EP0046346B1 EP 0046346 B1 EP0046346 B1 EP 0046346B1 EP 19810303473 EP19810303473 EP 19810303473 EP 81303473 A EP81303473 A EP 81303473A EP 0046346 B1 EP0046346 B1 EP 0046346B1
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Prior art keywords
filament
elastic
melt extruded
filaments
polyester
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English (en)
French (fr)
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EP0046346A2 (de
EP0046346A3 (en
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Aloysius Antonius Josephus Kramers
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Akzona Inc
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Akzona Inc
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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
    • D02G3/328—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic containing elastane
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

  • Elastic yarns notably spandex yarns
  • the use of such yarns is relatively expensive, not only because of the cost of the fiber, but also because in order to obtain the maximum benefits of the elastic properties of the yarn, the yarn must be woven or knitted in a stretched condition, requiring specially adapted machinery, which operates at processing speeds less than those employed with conventional non-elastic yarns.
  • the yarns of the invention can be processed in a non-stretched mode, as a conventional yarn, and when formed into a processed, e.g., woven, knitted or tufted article, can be contracted to provide an elastic particle.
  • Composite yarns comprising elastic yarns and a covering of entangled relatively inelastic filaments are disclosed in U.S. Patent No. 3,940,917. These yarns are formed by conducting the entangling step when the elastic yarn is in a stretched condition.
  • This invention relates to melt extruded latent contractable filaments which are formed by melt extruding certain segmented physically crosslinked thermoplastic polymers to form filaments, which filaments, when heat processed at elevated temperatures, significantly contract to yield an elastic filament.
  • This invention also relates to the formation of composite covered yarn comprising the latent contractable melt extruded filaments.
  • this invention relates to processes for forming articles from the latent contractable filaments or covered yarns and subsequently contracting the yarns to form an elastic article.
  • the present invention provides a method of forming an elastic filament which comprises melt extruding a segmented inherently elastic polyester-polyester or polyester-polyether thermoplastic polymer which contains interspersed relatively hard segments and relatively soft segments and then without prior deliberate drawing exposing the melt extruded polymer to an elevated temperature in the range of from 40°C to 125°C to linearly contract the melt extruded polymer at least 15% to provide an elastic filament.
  • the present invention provides a method of forming a composite elastic yarn wherein a melt extruded segmented inherently elastic polyester-polyester or polyester-polyether thermoplastic polymer is associated with inelastic fibres or filaments and without prior deliberate drawing the composite yarn is subjected to exposure to an elevated temperature in the range of from 40° to 125°C to cause the melt extruded polymer filament to cause by at least 15% in length.
  • the present invention provides a process for combining a latent contractable melt extruded filament formed from a segmented inherently elastic polyester-polyester or polyester-polyether thermoplastic polymer which contains interspersed relatively hard segments and relatively soft segments with a relatively inelastic synthetic polymer filament to produce a composite yarn which comprises continuously feeding at least one latent contractable melt extruded filament at a first predetermined feed rate and at least one relatively inelastic filament and at a second predetermined feed rate through a jetted high velocity fluid and impinging the jetted fluid on the filament axis at an angle of 90° + 45° to separate the inelastic filaments and entangle the inelastic filaments around the melt extruded filament at spaced intervals; the rate of feed of the inelastic filaments being adjusted with respect to the rate of feed of the melt extruded filaments so that the rate of feed of the inelastic filaments is less than twice the rate of feed of the melt extruded filament and is a
  • the present invention provides a process of forming a stretchable textile article which comprises forming a predetermined over-sized article with yarns comprising a latent contractable filament formed form a segmented inherently elastic polyester-polyester or polyester-polyether thermoplastic polymer which contains interspersed relatively hard segments and relatively soft segments which contracts at least 15% as compared to its original length when exposed without prior deliberate drawing to an elevated contraction inducing temperature to provide an elastic filament and exposing the resultant textile article to an elevated temperature sufficient to contract the latent contractable filament at lest 15% to form a stretchable article of a desired size.
  • the ordinarily relatively unoriented soft segment is oriented, at least to some degree, followed by cooling, which fixes the filament in a relatively oriented state.
  • the orientation of the soft segment created by the melt extrusion is dissipated, causing contraction of the filament and the creation of substantially increased elastic properties in the filament.
  • polyester-polyester or polyester-polyether polymers which can be employed are polymers consisting of a hard segment and a soft segment capable of forming one phase in the melt, which yield a poorly phase separated morphology when quenched and that, upon latent contraction by a heat treatment, produce a well phase separated morphology.
  • thermoplastics segmented copolyester polyethers consisting essentially of a multiplicity of randomly occurring intrachain segments of long-chain (soft segments) and short chains (hard segments) ester units, the long-chain ester units being represented by the following structure: where L is- a divalent radical remaining after the removal of terminal hydroxyl groups from poly(oxyalkylene) glycols having at least 1 nitrogen containing ring per molecule, a carbon to nitrogen ratio in the range of from 3/1 to 350/1, and a molecular weight in the range of from 200 to 8,000, and R is a divalent radical remaining after the removal of the carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300.
  • Short-chain ester units are represented by the following structure: where E is a divalent radical remaining after the removal of hydroxyl groups from a low molecular weight diol having from 2 to 15 carbon atoms per molecule and a molecular weight in the range of from 50 to 250, and R is the divalent radical described for (a) above.
  • a foreign repeat unit in the back bone of a crystallizable soft segment such as a polyether
  • a crystallizable soft segment such as a polyether
  • Such a foreign unit must be stable to processing temperatures and must not be so rigid as to reduce the mobility (raise the glass transition temperature) of the soft segment itself.
  • the foregoing unit should be nonreactive during the synthesis of the segmented thermoplastic elastomer, and should be present in a concentration of at least 1 unit per polyether molecule
  • the polyether unit (or -OLO- in formula (a) above) of the soft segment may be represented by the following structures, in which the foreign unit X is alkoxylated:
  • the unit X is placed near the center of the polyether chain, and may be one foreign unit or a series of foreign units covalently linked together.
  • the unit x is one or more foregin repeat units as in (c), but these units are placed along the length of the linear polyether chain.
  • X is a nitrogen containing heterocyclic ring, giving the polyether soft segment a carbon to nitrogen ratio in the range of from 3/1 to 350/1, and a molecular weight in the range of from 200 to 8,000.
  • the sum of m plus n is within the range of 5 to 180, and x in formula (d) has a maximum value of 10.
  • Covalent links to the polyether in (c) or (d) may be an amide link or imide link, both of which are capable of withstanding high temperature processing. These links, the polyester units themselves, and the foreign unit(s) X in (c) or (d) form the soft segment.
  • the lower mole percentage of the soft segment increases the melting point of the copolymer due to the higher mole percentage of the hard segment.
  • a more regular chain is obtained, which may result in better separation of the hard and soft phases. Better phase separation results in a higher tenacity, a lower glass transition temperature for the soft segment, and an improved elastomeric performance.
  • foreign repeat unit refers to heterocyclic, nitrogen- containing rings which may covalently link (as amide or imide) along the soft segment chain as described previously.
  • Representative units are: 1,3-divalent-5,5-dialkylhydantoin (including alkyl groups connected in a cyclic fashion to the 5,5 positions); 2,5-divalent-1,3,4-triazole; 2,5-divalent-1,3,4-thiadiazole; 2,5-divalent-1,3,4-thiadiazole; 1,3-divalent-1,2,4-triazolidine-3,5-dione; 4,5-divalent-1,2-isothiazole, 4,5-divalent-1,2-oxazole, 4,5-divalent-1,3-diazole-; 2,5-divalent-1,3-oxazole; 2,4-divalent-imidazole; divalent (N position) hypoxanthine; and 2,5-divalent-1
  • a preferred unit is 5,5-dialkyl hydantoin having the following formula: wherein R' and R" are lower alkyl, e.g., methyl, ethyl, propyl, which can be converted to a polyoxyalkylene glycol represented by (e) or (f) by oxyalkylation with ethylene oxide as disclosed in the above mentioned U.S. Patent No. 4262114.
  • long-chain ester units as applied to units in the copolymer chain refers to the reaction product of a long chain glycol with a dicarboxylic acid. Such "long-chain ester units", which are selected from repeating units in the copolyesters of this invention, correspond to formula (a) above.
  • the long-chain glycols are polymeric glycols having terminal hydroxy groups and a molecular weight about 400 and preferably of from 1,000 to 3,000 for (c).
  • the long-chain glycol used to prepare the copolyesters of this invention are poly(oxyalkylene) glycols having foreign repeat units represented by formulas (e) and (f).
  • the poly(oxyalkylene) glycols have carbon to nitrogen ratios in the range of from 3/1 to 350/1, molecular, weights in the range of from 200 to 8,000 m plus n is within the range of from 5 to 180, and x in formula (f) has a maximum value of 10.
  • the poly(oxyalkylene) glycols have carbon to nitrogen ratios in the range of from 8.5/1 to 23/1 and molecular weights in the range of from 450 to 8,000.
  • Representative long-chain glycols are poly(oxyethylene)glycol, poly(oxypropylene) glycol, poly(oxymethylethylene) glycol, poly(oxytetramethylene) glycol, and random or block copolymers of ethylene oxide and 1,2-propylene oxide.
  • short-chain ester units refers to low molecular weight compounds for polymer chain units having molecular weights of less than about 500. They are made by reacting a low molecular weight diol (below about 250) with a dicarboxylic acid to form ester units represented by the formula (b) above.
  • diols which react to form the short-chain ester units are cyclic, alicyclic, and aromatic dihydroxy compounds.
  • diols containing from 2 to 15 carbon atoms, such as ethylene, propylene, 1,4-butane, pentamethylene, 2,2-dimethyl trimethylene, hexamethylene, and decamethylene glycol, dihydroxycyclohexane, cyclohexane dimethanol, resorcinol, hydroquinone, 1,5-dihydroxy naphthaline, etc.
  • aliphatic diols containing from 2 to 8 carbon atoms.
  • Equivalent ester-forming derivatives of diols are useful (e.g., ethylene oxide or ethylene carbonate can be used in place of ethylene glycol).
  • low molecular weight diols as used herein includes such equivalent ester-forming derivatives; provided, however, that the molecular weight requirement pertains to diol only and not to its derivatives.
  • Dicarboxylic acids which are reacted with the forgoing long-chain glycols (L in formula a) and low molecular weight diols (E in formula b) are aliphatic, cycloaliphatic, or aromatic dicarboxylic acids of a low molecular weight, i.e., having a molecular weight of less than about 300.
  • the term "dicarboxylic acids” as used herein includes equivalents of carboxylic acids having 2 functional carboxyl groups which perform substantially like dicarboxylic acids in reaction with glycols and diols in forming copolyester polymers. These equivalents include esters and ester-forming derivatives, such as acid halides and anhydrides.
  • the molecular weight requirement pertains to the acid, and not to its equivalent ester or ester-forming derivative.
  • an ester of a dicarboxylic acid having a molecular weight above 300 or an acid equivalent of a dicarboxylic acid having a molecular weight above 300 are included, provided the corresponding acid has a molecular weight below about 300.
  • the dicarboxylic acids may contain any substituent groups or combinations which do not substantially interfere with the copolyester polymer formation and the use of the polymer.
  • Aliphatic dicarboxylic acids refers to the carboxylic acids having 2 carboxyl groups, each attached to a saturated carbon atom. If the carbon atom to which the carboxylic acid group is attached is saturated and is in a ring, the acid is cycloaliphatic. Aliphatic or cycloaliphatic acids having conjugated unsaturation often can be used, provided that they are thermally stable at polymerization temperatures and do not undergo homopolymerization.
  • Aromatic dicarboxylic acids are dicarboxylic acids having 2 carboxyl groups attached to a carbon atom in an isolated or fused benzene ring. It is not necessary that both functional carboxyl groups be attached to the same aromatic ring, and where more than 1 ring is present, they can be joined by aliphatic or aromatic divalent radicals, such as -0- or-S02 .
  • aliphatic and cycloaliphatic acids which can be used for this invention are sebasic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, succinic acid, carbonic acid, oxalic acid, azelaic acid, dimethylmalonic acid, allylmalonic acid, 4-cyclohexene-1, 2-dicarboxylic acid, 2-ethyl suberic acid, 2,2,3,3-tetramethyl succinic acid, cyclopentane dicarboxylic acid, decahydro-1, 5-naphthalene dicarboxylic acid, 4,4'-bicyclohexyl dicarboxylic acid, decahydro-2,6-naphthalene dicarboxylic acid, 4,4'-methylene bis(cyclohexane carboxylic acid), 3,4-furan dicarboxylic acid, and 1,1-cyclobutan
  • aromatic dicarboxylic acids which can be used include terephthalic phthalic and isophthalic acids, dibenzoic acid, substituted dicarboxylic acids with two benzene nuclei such as Bis(p-carboxyphenyl)methane, p-oxy-(p-carboxyphenyl)benzoic acid, ethylene-Bis (p-oxybenzoic acid), 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phen- anthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid, and C 1 -C 12 alkyl and ring substitution derivatives thereof, such as halo, alkoxy; and aryl derivatives. Hydroxy acids such as ( ⁇ -hydroxy ethoxy) benzoic acid can also be used, provided an aromatic dicarboxylic acid
  • Aromatic dicarboxylic acids are a preferred class for preparing the copolyester polymers.
  • aromatic acids those with from 8 to 16 carbon atoms are preferred, particularly the phenylene dicarboxylic acids, i.e., terephthalic, phthalic and isophthalic acids.
  • polymers described herein can be made conveniently by a conventional ester interchange such as that described in U.S. Patent No. 3,763,109.
  • Other special polymerization techniques for example, interfacial polymerization, may prove useful for the preparation of specific polymers. Both batch and continuous methods may be used for any stage of copolyester polymer preparation.
  • Polycondensation of prepolymers can also be accomplished in the solid phase by heatng divided solid prepolymer in a vacuum or in a stream of inert gas to remove liberated low molecular weight diol. This method has the advantage of reducing degradation, because it must be used at temperatures below the softening point of the prepolymer.
  • the copolyesters possess many desirable properties, it is advisable to stabilize certain of the compositions to heat or ultraviolet radiation, and this can be done by incorporating stabilizers into the polyester compositions.
  • Satisfactory stabilizers comprise phenols and their derivatives, amines and their derivatives, compounds containing both hydroxyl and amine groups, hydroxyazine, oximes, polymeric phenolic esters and salts of multivalent metals in which the metal is in its lower valent state.
  • Particularly useful stabilizers of the preferred segmented co-polyester polyethers are derivatives of 2,2,6,6-tetramethyl piperidine.
  • copolyesters can be modified by the incorporation of various conventional inorganic compounds such as titanium dioxide, carbon black, silica gel, alumina, clays, and chopped fiberglass.
  • a particularly preferred polymer within the above described class is a polymer consisting essentially of from 30% to 60% by weight of polybutyleneterephthalate units and from 40% to 70% by weight of hydantoin polyether units and further characterised as above.
  • polyester-polyether polymers are the so-called Hytrel type copolyesters which contain a dimethyl-terephthalate-polytetramethylene ether glycol (molecular weight about 600 to 3000) derived soft segment and a dimethyl-terephthalate-1,4 butanediol derived hard segment.
  • these polymers contain at least 40% soft segment.
  • segmented polyester copolymers having both polyester hard segments and polyester soft segments.
  • Segmented polymers of this type can be prepared by forming acide chloride terminated hard segments, for example, formed by reacting terephthalic acid chloride with ethylene glycol and then reacting this hard segment with a soft segment polyester, for example, hydroxyl terminated polybutyleneadipate.
  • these polyester-polyethers contain at least 35% soft segment and most preferably at least 40% soft segment.
  • the latent contractable filaments are formed by melt extruding the inherently elastomeric polymer in a conventional manner, preferably to form a filament having a denier of less than 300, preferably between 2 and 250 denier, and most preferably between 10 and about 75 denier.
  • the resultant_melt extruded filaments at least have a reduced degree of elasticity as compared to the subsequent contracted filament.
  • the latent contractable, melt extruded filaments are contracted without prior deliberate drawing by heat processing at an elevated temperature which is a contraction inducing temperature below the polymer softening temperature generally in the range of from 40°C to 125°C, preferably from 80° to 100°C and for a time sufficient to contract the length of the melt extruded filament at least 25% and preferably at least 40% as compared to its precontracted length.
  • the temperature employed is at least 15°C lower than the polymer softening point.
  • the time required for contraction varies with the type of polymer and the temperature. Thirty minutes at 90°-100°C is generally effective to obtain significant contraction.
  • the preferred method of the invention comprises processing the filaments in an aqueous medium at a contraction-inducing temperature of at least 40°C to 60°C for a time sufficient to cause the filament to contract linearly at least 15% and preferably at least 40% of its original length.
  • the contractable inherently elastic filaments of the invention are especially useful in the formation of a stretchable textile article which comprises forming a predetermined over-sized article with yarns comprising a latent contractable filament which contracts at least 15% as compared to its original length when exposed to a contraction inducing temperature to provide an elastic filament and exposing the resultant textile article to an elevated temperature sufficient to contract the latent contractable filament at least 15% to form a stretchable article of the desired size.
  • the contractable filament is employed in conjunction with other inelastic yarns and is interspersed unidirectionally or multidirectionally within the textile article.
  • the melt extruded filaments prior to wet processing, are processed into a textile article, either as the sole filament, or most usually intermixed with other fibers, typically in a manner such that the melt extruded latent contractable filament is unidirectionally or biaxially directed and spaced apart within the textile to provide a desired stretch characteristic to the fabric, in a manner generally known in the textile art.
  • the textile articles of the invention are processed to a relaxed size which is larger than the desired finished end product.
  • the woven, knitted or otherwise processed textile product is then subjected to wet processing at a temperature and for a time sufficient to cause the melt extruded elastomeric polymer to contract and achieve its ultimate desired elasticity. As a result of this contraction, the dimensions of the textile article are reduced resulting in a textile article having the desired dimensions and elastic stretchability.
  • wet processing step of the invention need not be carried out as a separate step, but can be and most desirably is conducted in conjunction with at least one other aqueous, elevated temperature treatment step such as washing, dyeing, sizing or the like.
  • the original precontracted dimensions of the textile article can be readily determined based upon the latent contraction characteristics of the particular melt extruded elastomeric polymer employed and the quantity of polymer filaments per unit area, coupled with the heat processing conditions employed. If necessary, a few trials will readily determine the necessary originally woven or knitted textile dimensions required to achieve a heat processed elastically stretchable textile article-having the desired finished dimensions.
  • the heat-processed contracted elastic filaments of the invention have an elastic modulus of at least about .01 g/D preferably between 0.05 g/D and 0.5 g/D and most preferably between 0.2 g/D and 0.4 g/D measured at 100% extension.
  • the preferred filaments of the invention are those which have a medium elastic modulus, i.e. between 0.2 g/D and 0.4 g/d at 100% extension. These filaments provide processed articles which provide relatively high compression and relatively low extension.
  • contractable elastic filaments of the invention having useful stretch properties are contemplated, including some desirably having relatively high compression forces at low elongation.
  • Some typical uses of stretch fabrics falling within the invention include undergarments, such as panty hose, girdles, bras and waist bands; outergarments, such as socks, jeans, ski apparel, swimsuits, tube tops, etc.; and elastic bandages.
  • the contractable elastic filaments themselves may be especially useful in certain applications, e.g., elastic string for packaging, and label cords.
  • the latent-contractable filaments of this invention can be processed into a textile product as extruded.
  • relatively inelastic filaments i.e., hard fibers
  • Elastic yarn covering techniques are known in the art. However, in the prior processes, the elastic yarn was covered in a stretched condition in order to prevent the covering hard fibers from retarding the desired extensibility.
  • the latent-contractable elastic filaments are covered in their melt extruded precontracted state.
  • the elastic filaments of the invention may be single wrapped with a yarn, i.e., one or more covering yarns being wrapped spirally in a single direction with the elastic filament, or double covered, an additional yarn also being wrapped about the composite yarn with an opposite direction of false twist from the first cover yarn.
  • the precontraction melt extruded filaments of the invention are comingled with at least one and preferably at least three relatively inelastic filaments (hard fibers) to protect the elastic filament and provide desirable textile properties.
  • the resultant composite yarn upon heat (preferably wet) processing yields a contracted bulky, elastic yarn which is capable of being extended at least 50% and preferably 100% of its contracted relaxed length when stretched until the relatively inelastic filaments first become load bearing.
  • the composite yarn When stretched until the hard fibers firt become load-bearing, the composite yarn is characterized by load-bearing, relatively inelastic filaments entangled with the elastic yarn in intermittent zones of random braided structure and otherwise extending substantially parallel to the elastic yarn, there being an average entanglement spacing of less than 10 centimeters and the filaments being free from crunodal or other surface loops when the composite yarn is examined in the stretched condition.
  • the composite yarn preferably has substantially zero unidirectional torque.
  • the relatively inelastic filaments preferably have crimp when relaxed. The crimp is preferably such that the relatively inelastic filaments form undulations and twist pigtails when the composite yarn is relaxed. In accordance with a preferred embodiment, the relatively inelastic filaments form reversing helical coils when the composite yarn is relaxed.
  • the relatively inelastic filaments may be bicomponent filaments which crimp when relaxed before or after crimp development.
  • the composite yarn after latent contraction preferably has a break elongation of 50 to 350 percent or more.
  • the elastic portion of the composite yarn shows no evidence of crimp, twist or torque produced by the operation of combining the hard fiber filaments with the elastic yarn.
  • the composite yarn of this invention can be produced at feed rates of up to about 2000 meters per minute, or higher, by continuously feeding the elastic yarn with the relatively inelastic filaments through jetted high velocity fluid and impinging the jetted fluid on the yarn axis at an angle of 90° ⁇ 45° to entangle the filaments around the elastic yarn in intermittent zones of random braided structure.
  • the precontraction melt extruded filament is fed to the jetted fluid under predetermined tension sufficient to stretch the filament, if desired, or merely to maintain it relatively taut.
  • the relatively inelastic filaments (hard fibers) are simultaneously fed at a rate which is approximately equal to the rate at which the melt extruded filament is fed or which provides a net overfeed of hard fibers to be jetted fluid.
  • the composite yarn is wound on a package under controlled tension.
  • Suitable hard filber filaments or fibers include any synthetic textile filaments or fibers of relatively inelastic material such as nylon, e.g. nylon 6 and nylon 6,6; a polyester, e.g., polybutylene terephthalate, and polyethylene terephthalate, polypropylene, cellulose acetate; regenerated cellulose, etc.
  • the hard fiber filaments may be fed to the jetted fluid as a single filament or as a bundle of preferably at least three filaments and may be of more than one material. The bundle preferably has less than 1 turn per 5 centimeters of twist and the filaments must be capable of being separated by the jetted fluid.
  • two or more precontraction melt extruded filaments may be fed and comingled with the inelastic filaments, the plurality of melt extruded filaments being separated at least temporarily by the jetted fluid to, if desired, insert portions of the relatively inelastic filaments between the melt extruded filaments.
  • the fluid used is preferably compressed air, although other fluids can be used; it is usually used at ambient temperature.
  • the fluid is preferably impinged on the yarn from more than one direction, each substantially perpendicular to the yarn axis.
  • the rate of feed of the inelastic filaments in relation to the precontraction melt extruded filament is determined by the degree of extension desired in the composite yarn before the inelastic filaments become load-bearing. For any given filament and intended heat processing conditions, one can determine the amount of contraction to be obtained. Since it is desired that the contracted elastic filament of the invention be extendable at least 50% and preferably between about 100% and 350%, the amount of inelastic filament fed should be that amount which becomes load-bearing at the desired maximum extension of the contracted elastic filament.
  • the desired extensibility of the contracted elastic filament is the contracted relaxed length multiplied by about 1.75 to about 6 and, since typically the contracted relaxed length of the heat processed elastic filament is 40% to 75% of the precontraction melt extruded filament length, the desired rate of feed of the inelastic filament and the precontraction melt extruded filament can be readily calculated for a given desired composite yarn. For example, if a heat processed elastic filament is contracted 50% based on the starting melt extruded filament and the desired extensibility is 100% (contracted length x2) the rates of feed of the inelastic filaments and the melt extruded filament should be equal.
  • the rate of feed of the inelastic filaments should be 25% greater than the rate of feed of the melt extruded filament.
  • the elastic filament be intermingled with the inelastic yarn in a manner so that the relatively inelastic yarn becomes load-bearing at at least less than about 95% of the break elongation of the elastic filament.
  • a precontraction melt extruded filament 1 of the invention from a supply source, is supplied, at a given rate, by driven feed roll 2 to a fluid jet intermingling device 7, while relatively inelastic filaments 3, from a supply source, are supplied at a given rate by rolls 4, 5 and 6, the same as or different from the melt extruded filament supply rate to the fluid jet intermingling device 7.
  • the two filament supplies pass through a fluid intermingling jet with the device 7, which may have filament guides at the entrance and exit to center the filaments within the jet which intermingles the hard fiber filaments with the melt extruded filament.
  • the resultant composite yarn 8 then passes one or more wraps about roll 9 and then to a windup device and package 10.
  • a useful composite yarn comprises, for example, two heat contracted elastic filaments 11 and 12, intermingled with five inelastic filaments 13, 14, 15, 16 and 17.
  • the fluid jet intermingling device may be one of those described in U.S. Patent Nos. 3,364,537 and 3,115,691 U.S. Patent No. 3.426,405, for example, in which one or more fluid streams impinge on the yarn line at an angle of 90° ⁇ 45°.
  • the essential requirement is that the hard fiber filaments be subjected to a fluid stream having an appreciable component of force at right angles to the filaments to separate them and force them around the inherently elastic yarn and around and between other hard fiber filaments to intermingle the hard fiber filaments by a random braiding action intermittently along the length of the composite yarn.
  • Jets having a unidirectional twisting effect are suitable for the present process only when a yarn oscillates rapidly between a region of fluid torque operating in one direction and a region of opposite torque, as described in U.S. Patent No. 2,990,671.
  • melt extruded filament and the inelastic companion filaments can be fed at greatly varying rates relative to each other, because of the subsequent contractability of the melt extruded filament it is not necessary to overfeed the inelastic companion filaments at rates as high as heretofore considered appropriate.
  • a preferred process comprises continuously feeding at least one of the melt extruded filaments at a first predetermined feed rate and relatively inelastic filaments at a second predetermined feed rate through jetted high velocity fluid to entangle the inelastic filament around the melt extruded filament at spaced intervals, the rate of feed of the inelastic filaments being adjusted to the rate of feed of the melt extruded filaments so that the rate of feed of the inelastic filaments is less than twice the rate of feed of the melt extruded filament and is a rate such that after the resultant composite yarn is exposed to an elevated contraction inducing temperature whereby the melt extruded filament is contracted at least about 15% to provide an elastic filament, when the resultant composite yarn is stretched, the inelastic filaments become load-bearing at a predetermined percent of elastic stretching below the break elongation of the elastic filament.
  • the precontraction melt spun filament and inelastic filament are fed at rates adjusted to form a composite yarn which has the desired elastic extensibility properties after the composite yarns has been heat treated to contract the melt spun filament. Because the elastic filament formed by the heat treatment is shortened, the inelastic filament need not be overfed or at least need not be overfed at high rates to achieve the desired elastic extensibility. In any event, upon stretching, it is desired that the inelastic filaments become load bearing before the break elongation of the elastic filament is reached.
  • the hard fiber multifilaments consists of relatively inelastic continuous filaments of any commonly available textile material.
  • Nylon is generally preferred because of its high strength and low friction.
  • Either uncrimped or crimped yarn may be employed, but crimped-or crimpable yarns must be capable of being held loop-free at the tension required to entangle the filament around the core and wind the composite yarn on a package.
  • the tension-stable textured yarn described in U.S. Patent No. 2,783,609, for example, which has a crunodal surface loops when held at tension, is unsatisfactory for the purpose of the present invention.
  • Two or more different multifilaments yarns may be employed, for example, nylon to give strength at ultimate extension and cullose acetate to provide luxurious textile aesthetics when the fabric is relaxed.
  • Two yarns having differential shrinkage properties may be employed for certain effects.
  • an untextured polyester yarn having high potential shrinkage may be fed with a textured nylon yarn and be entangled around a melt extruded core yarn wherein both hard fiber yarns are at the same tension during entangling and, in contract to those of U.S. Patent No. 2,783,609 remain loop free when wound on the package.
  • the polyester will shrink while the nylon develops crimp.
  • the polyester will become the load-bearing member to limit the ultimate extension of the composite yarn and will permit the textured nylon to retain a degree of crimp and bulk even at ultimate extension of the composite.
  • the retractive power of such yarn may be less than that normally required when these filaments are used alone, since the elastic portion of the present composite yarn furnishes the major retractive power of the composite.
  • the hard fiber filaments therefore, need only have sufficient crimping ability to form the crimps, twists, or coils desired for imparting bulk, opacity or tactile aesthetics to the final fabric. These filaments, therefore, will be processed at higher speeds or under less stringent texturing conditions than would normally be required. This may permit falsetwist texturing, for example, to be performed on hard fiber which is then fed directly into the entangling step in a single continuous process.
  • the hard fiber feed yarns should have low twist, preferably not more than 0.4 to 1.0 turns per 5 centimeters known as "producer twist", or most preferably zero twist. High twist interferes with opening of the filament bundle during the process of intermingling and surrounding the elastic core.
  • Feed yarns having zero or low twist may interlace as described in U.S. Patent No. 2,985,995, but they should not have such a large degree of interlace that thefilaments are unable to separate for random braiding in the present process.
  • a yarn having the lowest degree of interlace consistent with processing, winding, and unwinding is preferred, no interlace being most preferable.
  • the yarns should not have size or finish of such a cohesive nature that it prevents the bundle from opening during the intermingling process although certain finishes may be desirable which allow the bundle to open but aid in retaining intermingling subsequently. Finishes disclosed in U.S. Patent 3,701,248, for example, may be used to improve the performance of yarns of this invention.
  • Yet another useful process for providing a covered yarn comprises spinning cut or staple fibres about the contractable inherently elastic filament by techniques known in the art as "core spinning".
  • Core spinning is described in U.S. Patents 3,380,244; 3,009,311; 3,017,740; and 3,038,295. It is noted that while it has generally been considered necessary to stretch the core filament (elastic filament) to provide a useful composite core-spun elastic yarn, in the present invention, if desired, it not necessary to appreciably stretch the melt extruded filament during the core spinning process.
  • the latent contraction when heat activated subsequent to core-spinning the relatively inelastic staple fibres about the melt extruded filament, allows subsequent elastic extension of the resultant core-spun yarn before the inelastic yarn becomes load bearing.
  • the ester interchange reaction was conducted to recover about 12 pounds of methanol.
  • the resultant reaction product was transferred to a polycondensation vessel and the reaction continued to recover about 4.8 kilograms of 1,4-butanediol and about 46 kilograms of the elastomeric polymer. (TINUVIN is a Registered Trade Mark).
  • the above 40 wt% PBT ⁇ 60 wt% HPOE elastomer in the form of polymer chips stored in bunker (A) were extruded through a 1.27 cm extruder (B), the zones I, II and III of the extruder being at temperatures of 215°C, 218°C and 220°C, respectively.
  • the extruder melt temperature was 205-207°C, and the pump yield for a 50 denier elastic yarn was 2.0 g/min.
  • the polymer was extruded through a 2-hole spinneret (250 ⁇ x 440 u) into a water bath (C) which was at room temperature (-22°C). The water bath temperature was maintained at approximately 20-22°C by constant inflow and outflow of water.
  • the distance between the spinneret and the water bath was approximately 5 inches.
  • a standard polyester finish was applied by means of a kiss-roll finish applicator (D).
  • the speed of the two godets (E and F) is 500 meters/min.
  • the elastic yarn was tangled with the companion yarn (G), 20/5 cationic dyeable textured nylon, by feeding both the yarns through a tangling jet (H).
  • the air pressure for tangling used was 60 psi.
  • the combined yarn was wound on a 15 cm long tube (0.63 cm thickness) using a Leesona winder (J).
  • the elastic yarn was knit in every fourth course of the panty portion at about 3 gram tension.
  • the stitch construction was set on a 1 x 1 rib.
  • the band was made in a 3 x 1 construction of a conventional 560 denier base spandex with a 50 denier cationic dyeable nylon filament, so that the entire panty hose top could be dyed with basic dyes for style purposes.
  • the leg portion knitted from regular dyeable nylon stretch filament yarn, plain or in combination with regular nylon covered spandex, can be dyed with acid dyes. After knitting, the toes of the hosiery panels were closed and the panty portions were slit to construct the total panty hose panty, while a pre- knitted cotton crotch was sewn in.
  • panty hose garment was dyed starting with clean hosiery paddle dyeing machines.
  • Dyeing formulations were added and initial dyeing was run for 10-15 minutes.
  • the bath temperature was raised to 100°C at a rate of about 20° per minute, at which temperature the hose were dyed for 30 to 40 minutes.
  • the latent contraction of the elastic filaments occurred during the dyeing step.
  • the chart direction was reversed after reaching 80% of the breaking elongations for the respective samples in order to exhibit the contraction modulus.
  • the diagram of the boiled-off yarn exhibits the typical elastic characteristics of the elastic composite yarn in finished fabrics. Eighty percent of the breaking elongation measures, in this case, 136% stretch at a load of 70 grams. In textile garment applications, the elastic yarn will usually perform in the 60%-100% elongation range and between 10-25 grams elastic force.
  • Hytrei (Registered Trade Mark) polyether: polyester (polyester hard segments:poly(ethylene terephthalate); polyether soft segments:poly(tetrahydrofuran)) (for preparation, see U.S. Patent 3,763,109) were extruded in the manner generally shown in Example 1 and separate samples of the extruded filament exposed to hot air (80°C) and boiling water for 30 minutes and the extent of latent contraction measures:
  • Example 1 In the general manner of Example 1, a segmented polyether: polyester was prepared consisting of 40% polybutyleneterephthalate hard segment and 60% polyoxyethyethylene (mol. wt. 1000) soft segment. The polymer was melt extruded into a 40 denier filament using a small laboratory ram extruder. Due to the long residence time inherent in the use of this extruder, a relatively weak fiber was produced having a tenacity (gm/denier) of about 0.2, and an elastic modulus at 100% extension of 0.1 gram/denier. The filament, upon exposure to boiling water for 30 minutes was an elastic filament which displayed a 33% contraction from its pre heat exposure length.
  • a segmented polyether polyester was prepared consisting of 40% polybutyleneterephthalate hard segment and 60% polyoxyethyethylene (mol. wt. 1000) soft segment.
  • the polymer was melt extruded into a 40 denier filament using a small laboratory ram extruder. Due to the long residence time inherent in the use
  • a 60% poly(butyleneterephthalate) 40% poly(butylene adipate) polyester polyester with soft and hard segments formed through urethane links was melt spun in a Killian 1 ⁇ 2-inch extruder at 210°C through a 1000 p x 3000 ⁇ spinneret, into water at ambient temperature, and taken up at 300 meter/minutes, to yield a filament having a denier of 73.
  • the filament upon exposure to boiling water for 30 minutes, displayed a 33% contraction of its original length.
  • the filament prior to heat treatment had an elongation of 213% and after heat treatment had an elongation of 382%.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Artificial Filaments (AREA)

Claims (11)

1. Verfahren zur Erzeugung eines elastischen Fadens (Filaments), wobei ein segmentiertes, inhärent elastisches thermoplastisches Polyester-Polyester- oder Polyester-Polyäther-Polymer schmelzextrudiert und das schmelzextrudierte Polymer einer erhöhten Temperatur ausgesetzt wird, dadurch gekennzeichnet, daß das thermoplastische Polymer verhältnismäßig harte und verhältnismäßig weiche Segmente eingestreut enthält und daß das schmelzextrudierte Polymer, ohne daß es zuvor absichtlich gezogen wird, einer erhöhten Temperatur im Bereich von 40-125°C ausgesetzt wird, um das schmelzextrudierte Polymer um mindestens 15% linear zu kontrahieren und um einen elastischen Faden zu erzeugen.
2. Verfahren nach Anspruch 1, worin das schmelzextrudierte Polymer einen segmentierten thermoplastischen Co-Polyester darstellt, der im wesentlichen aus einer Vielzahl von wiederkehrenden langkettigen und kurzkettigen Estereinheiten besteht, welche über Esterbindungen "Kopf-an-Schwanz" miteinander verbunden sind, wobei die langkettigen Estereinheiten mindestens 40 bis 70 Gew.-% des CoPolyesters ausmachen und durch die Formel
Figure imgb0017
dargestellt sind und wobei die kurzkettigen Estereinheiten durch die Formel
Figure imgb0018
dargestellt sind, worin bedeuten:
L in der langkettigen Einheit bedeutet einen zweiwertigen Rest, der nach Entfernung der entständigen Hydroxylgruppen aus einem Poly-(Oxyalkylen)-Glykol hinterbleibt und der mindestens einen stickstoffhaltigen Ring je Molekül, ein Kohlenstoff/Stickstoff-Verhältnis im Bereich von 3/1 zu 350/1 sowie ein numerisches durchschnittliches Molekulargewicht im Bereich von 200 bis 8000 aufweist;
R bedeutet einen zweiwertigen Rest, der nach Entfernung der Carboxylgruppen aus einer Dicarbonsäure hinterbleibt und der ein Molekulargewicht von weniger als 300 hat;
und E in der kurzkettigen Einheit bedeutet einen zweiwertigen Rest, der nach Entfernung der Hydroxylgruppen aus einem niedrigmolekularen Diol hinterbleibt und der 2 bis 15 Kohlenstoffatome je Molekül enthält und ein Molekulargewicht von weniger als 250 hat.
3. Verfahren nach Anspruch 2, worin in den langkettigen und in den kurzkettigen Estereinheiten, die das Polymer bilden, praktisch die gesamte Dicarbonsäure Terephthalsäure darstellt und worin in den kurzkettigen Estereinheiten, die das Polymer bilden, praktisch der gesamte Diol mit einem Molekulargewicht von weniger als 250 1,4-Butandiol darstellt.
4. Verfahren nach Anspruch 2, worin in den langkettigen Estereinheiten, die das Polymer bilden, die Gruppe -OLO- eine Poly-(Oxyalkylen)-Glykol-Einheit darstellt, die durch die Oxyalkilierung von
Figure imgb0019
gebildet worden ist, worin R' und R" niedere Alkylgruppen mit 1 bis 3 C-Atomen darstellen.
5. Verfahren nach einem der Ansprüche 1 bis 4, worin das Polymer einer Temperatur im Bereich von 80 bis 100°C ausgesetzt wird.
6. Verfahren nach einem der Ansprüche 1 bis 4, worin das Polymer einer Temperatur von mindestens 40 bis 60°C ausgesetzt wird, und zwar über einen Zeitraum, der ausreicht, um die Länge des schmelzextrudierten Fadens um mindestens 40%, verglichen mit der Länge im nicht-kontrahierten Zustand, zu kontrahieren.
7. Verfahren zur Herstellung eines elastischen Verbundgarns, worin ein schmelzextrudiertes, segmentiertes, inhärent elastisches thermoplastisches Polyester-Polyester- oder Polyester-Polyäther-Polymer mit unelastischen Fasern oder Fäden vereinigt und das zusammengesetzte Garn einer erhöhten Temperatur ausgesetzt wird, dadurch gekennzeichnet, daß das thermoplastische Polymer verhältnismäßig harte und verhältnismäßig weiche Segmente eingestreut enthält und daß das schmelzextrudierte Polymer, ohne daß es zuvor absichtlich gezogen wird, einer erhöhten Temperatur im Bereich von 40-125°C ausgesetzt wird, um den schmelzextrudierten polymeren Faden um mindestens 15% seiner Länge zu kontrahieren.
8. Verfahren zum Vereinigen eines latent kontrahierbaren, schmelzextrudierten Fadens, der aus einem segmentierten, inhärent elastischen, thermoplastischen Polyester-Polyester- oder Polyester-Polyäther-Polymer gebildet ist, mit einer verhältnismäßig unelastischen, synthetischen Polymerfaden, um ein Verbundgarn herzustellen, wobei mindestens ein latent kontrahierbarer, schmelzextrudierter Faden mit einer esten, vorherbestimmten Zugabegeschwindigkeit und mindestens ein verhältnismäßig unelastischer Faden mit einer zeitlich vorherbestimmten Zugabegeschwindigkeit kontinuierlich durch einen Fluidstrahl mit hoher Geschwindigkeit geleitet werden, wobei der Fluidstrahl unter einem Winkel von 90° ± 45° auf die Fadenachse auftrifft, um die unelastischen Fäden zu trennen und um die unelastischen Fäden um den schmelzextrudierten Faden zu verwickeln; wobei die Zugabegeschwindigkeit der unelastischen Fäden gegenüber der Zugabegeschwindigkeit der schmelzextrudierten Fäden so eingestellt wird, daß die Zugabegeschwindigkeit der unelastischen Fäden weniger als das Doppelte der Zugabegeschwindigkeit der schmelzextrudierten Fäden beträgt; dadurch gekennzeichnet, daß das thermoplastische Polymer verhältnismäßig harte und verhältnismäßig weiche eingestreute Segmente enthält und daß, wenn das erhaltene Verbundgarn, ohne daß es zuvor absichtlich gezogen wurde, einer erhöhten Temperatur im Bereich von 40 bis 125°C ausgesetzt wird, der schmelzextrudierte Faden um mindestens 15% kontrahiert wird, um einen elastischen Faden zu erzeugen, und, wenn das erhaltene Verbundgarn gestreckt wird, die unelastischen Fäden bei einem vorherbestimmten prozentualen Anteil an elastischer Streckung unterhalb der Bruchdehnung des elastischen Fadens die Last aufnehmen.
9. Verfahren nach Anspruch 8, worin der schmelzextrudierte Faden und der unelastische Faden mit etwa der gleichen Geschwindigkeit zugeführt werden.
10. Verfahren zur Erzeugung eines streckbaren Textilgegenstandes, wobei ein vorherbestimmter Gegenstand in Übergröße mit Garnen, enthaltend latent kontrahierbare Fäden aus einem segmentierten, inhärent elastischen, thermoplastischen Polyester-Polyester- oder Polyester-Polyäther-Polymer erzeugt und der erhaltene Textilgegenstand einer erhöhten Temperatur ausgesetzt wird, die ausreicht, um den latent kontrahierbaren Faden zu kontrahieren, dadurch gekennzeichnet, daß das thermoplastische Polymer verhältnismäßig harte und verhältnismäßig weiche Segmente eingestreut .enthält und um mindestens 15%, bezogen auf seine ursprüngliche Länge, kontrahiert, wenn es, ohne daß es zuvor absichtlich gezogen wird, einer erhöhten Temperatur im Bereich von 40 bis 125°C ausgesetzt wird, um einen streckbaren Gegenstand mit der gewünschten Größe zu bilden.
11. Verfahren nach Anspruch 10, worin der latent kontrahierbare Faden mit einem verhältnismäßig unelastischen Begleitfaden oder -faser bedeckt wird.
EP19810303473 1980-08-18 1981-07-28 Latent schrumpfbare Elastomere, daraus zusammengesetzte Garne und Verfahren zu deren Herstellung und Anwendung Expired EP0046346B1 (de)

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US4631098A (en) * 1983-01-06 1986-12-23 Raychem Limited Heat-recoverable article
US4624720A (en) * 1983-01-06 1986-11-25 Raychem Ltd Dimensionally heat-recoverable article
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BR8603045A (pt) * 1986-06-30 1988-02-09 Du Pont Processo para produzir um fio de tapete com propensao estatica reduzida
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CN110512329B (zh) * 2019-09-12 2021-06-29 嘉兴学院 一种包缠结构弹力段彩纱及其制备方法

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