EP1595987B1 - Gemischte web- oder strickstoffe mit elastanfasern und herstellungsverfahren dafür - Google Patents

Gemischte web- oder strickstoffe mit elastanfasern und herstellungsverfahren dafür Download PDF

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Publication number
EP1595987B1
EP1595987B1 EP20030778770 EP03778770A EP1595987B1 EP 1595987 B1 EP1595987 B1 EP 1595987B1 EP 20030778770 EP20030778770 EP 20030778770 EP 03778770 A EP03778770 A EP 03778770A EP 1595987 B1 EP1595987 B1 EP 1595987B1
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EP
European Patent Office
Prior art keywords
yarn
polyurethane elastic
fabric
elastic
filaments
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EP20030778770
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English (en)
French (fr)
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EP1595987A4 (de
EP1595987A1 (de
Inventor
Kunihiro Tokushima Plant FUKUOKA
Kouji Tokushima Plant NISHIO
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Nisshinbo Holdings Inc
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Nisshinbo Industries Inc
Nisshin Spinning Co Ltd
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/18—Other fabrics or articles characterised primarily by the use of particular thread materials elastic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/16—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating synthetic threads
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/14—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes
    • D04B21/18—Fabrics characterised by the incorporation by knitting, in one or more thread, fleece, or fabric layers, of reinforcing, binding, or decorative threads; Fabrics incorporating small auxiliary elements, e.g. for decorative purposes incorporating elastic threads
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/04—Heat-responsive characteristics
    • D10B2401/041—Heat-responsive characteristics thermoplastic; thermosetting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065—Including strand which is of specific structural definition
    • Y10T442/313—Strand material formed of individual filaments having different chemical compositions

Definitions

  • the present invention relates to polyurethane elastic filaments, to woven or knit fabrics containing such polyurethane elastic filaments in combination with other fibers, and to a process for manufacturing such fabrics. More specifically, the invention relates to polyurethane elastic filament-containing blended woven or knit fabrics, including circular knit (e.g., plain, rib, purl) and other types of weft knit fabrics, warp knit fabrics (e.g., chain, denbigh, cord, atlas), and woven fabrics, which minimize the appearance of fabric defects such as deformation, yarn slippage and grinning from repeated stretching when articles made from such woven or knit fabrics are worn, fraying in which threads are lost from cut edges of the fabric, damage or defects of the type known as laddering or running that arise in the fabric structure, edge curling of the fabric, and the effect sometimes referred to as "slip-in” where just the elastic filaments pull away from a seam in an article that has been cut and sewn, causing the fabric to lose its stretch in places.
  • the invention relates
  • JP-A 2001-159052 describes a method for preventing yarn slippage by heat-treating at 200°C a woven or knit fabric made with two kinds of polyether ester elastic filament having different melting points.
  • polyether ester elastic filaments have a performance inferior to that of polyurethane elastic filaments, and are thus unsatisfactory.
  • JP 2000-303326 concerns the production of elastic fabrics including elastic yarns made from a polyurethane based on a saturated hydrocarbon-based polymer having hydroxy-groups at the molecular terminals.
  • the elastic in polyurethane yarns are covered with other yarns, e.g. of cotton, wool or silk.
  • the fabrics are said to have excellent resistance to heat and hot water.
  • the present invention provides highly fusible polyurethane elastic filaments having at least 50% retention of tenacity after dry heat treatment at 150°C for 45 seconds at 100% extension and a melting point of 180°C or below.
  • Such filaments may be melt-spun from a polymer obtained by reacting
  • the blended woven or knit fabric may further include high-melting polyurethane elastic filaments having a melting point of 200°C or higher, said fabric being obtained by thermally fusing the highly fusible polyurethane elastic filaments with the high-melting polyurethane elastic filaments at crossover points therebetween.
  • a process for manufacturing a blended woven or knit fabric containing polyurethane elastic filament may comprise the steps of forming a woven or knit fabric using highly fusible polyurethane elastic filaments having at least 50% retention of tenacity after dry heat treatment of 150°C for 45 seconds at 100% extension and a melting point of 180°C or below and at least one kind of non-elastic yarn and dry or wet heat setting the woven or knit fabric so as to thermally fuse the highly fusible polyurethane elastic filaments to each other or to the non-elastic yarns, preferably to the non-elastic yarns, at crossover points therebetween.
  • the blended woven or knit fabric manufacturing process may additionally use high-melting polyurethane elastic filaments having a melting point of 200°C or higher, and thermally fuse the highly fusible polyurethane elastic filaments with the high-melting polyurethane elastic filaments at crossover points therebetween.
  • the polyurethane elastic filaments used in the invention are not subject to any particular limitations with regard to composition or method of production.
  • Suitable methods of production include processes in which a polyol is reacted with an excess molar amount of diisocyanate to form a polyurethane intermediate polymer having isocyanates at both ends, the intermediate polymer is reacted in an inert organic solvent with a low-molecular-weight diamine or diol having active hydrogens capable of reacting with the isocyanate groups on the intermediate polymer so as to form a polyurethane solution (polymer solution), then the solvent is removed and the polymer is shaped into filaments; processes in which a polymer formed by reacting a polyol and a diisocyanate with a low-molecular-weight diamine or diol is solidified, then dissolved in a solvent, after which the solvent is removed and the poly
  • the polyol used in prepolymers (A) and (B) may be the same or different. In both cases, the use of a polymer diol having a number-average molecular weight in a range of about 800 to 3,000 is preferred.
  • Such polymer diols that are suitable for use include polyether glycols, polyester glycols and polycarbonate glycols.
  • polyether glycols include polyether diols obtained by the ring-opening polymerization of a cyclic ether such as ethylene oxide, propylene oxide or tetrahydrofuran; and polyether glycols obtained by the polycondensation of a glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 3-methyl-1,5-pentanediol.
  • a glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 3-methyl-1,5-pentanediol.
  • polyester glycols include polyester glycols obtained by the polycondensation of at least one glycol selected from among ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 3-methyl-1,5-pentanediol with at least one dibasic acid selected from among adipic acid, sebacic acid and azelaic acid; and polyester glycols obtained by the ring-opening polymerization of a lactone such as ⁇ -caprolactone or valerolactone.
  • a lactone such as ⁇ -caprolactone or valerolactone
  • polycarbonate glycols include those obtained by the transesterification of at least one organic carbonate selected from among dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, and diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate, with at least one aliphatic diol selected from among ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and 3-methyl-1,5-pentanediol.
  • organic carbonate selected from among dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, and diaryl carbonates such as diphenyl carbonate and dinaphthyl carbonate
  • at least one aliphatic diol selected from among
  • polyether glycol, polyester glycol or polycarbonate glycol may be used singly or as combinations of two or more thereof.
  • the polyether diol component it is desirable for the polyether diol component to account for at least 50 wt%, and preferably at least 60 wt%, of the total amount of polymer diol used.
  • the polyether diol component may even account for 100 wt% of the polymer diol used.
  • Polytetramethylene ether glycol is especially preferred as the polyether diol component.
  • the diisocyanate used in prepolymers (A) and (B) may be any type of diisocyanate commonly used in the production of polyurethanes, such as aliphatic, alicyclic, aromatic and aromatic-aliphatic diisocyanates.
  • diisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, p-phenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, m-tetramethylxylene diisocyanate and p-tetramethylxylene diisocyanate. Any one or combination thereof may be used. Of these, 4,4'-diphenylmethane diisocyanate and 4,4'-dicyclohexylmethane diisocyanate are preferred.
  • the low-molecular weight diol or low-molecular-weight diamine which serves as a chain extender, is preferably one which has a suitable reaction rate and imparts an appropriate heat resistance.
  • a low-molecular-weight compound with two active hydrogen atoms capable of reacting with isocyanate and generally having a molecular weight of 500 or less is used.
  • Suitable examples of such low-molecular-weight diols include aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol. Trifunctional glycols such as glycerol can also be used provided the spinnability is not compromised. Any one or combination of two or more of these compounds may be used, although ethylene glycol and 1,4-butanediol are preferred for good workability and for imparting suitable properties to the resulting fibers.
  • low-molecular-weight diamines examples include ethylenediamine, butanediamine, propylenediamine, hexamethylenediamine, xylylenediamine, 4,4-diaminodiphenylmethane and hydrazine.
  • a monohydric alcohol such as butanol or a monoamine such as diethylamine or dibutylamine may be used in admixture to regulate the reaction or the degree of polymerization.
  • Illustrative examples of the inert solvent used during the polyurethane polymerization reaction or as the spinning solution include polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N,N',N'-tetramethylurea, N-methylpyrrolidone and dimethylsulfoxide.
  • the prepolymers serving as above components (A) and (B) may have added thereto optional ingredients such as ultraviolet absorbers, antioxidants and light stabilizers to improve weather resistance, heat and oxidation resistance and yellowing resistance.
  • optional ingredients such as ultraviolet absorbers, antioxidants and light stabilizers to improve weather resistance, heat and oxidation resistance and yellowing resistance.
  • ultraviolet absorbers include benzotriazole compounds such as 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and 2-(2-hydroxy-3,5-bisphenyl)benzotriazole.
  • antioxidants include hindered phenol antioxidants such as 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate].
  • hindered phenol antioxidants such as 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(4-t-butyl-3-hydroxy-2
  • Illustrative examples of light stabilizers include hindered amine light stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, and the dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensation product of succinic acid.
  • hindered amine light stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, and the dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensation product of succinic acid.
  • polyurethane elastic filaments of the invention are obtained is not subject to any particular limitation.
  • melt spinning techniques include the following.
  • Process (3) is preferred because it does not include a polyurethane elastomer chip handling step and is thus simpler than Processes (1) and (2). Also, in this process, by adjusting the proportion of prepolymer added to the reactor, the amount of residual isocyanate groups left in the polyurethane elastic filaments after spinning can be controlled, making it possible to achieve an improved heat resistance from chain extending reactions by these residual isocyanate groups. Moreover, in Process (3), as described in JP-A 11-839030 , the low-molecular-weight diol can be reacted beforehand with some of the prepolymer to form a prepolymer having excess hydroxyl groups which is then added to the reactor.
  • Synthesis of the spinning polymer in this way involves three reactions: (I) synthesis of an isocyanate-terminated prepolymer, (II) synthesis of a hydroxy-terminated prepolymer, and (III) synthesis of a polymer for spinning by feeding these two prepolymers to a reactor and continuous reaction.
  • the compositional ratio of the starting materials for the three above reactions as a whole when expressed as the ratio of the number of moles of all the diisocyanate to the combined number of moles of all the polymer diol and all the low-molecular-weight diol, is preferably from 1.02 to 1.20.
  • the above isocyanate-terminated prepolymer (I) can be obtained by, for example, charging a given amount of diisocyanate into a tank equipped with a warm-water jacket and a stirrer, then adding a given amount of polymer diol under stirring, and stirring at 80°C for 1 hour under a nitrogen purge.
  • the isocyanate-terminated prepolymer obtained from this reaction is then fed by a jacketed gear pump (e.g., KAP-1, manufactured by Kawasaki Heavy Industries, Ltd.) to a reactor for polyurethane elastic filament production.
  • a jacketed gear pump e.g., KAP-1, manufactured by Kawasaki Heavy Industries, Ltd.
  • the above hydroxy-terminated prepolymer (II) can be obtained by charging a given amount of diisocyanate into a tank equipped with a warm-water jacket and a stirrer, adding a given amount of polymer diol under stirring, then stirring at 80°C for 1 hour under a nitrogen purge to give a precursor, and subsequently adding a low-molecular-weight diol and reacting it with the precursor under stirring.
  • the resulting hydroxy-terminated prepolymer is then fed by a jacketed gear pump (e.g., KAP-1, manufactured by Kawasaki Heavy Industries, Ltd.) to the reactor for polyurethane elastic filament production.
  • a jacketed gear pump e.g., KAP-1, manufactured by Kawasaki Heavy Industries, Ltd.
  • the various chemicals mentioned above may be added to improve such properties as the weather resistance, heat and oxidation resistance, and yellowing resistance.
  • the spinning polymer (III) can be synthesized by continuously reacting prepolymers (A) and (B) fed to the reactor in fixed proportions.
  • the reactor may be one commonly used in polyurethane elastic filament melt spinning processes and is preferably equipped with mechanisms for stirring and reacting the molten mixture, heating the spinning polymer, and transferring the polymer to a spinning head. Reaction is typically carried out at 160 to 220°C for 1 to 90 minutes, and preferably at 180 to 210°C for 3 to 80 minutes.
  • the polyurethane elastic filaments of the invention can be obtained by transferring the synthesized spinning polymer, without allowing it to solidify, to a spinning head, and spinning the polymer by discharging it from a nozzle.
  • the polyurethane elastic filament can be obtained by continuous extrusion from the nozzle at a spinning temperature of 180 to 230°C, followed by cooling, the application of a spin finish, and wind-up.
  • the ratio between the isocyanate-terminated prepolymer and the hydroxy-terminated prepolymer is advantageous for the ratio between the isocyanate-terminated prepolymer and the hydroxy-terminated prepolymer to be set by suitably adjusting the speed ratio between the gear pumps used for injecting the feedstocks so that the amount of isocyanate groups remaining in the just-spun filaments is 0.3 to 1 wt%, and preferably 0.35 to 0.85 wt%.
  • the presence of isocyanate groups in an excess of at least 0.3 wt% enables physical properties such as tenacity, elongation and heat resistance to be improved by chain extension reactions after spinning.
  • the presence of less than 0.3 wt% of isocyanate groups may lower the retention of tenacity under heating of the resulting polyurethane elastic filament, whereas the presence of more than 1 wt% may lower the viscosity of the spinning polymer and make spinning difficult to carry out.
  • the content of isocyanate groups in the spun filament is measured as follows.
  • polyurethane elastic filament used in this invention is especially preferable for the polyurethane elastic filament used in this invention to be produced as described above by a melt-reaction spinning process using polyether diol as a primary starting material.
  • the polyurethane elastic filament used in the invention has at least 50%, and preferably at least 55%, retention of tenacity following dry heat treatment at 150°C for 45 seconds at 100% extension. At less than 50% retention of tenacity, the heat-set article will have reduced stretch.
  • the polyurethane elastic filament has a melting point of 180°C or less, and preferably 175°C or less. At a melting point above 180°C, the heat treatment temperature required for fusion is too high, adversely affecting such qualities of the textile product as its hand and colorfastness.
  • a melting point of at least 150°C, and preferably at least 155°C, is advantageous in terms of dimensional stability when the above filament is used in combination with a high-melting polyurethane elastic filament, and also in terms of the fabric's recovery from extension.
  • the polyurethane elastic filament-containing blended woven or knit fabric of the invention may be a fabric having one of the following constructions obtained by using the above-described highly fusible polyurethane elastic filament in combination with a non-elastic yarn, and also incorporating, for example, a high-melting polyurethane elastic filament having a melting point of at least 200°C.
  • guide bars L1 and L2 are fully threaded (All in).
  • guide bars L1 and L2 and guide bars L3 and L4 are threaded at every other guide (1 in - 1 out).
  • guide bars L1, L2 and L3 are fully threaded (All in).
  • a represents a non-elastic yarn
  • b represents the highly fusible polyurethane elastic filament of the invention either used alone or doubled with a high-melting polyurethane elastic filament.
  • c may represent the use of either two highly fusible polyurethane elastic filaments of the invention or the use of one highly fusible polyurethane elastic filament of the invention and one high-melting polyurethane elastic filament.
  • non-elastic yarn used together with the highly fusible polyurethane elastic filament No particular limitation is imposed on the non-elastic yarn used together with the highly fusible polyurethane elastic filament.
  • Illustrative examples include natural fibers such as cotton, linen, wool and silk; regenerated fibers such as rayon, cuprammonium rayon and polynosic; semisynthetic fibers such as acetate; and synthetic fibers such as nylon, polyester and acrylic.
  • the polyurethane elastic filaments are included in a ratio of preferably about 1 to 40 wt%.
  • a woven or knit fabric that has a good elastic performance while remaining fusion property can be obtained by also incorporating high-melting polyurethane elastic filaments of excellent heat resistance and elastic recovery which have been dry-spun in a process involving a chain extension reaction with diamine and which melt at 200°C or more, and preferably at 210°C or more.
  • the amount of such high-melting polyurethane elastic filaments used in this case is preferably about 2 to 40 wt%.
  • Dry heat setting can be carried out using a draft of hot air in a heat setting machine such as a pin tenter. This process is typically carried out at a temperature of 140 to 200°C, preferably 170 to 190°C, and for a period of 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes.
  • Wet heat setting can be carried out by boarding the knitted article on a form in saturated steam at a predetermined pressure. This process is typically carried out at a temperature of 100 to 130°C, preferably 105 to 125°C, and for a period of typically 2 to 60 seconds, preferably 5 to 30 seconds.
  • the present invention enables polyurethane elastic filament-containing blended woven or knit fabrics to be obtained which can be treated at a low heat setting temperature and are resistant to such effects as yarn slippage, grinning, fraying, running, edge curling and slip-in.
  • a reactor sealed with nitrogen and equipped with a 80°C warm-water jacket was charged with 25 parts of 4,4'-diphenylmethane diisocyanate (MDI) as the diisocyanate, following which 100 parts of polytetramethylene ether glycol (PTMG) having a number-average molecular weight of 2,000 was added under stirring as the polymer diol. After one hour of reaction, 27.6 parts of 1,4-butanediol was added as the low-molecular-weight diol, thereby forming a hydroxy-terminated prepolymer.
  • MDI 4,4'-diphenylmethane diisocyanate
  • PTMG polytetramethylene ether glycol
  • a nitrogen-sealed 80°C reactor was charged with 47.4 parts of MDI as the diisocyanate and 2.2 parts of a mixture composed of an ultraviolet absorber (2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole: 20%), an antioxidant (3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane: 50%) and a light stabilizer (bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate: 30%), following which 100 parts of PTMG having a number-average molecular weight of 2,000 was added under stirring as the polymer diol. Stirring was continued for one hour, thereby giving an isocyanate-terminated prepolymer.
  • an ultraviolet absorber 2-(3,5-di-t-amyl-2-hydroxy
  • the resulting isocyanate-terminated prepolymer and hydroxy-terminated prepolymer were continuously fed in a weight ratio of 1:0.475 to a 2,200 ml cylindrical reactor for polyurethane elastic filament production equipped with a stirring element.
  • the feed rates were 28.93 g/min for the isocyanate-terminated prepolymer and 13.74 g/min for the hydroxy-terminated prepolymer.
  • the average retention time within the reactor was about 1 hour, and the reaction temperature was about 190°C.
  • the resulting polymer was fed without solidification to two 8-nozzle spinning heads held at 192°C.
  • the spinning polymer was metered and pressurized by gear pumps mounted on the heads, then passed through a filter, discharged from 0.6 mm diameter single-hole nozzles at a rate per nozzle of 2.67 g/min into a 6 m long spinning chimney (total discharge rate from all nozzles, 42.67 g/min), and wound up at a speed of 600 m/min while having a finish applied thereto, giving 44-decitex polyurethane elastic filaments.
  • the polyurethane elastic filament immediately after discharge had an isocyanate group content of 0.42 wt%.
  • the physical properties of the elastic filament was measured by the methods described below.
  • the filament had a melting point of 168°C and 65% retention of tenacity under heating.
  • the elastic filament was used to produce knit fabrics as described below. The unraveling tension of the fabric after it had been heat set was measured. The results are shown in Table 1.
  • a polyurethane elastic filament was gripped at a clamp interval of 10 cm and extended to 20 cm. In this extended state, the filament was placed for 45 seconds in a hot air dryer held at 150°C and heat treated. The tenacity of this heat-treated polyurethane elastic filament was then measured using a constant-rate-of-extension tensile testing machine at a clamp interval of 5 cm and a rate of extension of 500 mm/min. Measurement was carried out at an ambient temperature of 20°C and 65% relative humidity.
  • Combination knitting was carried out by feeding 13 dtex, 7 filament nylon-6 yarns to feeders 2 and 4, and polyurethane elastic filaments to feeders 1 and 3 on a pantyhose knitting machine (manufactured by Lonati S.p.A., 400 needles).
  • the knitted fabric was dry heat treated for 1 minute in a dryer held at 160°C or 180°C.
  • the unraveling tensions of the nylon yarn and the polyurethane elastic filament from the knit fabric were measured.
  • the unraveling speed was set at 100 mm/min, and the average tension over a one minute period was determined.
  • polyurethane elastic filament made with polyester diol was obtained in the same way as in Example 1.
  • the isocyanate group content of the polyurethane elastic filament immediately after discharge from the spinneret was 0.45 wt%.
  • Measurement of the physical properties carried out as in Example 1 showed that the resulting 44-dtex polyurethane elastic filament had a melting point of 170°C and 62% retention of tenacity under heating.
  • a 44-dtex polyurethane elastic filament (Mobilon P type yarn, manufactured by Nisshinbo Industries, Inc.) made with PTMG as the polymer diol and a diamine as the chain extender was used. Measurement of the physical properties carried out as in Example 1 showed that these polyurethane elastic filament had a melting point of 221°C and 95% retention of tenacity under heating.
  • a spinning polymer was synthesized by the same method as in Example 1, extruded from the reactor through a 4 mm diameter orifice as a strand, cooled, then cut so as to give polyurethane elastomer pellets.
  • the pellets were dried in a vacuum dryer, then re-melted in a single-screw extruder, metered and pressurized with a gear pump mounted on the spinning head as in Example 1 and passed through a filter, then discharged from 0.6 mm single-hole nozzles at a rate per nozzle of 2.67 g/min into a 6 meter long spinning chimney (total discharge from all nozzles, 42.67 g/min) and wound up at a speed of 600 m/min while having a finish applied thereto, giving 44-decitex polyurethane elastic filament.
  • the polyurethane elastic filament immediately after discharge had an isocyanate group content of 0.13 wt%.
  • Example 1 Measurement of the properties carried out as in Example 1 showed that the polyurethane elastic filament had a melting point of 152°C and 38% retention of tenacity under heating. Using the elastic filament, a knitted fabric was produced in the same way as in Example 1. The unraveling tension of the knitted fabric after it had been heat set was measured. The results are shown in Table 1.
  • Example 1 the unraveling tension was high on account of fusion.
  • the polyurethane elastic filament made with polyether diol in Example 1 had a particularly high unraveling tension.
  • these elastic filaments within the knit fabric did not break even when the fabric had been heat set at 180°C.
  • the knit fabric had a high unraveling tension after being heat set at 160°C, but polyurethane elastic filament breakage occurred within the fabric when heat setting was carried out at 180°C.
  • a knit fabric produced by the method described below using the polyurethane elastic filament obtained in Example 1 was heat set, then subjected to a laundering test, following which the fabric was visually inspected for fraying, slip-in and the surface properties. The results are shown in Table 2.
  • a knit fabric having a plated structure was produced by feeding false-twisted Z-twist 33 dtex, 10 filament nylon-6 yarn to yarn feeders 1 and 3, feeding false-twisted S-twist 33 dtex, 10 filament nylon-6 yarn to feeders 2 and 4, and also feeding polyurethane elastic filaments to all four feeders on a pantyhose knitting machine (Lonati, 400 needles).
  • the knit-in ratio was set at 2.5.
  • the knitted fabric was dry heat treated for 1 minute in a dryer held at 180°C.
  • Specimens measuring 15 ⁇ 20 cm were cut from the knit fabric after it had been heat set. The specimens were repeatedly washed (20 wash cycles) in a laundering test machine (LM-160, produced by Suga Test Instruments Co., Ltd.).
  • a knit fabric was produced on the same knitting machine and in the same way as in Example 3 by feeding the polyurethane elastic filaments of Example 1 to yarn feeders 1 and 3, and the elastic filaments of Comparative Example 1 to feeders 2 and 4. The fabric was then subjected to the same tests as in Example 3. The results are presented in Table 2.
  • a knit fabric was produced as in Example 3 using only the elastic filament of Comparative Example 1, and was tested in the same way. The results are shown in Table 2.
  • Example 3 A knit fabric was produced as in Example 3 using only the elastic filament of Comparative Example 2, and was tested in the same way. The results are shown in Table 2.
  • Table 2 Results of Knit Fabric Inspection Fraying Slip-in (%) Yarn slippage Curling Example 3 no 0 smooth no
  • Example 4 no 5 smooth no Comparative Example 3 yes 55 surface uneven slight curling Comparative Example 4 no 0 surface uneven no
  • Polyurethane elastic filament (156 dtex) was obtained by the same method as in Example 1. Measurement of the physical properties as in Example 1 revealed that this filament had a melting point of 170°C and 68% retention of tenacity under heating. This elastic filament was used to produce a warp knit fabric by the method described below. The fabric was then heat set, following which the resistance to pullout of the polyurethane elastic filament was measured. The results are shown in Table 3.
  • a warp knit fabric was produced on a raschel knitting machine (manufactured by Karl Mayer GmbH, 28 gauge) using a 56 dtex, 17 filament nylon-6 yarn as yarn a on guide bar L1 and yarn c on guide bar L3 in FIG. 9 , and using the above polyurethane elastic filament as yarn b on guide bar L2.
  • the knitted fabric was dry heat treated for 1 minute in a dryer held at 190°C.
  • Test specimens measuring 25 mm in the filling direction (width) by 100 mm in the warp direction (length), as shown in FIG. 10 were taken from the above knit fabric. A total of 10 specimens were collected, five for pullout of the polyurethane elastic filament from the end knitted first and five for pullout from the end knitted last.
  • test specimens were prepared as shown in FIG. 10 .
  • Each test specimen was cut away at a position (B-B') 40 mm from the lower end (D-D') so as to leave a single polyurethane elastic filament 1 inserted in the warp direction.
  • this remaining polyurethane elastic filament was freed from a 5 mm portion (E-F) of the fabric in the direction of an upper clamp 2.
  • a 3 mm long slit 3 was made in the filling direction at a position 30 mm from the upper end of the specimen on a linear extension of the polyurethane elastic filament.
  • the testing machine clamp interval was adjusted to 40 mm, following which the top of the test specimen was gripped by the upper clamp 2 over a clamping length of 25 mm (the portion above A-A') and an initial load of 0.1 cN was applied to the polyurethane elastic filament.
  • the polyurethane elastic filament was then gripped with a lower clamp 4 over a clamping length of 35 mm (the portion below C-C'), pulled at a rate of 100 mm/min, and the maximum pulling load up until the filament completely pulled out of the fabric was measured.
  • This test was carried out a total of ten times, five times from the end knitted first and five times from the end knitted last, and the average of these results was calculated, thereby giving the pullout resistance.
  • a warp knit fabric was produced on the same type of knitting machine as in Example 5 using a 56 dtex, 17 filament nylon-6 yarn as yarn a on guide bar L1 in FIG. 3 and using the polyurethane elastic filament of Example 5 as yarn b on guide bar L2.
  • the fabric was tested in the same way as in Example 5. The results are given in Table 3.
  • a warp knit fabric was produced on the same type of knitting machine as in Example 5 using 56 dtex, 17 filament nylon-6 yarn as the a yarns on guide bars L1 and L2 in FIG. 4 and using the polyurethane elastic filaments of Example 5 as the b yarns on guide bars L3 and L4.
  • the fabric was tested in the same way as in Example 5. The results are given in Table 3.
  • Example 5 and 7 the pullout resistance was high due to fusion.
  • Example 6 fusion was of a degree that the filament could not be pulled out.
  • fabrics resistant to yarn slippage and grinning were obtained.
  • Combination with high-melting polyurethane elastic filaments in Comparative Examples 5, 6 and 7 discouraged fusion, resulting in a low pullout resistance. Yarn slippage and grinning occurred in these latter cases.
  • a knit fabric was produced by the method described below and heat set, following which the unraveling tension of the fabric was measured, the state of fusion between polyurethane elastic filaments was checked, and fabric damage from laundering tests (laundering durability) was visually evaluated.
  • the results are given in Table 4.
  • a knit fabric of the structure shown in FIG. 5 was produced on a raschel machine (Karl Mayer GmbH, 28 gauge).
  • a warp knit fabric was made in the form of main pieces of fabric using a 56 dtex, 17 filament nylon-6 yarn as yarn a on guide bar L1 in FIG. 5 , using the elastic filament of Comparative Example 5 as yarn c on guide bar L2, and using the polyurethane elastic filament of Example 1 as yarn c on guide bar L3.
  • 110 dtex, 24 filament nylon yarn was used as draw threads between the main pieces of fabric to create the warp knit fabric.
  • the knitted fabric was dry heat treated for 1 minute in a dryer held at 190°C.
  • the unraveling tension of the nylon yarn used as the draw threads was measured.
  • the unraveling speed was set at 100 mm/min, the unraveling tension was measured over a one minute period, and the average of five peak values was determined.
  • the nylon yarn in the main fabric pieces was dissolved with 20% dilute hydrochloric acid, and the fused state at points of contact between the polyurethane elastic filaments was examined.
  • a sample strip measuring 3.3 cm long in the knitting direction and 24.0 cm wide was cut from the heat-set fabric.
  • a cut was made in the fabric from the widthwise edge of the strip at an angle of 40° to the knitting direction, separating the fabric into a "first knitted side” and a “last knitted side,” then the cut edges of the strip in the knitting direction were joined together and sewn with an overlock sewing machine to form an annular specimen.
  • washing machine Two-tub household washing machine
  • Amount of detergent Adjusted to 1.3 g/L (used weakly alkaline detergent)
  • Amount of water 30 L
  • Loading fabric 1.0 kg of bare, plain knit fabric made with a combination of cotton and polyurethane elastic filament
  • Ratings of "Substantial” or “Severe” indicate a degree of damage that would make one hesitate to wear the item if it were an article of apparel. Ratings of "None” or “Minimal” indicate good durability to laundering.
  • Example 8 Aside from using the elastic filament of Comparative Example 1 as yarn c on guide bar L3 in FIG. 5 , a warp knit fabric was produced in the same way as in Example 8. After the fabric was heat set, the unraveling tension of the draw thread was measured, the fused state of the polyurethane elastic filaments was checked, and the same tests as in Example 8 were carried out. The results are shown in Table 4.
  • a warp knit fabric was produced on the same type of knitting machine as in Example 8 using a 56 dtex, 17 filament nylon-6 yarn as yarn a on guide bar L1 in FIG. 6 , using the polyurethane elastic filament of Comparative Example 1 as yarn c on guide bar L2, and using the polyurethane elastic filament of Example 1 as yarn c on guide bar L3.
  • the fabric was tested in the same way as in Example 8. The results are given in Table 4.
  • a warp knit fabric was produced on the same type of knitting machine as in Example 8 using a 56 dtex, 17 filament nylon-6 yarn as yarn a on guide bar L1 in FIG. 7 , using the polyurethane elastic filament of Example 1 as yarn b on guide bar L2, and using no draw threads.
  • the fabric was tested in the same way as in Example 8. The results are given in Table 4.
  • a warp knit fabric was produced on the same type of knitting machine as in Example 8 using a 56 dtex, 17 filament nylon-6 yarn as yarn a on guide bar L1 in FIG. 8 , using the polyurethane elastic filament of Example 1 as yarn b on guide bar L2, and using no draw threads.
  • the fabric was tested in the same way as in Example 8. The results are given in Table 4.
  • Example 8 and 9 the draw thread unraveling tension was high, indicating that the draw thread and the highly fusible polyurethane elastic filaments had strongly fused with each other. In Comparative Examples 8 and 9, the draw thread unraveling tension was low, indicating that fusion with the high-melting polyurethane elastic filaments did not readily occur. Concerning the state of fusion between the polyurethane elastic filaments, in Examples 8 and 9 according to the invention, the highly fusible polyurethane elastic filaments fused completely with the high-melting polyurethane elastic filaments; points of contact between these filaments could not be separated by pulling. In Comparative Examples 8 and 9, fusion between high-melting polyurethane elastic filaments was weak; places of contact between these filaments separated when pulled.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Knitting Of Fabric (AREA)
  • Artificial Filaments (AREA)
  • Woven Fabrics (AREA)
  • Treatment Of Fiber Materials (AREA)

Claims (16)

  1. Leicht schmelzbare elastische Polyurethanfasern mit zumindest 50 % Beibehaltung der Festigkeit nach einer 45 s langen Trockenhitzebehandlung bei 150 °C und 100 % Ausdehnung und einem Schmelzpunkt von 180 °C oder weniger.
  2. Leicht schmelzbare elastische Polyurethanfasern nach Anspruch 1, die aus einem Polymer schmelzgesponnen werden, das durch das Umsetzen von (a) einem an beiden Enden mit Isocyanat abgeschlossenen Präpolymer, das durch die Reaktion eines Polyols und eines Diisocyanats hergestellt wurde, mit (b) einem an beiden Enden mit Hydroxy abgeschlossenen Präpolymer, das durch die Reaktion eines Polyols, eines Diisocyanats und eines niedermolekularen Diols hergestellt wurde,
    gewonnen wird, worin es sich bei zumindest 50 Gew.-% des Ausgangspolyols um Polyetherpolyol handelt.
  3. Leicht schmelzbare elastische Polyurethanfasern nach Anspruch 2, worin das Polyol ein zahlenmittleres Molekulargewicht von 800 bis 3.000 aufweist, das Molverhältnis zwischen der Anzahl an Molen des gesamten Diisocyanats und der Anzahl an Molen des gesamten Polyols und des gesamten niedermolekularen Diols zusammengenommen für die Reaktion insgesamt 1,02 bis 1,20 beträgt und die Menge an verbleibenden Isocyanatgruppen in den frisch gesponnenen Fasern 0,3 bis 1 Gew.-% beträgt.
  4. Verfahren zur Herstellung leicht schmelzbarer Polyurethanfasern, das die folgenden Schritte umfasst:
    das Synthetisieren eines Spinnpolymers durch das Umsetzen von
    (A) einem an beiden Enden mit Isocyanat abgeschlossenen Präpolymer, das durch die Reaktion eines Polyols und eines Diisocyanats hergestellt wurde, mit
    (B) einem an beiden Enden mit Hydroxy abgeschlossenen Präpolymer, das durch die Reaktion eines Polyols, eines Diisocyanats und eines niedermolekularen Diols hergestellt wurde,
    und das Schmelzspinnen des Polymers ohne zuvor stattgefundene Verfestigung, worin es sich bei zumindest 50 Gew.-% des Ausgangspolyols um Polyetherpolyol handelt.
  5. Gewobener oder gestrickter Mischstoff, umfassend:
    leicht schmelzbare elastische Polyurethanfasern nach Anspruch 1, Anspruch 2 oder Anspruch 3 und
    zumindest eine Art nicht elastisches Garn,
    wobei der Stoff durch trockenes oder feuchtes Thermofixieren, sodass die leicht schmelzbaren elastischen Polyurethanfasern miteinander oder mit den nicht elastischen Garnen an Überkreuzungsstellen dazwischen wärmeverschmolzen werden, gewonnen wird.
  6. Gewobener oder gestrickter Mischstoff nach Anspruch 5, weiters umfassend hochschmelzende elastische Polyurethanfasern mit einem Schmelzpunkt von 200 °C oder darüber,
    wobei der Stoff durch Wärmeverschmelzen der leicht schmelzbaren elastischen Polyurethanfaser mit den hochschmelzenden elastischen Polyurethanfasern an Überkreuzungsstellen dazwischen gewonnen wird.
  7. Gewobener oder gestrickter Mischstoff nach Anspruch 5 oder 6, wobei es sich um einen Einschlagstrickstoff handelt, worin die leicht schmelzbare elastische Polyurethanfaser und zumindest eine Art nicht elastisches Garn gemeinsam in denselben Bahnen verwendet werden, worin die leicht schmelzbare elastische Polyurethanfaser und das nicht elastische Garn entweder in abwechselnder Anordnung oder in einem sonstigen geeigneten Abstand verstrickt sind.
  8. Gewobener oder gestrickter Mischstoff nach Anspruch 5 oder 6, wobei es sich um einen Einschlagstrickstoff mit abwechselnden Bahnen handelt, hergestellt durch das Speisen einer Einschlagstrickmaschine mit vier Einspeisungen:
    (a)
    Einspeisung 1: leicht schmelzbares Garn und nicht elastisches Garn,
    Einspeisung 2: nicht elastisches Garn,
    Einspeisung 3: leicht schmelzbares Garn und nicht elastisches Garn,
    Einspeisung 4: nicht elastisches Garn, oder
    (b)
    Einspeisung 1: leicht schmelzbares Garn und nicht elastisches Garn,
    Einspeisung 2: hochschmelzendes Garn mit einem Schmelzpunkt von zumindest 200 °C und nicht elastisches Garn,
    Einspeisung 3: leicht schmelzbares Garn und nicht elastisches Garn,
    Einspeisung 4: hochschmelzendes Garn mit einem Schmelzpunkt von zumindest 200 °C und nicht elastisches Garn, oder
    (c)
    Einspeisung 1: leicht schmelzbares Garn,
    Einspeisung 2: nicht elastisches Garn oder leicht schmelzbares Garn und nicht elastisches Garn,
    Einspeisung 3: leicht schmelzbares Garn,
    Einspeisung 4: nicht elastisches Garn oder leicht schmelzbares Garn und nicht elastisches Garn.
  9. Gewobener oder gestrickter Mischstoff nach Anspruch 5 oder 6, wobei es sich um einen Einschlagstrickstoff handelt, worin die leicht schmelzbare elastische Polyurethanfaser als Verbundgarn neben dem nicht elastischen Garn verwendet wird.
  10. Gewobener oder gestrickter Mischstoff nach einem der Ansprüche 5 bis 9, worin die leicht schmelzbare elastische Polyurethanfaser entweder eingelegt, eingestrickt oder plattiert ist.
  11. Gewobener oder gestrickter Mischstoff nach Anspruch 5 oder 6, wobei es sich um einen Kettenwirkereistoff handelt, worin die leicht schmelzbare elastische Polyurethanfaser und zumindest eine Art nicht elastisches Garn in Kombination verwendet werden, wobei die leicht schmelzbare elastische Polyurethanfaser über den gesamten Stoff eingestrickt oder in geeigneten Abständen eingestrickt ist und gegebenenfalls auch hochschmelzende elastische Polyurethanfasern mit einem Schmelzpunkt von zumindest 200 °C eingearbeitet sind.
  12. Stoff nach Anspruch 11, worin die leicht schmelzbare elastische Polyurethanfaser entweder eingelegt oder eingestrickt ist.
  13. Verwendung eines gewobenen oder gestrickten Mischstoffs nach einem der Ansprüche 5 bis 12 zur Herstellung von Gegenständen, worin der Stoff geschnitten und ohne Vernähen der abgeschnittenen Ränder verwendet wird.
  14. Verfahren zur Herstellung eines elastische Polyurethanfasern enthaltenden gewobenen oder gestrickten Mischstoffs, das die folgenden Schritte umfasst:
    das Ausbilden eines gewobenen oder gestrickten Stoffes unter Verwendung leicht schmelzbarer elastischer Polyurethanfasern nach Anspruch 1, 2 oder 3 und zumindest einer Art elastischen Garns und
    das trockene oder feuchte Thermofixieren des gewobenen oder gestrickten Stoffes, wodurch die leicht schmelzbaren elastischen Polyurethanfasern miteinander oder mit den nicht elastischen Garnen an Überkreuzungsstellen dazwischen wärmeverschmolzen werden.
  15. Verfahren zur Herstellung eines gewobenen oder gestrickten Mischstoffs nach Anspruch 14, wobei zusätzlich hochschmelzende elastische Polyurethanfasern mit einem Schmelzpunkt von 200 °C oder mehr verwendet werden und die leicht schmelzbaren elastischen Polyurethanfasern mit den hochschmelzenden elastischen Polyurethanfasern an Überkreuzungsstellen dazwischen wärmeverschmolzen werden.
  16. Kleidungsstück, hergestellt aus einem Stoff nach einem der Ansprüche 5 bis 12.
EP20030778770 2002-12-12 2003-12-10 Gemischte web- oder strickstoffe mit elastanfasern und herstellungsverfahren dafür Expired - Lifetime EP1595987B1 (de)

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KR101165244B1 (ko) 2012-07-17
JP4193064B2 (ja) 2008-12-10
TW200427884A (en) 2004-12-16
CN100567604C (zh) 2009-12-09
TWI334892B (de) 2010-12-21
CN1723307A (zh) 2006-01-18
KR20050085304A (ko) 2005-08-29
US20060030229A1 (en) 2006-02-09
EP1595987A4 (de) 2009-06-24
AU2003289006A1 (en) 2004-06-30
WO2004053218A1 (ja) 2004-06-24
EP1595987A1 (de) 2005-11-16
JPWO2004053218A1 (ja) 2006-04-13

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