EP0454160A2 - Filaments composés élastiques du type "âme-gaine" et structures textiles contenant ces filaments - Google Patents

Filaments composés élastiques du type "âme-gaine" et structures textiles contenant ces filaments Download PDF

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Publication number
EP0454160A2
EP0454160A2 EP91106833A EP91106833A EP0454160A2 EP 0454160 A2 EP0454160 A2 EP 0454160A2 EP 91106833 A EP91106833 A EP 91106833A EP 91106833 A EP91106833 A EP 91106833A EP 0454160 A2 EP0454160 A2 EP 0454160A2
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EP
European Patent Office
Prior art keywords
polyurethane
core
yarn
sheath
filament
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP91106833A
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German (de)
English (en)
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EP0454160A3 (en
Inventor
Yasuo Muramoto
Kiyoshi Yoshimoto
Masao Matsui
Masami Fujimoto
Yoshiaki Morishige
Tsutomu Naruse
Yoshinori Murafuji
Souichi Murakami
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Kanebo Ltd
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Kanebo Ltd
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Priority claimed from JP2114130A external-priority patent/JP2786514B2/ja
Priority claimed from JP3090011A external-priority patent/JP2869206B2/ja
Application filed by Kanebo Ltd filed Critical Kanebo Ltd
Publication of EP0454160A2 publication Critical patent/EP0454160A2/fr
Publication of EP0454160A3 publication Critical patent/EP0454160A3/en
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent

Definitions

  • the present invention relates to an elastic core and sheath type composite filament consisting of a sheath component of a fiber-forming thermoplastic non-elastomer and a core component of a polyurethane, and textile structures comprising such a composite filament.
  • Polyurethane elastomer yarns have hitherto been applied in diversified fields, with peculiar properties thereof being utilized.
  • these polyurethane elastomer yarns different from usual synthetic filament yarns, stick to each others due to tackiness inherent therein, whereby not only an excessive tensile force for drawing out from yarn packages is required but also great variations in tension occur when taken-up yarns are unwound.
  • the polyurethane elastomer yarns elongate with a little tensile stress and also have a high coefficient of friction, the yarns are low in workability and difficult to handle in succeeding steps, so that they are followed about by problems of yarn breakages, uneven knitting, etc. even under a strict process control.
  • an oiling agent for example, an oiling agent predominantly comprising dimethyl silicone, admixed with a metallic soap, monoamines or the like: as disclosed in Japanese Patent Publications Nos. 40-5,557 and 46-16,312).
  • core and sheath type composite filament yarns such as an elastic yarn consisting of concentric polyurethane core and polyurethane sheath composite filaments (for example, Japanese Patent Publication No. 61-14,245, proposed by the present inventors), and an elastic yarn consisting polyurethane core and polyolefin sheath composite filaments (for example, Japanese Patent Publication No. 61-194,221).
  • the above elastic, polyurethane-polyurethane type concentric composite filament yarn since the sheath is composed of a polyurethane, has disadvantages in respects of tackiness inherent therein, a high-speed take-up ability at spinning step, workability at succeeding steps, tactile properties of goods formed therefrom, etc. Additionally, this yarn has a difficulty in blending with polyester yarns.
  • textile structures composed of polyurethane elastomer yarns have undesirable tactile properties such as hand or touch, and also are poor in dyeability and color fastness. Accordingly, the textile structures composed of a polyurethane elastomer yarn alone scarcely appear in the market, since production processes are accompanied by extreme difficulties.
  • covering yarns comprising a polyurethane core yarn and a nylon plating yarn wound around the core yarn have been proposed and applied to many uses.
  • the covering yarns have an increased thickness as compared with polyurethane bare yarns, due to the wound plate yarns, so that stockings knit with such yarns are heavy and lack transparency.
  • processes for manufacturing such a yarn require a covering step, causing a different problem of an extremely low output rate.
  • crimp-potential composite filament yarns For example, a crimped yarn consisting of eccentric polyurethane core and polycapramide sheath composite filaments, which allows the covering step to be omitted (Japanese Patent Publication No. 55-27,175) and an elastic yarn consisting of composite filaments comprising an eccentric core of a crosslinked polyurethane elastomer (Japanese Patent Publication No. 1-118,619) have been known.
  • the eccentric polyurethane core and polycapramide sheath composite filament yarn has drawbacks such that it requires a step of draw and relax treatment to develop a crimp recovering force and has a rather low modulus of stretch recovery as it is rendered by crimps. Further, it is necessary to give great care to uniformity of the crimps. Moreover, stockings composed of such a yarn have problems such as of lacking transparency, having a poor knit texture, providing undesirable appearance to the legs wearing them, or the like.
  • polyurethane elastomer yarns have a hot water shrinkage at 100°C of at most 10-odd percent.
  • a hot or cold drawing process As a process for increasing this value, there has been a hot or cold drawing process.
  • hot drawing for example, a 2-3 times drawing at 120°C
  • a hot water shrink percentage becomes generally in the twenties to thirties.
  • the drawn polyurethane elastomer yarns spontaneously shrink at room temperature before measurement of such a hot water shrinkage is conducted.
  • the polyurethane elastomer yarns are hardly set and thereby very difficult to handle. Namely, during lying, the yarns spontaneously shrink even if they are not heated and thus present a further problem of dimensional instability.
  • Japanese Patent Publication No. 55-9,093 proposes a process of conjugating a non-elastomer with a polyurethane polymer having an unreacted isocyanate group incorporated thereinto in an amount of 1-45 ⁇ g eg. per 1 g of polymer at the time of conjugate-spinning.
  • this process has a difficulty such that the isocyanate group content in the polyurethane must be controlled on the above level until spinning, as well as a problem of a low elastic stretch recovery of the resulting composite filaments since a polyurethane having a melting point temperature of 200-235°C which has hard segments considerably increased is employed.
  • a first object of the present invention is to provide a novel elastic, composite filament yarn having an excellent elastic stretchability and an improved workability in spinning and take-up steps as well as in succeeding steps, owing to tackiness-free.
  • a second object of the present invention is to provide a polyurethane filament yarn having an excellent dyeability and exhibiting a high shrinkage through hot water treatment.
  • a third object of the present invention is to provide novel textile structures, particularly ladies' hosiery, having novel properties entirely different from conventional textile structures comprising a polyurethane bare yarn, such as excellent elastic stretch, heat resistance, tactile properties when being put on, and transparency.
  • the filament according to the present invention to achieve the above objects is an elastic, core and sheath type composite filament characterized by consisting of a fiber-forming thermoplastic non-elastomer sheath component and a polyurethane core component, which is characterized in that a core/sheath conjugate ratio X and a crosslink density Y ( ⁇ mol/g) of the polyurethane satisfy simultaneously the following inequalities: 3 ⁇ X ⁇ 100, Y ⁇ 0 and Y ⁇ -8.7X + 52.
  • the above non-elastomer taking a balance with a melt viscosity of the polyurethane during spinning into consideration, is preferred to have an optimum melt-spinning temperature of at most 238°C.
  • a first embodiment of the present invention is the aforesaid filament wherein the non-elastomer is a polyamide having at least one of characteristics: a melting point determined with a differential scanning calorimeter (DSC) being within the range between 80°C and 220°C; and a relative viscosity determined at 25°C with a solution of 1 g polymer in 100 ml of 98% sulfuric acid being at most 2.3.
  • DSC differential scanning calorimeter
  • a second embodiment of the present invention is the aforesaid filament wherein the non-elastomer is a copolyester comprising polyethylene terephthalate as a principal constituent and 12-50 mol % of an isophthalate comonomer.
  • a third embodiment of the present invention is the aforesaid filament wherein the non-elastomer is a copolyester obtained from a dicarboxylic acid ingredient comprising 60-88 mol % terephthalic acid and 12-40 mol % isophthalic acid and a diol ingredient comprising 75-90 mol % ethylene glycol and 10-25 mol % of at least one glycol selected from the group consisting of diethylene glycol, triethylene glycol, neopentyl glycol and butanediol.
  • the non-elastomer is a copolyester obtained from a dicarboxylic acid ingredient comprising 60-88 mol % terephthalic acid and 12-40 mol % isophthalic acid and a diol ingredient comprising 75-90 mol % ethylene glycol and 10-25 mol % of at least one glycol selected from the group consisting of diethylene glycol, triethylene glycol, neopentyl glycol and
  • a fourth embodiment of the present invention is the aforesaid filament wherein the non-elastomer is a polyolefin selected from the group consisting of polyethylene, polypropylene, polystyrene and polybutene and the polyurethane has a crosslink density Y of at least 6 ⁇ mol/g, preferably at least 10 ⁇ mol/g.
  • the polyurethane core component of the present invention preferably comprises a polyurethane crosslinked by polyisocyanate, having a crosslink density Y of at least 6 ⁇ mol/g, preferably at least 10 ⁇ mol/g.
  • Such a crosslinked polyurethane is preferred to have predominantly an allophanate crosslinked structure.
  • the filament of the present invention is most preferred to have a cross-sectional shape wherein the core component and the sheath component have substantially a common center of gravity.
  • the present invention includes a textile structure comprising the above elastic, core and sheath type composite filament.
  • the textile structure according to the present invention comprises an elastic, core and sheath type composite filament characterized by consisting of a fiber-forming thermoplastic non-elastomer sheath component and a polyurethane core component, which is characterized in that a core/sheath conjugate ratio X and a crosslink density Y ( ⁇ mol/g) of the polyurethane satisfy simultaneously the following inequalities: 3 ⁇ X ⁇ 100, Y ⁇ 0 and Y ⁇ -8.7X + 52.
  • Such a textile structure of the present invention is preferably embodied in a ladies' hosiery whose non-elastomer is a polyamide.
  • the polyamide is most preferred to be nylon-12.
  • Fig. 1 is a schematical vertical sectional view of a spinneret to be employed in the manufacture of the filament of the present invention, in particular, showing a portion where flows of two molten components meet, of the spinneret.
  • nylon-6 and a modified nylon-66.
  • homopolyamides such as nylon-8, nylon-9, nylon-10, nylon-11, nylon-12 or the like, copolyamides such as nylon-6/66, nylon-6/12 or the like, terpolyamides such as nylon-6/12/10 or the like, further multipolyamides and mixtures thereof, also can be preferably employed.
  • nylon-12 is particularly preferred for application to ladies' hosiery.
  • these non-elastomers preferably have an optimum melt-spinning temperature of not exceeding 238°C which is also the upper limit of the optimum melt-spinning temperature of polyurethanes.
  • optimum melt-spinning temperature relative viscosity or melting point temperature may be adopted.
  • nylon-6 it is particularly preferred to select those having a relative viscosity of at most 2.3, which is determined at 25°C with a solution of 1 g nylon sample in 100 ml of 98% sulfuric acid.
  • nylons such as a modified nylon-66, nylon-8, nylon-9, nylon-10, nylon-11, nylon-12, copolymers thereof, blend polymers thereof, or the like, having a melting point temperature determined with a differential scanning calorimeter (DSC) of 80-220°C are also preferred. If the melting point temperature exceeds 220°C, the melt-stability and resistance to heat of the polyurethane of the core component will lower to unbalance the melt-viscosity of the core component with that of the sheath component during conjugate-spinning and the resulting filaments will have a low modulus of stretch recovery, so that it is not preferred.
  • a melting point temperature of less than 80°C is also not preferred, because the non-elastomer will have a poor fiber-formability and become tacky.
  • polyesters to be applied to the sheath component are copolyester comprising polyethylene terephthalate as a principal constituent and 12-50 mol % of acid ingredients being isophthalic acid. If the isophthalic acid percent in the acid ingredient exceeds 50 mol %, polymer pellets may stick with each others to form bridging during drying or spun filament yarns may cause troubles such as sticking or the like, so that it is not preferred. Contrariwise, if the isophthalic acid percent is less than 12 mol %, the optimum melt-spinning temperature will increase to such an extent that the melt viscosity becomes hardly balanced with that of the core component during spinning, and so it is not preferred. Therefore, the range between 15 mol % and 45 mol % is preferred.
  • the third embodiment of the present intention comprises, as a sheath component, a copolyester obtained from a dicarboxylic acid ingredient comprising 60-88 mol % terephthalic acid and 12-40 mol % isophthalic acid and a diol ingredient comprising 75-90 mol % ethylene glycol and 10-25 mol % of at least one glycol selected from the group consisting of diethylene glycol, triethylene glycol, neopentyl glycol and butanediol.
  • a copolyester obtained from a dicarboxylic acid ingredient comprising 60-88 mol % terephthalic acid and 12-40 mol % isophthalic acid and a diol ingredient comprising 75-90 mol % ethylene glycol and 10-25 mol % of at least one glycol selected from the group consisting of diethylene glycol, triethylene glycol, neopentyl glycol and butanediol.
  • the above diols other than ethylene glycol is less than 10 mol %, it is hard to lower the shrink commencement temperature, so that a preferable effet is hardly obtained.
  • the shrink commencement temperature will lower to such a great extent that there may arise a fear of inducing spontaneous shrink.
  • isophthalic acid as a dicarboxylic acid ingredient presents in an amount of less than 12 mol %, an improvement as expected of the heat shrinkage will not be attained, while isophthalic acid exceeding 40 mol % is not preferred, since polymer pellets tend to become tacky or aggregate, thereby causing a difficulty in biting of the pellets by screws of an extruder during spinning.
  • the copolyester to be employed in the present invention are preferred to have a glass transition temperature within the range between 55°C and 80°C. If it is less than 55°C, the shrink commencement temperature lowers to such a great extent that there will arise a fear of inducing spontaneous shrink. Alternatively, if it exceeds 80°C, the shrink commencement temperature will rise too much to obtain expected effects.
  • the sheath component is composed of at least one polyolefin selected from the group consisting of polyethylene, polystyrene, polypropylene and polybutene.
  • the polyurethane of the core component has a crosslink density Y of at least 6 ⁇ mol/g, preferably at least 10 ⁇ mol/g. Since the sheath component is thermally very weak, if the crosslink density Y is less than 6 ⁇ mol/g, the composite filament yarns tend to exhibit a low heat resistance and a poor elastic stretch recovery.
  • Fiber-forming thermoplastic non-elastomers for the core component of the filament according to the present invention may be admixed with known polymer-modifiers, such as delustrants, for example, titanium dioxide, antioxidants, electroconductive agents, antifungus agents, dyes, pigments or the like.
  • delustrants for example, titanium dioxide, antioxidants, electroconductive agents, antifungus agents, dyes, pigments or the like.
  • the polyurethanes for the core component of the composite filament according to the invention are not specifically limited insofar as they have fiber-formability. However, thermoplastic polyurethanes or crosslinked polyurethanes are preferred.
  • the thermoplastic polyurethanes are melt-spinnable polymers which can be obtained by reacting a high molecular diol and an organic diisocyanate with a chain extender.
  • the high molecular diols are glycols having both terminal hydroxyl groups and a molecular weight of 500-5,000, for example, etheric polyols, such as polytetramethylene glycol, polypropylene glycol or the like, and esteric polyols such as polyhexamethylene adipate, polybutylene adipate, polycarbonate diol, polycaprolactone diol or the like. These may be used alone or in combination.
  • 1,4-butane diol ethylene glycol, propylene glycol, bis-hydroxyethoxy benzene or the like, which has a molecular weight of at most 500.
  • 1,4-butane diol and bis-hydroxyethoxy benzene are particularly preferred.
  • organic diisocyanate mention maybe made of tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), non-yellowing diisocyanates such as 1,6-hexane diisocyanate or the like, and mixtures thereof. Among the others, MDI is particularly preferred.
  • the polyurethanes are preferred to have a Shore A hardness within the range between 60 and 98. If the hardness is less than 60, undesirable problems will arise such that the resulting composite filament yarns exhibit a low elastic stretch recovery and spinning stability lowers. Alternatively, if the hardness exceeds 98, the polyurethane itself has such a low elastic stretch recovery that the stretch recovery of the yarn cannot be expected unless depending on a crimped structure and, further, there will arise an undesirable problem such that an optimum condition for melt-spinning polyurethanes having such a hardness is limited in a very narrow range.
  • the preferred range of the hardness may be between 65 and 95.
  • Such a polyurethane may be admixed with known polymer-modifiers, such as dyes, pigments, UV stabilizers, UV absorbers, antifungus agents, or the like.
  • a crosslinked polyurethane obtained by reacting the above polyurethane with a polyisocyanate may be arranged in the core component.
  • a crosslinking process use may be made of the process described in Japanese Patent Publication No. 58-46,573 proposed by the present inventors, namely, a process wherein a molten thermoplastic polyurethane is admixed with a polyisocyanate and an allophanate crosslinkage is completed thereby during or after spinning.
  • the polyisocyanate is a compound consisting of a polyol component and an isocyanate component, having at least 2, preferably 2-3 isocyanate groups (NCO groups) in the molecule.
  • a polyol component mixtures of a diol with a triol, having an average functionality of hydroxyl group of 2-3, or synthetic polyols having a functionality of 2-3, may be as suitably employed as the aforementioned diols having a molecular weight of 300-4,000 which are used for synthesis of polyurethanes.
  • an isocyanate component may be employed the aforementioned diisocyanates to be used for synthesis of polyurethanes, trimers of an organic diisocyanate, reaction products of trimethylol propane with an organic diisocyanate, isocyanates having a functionality ranging 2-3 (for example, carbodiimide-modified isocyanate), etc. and mixtures thereof.
  • the reaction of both the above components can be conducted according to any known processes. However, it is preferred to conduct the reaction in such a manner that the content of the isocyanate group may be in excess, namely, the isocyanate group (NCO group) may be contained in an amount of 3-22% by weight in the reaction product. Needless to say, this amount depends upon the objective physical properties such as heat resistance, elastic stretch recovery or the like and polyols employed.
  • Loads of the polyisocyanate are preferably in the range of 6-40% by weight based on the polyurethane/polyisocyanate mixture to be used for the core component.
  • the loads depend upon the NCO-group content and the kind of the isocyanate to be used. If the loads exceed 40% by weight, the spinning operation will be unstabilized due to uneven mixing or the resulting filament yarns will have unsatisfactory mechanical properties, and so it is not preferred. Alternatively, if the loads are less than 6% by weight, the resulting yarns will be deficient in heat resistance, and so it is also not preferred.
  • a further preferable range is 10-30% by weight.
  • a crosslink structure predominantly comprising allophanate crosslinkages is formed in the polyurethane core component.
  • a crosslink structure formed mainly by biuret linkages is not preferred, as it will deteriorate spinnability to the utmost extent. Namely, since the biuret crosslinkages are formed at a larger rate than the allophanate crosslinkages, viscosity of the system will increase during spinning to such an extent that a stabilized spinning operation may be apt to be hardly performed.
  • the core/sheath conjugate ratio X is generally in the range of 3-100, preferably 5-90, more preferably 10-80, most preferably 20-70, as a cross-sectional area ratio. If the core/sheath ratio is less than 3, the filament yarn will be deficient in elastic recovery, stretch recovery at high temperatures and heat resistance. Alternatively, if this ratio exceeds 100, the sheath is apt to break or the filament is apt to be formed so as to expose the core component on the surface of the filament, whereby spinnability and light-stability will be badly affected.
  • the conjugate ratio X and crosslink density Y must be in the relation satisfying simultaneously the following inequalities: Y ⁇ 0 and Y ⁇ -8.7 ⁇ X + 52. Namely, when the crosslink density is low, the conjugate ratio must be increased according to the above second inequality and alternatively, when the crosslink density is high, the applicable range of the conjugate ratio can be extended.
  • Such a filament as being constituted not to satisfy the above second inequality is not preferred as it is inferior in performance as a composite filament, such as an elastic stretch recovery.
  • the crosslink density is preferred to be at least 6 ⁇ mol/g, preferably at least 10 ⁇ mol/g.
  • the crosslink density referred to in the present invention is to mean a crosslink density of a polyurethane in the core component which is determined by the following procedure: In the case of a nylon sheath component, a sample of the polyurethane core is prepared by removing the nylon with a solvent such as formic acid or the like. In the case of a sheath component being other polymers, an appropriate solvent is selected to remove the sheath.
  • the filament is preferred to have a cross-sectional shape wherein the core component and the sheath component have substantially a common center of gravity, from the viewpoints of spinning stability and yarn uniformity.
  • the cross-sectional shape of the composite filament according to the present invention may be circular or non-circular. Among the others, a concentric circular shape is particularly preferred.
  • the composite filaments of the present invention have a very good spinnability, even if both the viscosities of the core and sheath components are somewhat unbalanced with each other. This is an outstanding feature of the present invention which is not seen in eccentric type composite filaments.
  • thermoplastic polyurethane pellets are fed from a hopper and heat-melted in an extruder.
  • the suitable temperature for melting is in the range between 190°C and 230°C.
  • a polyisocyanate is melted at a temperature of 100°C or less in a supply tank and defoamed in advance. If the melting temperature is too high, the polyisocyanate is prone to denaturation. Accordingly, a lower temperature is desirable within a possible range for melting. Generally, a temperature between room temperature and 100°C is appropriately adopted.
  • the conjugate-spinning is preferably conducted with a melt-conjugate-spinning apparatus equipped with a means for melt-extruding a thermoplastic polyurethane provided with a polyisocyanate admixing means, a sheath component polymer melt-extruding means and a spinning head comprising a spinneret for core and sheath type conjugate-spinning.
  • a polyisocyanate admixing means use may be made of known devices for metering a molten polyisocyanate with a metering pump, filtering the melt with a filter if required, and then incorporating it to a molten polyurethane at a core and sheath components meeting portion in the nose of the extruder.
  • mixing devices having a rotary mixing element can be applied as the polyisocyanate admixing means.
  • a mixing device having a static mixing element As such a device, a known static mixer may be employed.
  • the shape and number of the static mixing elements depend upon use conditions, they are important to be selected so as to allow a thorough mixing of the thermoplastic polyurethane and polyisocyanate to complete before entering the spinneret for conjugate-spinning. Generally, 20-90 elements are provided.
  • the core component polyurethane thus admixed with the polyisocyanate is metered with a metering pump and introduced into the spinning head.
  • the spinning head is preferred to be designed to reduce to a possible extent a dwell space for the mixture.
  • the mixture is introduced into the spinneret for core and sheath type conjugate-spinning, and conjugated with a sheath component, i.e., fiber-forming thermoplastic non-elastomer, which has been molten in another extruder.
  • a sheath component i.e., fiber-forming thermoplastic non-elastomer
  • conjugated melts are spun from the spinneret, air-quenched, oil-applied and then taken-up on a take-up roll.
  • the take-up speed is generally 400-1,500 m/min.
  • the structure of the core and sheath components meeting portion in the spinneret is preferred to be designed as shown in Fig. 1.
  • the horizontal approach of the sheath component B is constructed to have a small depth D, for example, 2.0 mm, which is further decreased, for example, to 0.05-1.0 mm, near around the vertical conduit for the core component A.
  • the space H between the lower end of the upper vertical conduit 1 and the upper end of the lower vertical conduit 2 is smaller than the depth D.
  • the changes with time or heat-treatment, of the properties and thermal characteristics of the thus spun composite filaments are caused by a reaction which is not yet completed and further progresses between the thermoplastic polyurethane used as a spinning material and the polyisocyanate admixed therewith.
  • This reaction produces a polyurethane polymer branched or crosslinked by allophanate linking with the polyisocyanate, and further, the improvement of compatibility with the polyisocyanate is considered to be caused by a reaction between the polyisocyanate and reactive groups in the non-elastomer used, such as an amino, amide or carboxyl group in a polyamide based polymer.
  • the filament yarns according to the present invention can be used as an as-spun yarn or a drawn yarn.
  • a composite filament of the invention which comprises a sheath component of a copolyester comprising diethylene glycol as a diol ingredient is left to stand and then hot- or cold-drawn 1.2-5.0 times its original length, the filament may increase hot water shrinkage.
  • the draw ratio and heating temperature can be determined according to the aiming desired hot water shrinkage.
  • the sheath component is a fiber-forming thermoplastic non-elastomer and the core component is a polyurethane
  • the composite filament yarns of the invention have a good elastic stretch recovery.
  • the non-elastomer sheath component can in no way expect originally an elastic property
  • the filament yarns using a polyurethane as a core component and having a specified conjugate shape according to the present invention astonishingly exhibit a good elastic stretchability which is attributable not to a crimped structure but to yarns' own elastic property and, further, have an excellent performance such that a permanent strain at 100% elongation is small.
  • the polyisocyanate is incorporated into the core component, not only the elastic stretch recovery and heat resistance but also compatibility of the core component with the sheath component improves due to a further reaction progress at boundary of these components.
  • the yarns of the invention are absolutely free from tackiness, as the core component is entirely enclosed in the non-elastomer sheath component. Therefore, in succeeding steps, the yarns can be very easily unwound from a yarn package, such as a bobbin, in the axial direction thereof, which could not be performed by conventional polyurethane yarns.
  • a non-expensive emulsion oiling agent can be employed in the oil-application in spinning and take-up steps.
  • the yarn of the invention can be wound at a high speed, such as 1,000 m/min, on a bobbin or paper pirn of a small diameter.
  • the yarns of the invention have an advantage in a commercial production rate owing to the melt-spinning process applied.
  • the yarns of the invention is excellent in mildew resistance and operability in succeeding steps, such as knitting, weaving or the like.
  • the filament yarns comprising a polyamide or copolyamide sheath component according to the invention have an excellent dyeability.
  • the composite filament yarns according to the invention since they have many excellent features as mentioned above, can be applied to fabrication of various textile structures, such as ladies' stockings, swimsuits, socks, foundation, or the like.
  • the stockings according to the invention have a good transparency, excellent appearance, desirable tactile properties or the like, as compared with conventional stockings.
  • the stockings referred to in this invention include all kinds of over-knee stockings, full-length stockings up to groin and panty stockings combining stocking portion with a panty portion, which are knit with the composite filament yarn of the invention, alone or in combination with an ordinary nylon yarn, a false-twisted yarn, a covering yarn comprising a polyurethane filament core yarn, or the like, by means of mix-knitting or blend-spinning.
  • thermoplastic polyurethane was melted in an extruder, the above polyisocyanate was incorporated at various feed rates into the molten polyurethane flow and then these polymers were thoroughly mixed with each other by a static mixer equipped with 35 mixing elements (manufactured by Kenics).
  • the above nylon was melted in a separate extruder.
  • the above two melts were severally metered and introduced into a spinneret for conjugate-spinning, having 8 orifices of a 0.5 mm diameter.
  • Example 1 Varying the core/sheath conjugate ratio, a 40 denier monofilament yarn was spun at a spinning rate of 600 m/min (Examples 2-5 and Comparative Examples 1 and 2). Alternatively, a similar yarn was spun in the same manner except that the polyisocyanate was not incorporated (Example 1).
  • Panty stockings were knit with the yarn of Examples 1 ⁇ 4, using a four-feeder knitting machine. These stockings had an excellent transparency as well as good knit texture, stretchability, etc., as compared with conventional stockings.
  • Example 2 Spinning was conducted in the same manner as Example 1 except that the hardness of the polyurethane core component was varied, the core/sheath conjugate ratio was 15 and the crosslink density of the core component was 14 ⁇ mol/g.
  • thermoplastic polyurethane and polyamide were separately melted and metered, and then led to a spinneret for spinning composite filaments comprising the polyurethane as a core concentrically conjugated with the polyamide sheath.
  • Conjugate-spinning was conducted at a spinning rate of 600 m/min. and a 20 denier, concentric core and sheath type composite monofilament having a core/sheath conjugate ratio in cross-sectional shape of 20 (Yarn-A) was obtained.
  • thermoplastic polyurethane was melted in the extruder and the aforesaid polyisocyanate was incorporated into the polyurethane on the way to the spinneret for conjugate-spinning.
  • the combined melts were thoroughly mixed by a static mixer having 35 mixing elements (manufactured by Kenics) and then a 20 denier composite monofilament (Yarn-B) was obtained in the same manner as the manufacture of Yarn-A.
  • the polyurethane of Yarn-B had a cross link density of 29 ⁇ mol/g.
  • the stockings using Yarn-A and Yarn-B according to the present invention had an elastic stretch recovery (fit property and support feel) on the same level as those of Yarn-C (polyurethane filament yarn) and improved tactile properties which are drawbacks of polyurethane filaments, so that the stockings of the invention had a very good wear property.
  • the stockings knit with Yarn-F, the convering yarn had an inferior fabric texture and lacked transparency.
  • the yarns other than the present invention respectively had such drawbacks that they could not provide stockings of high quality.
  • Yarn-E Light transmission was hindered by Yarn-E due to its crimp as well as by Yarn-F due to its bulkiness.
  • Yarn-A and Yarn-B provided highly transparent stockings because of flatness of these yarns.
  • the yarns of the present invention provided a strong elastic power and an excellent fit feel when the stockings were stretched, not given by a spring stress of crimps but by making use of the yarns' own tensile stress.
  • Hoses were knit with a one-feeder circular knitting machine, using Yarn-B and Yarn-C of Example 7 and Yarn-G. The properties of the hose after scouring and dyeing were investigated. The results are shown in Table 4.
  • the slipperiness was determined as follows: An aluminum frame was inserted into a knit hose and placed in the horizontal position. Then, a disc of a 23 g weight and a 25 mm diameter was put on the hose and the aluminum frame was gradually inclined. The angle of inclination when the disc started to slip down represented the slipperiness of the hose fabric.
  • thermoplastic polyurethane was melted in an extruder, the above polyisocyanate was incorporated into the molten polyurethane flow and then these polymers were thoroughly mixed with each other by a static mixer equipped with 35 mixing elements (manufactured by Kenics).
  • the above copolyester was melted in a separate extruder.
  • the above two melts were severally metered and introduced into a spinneret for concentric-conjugate-spinning, having 8 orifices of a 0.5 mm diameter.
  • the melt-spinning temperature was required to be increased, so that the heat stability of the polyurethane was too much deteriorated to conduct conjugate-spinning.
  • this ratio was 60 mol%, the pellets aggregated due to tackiness thereof and formed bridging during drying and were not bitten by the screws of the extruder, so that spinning was impossible.
  • thermoplastic polyurethane was employed in lieu of the copolyester as a sheath component and conjugate-spinning was conducted in the same manner as the above.
  • dimethylsilicone in combination with 5% or 0.2% of an amino-modified silicone was used (Comparative Example 4 or 5).
  • the yarn of Comparative Example 4 was free from tackiness.
  • Examples of the present invention it is found that the unwinding property, take-up property and high pressure dyeability are all excellent. It is also found from Examples 9 and 10 that the heat resistance largely depends upon whether or not crosslinkages are present in the core component. Further, it is also found from Examples 11-13 that if the core/sheath conjugate ratio increases, i.e., the sheath component ratio decreases, the physical properties approach to that of the polyurethane-polyrethane type composite filament.
  • thermoplastic polyurethane of Example 9 was melted in an extruder, the isocyanate used in Example 10 was incorporated into the molten polyurethane flow and then these polyesters were thoroughly mixed with each other by a static mixer equipped with 35 mixing elements (manufactured by Kenics).
  • the above copolyester was melted in a separate extruder.
  • Those two polymer melts were severally metered and introduced into a spinneret for concentric-conjugate-spinning, having a 8 orifices of a 0.5 mm diameter. Varying the core/sheath conjugate ratio over 2 to 20, 40 denier monofilament yarns were spun at a spinning rate of 600 m/min. In the spinning step, a 15% aqueous emulsion was applied as an oiling agent.
  • yarns having no polyisocyanate incorporated thereinto were spun in the same manner as the above.
  • a filament yarn consisting of this sheath component polymer alone had tensile strength of 0.60 g/d, an elongation at break of 0% and an elastic stretch recovery of 0%, so that it is surprising that the present invention provides a yarn comprising such a polymer with an excellent stretchability.
  • Example 16 and Comparative Example 4 were drawn at 90°C 2 times their original length. Then, the yarns having an initial load of 1.0 mg/d attached thereto were soaked in hot water at 100°C for 30 min. and air dried. Then, the length L (mm) was determined.
  • the heat shrinkage was found by the following equation: wherein L1 is the length before soaking in hot water. Let the original length be L O , then L O >L1 in the case of spontaneous shrinking. This spontaneous shrinkage was found by the following equation:
  • the yarn of the invention has a low spontaneous shrinkage and a high hot water shrinkage, and the polyurethane-polyurethane composite filament yarn is not set by drawing.
  • a filament yarn consisting of this sheath component polymer alone had a tensile strength of 0.12 g/d and a melting point temperature of 100°C, so that it is surprising that the present invention largely improves the tensile strength and heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Multicomponent Fibers (AREA)
EP19910106833 1990-04-27 1991-04-26 Elastic core and sheath type composite filaments and textile structures comprising the same Withdrawn EP0454160A3 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2114130A JP2786514B2 (ja) 1990-04-27 1990-04-27 複合糸及びストッキング
JP114130/90 1990-04-27
JP3090011A JP2869206B2 (ja) 1991-03-27 1991-03-27 ポリエステル／ポリウレタン複合弾性糸
JP90011/91 1991-03-27

Publications (2)

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EP0454160A2 true EP0454160A2 (fr) 1991-10-30
EP0454160A3 EP0454160A3 (en) 1992-03-04

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EP (1) EP0454160A3 (fr)
CN (1) CN1058813A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
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US5565270A (en) * 1994-04-25 1996-10-15 Bayer Aktiengesellschaft Process for the production of elastane filaments
US6637181B1 (en) 1998-06-02 2003-10-28 Bayer Aktiengesellschaft Elastane threads and method for the production thereof
WO2014194070A1 (fr) 2013-05-29 2014-12-04 Invista North America S.A.R.L. Élasthanne à deux composants fusibles
CN109970946A (zh) * 2017-12-27 2019-07-05 上海优迈材料科技有限公司 一种环保低硬度聚氨酯弹性体的制备方法
WO2019215104A1 (fr) * 2018-05-11 2019-11-14 Covestro Deutschland Ag Composition de polyuréthane thermoplastique et son utilisation
CN115142151A (zh) * 2022-07-20 2022-10-04 上海华峰新材料研发科技有限公司 一种聚酯/氨纶弹性复合纤维及其制备方法和应用
LU502631B1 (en) * 2022-08-05 2024-02-07 Luxembourg Inst Science & Tech List Multilayer continuous fiber filament with a dually reactive matrix and method for manufacturing thereof

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EP0905291B1 (fr) * 1996-06-03 2003-09-17 Kanebo, Ltd. Fil elastique en polyurethanne
BRPI0915235B1 (pt) * 2008-10-17 2018-10-09 Invista Tech Sarl fibras, tecido e processo para preparação de uma fibra elástica, fusível, fiada em solução, com múltiplos componentes
JP6086872B2 (ja) * 2012-01-20 2017-03-01 株式会社島精機製作所 フットウェア、および編地の編成方法
CN105133087B (zh) * 2015-09-30 2017-06-06 华南理工大学 用于z箍缩丝阵负载的抗紫外线皮芯复合自适应纤维及其制备方法
CN105541149B (zh) * 2015-12-08 2018-01-09 余姚市交通规划设计研究院 一种用于沥青路面面层的改性同芯复合细纤维及应用
CN107287694A (zh) * 2017-06-27 2017-10-24 太仓市玛雅针织有限公司 抗静电性能良好的复合纤维
JP7124703B2 (ja) * 2017-08-31 2022-08-24 東レ株式会社 海島複合繊維、吸着用担体及び該吸着用担体を備える医療用カラム
CN107435171B (zh) * 2017-08-31 2019-10-29 浙江理工大学 一种交联结构取向填充增强化纤的制备方法
CN110886033A (zh) * 2019-07-03 2020-03-17 海西纺织新材料工业技术晋江研究院 低模量弹性纤维的弹力丝及其制备方法
CN115012069B (zh) * 2022-07-20 2023-11-03 上海华峰新材料研发科技有限公司 一种具有皮芯结构的复合纤维及其制备方法和应用
CN115896965A (zh) * 2022-11-16 2023-04-04 中纺院（浙江）技术研究院有限公司 一种偏心皮芯型锦氨复合全牵伸丝及其制备方法

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5565270A (en) * 1994-04-25 1996-10-15 Bayer Aktiengesellschaft Process for the production of elastane filaments
US6637181B1 (en) 1998-06-02 2003-10-28 Bayer Aktiengesellschaft Elastane threads and method for the production thereof
US11274381B2 (en) * 2013-05-29 2022-03-15 The Lycra Company Llc Fusible bicomponent spandex
WO2014194070A1 (fr) 2013-05-29 2014-12-04 Invista North America S.A.R.L. Élasthanne à deux composants fusibles
US20160122907A1 (en) * 2013-05-29 2016-05-05 Invista North America S.A.R.I. Fusible bicomponent spandex
EP3004437A4 (fr) * 2013-05-29 2017-01-11 INVISTA Technologies S.à.r.l. Élasthanne à deux composants fusibles
CN109970946A (zh) * 2017-12-27 2019-07-05 上海优迈材料科技有限公司 一种环保低硬度聚氨酯弹性体的制备方法
WO2019215104A1 (fr) * 2018-05-11 2019-11-14 Covestro Deutschland Ag Composition de polyuréthane thermoplastique et son utilisation
CN112771093A (zh) * 2018-05-11 2021-05-07 科思创知识产权两合公司 热塑性聚氨酯组合物及其用途
CN115142151A (zh) * 2022-07-20 2022-10-04 上海华峰新材料研发科技有限公司 一种聚酯/氨纶弹性复合纤维及其制备方法和应用
CN115142151B (zh) * 2022-07-20 2024-03-19 上海华峰新材料研发科技有限公司 一种聚酯/氨纶弹性复合纤维及其制备方法和应用
LU502631B1 (en) * 2022-08-05 2024-02-07 Luxembourg Inst Science & Tech List Multilayer continuous fiber filament with a dually reactive matrix and method for manufacturing thereof
WO2024028489A1 (fr) * 2022-08-05 2024-02-08 Luxembourg Institute Of Science And Technology (List) Filament de fibre continue multicouche à matrice réellement réactive et son procédé de fabrication

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EP0454160A3 (en) 1992-03-04
CN1058813A (zh) 1992-02-19

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