TW201035399A - Fusible bicomponent spandex - Google Patents
Fusible bicomponent spandex Download PDFInfo
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- TW201035399A TW201035399A TW98134980A TW98134980A TW201035399A TW 201035399 A TW201035399 A TW 201035399A TW 98134980 A TW98134980 A TW 98134980A TW 98134980 A TW98134980 A TW 98134980A TW 201035399 A TW201035399 A TW 201035399A
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- fiber
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- polyurethane
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
- D02G3/326—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic the elastic properties due to the construction rather than to the use of elastic material
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/56—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads elastic
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
- D04B1/18—Other fabrics or articles characterised primarily by the use of particular thread materials elastic threads
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
- D10B2401/041—Heat-responsive characteristics thermoplastic; thermosetting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/30—Woven fabric [i.e., woven strand or strip material]
- Y10T442/3008—Woven fabric has an elastic quality
- Y10T442/3024—Including elastic strand or strip
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/40—Knit fabric [i.e., knit strand or strip material]
- Y10T442/413—Including an elastic strand
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/601—Nonwoven fabric has an elastic quality
- Y10T442/602—Nonwoven fabric comprises an elastic strand or fiber material
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Woven Fabrics (AREA)
- Knitting Of Fabric (AREA)
Abstract
Description
201035399 4 六、發明說明： 【發明所屬之技術領域】 本發明包含一種藉由諸如彈性纖維紡絲之溶液紡絲方法 製成之多成份彈性纖維，其包含聚胺基甲酸酯脲與聚胺基 他旨組合物1具有包含至少兩個分開㈣域與可界定邊 ，卩之橫截面，其中至少一個由該橫截面之邊界界定之區域 包含聚胺基曱酸酯脲或聚胺基曱酸酯組合物。纖維之一個 區域包含改善可熔性之添加劑，用以改善纖維本身或對基 ❹ 質之黏性。 【先前技術】 聚胺基甲酸酯或聚胺基甲酸酯脲（pu或puu)彈性紗線可 提供高度拉伸性、良好的自伸長恢復的能力及對諸如緯編 針織物、經編針織物、編織物、不織布及其他紡織物之由 其製成物件之良好適應力。然而，對於包含ρυ*ρυυ彈性 紗線之物件，重覆拉伸、到擦或切割常常引起爬格、跑針 &捲曲之問題。該等問題包含：可能產生階梯樣斷裂與缺 口，彈性紗線可能在切割邊緣滑出、裂開、磨損，且可能 導致破壞物件一致性與外觀的織物捲曲。在切割與縫紉製 程中，谷易產生在重複的拉伸下，PU* ρυυ彈性紗線自接 縫拉出的現象，且導致織物拉伸性損失，其亦稱為「滑 入」或接縫滑動。雖然該等效應亦會發生於除pi^tpuu紗 線外之彈性紗線，但由於PU或PUU彈性紗線之高度可拉伸 性，故其對PU或PUU彈性紗線尤其顯著。另外，對於一些 物件’需要高蒸汽或熱定型效率，尤其係襪子應用。 143877.doc 201035399 已有大量研究心力被投注於發展熱熔性及可蒸汽定型之 PU或PUU彈性紗線上。美國專利申請公開案第 2006/0030229A1號及第2008/0032580A1號揭示一種藉由將 聚合物熔融紡絲而製成之高度可熔性聚胺基曱酸酯彈性長 絲，該聚合物之合成方法為使以異氰酸酯封端之預聚合物 (由多元醇與二異氰酸酯反應而製成）與以羥基封端之預聚 合物（由多元醇、二異氰酸酯與低分子量二元醇反應而製 成）反應。該可熔性PU長絲之熔點為i 80«c或更低。在 100%伸長度下，於150°C下乾熱處理45秒鐘可使得該PU| 絲互相或與其他彈性或非彈性長絲在交叉點處熔融。然 而，PU長絲之低熔點導致在正常消費者使用下對蠕變之不 令人滿意的耐熱性，其導致成衣廉價。 需要經改善的彈性纖維紗線，其可提供可熔性、在成衣 製造期間之蒸汽定型能力、及更佳之拉伸回彈性，以克服 現有纖維之一或多種缺點。 【發明内容】 ,本發明係關於一種具改善功能性的多成份彈性纖維及其 製造方法。其包含經溶液紡絲之聚胺基甲酸酯或聚胺基甲 酸酯脲，其提供更佳拉伸/恢復性能及熱回彈性且可由雙 成份紡絲法製備，纟包含可熔性良好之添加劑，且產生適 用於諸如防止紗線攸格、滑動，及改善黏性之炼融應用的 可熔性紗線。 在—些實施例中為包含一橫截面之彈性、多成份、經溶 液纺絲之纖維，其中至少該橫截面之一第一區域包含彈性 143877.doc 201035399 聚胺基甲酸酯、或聚胺基曱酸酯脲、或其混合物；且該橫 截面包含一第二區域，其包含彈性聚胺基甲酸酯、或聚胺 基甲酸酯脲、或其混合物，與至少一種改善可熔性之添加 劑。 纖維可具有一或多根長絲，諸如單根單長絲、雙（兩根 長絲）、三根長絲等。當纖維具有多於一根長絲時，每一 長絲可包含一具有兩個或兩個以上區域之多成份橫截面。201035399 4 VI. Description of the Invention: [Technical Field of the Invention] The present invention comprises a multicomponent elastic fiber prepared by a solution spinning method such as elastic fiber spinning, which comprises polyurethane and polyamine The basal composition 1 has a cross section comprising at least two separate (four) domains and definable edges, at least one of which is defined by the boundary of the cross section comprising polyamine phthalate urea or polyamino decanoic acid Ester composition. One area of the fiber contains an additive that improves the meltability to improve the fiber itself or the adhesion to the base. [Prior Art] Polyurethane or polyurethane urethane (pu or puu) elastic yarns provide high stretchability, good self-elongation recovery and resistance to fabrics such as weft knitted fabrics, warp knitted fabrics Good adaptability of articles made of woven fabrics, non-woven fabrics and other textiles. However, for articles containing ρυ*ρυυ elastic yarns, repeated stretching, rubbing or cutting often causes problems with crawling, running, and curling. These problems include the possibility of step-like breaks and gaps, elastic yarns that may slip, crack, wear at the edge of the cut, and may cause fabric curl that disrupts object consistency and appearance. In the cutting and sewing process, it is easy for the PU* ρυυ elastic yarn to be pulled out from the seam under repeated stretching, and the fabric stretchability loss is also called “sliding in” or seam. slide. Although these effects also occur in elastic yarns other than the pi^tpuu yarn, PU or PUU elastic yarns are particularly remarkable for PU or PUU elastic yarns because of their high stretchability. In addition, high steam or heat setting efficiency is required for some items, especially for socks. 143877.doc 201035399 A great deal of research has been devoted to the development of hot-melt and steam-settable PU or PUU elastic yarns. US Patent Application Publication Nos. 2006/0030229 A1 and 2008/0032580 A1 disclose a highly fusible polyamine phthalate elastic filament made by melt spinning a polymer, the synthesis method of the polymer To react an isocyanate-terminated prepolymer (made by reacting a polyol with a diisocyanate) with a hydroxyl terminated prepolymer (made by reacting a polyol, a diisocyanate with a low molecular weight diol) . The fusible PU filament has a melting point of i 80 «c or lower. Dry heat treatment at 150 ° C for 45 seconds at 100% elongation allows the PU| filaments to melt at the intersections with each other or with other elastic or inelastic filaments. However, the low melting point of PU filaments results in unsatisfactory heat resistance to creep under normal consumer use, which results in inexpensive garments. There is a need for improved elastane yarns that provide meltability, steam setability during garment manufacturing, and better stretch resilience to overcome one or more of the shortcomings of existing fibers. SUMMARY OF THE INVENTION The present invention relates to a multicomponent elastic fiber having improved functionality and a method of producing the same. It comprises a solution-spun polyurethane or polyurethaneurea which provides better stretch/recovery properties and thermal resilience and can be prepared by a two-component spinning process with good fusibility The additive, and produces a fusible yarn suitable for use in refining applications such as preventing yarn snagging, slipping, and improving stickiness. In some embodiments, an elastic, multi-component, solution-spun fiber comprising a cross-section, wherein at least one of the first regions of the cross-section comprises elasticity 143877.doc 201035399 polyurethane, or polyamine a phthalic acid urea, or a mixture thereof; and the cross section comprises a second region comprising an elastomeric polyurethane, or a polyurethane urethane, or a mixture thereof, and at least one improved meltability Additives. The fibers may have one or more filaments, such as a single filament, a double (two filaments), three filaments, and the like. When the fiber has more than one filament, each filament may comprise a multi-component cross-section having two or more regions.
在另一實施例中為包含含有一橫截面之彈性、多種組 份、經溶液紡絲纖維的織物，其中至少該橫截面之一第一 區域包含至少一種彈性聚胺基曱酸酯、聚胺基甲酸酯脲組 合物、或其混合物；且該橫截面包含一第二區域，其含有 至少一種彈性聚胺基甲酸酯、聚胺基曱酸酯脲組合物、或 其混合物，與至少一種改善可熔性之添加劑。 本發明亦包含一種製備可熔'彈性、多成份之經溶液紡 絲纖維的方法，其包含： (a)提供第一與第二聚合物溶液； ⑻通過分佈板與孔口組合該等溶液，形成具有一橫截 面之長絲； (c) 通過一共同毛細管擠出該等長絲；且 (d) 自該等長絲移除溶劑； 其中該^截面包3 -介於該等聚合物溶液間之邊界； 其中第與第一聚合物溶液各獨立地包含彈性聚胺基甲 酸酷、聚胺基甲酸㈣、或其混合物；且 其中該等第二聚合物溶液包含改善可熔性之添加劑； 143877.doc 201035399 其中该可熔性'彈性、多成份之經溶液紡絲纖維包含一 多區域橫截面，其t第一聚合物溶液對應於該橫截面之第 一區域且第二聚合物溶液對應於該橫截面之第二區域。 在另實施例中為一種包括含有一橫截面之彈性'多成 份之經溶液紡絲纖維的纖維，其中至少該橫截面之—第一 區域包含彈性聚胺基甲酸酯、或聚胺基甲酸酯脲、或其混 合物；且其包含一第二區域，其包含彈性聚胺基f酸酯、 或聚胺基甲酸酯脲、或其混合物，與至少—種改善可熔性 之添加劑，該添加劑包含至少一種熔點為約i〇〇艺至約 1 80°C之低熔點聚胺基甲酸酯；且 其中該第一區域包含熔點為約19(rc至約25〇。〇之高熔點 彈性聚胺基甲酸酯。 【實施方式】 定義 如文中所用，術言吾「多成份纖維」意指具有至少兩個不 同組成而具有可辨別邊界的不同分開區域之纖維，亦即具 有兩個或兩個以上沿著纖維長度連續延伸之不同組成區 域。其與聚胺基甲酸酯或聚胺基曱酸酯脲摻合物相反，後 者組合多種組合物，形成沿纖維長度無不同且連續邊 界的纖維。術語「多成分纖維」與「多成份纖維」同義且 於文中相互交換地使用。 術語「組成上丨同」係、定義&包含不同聚合物、共聚物 或摻合物之兩種或兩種以上組合物，或具有—種或多種不 同添加劑之兩種或兩種以上組合物，纟中包含於組合物中 143877.doc 201035399 之聚合物可相同或不同。若兩種對照的組合物包含不同聚 合物與不同添加劑，則其亦為「組成上不同」。 術浯「邊界」、及「邊界區域」係用於闡述多成份纖維 . 職面之不同區域之間的接觸點。若於兩個區域的組合物 之間存在最少量或不存在重疊，則該接觸點係「清晰界 定」。若於兩個區域之間確實存在重疊，則該邊界區域將 包含兩個區域之摻合。該摻合區域可為分開的均勻摻合部 份，其於摻合邊界區域與另外兩區域之每一者之間具有分 ❾f:的邊界。或者，該邊界區域可包含靠近第—區域為較： 濃度之第一區域組合物至靠近第二區域為較高濃度之第二 區域組合物的梯度。 如文中所用，浴劑」思指諸如二甲基乙醯胺（dmAC)、 二甲基甲醯胺（DMF)與N-甲基吡咯啶酮之有機溶劑。 如文中所用，術語「溶液纺絲」包含自溶液製備纖維， 其可為濕式紡絲或乾式紡絲方法，其二者皆為生產纖維之 常用技術。 ❹ β 提供良好蒸汽定型能力與極佳黏著性之低熔點聚胺基甲 酸酯（PU)組合物（Tm<180°c )通常產生不良的抗蠕變性、低 強度、與低劣的拉伸回彈性。此外，該等低熔點PU組合物 不適於形成纖維之製程與高溫紡織物之加工需求。本發明 將基於經溶液纺絲之聚胺基甲酸酯/聚胺基甲酸酯脲組合 物之優良拉伸與恢復性與低熔點黏著調配物組合於多成分 纖維結構（諸如雙成份纖維結構）中。 聚胺基甲酸酯嵌段共聚物之性質取決於胺基甲酸酯與多 143877.doc 201035399 元醇鏈段之相分離，以致硬的胺基曱酸酯區域係作為軟鏈 段基質中之交聯物。胺基甲酸酯區域係由所選之鏈延長劑 的含量與品質來控制。市售之重要二元醇鏈延長劑包含， 但不限於，乙二醇、丨，3_丙二醇（PD〇)、ι，4·丁二醇（1，4· BDO或BDO)、及丨’6-己二醇（HD〇)。所有該等二元醇鏈延 長劑皆形成充分相分離之聚胺基甲酸酯且形成清晰界定之 硬鏈段區域’且除乙二醇外均適用於熱塑性聚胺基甲酸 酯。因為其所衍生之胺基甲酸酯在高硬鏈段含量下會經歷 不利的降解。表1列出衍生自一些常用鏈延長劑之聚胺基 甲酸酯的典型硬鏈段熔融範圍。高於2〇(rc之加工溫度對 於一般的TPU組合物係不利的，此係因在加工期間的熱降 解及伴隨的性質損失。另外，衍生自高溫硬鏈段熔融組合 物之PU通常產生改善的彈性與熱回彈性，且更適用於紡織 物加工。為產生優良的拉伸/恢復性質，該等具有高硬鏈 段熔點之聚胺基甲酸酯纖維僅可自傳統的溶液紡絲方法製 成0 表1-硬鏈段多態結構之DSC分佈 鍵延長劑 吸熱（°C ) 1,6-己二醇（HDO) 180-190 ~" 1,4-丁二醇（bd〇) 205-215 1,3-丙二醇（PDO) 210-225 乙二醇（EDO) 245-260 有多種不同的聚胺基甲酸S旨或聚胺基甲酸8旨脲組合物適 143877.doc 201035399 2於本發明之第—及第二區域中之任-者或兩者。亦可包 , 週用之聚胺基甲酸酯/聚胺基甲酸酯脲組 合物詳細闡述於下文。 、’In another embodiment is a fabric comprising a cross-section of elastic, multi-component, solution-spun fibers, wherein at least one of the first regions of the cross-section comprises at least one elastomeric polyamine phthalate, polyamine a urethane urea composition, or a mixture thereof; and the cross section comprises a second region comprising at least one elastomeric polyurethane, a polyamine phthalate urea composition, or a mixture thereof, and at least An additive that improves meltability. The present invention also encompasses a method of preparing a fusible 'elastic, multi-component solution-spun fiber comprising: (a) providing a first and second polymer solution; (8) combining the solutions by a distribution plate and an orifice, Forming a filament having a cross section; (c) extruding the filaments through a common capillary; and (d) removing the solvent from the filaments; wherein the section 3 is between the polymer solutions a boundary between the first and second polymer solutions, each independently comprising an elastomeric polyurethane, a polyaminocarbamate, or a mixture thereof; and wherein the second polymer solution comprises an additive that improves fusibility; 143877.doc 201035399 wherein the fusible 'elastic, multi-component solution-spun fiber comprises a multi-region cross-section, the t first polymer solution corresponding to the first region of the cross-section and the second polymer solution corresponding In the second region of the cross section. In another embodiment, a fiber comprising a solution-spun fiber having a cross-section of an elastic 'multi-component, wherein at least the cross-section - the first region comprises an elastomeric polyurethane, or a polyamine a urea ester, or a mixture thereof; and comprising a second region comprising an elastomeric polyamine f-ester, or a polyurethane urethane, or a mixture thereof, and at least one additive for improving meltability, The additive comprises at least one low melting point polyurethane having a melting point of from about 1 to about 80 ° C; and wherein the first region comprises a melting point of from about 19 (rc to about 25 Å. Elastomeric Polyurethane. [Embodiment] Definitions As used herein, the term "multi-component fiber" means a fiber having at least two distinct regions having distinct boundaries and having distinguishable boundaries, that is, having two Or two or more different constituent regions extending continuously along the length of the fiber. In contrast to polyurethane or polyamine phthalate urea blends, the latter combining a plurality of compositions to form a continuous and non-different and continuous fiber length Boundary fiber The term "multi-component fiber" is synonymous with "multi-component fiber" and is used interchangeably herein. The term "compositionally identical", definition & includes two or two different polymers, copolymers or blends. The above composition, or two or more compositions having one or more different additives, the polymers contained in the composition of 143877.doc 201035399 may be the same or different. If the two control compositions contain different Polymers and different additives are also "compositionally different." The "border" and "boundary area" are used to describe the contact points between different regions of the multi-component fiber. If there is minimal or no overlap between the compositions of the region, then the contact is "clearly defined." If there is indeed an overlap between the two regions, the boundary region will contain a blend of the two regions. The merged region may be a separate uniform blending portion having a boundary of a branching f: between the blending boundary region and each of the other two regions. Alternatively, the boundary region may include near the first The domains are: a gradient of the concentration of the first zone composition to a second zone composition of the second zone that is at a higher concentration. As used herein, a bath agent means, for example, dimethylacetamide (dmAC), two An organic solvent of methylformamide (DMF) and N-methylpyrrolidone. As used herein, the term "solution spinning" comprises preparing a fiber from a solution, which may be a wet spinning or dry spinning process. Both are common techniques for the production of fibers. ❹ β Low-melting polyurethane (PU) compositions (Tm <180°c) that provide good steam setability and excellent adhesion often produce undesirable creep resistance. Sexual, low-strength, and inferior stretch resilience. In addition, these low-melting PU compositions are not suitable for the process of forming fibers and processing requirements for high-temperature textiles. The present invention will be based on solution-spun polyaminocarboxylic acid. The excellent stretch and recovery properties of the ester/polyurethane urea compositions are combined with low melting point adhesion formulations in multicomponent fiber structures, such as bicomponent fiber structures. The nature of the polyurethane block copolymer depends on the phase separation of the carbamate from the 143877.doc 201035399 diol segment, such that the hard amine phthalate region acts as a soft segment matrix. Crosslinks. The urethane zone is controlled by the amount and quality of the chain extender selected. Commercially available important glycol chain extenders include, but are not limited to, ethylene glycol, hydrazine, 3-propylene glycol (PD〇), iota, butanediol (1,4·BDO or BDO), and 丨' 6-hexanediol (HD〇). All of these glycol chain extenders form a sufficiently phase separated polyurethane and form a clearly defined hard segment region' and are suitable for thermoplastic polyurethanes except for ethylene glycol. Because the urethane derived therefrom undergoes unfavorable degradation at high hard segment content. Table 1 lists the typical hard segment melting ranges of polyurethanes derived from some common chain extenders. Above 2 〇 (the processing temperature of rc is detrimental to typical TPU compositions due to thermal degradation during processing and concomitant loss of properties. Additionally, PUs derived from high temperature hard segment melt compositions generally produce improvements. Resilience and thermal resilience, and more suitable for textile processing. In order to produce excellent tensile/recovery properties, these polyurethane fibers with high hard segment melting point can only be used from traditional solution spinning methods. Made of 0 Table 1 - Hard segment polymorphic structure DSC distribution bond extender endothermic (°C) 1,6-hexanediol (HDO) 180-190 ~" 1,4-butanediol (bd〇) 205-215 1,3-propanediol (PDO) 210-225 Ethylene glycol (EDO) 245-260 There are a variety of different polyurethanes or polyureacarboxylic acid 8 urea composition suitable for 143877.doc 201035399 2 Any or both of the first and second regions of the present invention may also be packaged, and the weekly polyurethane/polyurethane urea composition is described in detail below.
一項實施例提供經溶液紡絲（乾式紡絲或濕式紡絲）之熱 溶性及可蒸汽；t型之彈性纖維彈性紗線。該纖維包含單根 長絲結構或多根長絲結構。該纖維之每—長絲（或單長絲 之纖維本身)為沿纖維之橫截面具有諸如鞘-芯構形或並列 式構形之可辨別區域之雙成份纖維。芯為第-區域及勒為 第一區域。可包含額外的區域’以提供不同之橫截面，諸 如並列式構形與鞘-芯之組合，或鞘-芯與另一鞘區域。 對於可溶性纖維，特別適用於第二區域（其可為勒）之組 合物可包含： A. —聚合物摻合物，其中第一組分包含至少一種具有 高熔點之聚胺基甲酸酯，諸如熔點為約19〇。(：至約25〇它 之聚胺基甲酸酯，以及彼等熔點為約200。(：或更高者， 與諸如低溫熔融聚胺基曱酸酯之改善可熔性之添加劑。 適用之低熔點聚胺基甲酸酯包含熔點為約5〇。〇至約 150C之聚胺基甲酸酯，尤其係熔點低於12〇£>(：之聚胺基 甲酸自旨；或 B. —摻合物，其中第一組分包含至少一種具高熔點之 聚胺基甲酸酯，諸如熔點為約190°c至約25(rc之聚胺基 曱酸醋’以及熔點為約200〇c或更高之聚胺基曱酸酯， 與至少一種供隨後基質鍵合用的黏性物質或改善可熔性 之添加劑’其中該黏性物質為改善可熔性之添加劑；或 143877.doc 201035399 c.至少-種聚胺基甲酸醋與至少一種改善可熔性之黏 性添加劑的摻合物。 亦涵蓋A、8及。之排列組合。亦可包含其他添加劑。 對於可熔性纖維，特別適用於第—區域（其可為芯）之組 合物可包含： 1:至少-種具有高熔點之聚胺基甲酸醋，諸如熔點為約 190 C至約250°C之聚胺基甲酸酯，以及熔點為約2〇(rc或 更高之聚胺基甲酸酯；或 2) 具有20(TC至25(TC範圍之高熔點的聚胺基甲酸醋與具 有低於180°C之低熔點的聚胺基甲酸酯的摻合物；或 3) 至少-種聚胺|甲酸酯與至少一種聚胺|甲酸酯脲之 摻合物；或 4) 聚胺基甲酸酯脲，包含彼等具有高於24〇它之熔點 者。 一些實施例之雙成份纖維可包含廣範圍之第一區域與第 二區域的比例。該第二區域（其亦可為鞘_芯構形中之鞘）含 量可占基於纖維重量之約1%至約6〇%，包含占纖維重量之 約1%至約50%，占纖維重量之約1〇%至約35%，及占纖維 重量之約5%至約30%。 一些實施例之可熔性纖維可具有大於5〇%之蒸汽定型效 率。纖維亦可具有大於〇.15cN/分德士（dtex)之熔融強度。 -些實施例為多成份、或雙成份纖維，其包括含有聚胺 基曱酸酯、聚胺基曱酸酯脲或其混合物之經溶液紡絲之聚 合物組合物。用於多成份纖維之不同區域之組合物包含不 143877.doc -10· 201035399 同的聚合物組合物’其中聚合物不同、添加劑不同、或/ 合物與添加劑皆不同。亦包含具有經溶液紡絲部份與經： 融紡絲部份之多成分纖維。 '' 聚胺基甲酸醋腺及聚胺基甲酸酯組合物 適用於製備纖維或長鏈合成聚合物之聚胺基曱酸酯脲組 口物包含至少85重量％之嵌段聚胺基曱酸酯。其通常包含 聚合二元醇，其與二異氰酸酯反應形成以NCO-封端之^ 聚口物（經封端之二元醇」），其隨後溶解於諸如二甲基 乙醯胺、二曱基甲醯胺、或N-甲基吡咯啶酮之適宜溶劑 中，且隨後與雙官能鏈延長劑反應。當鏈延長劑為二醇時 可在無溶劑時製成），於第二步驟形成聚胺基甲酸酯。 當鏈延長劑為二胺時，形成聚胺基甲酸酷腺（―種聚胺基 甲酸知之亞類）。在製備可經紡絲成彈性纖維之聚胺基曱 酸酯脲聚合物時，#由羥基端基與二異氰酸酯及一或多種 二胺之連續反應延長二元醇。在每一情形下，二元醇必需 ㈣鏈延長，以提供具有所需性f (包含黏度）之聚合物。 若需要’可使用二月桂酸二丁基錫、辛酸亞錫、礦物酸、 諸如二乙胺之第三胺、N，N，·二甲基哌嗪等、及其他已知 之催化劑於協助封端步驟。 適且的聚合二元醇成份包含數量平均分子量為約600至 約3500之聚醚二元醇、聚碳酸酯二元醇、及聚酯二元醇。 可包含兩種或兩種以上之聚合二元醇或共聚物之混合物。 可使用之聚醚二元醇之實例包含彼等二元醇：具有兩個 或兩個以上經基，衍生自環氧乙烷、環氧丙烷、丨，3-環氧 143877.doc 201035399 丙烷、四氫呋喃、及3-甲基四氫呋喃之開環聚合反應及/或 共聚合反應，或衍生自諸如每—分子中含有少於12個碳原 子的二元醇或一元醇混合物（諸如乙二醇、丨，3-丙二醇、 1，4-丁二醇、1，5-戊二醇、l，6-己二醇、2,2_二曱基义弘丙 一醇、3-甲基-1，5-戊二醇、1，7_庚二醇、1ί8_辛二醇、I、 壬二醇、1，10-癸二醇及1，12-十二烷二醇）之多元醇的縮合 聚合反應。以直鏈、雙官能聚醚多元醇為較佳，且諸如官 能度為 2之 Terathane® 1800 (INVISTA of Wichita，KS)之分 子量約1700至約2100之聚（四亞甲基醚）二醇為特定適宜二 元醇的一貫例。共聚物可包含聚（四亞甲基共-伸乙基醚） 二酵。 可使用之聚酯多元醇之實例包含彼等酯二元醇：具有兩 個或兩個以上羥基，由每一分子中含有不多於12個碳原子 的低分子量脂族多元羧酸與多元醇、或其混合物之縮合聚 合反應製得。適宜的多元羧酸實例為丙二酸、琥珀酸、戊 二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一 烷二羧酸、及十二烷二羧酸。適用於製備聚酯多元醇之多 元醇實例為乙二醇、1，3_丙二醇、丨，4_丁二醇、U戊二 醇、1，6-己二醇、新戊二醇、3_甲基_U5_戊二醇、I、庚二 醇、1，8-辛二醇、i，9·壬二醇、〗，1〇_癸二醇及112_十二烷 二醇。熔點約5。(：至約5〇t之直鏈雙官能聚酯多元醇為特 疋之聚S旨多元醇實例。 可使用的聚碳酸酯多元醇實例包含彼等碳酸酯二元醇： 具有兩個或兩個以上羥基、由每—分子中碳原子數不多於 143877.doc -12· 201035399 i2個之低分子量之光氣、氯甲酸酷、二燒基碳㈣或二稀 丙基碳㈣與脂族多元醇、或其混合物之縮合聚合反應製 得。適用於製備聚碳酸酷多元醇之多元醇實例為二甘醇、 i’3-丙二酵、M_ 丁二醇、仏戊二醇、W己二醇、新戊 二醇、3_曱基-戊二醇、1>7_庚二醇、以-辛二醇、 壬一醇1,10癸一醇及l5l2_十二烧二醇。溶點約穴至約 5(TC之直鏈雙官能聚碳酸s旨多元醇為特定聚碳酸醋多元醇 之實例。One embodiment provides a hot melt and steamable t-type elastic fiber elastic yarn that is solution spun (dry or wet spun). The fiber comprises a single filament structure or a plurality of filament structures. Each of the fibers - the filaments (or the fibers of the individual filaments themselves) are bicomponent fibers having a discernible region such as a sheath-core configuration or a side-by-side configuration along the cross-section of the fibers. The core is the first region and the first region is the first region. Additional regions may be included to provide different cross-sections, such as a side-by-side configuration with a sheath-core combination, or a sheath-core and another sheath region. For soluble fibers, a composition particularly suitable for use in the second region (which may be Leh) may comprise: A. a polymer blend, wherein the first component comprises at least one polyurethane having a high melting point, Such as a melting point of about 19 〇. (: to about 25 Å of its polyurethane, and their melting point is about 200. (or higher, with additives such as low temperature molten polyamine phthalate to improve the meltability.) The low-melting polyurethane comprises a polyurethane having a melting point of about 5 Å. 〇 to about 150 C, especially a melting point of less than 12 & ( : : ; ; ; ;; a blend wherein the first component comprises at least one polyurethane having a high melting point, such as a polyalkyl phthalate having a melting point of from about 190 ° C to about 25 (and a melting point of about 200 〇) a polyamine phthalate of c or higher, with at least one viscous material for subsequent matrix bonding or an additive for improving meltability, wherein the viscous material is an additive for improving meltability; or 143877.doc 201035399 c. blend of at least one type of polyurethane carboxylic acid with at least one viscous additive for improving meltability. Also encompasses the arrangement of A, 8 and . It may also contain other additives. For fusible fibers, special A composition suitable for the first region (which may be a core) may comprise: 1: at least one having a high melting point Amino carboxylic acid vinegar, such as a polyurethane having a melting point of from about 190 C to about 250 ° C, and a polyurethane having a melting point of about 2 〇 (rc or higher; or 2) having 20 (TC) a blend of 25 to a high melting point polyurethane in the TC range and a polyurethane having a low melting point below 180 ° C; or 3) at least a polyamine | formate and at least a polyamine|formate urea blend; or 4) a polyurethane urea comprising those having a melting point above 24 Torr. The bicomponent fibers of some embodiments may comprise a wide range of a ratio of a region to a second region. The second region (which may also be a sheath in a sheath-core configuration) may comprise from about 1% to about 6% by weight based on the weight of the fiber, and comprises about 1% by weight of the fiber. From about 50% to about 50% by weight, from about 1% to about 35% by weight of the fiber, and from about 5% to about 30% by weight of the fiber. The fusible fibers of some embodiments may have a steam setting efficiency of greater than 5% by weight. The fibers may also have a melt strength greater than 1515 cN/dtex. - Some examples are multi-component, or bi-component fibers, including polyamine phthalates, polyamines. A solution-spun polymer composition of phthalate urea or a mixture thereof. The composition for different regions of the multi-component fiber comprises a polymer composition of the same polymer composition, which is not 143877.doc -10· 201035399 The additives are different, or the compounds are different from the additives. Also included are multi-component fibers with a solution-spun portion and a melt-spun portion. '' Polyurethane sulphate and polyurethane combination A polyamino phthalate urea composition suitable for use in the preparation of a fiber or long chain synthetic polymer comprises at least 85% by weight of a block polyamino phthalate. It typically comprises a polymeric diol which is reacted with a diisocyanate. Forming an NCO-terminated material (blocked glycol) which is subsequently dissolved in, for example, dimethylacetamide, dimethylformamide, or N-methylpyrrolidone Suitably in a solvent and subsequently reacted with a bifunctional chain extender. When the chain extender is a diol, it can be made without a solvent, and in the second step, a polyurethane is formed. When the chain extender is a diamine, a polyamine carbamate gland (a subclass of polyaminocarbamic acid) is formed. In the preparation of a polyamine phthalate urea polymer which can be spun into an elastic fiber, the diol is extended by a continuous reaction of a hydroxyl end group with a diisocyanate and one or more diamines. In each case, the diol must be (4) chain extended to provide a polymer having the desired properties f (including viscosity). If desired, dibutyltin dilaurate, stannous octoate, mineral acid, a third amine such as diethylamine, N,N,-dimethylpiperazine, and the like, and other known catalysts may be used to assist in the capping step. Suitable polymeric diol components comprise polyether diols, polycarbonate diols, and polyester diols having a number average molecular weight of from about 600 to about 3,500. Mixtures of two or more polymeric diols or copolymers may be included. Examples of polyether diols that may be used include those diols having two or more trans groups derived from ethylene oxide, propylene oxide, hydrazine, 3-epoxy 143877.doc 201035399 propane, Ring-opening polymerization and/or copolymerization of tetrahydrofuran, and 3-methyltetrahydrofuran, or from a mixture of glycols or monohydric alcohols such as ethylene glycol or hydrazine containing less than 12 carbon atoms per molecule. , 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-didecyl-i-propanol, 3-methyl-1,5 Condensation polymerization of polyols of pentanediol, 1,7-heptanediol, 1 88-octanediol, I, decanediol, 1,10-nonanediol and 1,12-dodecanediol . A linear, difunctional polyether polyol is preferred, and a poly(tetramethylene ether) glycol having a molecular weight of from about 1,700 to about 2,100, such as Terathane® 1800 (INVISTA of Wichita, KS) having a functionality of 2, is A consistent example of a particular suitable glycol. The copolymer may comprise poly(tetramethylene co-extension ethyl ether) difer. Examples of polyester polyols that can be used include their ester diols: low molecular weight aliphatic polycarboxylic acids and polyols having two or more hydroxyl groups containing no more than 12 carbon atoms per molecule. , or a mixture thereof, obtained by condensation polymerization. Examples of suitable polycarboxylic acids are malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecane two. carboxylic acid. Examples of polyols suitable for the preparation of polyester polyols are ethylene glycol, 1,3-propanediol, hydrazine, 4-butanediol, U-pentanediol, 1,6-hexanediol, neopentyl glycol, 3_ Methyl_U5_pentanediol, I, heptanediol, 1,8-octanediol, i,9·nonanediol, 〗 1, 1 癸 癸 diol and 112 _ dodecane diol. The melting point is about 5. (: Straight-chain difunctional polyester polyol to about 5 〇t is an example of a poly-polyol which is particularly useful. Examples of polycarbonate polyols that can be used include these carbonate diols: having two or two More than one hydroxyl group, the number of carbon atoms per molecule is not more than 143877.doc -12· 201035399 i2 low molecular weight phosgene, chloroformic acid, dialkyl carbon (tetra) or diisopropyl carbon (four) and aliphatic A polyhydric alcohol, or a mixture thereof, obtained by condensation polymerization. Examples of polyhydric alcohols suitable for the preparation of polycarbonate cool polyols are diethylene glycol, i'3-propanol, M-butanediol, decanediol, and W Glycol, neopentyl glycol, 3_mercapto-pentanediol, 1>7-heptanediol, to-octanediol, decyl alcohol 1,10-decyl alcohol, and l5l2-didecyl diol Pointing from about a hole to about 5 (TC's linear difunctional polycarbonate) polyol is an example of a specific polycarbonate polyol.
二異氰酸酯成份亦可包含單種二異氰酸酯或不同二異氰 酸醋之混合物，包括含有4,4,_亞甲基雙（異氰酸苯醋）與 2,4亞曱基雙（異氰酸苯醋）之二笨曱院二異氰酸醋（_工）之 異構混合物。可包含任一適宜的芳族或脂族二異氰酸酯。 可使用之一異氰酸酯之實例包含，但不限於，4,4，_亞甲基 雙（苯基異氰酸醋）、2,4'-亞甲基雙（苯基異氰酸醋）、4,4,_ 亞甲基雙（環己基異氰酸酯）、1，3_二異氰酸基_4_甲基_苯、 2,2 -甲苯二異氰酸酯、2,4’_甲苯二異氰酸酯、及其混合 物。特定之聚異氰酸酯成份實例包含M〇ndur⑧ML(Bayer)、The diisocyanate component may also comprise a single diisocyanate or a mixture of different diisocyanates, including 4,4,-methylene bis(isocyanato benzene vinegar) and 2,4 fluorenylene bis (isocyanate). Benzene vinegar) is a mixture of two amateur broths of isocyanine vinegar (_ work). Any suitable aromatic or aliphatic diisocyanate may be included. Examples of one of the isocyanates that may be used include, but are not limited to, 4,4,-methylene bis(phenylisocyanate), 2,4'-methylenebis(phenylisocyanate), 4 , 4,_ methylene bis(cyclohexyl isocyanate), 1,3-diisocyanato-4-methyl-benzene, 2,2-toluene diisocyanate, 2,4'-toluene diisocyanate, and mixture. An example of a specific polyisocyanate component comprises M〇ndur8ML (Bayer),
Lupranate® MI(BASF)、及Isonate® 50 〇,p，（Dow Chemical)、 及其組合。 用於聚胺基甲酸酯脲之鏈延長劑可為水或二胺鏈延長 劑。可包含不同鏈延長劑之組合’其取決於聚胺基甲酸酯 脲與所得纖維之所需性質。適宜的二胺鏈延長劑實例包 含·聯胺、1,2-乙二胺、1,4-丁二胺、ι，2_ 丁二胺、1,3-丁 二胺、1，3-二胺基-2,2-二甲基丁烷、1}6_六亞甲基二胺、 143877.doc -13- 201035399 1，12-十二燒二胺、ι，2-丙二胺、ι，3_丙二胺、2_曱基“，弓-戊二胺、1-胺基-3,3,5-三甲基-5-胺基甲基環己烷、2,4_二 胺基-1-曱基環己烷、N-曱基胺基-雙（3_丙基胺）、丨，2_環己 烷二胺、1，4-環己烷二胺、4,4'-亞甲基·雙（環己基胺）、異 佛爾酮二胺、2,2-二曱基_1，3-丙二胺、間四甲基二曱苯二 胺、1，3-二胺基_4_曱基環己烷、環己烷_二胺、ΐ}ΐ•亞 甲基-雙（4,4，-二胺基己烷）、3-胺基甲基_3,5,5_三甲基環 己烷、1，3-戊二胺（1,3-二胺基戊烷）、間二曱苯二胺、及Lupranate® MI (BASF), and Isonate® 50®, p, (Dow Chemical), and combinations thereof. The chain extender for the polyurethane urea can be water or a diamine chain extender. Combinations of different chain extenders can be included which depend on the desired properties of the polyurethane and the resulting fiber. Examples of suitable diamine chain extenders include hydrazine, 1,2-ethylenediamine, 1,4-butanediamine, iota, 2-butanediamine, 1,3-butanediamine, 1,3-diamine Base-2,2-dimethylbutane, 1}6-hexamethylenediamine, 143877.doc -13- 201035399 1,12-dodecyldiamine, ι,2-propanediamine, ι, 3_propylenediamine, 2_fluorenyl", bow-pentanediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-diamino 1-nonylcyclohexane, N-decylamino-bis(3-propylamine), hydrazine, 2-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'- Methylene bis(cyclohexylamine), isophorone diamine, 2,2-dimercapto-1,3-propanediamine, m-tetramethyldiphenylene diamine, 1,3-diamine Base_4_decylcyclohexane, cyclohexane-diamine, ΐ}ΐ•methylene-bis(4,4,-diaminohexane), 3-aminomethyl_3,5, 5_trimethylcyclohexane, 1,3-pentanediamine (1,3-diaminopentane), m-diphenylene diamine, and
Jeffamine®(Texaco)。 外 || 當需要聚胺基甲酸酯時’鏈延長劑為二元醇。可使用之 該等二元醇之實例包含’但不限於，乙二醇、丨，3-丙二 醇、1，2-丙二醇、3_甲基—is戊二醇、2,2二甲基4,3-丙 二醇、2,2,4-三甲基-15-戊二醇、2-甲基_2_乙基丙二 醇、雙（羥乙氧基）苯、及1，4· 丁二醇、己二醇及其混合 物。 可視需要包含單官能醇或第一 /第二單官能胺，以控制 聚合物之分子量。亦可包含一種或多種單官能醇與一種或 〇 多種單官能胺之摻合物。 適用於本發明之單官能醇之實例包含至少一個選自由下 列組成之群之成員：具有1至18個碳之脂族及環脂族第一 ， 與第二醇；分子量小於約750(包含分子量小於5〇〇)之酚、 經取代酚、乙氧基化烷基酚與乙氧基化脂肪醇；羥基胺、 經羥甲基與羥乙基取代之第三胺、經羥甲基與羥乙基取代 之雜環化合物、及其組合，包含糠醇、四氫糠醇、N_(2_ 143877.doc _ 14· 201035399 羥乙基）琥珀醯亞胺、4-(2-羥乙基）嗎啉、曱醇、乙醇、丁 醇、新戊醇、己醇、環己酵、環己烷甲醇、苯曱醇、辛 醇、十八烷醇、Ν,Ν-二乙基羥基胺、2-(二乙胺基）乙醇、 2-二曱胺基乙醇、及4-哌啶乙醇、及其組合。Jeffamine® (Texaco). Outside || When a polyurethane is required, the 'chain extender is a glycol. Examples of such diols that may be used include, but are not limited to, ethylene glycol, hydrazine, 3-propanediol, 1,2-propanediol, 3-methyl-is pentanediol, 2,2-dimethyl4, 3-propanediol, 2,2,4-trimethyl-15-pentanediol, 2-methyl-2-ethylpropanediol, bis(hydroxyethoxy)benzene, and 1,4·butanediol, Glycols and mixtures thereof. A monofunctional alcohol or a first/second monofunctional amine may optionally be included to control the molecular weight of the polymer. Blends of one or more monofunctional alcohols with one or more monofunctional amines may also be included. Examples of monofunctional alcohols suitable for use in the present invention comprise at least one member selected from the group consisting of aliphatic and cycloaliphatic firsts having from 1 to 18 carbons, and second alcohols; molecular weights less than about 750 (including molecular weights) Less than 5 〇〇) phenol, substituted phenol, ethoxylated alkyl phenol and ethoxylated fatty alcohol; hydroxylamine, third amine substituted with hydroxymethyl and hydroxyethyl, hydroxymethyl and hydroxy Ethyl-substituted heterocyclic compounds, and combinations thereof, comprising decyl alcohol, tetrahydrofurfuryl alcohol, N_(2_143877.doc _ 14· 201035399 hydroxyethyl) succinimide, 4-(2-hydroxyethyl)morpholine, Sterol, ethanol, butanol, neopentyl alcohol, hexanol, cyclohexane, cyclohexane methanol, phenyl decyl alcohol, octanol, stearyl alcohol, hydrazine, hydrazine-diethylhydroxylamine, 2-(two Ethylamine)ethanol, 2-diamidinoethanol, and 4-piperidineethanol, and combinations thereof.
適宜之單官能二烷基胺封端劑的實例包含：Ν，Ν-二乙基 胺、Ν-乙基-Ν-丙基胺、Ν，Ν-二異丙基胺' Ν-第三丁基-Ν-甲基胺、Ν-第三丁基-Ν-苯甲基胺、Ν，Ν-二環己基胺、Ν_ 乙基-Ν-異丙基胺、Ν-第三丁基-Ν-異丙基胺、Ν_異丙基_ Ν-環己基胺、Ν-乙基-Ν-環己基胺、Ν，Ν_二乙醇胺、及 2,2,6,6-四曱基〇底咬。 其他聚合物 適用於本發明之多成分及/或雙成份纖維之其他聚合物 包含可溶性或具有有限溶解度或可以顆粒形式（例如，微 細顆粒）包含之其他聚合物。該等聚合物可分散於或溶解 於聚胺基甲酸酯或聚胺基甲酸酯脲溶液中或與經溶液紡絲 之聚胺基甲酸酯或聚胺基甲酸酯脲組合物共擠出。共擠出 之結果可為具有並列式、同心鞘_芯、或偏心鞘-芯橫截面 之雙成份或多成分纖維，其中—種成份為聚胺基甲酸醋腺 溶液且另一種成份包含另一種聚合物。其他聚合物之實例 尤其包含低熔點聚胺基甲酸s|(如上所述）、聚酿胺、丙稀 &系g、聚㈣胺、及聚烯烴。在—些實施例中，非聚 胺基甲酸酯聚合物可為改善可熔性之添加劑，尤w該 聚合物之熔點低於約150oc時。 ”田" 可包含於該等多成分纖維中之其他聚合物包含尼龍6、 143877.doc •15- 201035399 匕龍6/6尼龍1〇、尼龍12、尼龍6/10、及尼龍6/12。聚稀 仁包3自(：2至(：2。單體製備之聚烯烴。其包含共聚物與三 元共聚物，諸如乙烯丙烯共聚物。適用之聚烯烴共聚物 κ例揭不於頒予Datta等人之美國專利第6,867,26〇號其 以引用的方式併入文中。 纖維橫截面構形 多種不同橫截面適用於本發明之—些實施例。其包含雙Examples of suitable monofunctional dialkylamine blocking agents include: hydrazine, hydrazine-diethylamine, hydrazine-ethyl-hydrazine-propylamine, hydrazine, hydrazine-diisopropylamine Ν-third butyl Ν-Ν-methylamine, hydrazine-t-butyl-hydrazine-benzylamine, hydrazine, hydrazine-dicyclohexylamine, hydrazine-ethyl-hydrazine-isopropylamine, hydrazine-tertiary butyl-hydrazine -isopropylamine, Ν_isopropyl__-cyclohexylamine, Ν-ethyl-Ν-cyclohexylamine, hydrazine, hydrazine-diethanolamine, and 2,2,6,6-tetradecyl fluorene bite. Other Polymers Other polymers suitable for use in the multi-component and/or bi-component fibers of the present invention comprise other polymers which are soluble or have limited solubility or which may be included in particulate form (e.g., fine particles). The polymers may be dispersed or dissolved in a polyurethane or polyurethane solution or with a solution-spun polyurethane or polyurethaneurea composition. Extrusion. The result of coextrusion may be a two-component or multi-component fiber having a side-by-side, concentric sheath-core, or eccentric sheath-core cross-section, wherein the component is a polyurethane sulphate solution and the other component contains another polymer. Examples of other polymers include, in particular, a low melting point polyaminocarboxylic acid s| (as described above), a polystyrene, a propylene & g, a poly(tetra)amine, and a polyolefin. In some embodiments, the non-polyurethane polymer can be an additive that improves the meltability, especially when the melting point of the polymer is less than about 150 oc. "Field" " Other polymers that may be included in these multicomponent fibers include nylon 6, 143,877.doc • 15-201035399 匕龙6/6 nylon 1 〇, nylon 12, nylon 6/10, and nylon 6/12 Polyester package 3 from (: 2 to (: 2. monomer-prepared polyolefin. It contains a copolymer and a terpolymer, such as ethylene propylene copolymer. The applicable polyolefin copolymer κ can not be awarded U.S. Patent No. 6,867, the entire disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety herein in
成份或多成份同心岑值、、败μ &被L 飞偏u鞘-忍與雙成份或多成份並列 式。亦涵蓋獨特的橫截面，只要該等橫截面包含至少兩個 分開的區域即可。替代性橫截面可具有扇形區構形或類似 於偏心勒-芯之構形，其中該勒僅部份包圍芯。換言之， 該橫截面之第二區域可部份或完全地包圍第一區域。適宜 之不同橫截面實例顯示於圖1。 可包含可熔性聚合物作為鞘或並列式構形或替代性構形 之主要或唯-成份，而不包含分開的改善可熔性之添加 劑，其中該可熔性聚合物具有所需熔點。 所有顯示於圖i之纖維橫截面皆具有組成上不同之第一 區域與第二區域。圖1AWB顯示44分德士（dtex)/3長絲紗 線，而圖1C與1D顯示44分德士/4長絲紗線。各者中之第一 區域包含顏料而第二區域則不含。圖丨八與⑶包含一 鞘·芯橫截面，·圖〗C包含一】7/83鞘_芯橫截面，·及圖⑴包 含一 50/50並列式橫截面。 各鞘-芯與並列式橫截面包含介於至少兩種組成上不同 之聚胺基f酸酯脲組合物之間之一邊界區。在每—該等圖 143877.(j〇c -16· 201035399 形中，該等區域呈現為— 含摻合區域。若邊界包含摻人/ 4界’但該邊界可包 區域，其為第一與第二第域，則邊界本身為-不同 第二、第四楚、 摻合。該摻合可為均勾摻合或可包含自第組合物之 域之濃度梯度。 自第—區域至第二區 添加劑 可視需要包含於聚胺基甲酸醋腺組 列舉如下。其包含_干一 物中之添加劑種類 ❹ ❿ • 例性且非限制性的列表。麸而，枯 術中熟知其他添加劑。 劑、著色劑、顏料、交聯劑、^物^化劑、UV安定 ^ 削相變物質（石蠟）、抗微生物 董*、海藻，、咖啡因、凝膠、 ίΡπ你^ 香枓或方香料）、奈米粒子 ^或碳）、碳_、阻燃劑、抗黏添加劑、抗氯降解 添加劑、維生素、藥物、香料、導電性添加劑、可染性及/ ^助染劑（諸如第四錄鹽）。可添加至聚胺基甲酸醋脲組合 物之其他添加劑包含黏附促進劑及改善可炫性之添加劑、 抗靜電劑、抗填變劑、光學增亮劑、聚結劑、導電性添加 劑、發光添加劑、濁滑劑、有機與無機填料、防腐劑、調 貝劑、熱變色添加劑、防蟲劑、及濕潤劑、安定劑（受阻 紛、氧化辞、受阻胺）、增滑劑（聚碎氧油）及其組合。 九添加劑可提供下列有益特性中之一種或多種，包含：可 染性、疏水性（即聚四氟乙稀（PTFE))、親水性（即纖維 素）摩t控制性、财氯性、财降解性（即抗氧化劑）、黏性 及/或可熔性(即黏著劑與黏附促進劑）、阻燃性、抗微生物 143877.doc •17- 201035399 行為（銀、銅、銨鹽）、障壁性、導電性（碳黑）、拉伸性 質、顏色、發光性、可再循環性、生物可降解性、香味、 黏性控制（即金屬硬脂酸鹽）、觸感性質、可變形性、熱調 節性（即相變物質）、營養藥物性、諸如二氧化鈦之去光 劑、諸如水滑石之安定劑、碳鈣鎂礦及水菱鎂礦之混合 物、uv防曬劑、及其組合。 添加劑包含量可為於適於獲得所需效果之任一量。 一些添加劑適用作為改善可熔性之添加劑，其具有低溶 融溫度，且包含於一些實施例中。其包含水份固化、熱黏 合、及反應性熱熔等級之基於聚醚、聚酯、聚碳酸酯、及 聚己内酯之直鏈、芳族熱塑性聚胺基甲酸酯、或其摻合 物。特定市售產品實例尤其包含Mor-Melt(R-5022) (Rohm and Haas)、Pellathane® 2103G(Dow)、Desmopan® 5377、 Desmopan 9375A ' Texin DP7-1197(Bayer Material Science) ' Pearlbond 104、106、122、123(Merquinsa Mercados Quimicos, S.L)、及TPUA-25 2A(TPUCO, Taiwan)。改善可熔性之添加 劑可以適於獲得纖維之所需可熔性的任何量包含。該改善 可熔性之添加劑可包含於纖維之鞘或第二區域，且占鞘或 第二區域之約10重量％至約90重量％，包含占鞘或第二區 域之約30重量％至約60重量％。基於多成份或雙成份纖維 總重量之改善可炫性之添加劑的重量百分比將取決於纖維 之芯或第一區域對鞠或第二區域之重量比。在一些情形 中，該第二鞘區域本身可為含或不含另外的改善可熔性之 添加劑的可、熔性聚合物。 143877.doc -18- 201035399 設備 雙成份纖維通常係藉由熔融紡絲方法製成。用於該等方 法之該等設備可經調適用於溶液紡絲方法。乾式紡絲及濕 式紡絲為熟知之溶液紡絲方法。 關於纖維及長絲（包含彼等人造雙成份纖維者）且以引用 的方式併入文中之習知參考文獻例如： a. Fundamentals of Fibre Formation—The Science ofConstituents or multi-component concentric annihilation, and μ μ & are L-sheaving u-sheath-tolerance with two-component or multi-component juxtaposition. A unique cross section is also encompassed as long as the cross sections contain at least two separate regions. Alternative cross-sections may have a sector configuration or a configuration similar to an eccentric core-core in which the portion only partially encloses the core. In other words, the second region of the cross section may partially or completely surround the first region. Examples of suitable different cross sections are shown in Figure 1. The fusible polymer may be included as a major or only component of the sheath or side-by-side configuration or alternative configuration without the inclusion of a separate improver for improving the meltability, wherein the fusible polymer has the desired melting point. All of the fiber cross-sections shown in Figure i have a compositionally distinct first and second regions. Fig. 1AWB shows 44 dtex/3 filament yarns, while Figs. 1C and 1D show 44 dtex/4 filament yarns. The first of the areas contains the pigment and the second area does not. Figures VIII and (3) contain a sheath-core cross-section, and Figure C contains a 7/83 sheath-core cross-section, and Figure (1) contains a 50/50 side-by-side cross section. Each sheath-core and side-by-side cross-section comprises a boundary zone between at least two compositionally different polyamine-based acid ester urea compositions. In each of the figures 143877. (j〇c -16· 201035399, these regions are presented as containing a blending region. If the boundary contains a blended / 4 bounds but the boundary can be a region, it is the first And the second domain, the boundary itself is - different second, fourth, blending. The blending may be a homogenous blending or a concentration gradient that may be included from the domain of the first composition. The two-zone additive may optionally be included in the polyurethane urethane gland group as listed below. It contains _ dry ones in the additive class ❹ ❿ • an illustrative and non-limiting list. Bran, other additives are well known in the dry process. Colorants, pigments, crosslinkers, chemical agents, UV stabilizers, phase change materials (paraffin), antimicrobials, seaweed, caffeine, gels, Ρ 你 ^ ^ ^ ^ ^ ^ ^ ^ ^ Nanoparticles ^ or carbon), carbon _, flame retardants, anti-adhesive additives, anti-chlorine degradation additives, vitamins, drugs, fragrances, conductive additives, dyeability and / ^ auxiliary agents (such as the fourth recorded salt) . Other additives which may be added to the polyurethane urethane composition include an adhesion promoter and an additive for improving dazzle resistance, an antistatic agent, an anti-filling agent, an optical brightener, a coalescent, a conductive additive, a luminescent additive , slippery agent, organic and inorganic fillers, preservatives, scallops, thermochromic additives, insect repellents, and wetting agents, stabilizers (blocked, oxidized, hindered amines), slip agents (polyoxygenated oils) ) and its combination. Nine additives can provide one or more of the following beneficial properties, including: dyeability, hydrophobicity (ie, polytetrafluoroethylene (PTFE)), hydrophilicity (ie, cellulose), controllability, chlorosis, wealth Degradability (ie antioxidant), viscosity and / or fusibility (ie adhesives and adhesion promoters), flame retardancy, antimicrobial 143877.doc • 17- 201035399 behavior (silver, copper, ammonium salt), barrier Properties, electrical conductivity (carbon black), tensile properties, color, luminosity, recyclability, biodegradability, aroma, viscosity control (ie, metal stearate), tactile properties, deformability, Thermally modulating (ie, phase change material), nutraceutical, delustering agents such as titanium dioxide, stabilizers such as hydrotalcite, mixtures of carbon calcium magnesium or hydromagnesite, uv sunscreens, and combinations thereof. The amount of additive included can be any amount suitable to achieve the desired effect. Some additives are useful as additives to improve meltability, have low melting temperatures, and are included in some embodiments. A linear, aromatic thermoplastic polyurethane based on polyether, polyester, polycarbonate, and polycaprolactone, or a blend thereof, comprising moisture cure, thermal bond, and reactive hot melt rating Things. Specific examples of commercially available products include, inter alia, Mor-Melt (R-5022) (Rohm and Haas), Pellathane® 2103G (Dow), Desmopan® 5377, Desmopan 9375A 'Texin DP7-1197 (Bayer Material Science) ' Pearlbond 104, 106, 122, 123 (Merquinsa Mercados Quimicos, SL), and TPUA-25 2A (TPUCO, Taiwan). Additives that improve fusibility may be included in any amount suitable to achieve the desired meltability of the fiber. The melt-improving additive may be included in the sheath or second region of the fiber and may comprise from about 10% to about 90% by weight of the sheath or second region, comprising from about 30% to about 30% by weight of the sheath or second region. 60% by weight. The weight percent of the additive that improves the scentability based on the total weight of the multi-component or bi-component fiber will depend on the weight of the core of the fiber or the first region versus the second region. In some cases, the second sheath region itself may be a fusible polymer with or without additional additives to improve meltability. 143877.doc -18- 201035399 Equipment Bicomponent fibers are usually made by melt spinning. Such equipment for use in such methods can be adapted for use in solution spinning processes. Dry spinning and wet spinning are well known solution spinning methods. References to fibers and filaments (including those of their artificial bicomponent fibers) and incorporated herein by reference: a. Fundamentals of Fibre Formation—The Science of
Fibre Spinning and Drawing, Adrezij Ziabicki John 05Fibre Spinning and Drawing, Adrezij Ziabicki John 05
Wiley and Sons, London/New York, 1976 ； b. Bicomponent Fibres, R Jeffries, Merrow 出版有限公 司，1971 ; c. Handbook of Fiber Science and Technology, T. F. Cooke，CRC 出版社，1993 ; 類似的參考文獻包含以引用的方式併入文中的美國專利 案苐5，162,074號及弟5,256,050號，其闡述用於製造雙成份 纖維之方法與設備。 0 利用習知設備完成通過一模頭擠出聚合物以形成纖維， 該設備例如擠壓機、齒輪泵等。較佳使用個別的齒輪泵於 向該模頭提供聚合物溶液。當為獲得功能性而摻合添加劑 時，較佳於靜態混合機中混合聚合物之摻合物，例如於齒 輪泵之上游，以獲得更均勻之成份分散物。作為擠出之預 備，可藉由具有受控温度之夾套容器分別加熱各彈性纖維 溶液並過濾，以提高紡絲收率。 在本發明之闡述性實施例中，向於40至9(rc下操作之分 143877.doc -19- 201035399 段、夾套熱交換器引入兩種不同聚合物溶液。根 維構形配置擠㈣頭與平板，其_於圖糾、需纖 細管正上方組合成份物流。經預熱之溶液自供： (5)導出，通過一筛網⑺’到達-分佈板(4)且進入由_ * 片（8)定位且由-螺帽（6)支持之一嘴絲頭⑼。 填 M述於仏3、及4之擦出模頭與平板 纖維紡絲早兀（諸如顯示於以引用的方式併入文中 專利案第6,248,273號中者）一起使用。 、、國 ❹ 雙成份彈性纖維亦可藉由公Μ & 芦Η糟由刀㈤的毛細管製成分 絲，隨後聚結該等長絲形成單根纖維。 本發明之特點與優點藉由下列實例更全面地顯示 該等實例係為Μ述之目的，且不應將其視作 所、 制本發明。 订方式限 製造纖維之方法 由聚胺基甲酸酯或聚胺基甲酸酯脲聚合物之含有習知之 胺基甲酸s旨聚合物溶劑（例如DMAe)的溶液’經溶液纺絲 (濕式紡絲或乾式紡絲）製成一些實施例之纖维。聚胺基甲、 酸酿或聚胺基甲酸g旨脲聚合物溶液可包含任—上述之組合 物或添加劑。該聚胺基甲酸酯脲之製法為在丨6至2.3，二 佳1.8至2.0範圍内之二異氰酸醋比二元醇的莫耳比下，令 有機二異氰酸酯與適宜的二元醇反應，產生「經封端的二 元醇」。該經封端的二元醇隨後與二胺鏈延長劑之混人 反應。在所得聚合物中，軟鏈段為聚合物鏈之聚醚/胺基 143877.doc •20· 201035399 甲酸醋部份。該等軟鏈段展示低於啊之炼點。硬鍵段為 聚合物鏈之聚胺基甲酸醋/尿素部份；其溶點高於2帆。 硬鏈段占聚合物總重量之5.5至12%，較佳占⑴㈣。聚 胺基甲酸酯聚合物之製法為在22至33， -一異氛酸醋比二元醇的莫耳比下，令有機二： 醋與適宜的二元醇反應，產生「經封端的二元醇」。該經 封端的二元醇隨後與二醇鏈延長劑之混合物反應。硬鏈段 為聚合物鏈之聚胺基甲酸酯鏈段；其熔點為15〇至24〇力。 〇 該等硬鏈段可組成聚合物總重量之10至20。/。，較佳組成13 至 7.5%。 在製備纖維之一項實施例中，將包含3〇至4〇%聚合物固 體之聚合物溶液計量通過期望配置之分佈板與孔口而形成 長絲。安置分佈板使得依同心鞘-芯、偏心鞘_芯、及並列 式配置中之一種組合聚合物流，隨後通過一共同毛細管擠 出。藉由引入300〇C至40(TC之熱的惰性氣體，且於至少 ◎ 1 〇 · 1之氣體：聚合物質量比下，乾燥經擠出之長絲，並 以每分鐘至少400米之速度（較佳為至少6〇〇 m/min)拉伸， 且隨後以每分鐘至少5 〇 〇米之速度（較佳為至少7 5 〇 m / m i η) 捲起。以下給出之所有實例均係以8(rc之擠出溫度，於熱 惰性氣體氛圍下’以762 m/min之捲取速度進行。標準加 工條件已於技術中熟知。 由根據本發明製得之彈性纖維形成之紗線通常具有至少 0.6 cN/分德士之斷裂韌性，至少400%之斷裂伸長率，於 300°/。伸長率下至少27 mg/分德士之卸載模量。 143877.doc •21 · 201035399 可藉由任一習知方法，自文中所述之彈性多成分纖維製 成紗線與織物。該等彈性紗線可由諸如硬紗線之第二紗線 包覆。適宜的硬紗線尤其包含尼龍、丙烯酸系樹脂、棉、 聚醋及其混合物。經包覆之紗線可包含單一包覆、雙重包 覆、空氣包覆、包芯紡絲紗線與併撚紗線。 一些實施例之彈性紗線可包含於多種結構物中，諸如針 織物（經編與緯編）、織物、及不織物。其適用於襪子、長 筒襪、襯衫、内衣、泳衣、襯底及不織布衛生結構物。 若需要紗線的溶融或黏著，則取決於改善可炼性之添加 劑的組成，可藉由暴露於熱及/或至多35&(bar)之靜壓來 達到。熱可以蒸汽或乾熱來施加。適用於襪子之熔融條件 可包含：當使用蒸汽熱時，暴露於約105t至約135t之溫 度下約3秒至約60秒；及當使用乾熱時，暴露於165它至 約195 °C下約3秒至約60秒。 適宜的熔融條件可取決於許多因素而變化，尤其包含所 選之改善可熔性之添加劑、聚合物化學、紗線線性密度、 及織物結構（亦即針織物、編織物等）。 對於機子，將織物暴露於多種加卫條件，包含暴露於熱 及/或壓力。因此，不需要分開的熱定型/炫融製程，因為 織物之熱定型亦將導致含有改善 乃人D j π性之添加劑或其他添 加劑之紗線之熔融。 根據：般方法ASTMD 273”2測量實例中彈性纖維之 強度及彈H 男。對於每_測量，使用三根2英寸（5㈣ 量規長度之長絲，經〇_3嶋之伸長循環。使樣本於每分鐘 143877.doc 201035399 50HU定伸長速率下循環五^在第―次循環時，於 2嶋伸長率下測量負荷力量(Μ2〇〇)_初次延長期間彈性纖 !上之應力，並記錄為對於給定丹尼爾之克-力。卸載力 1(麵)為在第五次卸载循環時於亀伸長下之應力， 亦。己錄為克-力。在第六次延長循環時測量斷裂伸長百 分比及勒性。亦於經歷五次〇_3〇〇%伸長/鬆弛循環之樣本 上測置變形百分比。隨後如下計算變形百分比似 Ο %S = l〇〇(Lf.Lo)/L〇 其中Lo及Lf分別為在五次伸長/鬆他循環之前及之後，在 無張力下保持筆直時之長絲（紗線）長度。 為測疋洛π疋型（其模擬機子加工與定形操作卜將一處 於筆直無張力條件下之遗中i 2 i 你忏T之選疋長度％(通常為⑺em)之樣本 拉伸至其原始長度之三倍’持續約2分鐘且隨後鬆弛。此 係模擬當以習知紗線包料，彈性纖維被拉伸之包覆操 〇 作。隨後將經如此拉伸與鬆弛之彈性纖維測試樣本置於沸 水浴中30分鐘。此暴露於濟水係模擬染色操作。隨後自該 浴移出樣本，經乾燥，並拉伸至其浴後鬆弛長度之兩倍。 當在此拉伸條件下時’冑該樣本暴露於i2it之蒸汽氛圍 下3〇秒：此蒸汽處理係模擬機子定形。在自蒸汽氛圍移出 後’使樣本乾燥’並測量其之筆直無張力長度竹。隨後根 據下式計算蒸汽定型（ss，％): %SS = 100(Yf-Y〇)/Y〇 藉由以下方法測定紗線可熔性：將一長15 樣本呈 143877.doc -23- 201035399 於可調節邊框上，使其頂角正中位於邊框上且 。將相同長度之第二條長絲安置於 、則，使侍兩條紗線相交且交又於單一個接觸點。 使纖維鬆弛至5 cm，隨後暴露於精煉浴一小時、經沖 洗、空氣乾燥，且隨後暴露於染料浴中30分鐘、經沖洗、 並空氣乾燥。 將載有纖維之邊框的長度自5 em調整至3〇 em，並暴露 於U1C之蒸汽30秒’經冷卻3分鐘，並鬆弛。將紗線自邊 框移出並轉移至拉伸測試機’夾住各紗線之-頭，且保留 接觸位於夹子之間。以【〇()%/min伸長紗線且將使接觸 點斷裂之力（克-力）記錄為熔化強度。 藉由下列實例更全面地顯示本發明之特點與優點，提供 違等實例係為闡述之目# ’且不應將其視為以任何方式限 制本發明。 實例 對於下列實例1至3，由含高熔點聚胺基曱酸酯彈性聚合 物的N，N-二曱基乙醯胺（DMAc)(CAS編碼為127_19_5〇)溶液 經乾式紡絲製成纖維。為對最終纖維提供充分的熱安定 性’如下製備高熔點聚胺基曱酸酯聚合物，並將其用作芯 及鞘組合物之基質。藉由以下步驟製備具有2 7〇之封端比 例之聚胺基甲酸酯預聚合物：將MDI(CAS編號為[26447-40-5]之l，i-亞曱基雙[異氰酸基苯])及2〇〇〇數目平均分子 量之卩丁1^〇(€八8編號為25190-06-1之聚（氧-1,4-丁二基）， α-氫-ω-羥基）的混合物加熱至乃充，保持2小時。隨後將預 143877.doc •24· 201035399 聚合物於DMAc中溶解至約39%固體之濃度。於75°C下， 藉由添加足量乙二醇（CAS編號107-21-1)延長預聚合物溶 液，以使40°C落球溶液黏度增加至4000泊。一旦溶液達到 目標黏度，則藉由添加單官能醇（CAS編號為71-36-3之1-丁醇）來終止聚合反應。 使包含35至40%聚合物固體之聚合物溶液計量通過期望 配置之分佈板與孔口而形成長絲。安置分佈板使得依同心 鞘-芯配置組合聚合物物，隨後再通過一共同毛細管擠 Ο 出。藉由引入320至440°c之熱的惰性氣體，且於至少10 : 1之氣體：聚合物質量比下乾燥經擠出之長絲，並以每分 鐘至少400米之速度（較佳至少600 m/min)拉伸，且隨後以 每分鐘至少500米之速度（較佳至少750 m/min)捲起。由此 等彈性纖維形成之紗線通常具有至少1 cN/分德士之斷裂 韌性，至少400%之斷裂伸長率，至少0.2 cN/分德士之 M200。 實例1 : 〇 將由 Merquinsa Mercados Quimicos, S.L(Pearlbond 122) 提供之基於聚己内酯之線型聚胺基甲酸酯溶解，並以30% 之重量比與經製備之高熔點PU聚合物（上述）摻合，而形成 35% DMAc溶液，並作為鞘組分擠出。芯溶液由含高溫PU 聚合物之DMAc溶液組成，並與鞘溶液依4 : 1之比組合， 而形成22分德士之雙長絲紗線。以700 m/min取出產品， 並於塗覆聚石夕氧油後以850 m/min收捲於包裝上。包含可 熔性、蒸汽定型效率、及拉伸性質之產品性質於表2中給 143877.doc -25- 201035399 出。示差掃描量熱跡線（圖5)闡述可熔性添加劑在約56它下 之低熔融轉變。 實例2 : 將由 Bayer Material Science，USA (Desm〇pan 5377八）供 應之熱塑性聚胺基甲酸酯彈性物（酯/醚）溶解，並以6〇%重 量比與經製備之高溫PU聚合物（上述）摻合，而形成36% DMAc溶液，且作為鞘組分擠出。芯溶液由存於dmAc* 之高熔點PU聚合物組成，且與鞘溶液依4 :丨之比例組合， 而形成22分德士之雙長絲紗線。以7〇〇 m/min拉出產品， 並於塗覆聚矽氧油後以850 m/min收捲於包裝上。包含可 熔性、蒸汽定型效率、及拉伸性質之產品性質於表2中給 出。 。 實例3(對照）： 將呈39% DMAc溶液之經製備之高溫1>11聚合物（上述）不 經修飾即作為鞘與芯組分，依4: i之比例擠出，形成。分 德士之雙長絲紗線。以700爪化“拉出產品，並於塗覆2 於聚矽氧之油劑後以850 m/min收捲於包裝上。包含可二 性、蒸汽定型效率、及拉伸性質之產品特性於表32中办 出。 於市售Menegatto或ICBT包覆機上以扁平丨丨分德士 /7長 絲之扁平聚醯胺66紗線包覆實例紗線（實例1至3)。彈性紗 線之拉伸比為2·8χ，且包覆因數為15〇〇 tpm。於諸如 Lonati 400圓形織襪機之市售針織機器上針織襪子樣本。° 該經包覆之紗線經針織入每一 織結構 路徑之三軸向編 143877.doc •26- 201035399 (tdeot constructi〇n)，使得於經針織結構之每一接觸點處 的彈性紗線熔化。若可熔性紗線係包含於交替路徑中亦 可獲得適宜的熔化。 經熱壓及組裝之標準操作後，將成衣置於標準定形設備 之蒸氣室中，於110。〇及130。(：下定形10至6〇 Se藉由將成 衣置於將產生於穿著期間典型之拉伸的開放平板上而測試 適宜之可雜。利用刀子或剪刀挑起彈性紗線造成破裂而 製k刺孔。若由於平板上拉伸所引起之彈性紗線之力量Wiley and Sons, London/New York, 1976; b. Bicomponent Fibres, R Jeffries, Merrow Publishing Ltd, 1971; c. Handbook of Fiber Science and Technology, TF Cooke, CRC Press, 1993; The methods and apparatus for making bicomponent fibers are described in U.S. Patent Nos. 5,162,074 and 5,256,050, each incorporated herein by reference. 0 The fiber is extruded through a die to form a fiber using a conventional apparatus such as an extruder, a gear pump or the like. It is preferred to use a separate gear pump to provide a polymer solution to the die. When the additive is blended for functionality, it is preferred to mix the blend of polymers in a static mixer, such as upstream of a gear pump, to obtain a more uniform dispersion of the components. As a preparation for extrusion, each of the elastic fiber solutions can be separately heated and filtered by a jacketed vessel having a controlled temperature to increase the spinning yield. In an illustrative embodiment of the invention, two different polymer solutions are introduced into the jacketed heat exchanger from 40 to 9 (operating at rc 143877.doc -19-201035399). The root-dimensional configuration is squeezed (4) The head and the plate are combined with the component stream directly above the slim tube. The preheated solution is self-supply: (5) is exported, passes through a screen (7) 'arrival-distribution plate (4) and enters by _ * piece (8) Positioning and supporting one of the mouthpieces (9) by the nut (6). Filling the die with the dies 3 and 4 and spinning the slab fiber (such as shown by way of reference) It is used together with the patents No. 6,248,273. The two-component elastic fiber can also be made into a filament by the capillary of the knife (5), and then the filaments are formed into a single sheet. The present invention is more fully shown by the following examples which are presented for purposes of illustration and are not to be construed as the invention. a urethane or polyurethane urea polymer containing a conventional urethane A solution of a solvent (such as DMAe) is prepared by solution spinning (wet spinning or dry spinning) into fibers of some embodiments. Polyamine, acid or polyurethane can be used as a urea polymer solution. Including the above-mentioned composition or additive. The polyurethane urethane is produced by a molar ratio of diisocyanate to diol in the range of 丨6 to 2.3, and preferably 1.8 to 2.0. The organic diisocyanate is reacted with a suitable diol to produce a "blocked diol." The blocked diol is then reacted with a diamine chain extender. In the resulting polymer, the soft segment It is a polyether/amine group of polymer chain 143877.doc •20· 201035399 formic acid vinegar part. These soft segments show lower than the melting point of the polymer. The hard bond segment is the polymer chain of polyamino carboxylic acid vinegar/urea. Part; its melting point is higher than 2 sails. Hard segments account for 5.5 to 12% of the total weight of the polymer, preferably (1) (4). Polyurethane polymer is produced at 22 to 33, - a different atmosphere The ratio of the acid vinegar to the molar ratio of the diol makes the organic two: vinegar react with a suitable diol to produce a "blocked diol". The blocked diol is then reacted with a mixture of diol chain extenders. The hard segment is a polyurethane chain of the polymer chain; its melting point is from 15 Torr to 24 Torr. 〇The hard segments The total weight of the polymer may be from 10 to 20% by weight, preferably from 13 to 7.5%. In one embodiment of the preparation of the fiber, a polymer solution comprising from 3 to 4% polymer solids is metered through the expectation. The distribution plate and the orifice are configured to form filaments. The distribution plate is arranged such that one of the concentric sheath-core, the eccentric sheath-core, and the side-by-side configuration combines the polymer flow, followed by extrusion through a common capillary. 〇C to 40 (TC of hot inert gas, and at least ◎ 1 〇 · 1 gas: polymer mass ratio, dry the extruded filament, and at a speed of at least 400 meters per minute (preferably Stretching at least 6 〇〇m/min) and then rolling at a rate of at least 5 mils per minute (preferably at least 7 5 〇m / mi η). All of the examples given below were carried out at 8 (rc extrusion temperature, under a hot inert gas atmosphere) at a take-up speed of 762 m/min. Standard processing conditions are well known in the art. The yarn formed from the elastic fibers generally has a fracture toughness of at least 0.6 cN/min, an elongation at break of at least 400%, and an unloading modulus of at least 27 mg/min. at an elongation of 300. / 143877. Doc • 21 · 201035399 Yarns and fabrics can be made from the elastic multi-component fibers described herein by any conventional method. These elastic yarns can be coated with a second yarn such as a hard yarn. Hard yarns include, inter alia, nylon, acrylic, cotton, polyester, and mixtures thereof. The coated yarn may comprise a single coating, a double coating, an air coating, a core spun yarn, and a twisted yarn. The elastic yarns of some embodiments may be included in a variety of structures, such as knitted fabrics (warp and weft), fabrics, and non-woven fabrics. Suitable for socks, stockings, shirts, underwear, swimwear, substrates. And non-woven sanitary structures. If yarn is needed The melting or sticking depends on the composition of the additive to improve the refinability, which can be achieved by exposure to heat and/or static pressure of up to 35 & (bar). Heat can be applied by steam or dry heat. Suitable for socks. The melting conditions may include: exposure to a temperature of from about 105 t to about 135 t for about 3 seconds to about 60 seconds when using steam heat; and exposure to 165 to about 195 ° C for about 3 seconds when dry heat is used; Up to about 60 seconds. Suitable melting conditions can vary depending on a number of factors, including, inter alia, selected additives to improve meltability, polymer chemistry, linear density of the yarn, and fabric structure (ie, knit, braid, etc.) For the machine, the fabric is exposed to a variety of curing conditions, including exposure to heat and/or pressure. Therefore, a separate heat setting/shaving process is not required, as the heat setting of the fabric will also result in an improvement in the person D. Melting of the yarn of j π additive or other additive. According to the general method ASTM D 273"2, the strength of the elastic fiber in the measurement example and the bomb H male. For each _ measurement, use three 2 inches (5 (four) gauge length wire,伸长 _3 嶋 elongation cycle. Make the sample cycle at 143877.doc 201035399 50HU per minute elongation rate ^ at the first cycle, measure the load force at 2嶋 elongation (Μ2〇〇)_ initial extension period The stress on the elastic fiber! is recorded as the gram-force for a given denier. The unloading force 1 (face) is the stress at the fifth elongation cycle, which is also the gram-force. The percent elongation at break and the linearity were measured at the sixth extended cycle. The percentage of deformation was also measured on the sample subjected to five 〇_3〇〇% elongation/relaxation cycles. The percentage of deformation was then calculated as follows: %S = l〇〇 (Lf.Lo) / L 〇 where Lo and Lf are the lengths of the filaments (yarns) which are kept straight under tension before and after the five elongation/loose cycles, respectively. For the measurement of the 疋 疋 疋 type (the simulation of the machine processing and shaping operation, a sample under the condition of straight tension-free, i 2 i, the length of the selected length of 忏T (usually (7)em) is stretched to Three times the original length 'lasts for about 2 minutes and then slacks. This is simulated by the conventional yarn package, the elastic fiber is stretched and coated. Then the elastic fiber test is so stretched and relaxed. The sample was placed in a boiling water bath for 30 minutes. This was exposed to a simulated dyeing operation of the water system. The sample was then removed from the bath, dried and stretched to twice the length of relaxation after bathing. When under this stretching condition'胄 The sample is exposed to i2it's steam atmosphere for 3 sec seconds: This steam treatment simulates the machine. After removing from the steam atmosphere, 'dry the sample' and measure its straight tension-free length bamboo. Then calculate the steam according to the following formula Styling (ss, %): %SS = 100(Yf-Y〇)/Y〇 The yarn fusibility is determined by the following method: a length of 15 samples is presented on 143877.doc -23- 201035399 on an adjustable frame. Having the top corner centered on the border and the same length The second filament is placed in, so that the two yarns intersect and intersect at a single point of contact. The fibers are relaxed to 5 cm, then exposed to the refining bath for one hour, rinsed, air dried, and subsequently exposed. In the dye bath for 30 minutes, rinsed, and air dried. Adjust the length of the fiber-bearing frame from 5 em to 3 〇em, and expose to U1C steam for 30 seconds' after cooling for 3 minutes, and relax. The wire is removed from the frame and transferred to the tensile tester 'clamping the head of each yarn, and the contact is placed between the clips. The force is [伸长()%/min elongation of the yarn and will break the contact point (g The force is recorded as the melt strength. The features and advantages of the present invention are more fully shown by the following examples, and the examples are provided as an illustration of the invention and should not be construed as limiting the invention in any way. The following Examples 1 to 3 were dry-spun into a fiber from a solution of N,N-dimercaptoacetamide (DMAc) (CAS code: 127_19_5 Torr) containing a high melting point polyamine phthalate elastomeric polymer. Provide sufficient thermal stability to the final fiber 'prepared as follows The polyamino phthalate polymer was used and used as a matrix for the core and sheath compositions. A polyurethane prepolymer having a blocking ratio of 27 Å was prepared by the following procedure: MDI ( CAS number [26447-40-5] l, i-arylene based bis[isocyanatobenzene] and 2 〇〇〇 number average molecular weight of 1丁1^〇 (€8 8号 is 25190-06 A mixture of -1 (oxy-1,4-butanediyl), α-hydro-ω-hydroxy) is heated to charge for 2 hours. Subsequently, 143877.doc •24· 201035399 polymer is added to DMAc. Dissolve to a concentration of about 39% solids. At 75 ° C, extend the prepolymer solution by adding sufficient ethylene glycol (CAS number 107-21-1) to increase the viscosity of the 40 ° C falling ball solution to 4000 poise . Once the solution reached the target viscosity, the polymerization was terminated by the addition of a monofunctional alcohol (1-butanol of CAS No. 71-36-3). Filaments are formed by metering a polymer solution comprising 35 to 40% polymer solids through a distribution plate and orifice of a desired configuration. The distribution plate is placed such that the concentric sheath-core configuration combines the polymer and is subsequently extruded through a common capillary. The extruded filaments are dried by introducing a hot inert gas of 320 to 440 ° C and at a gas: polymer mass ratio of at least 10:1, and at a rate of at least 400 meters per minute (preferably at least 600) m/min) is stretched and then rolled up at a speed of at least 500 meters per minute, preferably at least 750 m/min. The yarn formed from the elastic fibers thus has a fracture toughness of at least 1 cN/min, at least 400% elongation at break, and at least 0.2 cN/min. Example 1: 聚 The polycaprolactone-based linear polyurethane provided by Merquinsa Mercados Quimicos, SL (Pearlbond 122) was dissolved in a weight ratio of 30% to the prepared high melting PU polymer (described above) Blending, a 35% DMAc solution was formed and extruded as a sheath component. The core solution consists of a DMAc solution containing a high temperature PU polymer and is combined with a sheath solution in a ratio of 4:1 to form a 22 dtex twin filament yarn. The product was taken out at 700 m/min and wrapped on a package at 850 m/min after coating with polysulfate. The properties of the product containing fusibility, steam set efficiency, and tensile properties are given in Table 2 at 143877.doc -25-201035399. The differential scanning calorimetry trace (Figure 5) illustrates the low melt transition of the fusible additive at about 56. Example 2: A thermoplastic polyurethane elastomer (ester/ether) supplied by Bayer Material Science, USA (Desm〇pan 5377) was dissolved and prepared at a weight ratio of 6% by weight to a prepared high temperature PU polymer ( The above) was blended to form a 36% DMAc solution and extruded as a sheath component. The core solution consists of a high melting PU polymer stored in dmAc* and combined with a sheath solution in a ratio of 4: , to form a 22-point twin filament yarn. The product was pulled out at 7 〇〇 m/min and wrapped on a package at 850 m/min after coating with polyoxyxide oil. The properties of the product containing fusibility, steam setting efficiency, and tensile properties are given in Table 2. . Example 3 (Control): The prepared high temperature 1 > 11 polymer (described above) in a 39% DMAc solution was extruded as a sheath and core component, in a ratio of 4: i, without modification. Divided by the twin filament yarn. With 700 claws, the product was pulled out and coated on a package at 850 m/min after coating with an oil agent of polyoxymethylene. The product characteristics including bisexability, steam setting efficiency, and tensile properties were The results are as shown in Table 32. Example yarns (Examples 1 to 3) were coated on a commercially available Menegatto or ICBT coater with flat crepe/7 filament flat polyamide 66 yarns. The draw ratio is 2·8 χ and the wrap factor is 15 〇〇 tpm. The socks are knitted on a commercially available knitting machine such as the Lonati 400 circular hosiery machine. ° The coated yarn is knitted into each The three axial directions of a weave structure are 143877.doc •26- 201035399 (tdeot constructi〇n), which causes the elastic yarn at each contact point of the knitted structure to melt. If the fusible yarn is included in the alternation Appropriate melting can also be obtained in the path. After standard operation by hot pressing and assembly, the garment is placed in the steam chamber of the standard setting equipment at 110. 〇 and 130. (: 10 to 6 〇 Se is formed by The garment is placed on an open plate that will be produced during the typical stretching of the garment and tested to be suitable. Knife or scissors cause rupture provoking elastic yarns prepared k puncture. If the force caused by the elastic yarn due to the stretching of the plate
小於由彈性紗線炼融所產生之力量，則該洞之尺寸不會增 大。若彈性紗線之力量較大，則㈣融點將不會保持^ 整’且該針織結構將會散開（所謂的跑針❹㈣。以肉眼 觀察成衣之攸格性能，並顯示於矣 ^ , 肩不於表^針織襪（實例1)之黏 «形成及熔融品質的SEM分析顯示於 刀竹顯不於圖6，其中該雙長絲 組分22分德士紗線1〇具有熔融 且由尼龍包覆紗線12 的較小長絲包圍。 〇 表2-可熔性彈性纖維長絲性質Less than the force generated by the refining of the elastic yarn, the size of the hole does not increase. If the strength of the elastic yarn is large, then (4) the melting point will not remain constant and the knitting structure will spread out (the so-called running needle ❹ (4). The performance of the garment is observed with the naked eye and displayed in 矣^, shoulder not The SEM analysis of the adhesion «forming and melting quality of the table knit socks (Example 1) shows that the bamboo is not shown in Figure 6, wherein the double filament component 22 has a melt and is wrapped in nylon. The smaller filaments of the covered yarn 12 are surrounded. 〇 Table 2 - Fusible elastic fiber filament properties
穿刺後是否爬格 143877.doc ------- 2 3(對照） 383 ** ----- 420 1.5 1.6 0.31 0.25 0.30 0.31 一 28.7 27.1 — 0.4 0.5 66.8 57.0 —2.1 0.8 — 否 是 -27- 201035399 實例4-可熔性勒·· 將熱嫁性結晶熱塑性聚胺基甲酸酯黏著劑（獲自Whether to climb after puncture 143877.doc ------- 2 3 (control) 383 ** ----- 420 1.5 1.6 0.31 0.25 0.30 0.31 a 28.7 27.1 — 0.4 0.5 66.8 57.0 —2.1 0.8 — No Yes - 27- 201035399 Example 4 - Fusible Le·· Thermally Crystallized Thermoplastic Polyurethane Adhesive (obtained from
MerqUinsa Mercad〇s Qufmic〇s之pearib〇nd 122)與習知之嵌 #又聚胺基甲酸醋脲依5〇/5〇摻合製成於dmAc中之溶 液且作為鞘紡絲，與嵌段聚胺基甲酸酯脲習知彈性纖維 心一起製成44分德士/3長絲紗線。總鞘含量基於纖維重量 計為20%，而在加熱至8〇<t以上時製得可熔性紗線。 么優點為具有極佳㉟融特性結合優良拉伸/恢復性能之纖 、隹包3蒸》飞定型與熔融強度之物理測試結果列於表3 中。 、又 表3-含摻合鞘的嵌段聚胺基甲酸酯 脲纖維 %鞘（w/w) -~~~- 20% %黏著劑（w/w) —-------- 10% __ 伸長率％ 452 斷裂力（g) 39.8 M200 (g) ~~~--~—— 7.20 _ U200 (g) 0.93 %變形 —— 43 熔融強度（g) -- 10.2 ~---- 儘管已闌述目前據認為係本發明之較佳實施例，但熟 此項技術者當暸解在不脫離本發明精神下可對其進行= 與修改，且意欲包含所有屬於本發明真實範圍内的該 變與修改。 【圖式簡單說明】 143877.d〇( •28- 201035399 之 圖1A至ID顯示可在一些實施例中達成之纖維橫截面 實例。 圖2為一些實施例之噴絲頭橫截面之示意圖。 圖3為一些實施例之噴絲頭橫截面之示意圖。 圖4為一些實施例之噴絲頭橫截面之示意圖。 圖5為實例1纖維之示差掃描量熱結果的描述。 於-lOOt至350。(：間，以i〇t：/min進行掃描。 圖ό為一些實施例之熔融紗線的SEM顯微照片。 〇 【主要元件符號說明】 2 4 5 6 7 8 9MerqUinsa Mercad〇s Qufmic〇s's pearib〇nd 122) and the well-inlaid #also urethane acetic acid urea 5依/5〇 blended into a solution in dmAc and as a sheath spinning, with block polymerization The urethane urea is conventionally made into a 44 dtex/3 filament yarn together. The total sheath content was 20% based on the weight of the fiber, and a fusible yarn was obtained when heated to 8 Torr or more. The physical test results of the fiber type and the melt strength of the fiber with the excellent 35-melting characteristics combined with the excellent tensile/recovery properties are shown in Table 3. Table 3 - Blocked polyurethane polyurethane fiber sheath with sheath (w/w) -~~~- 20% % adhesive (w/w) --------- - 10% __ Elongation % 452 Breaking force (g) 39.8 M200 (g) ~~~--~~ 7.20 _ U200 (g) 0.93 % deformation - 43 Melt strength (g) -- 10.2 ~--- Having described the preferred embodiments of the present invention, it is to be understood that those skilled in the art will be able to carry out the modifications and modifications without departing from the spirit and scope of the invention. The change and modification. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A to ID of 129877.d〇 (28-201035399 shows an example of a fiber cross section which can be achieved in some embodiments. Fig. 2 is a schematic view showing a cross section of a spinneret of some embodiments. 3 is a schematic view of a cross section of a spinneret of some embodiments. Fig. 4 is a schematic view of a cross section of a spinneret of some embodiments. Fig. 5 is a depiction of the results of differential scanning calorimetry of the fibers of Example 1. From -100 to 350. (:, scanning with i〇t:/min. Figure ό is an SEM micrograph of the melt yarn of some examples. 〇 [Main component symbol description] 2 4 5 6 7 8 9
供應口 分佈板 供應口 螺帽 篩網 填片 喷絲頭 11 12 雙長絲組分2 2分德士紗線 熔融點 尼龍包覆紗線 143877.doc -29-Supply port Distribution plate Supply port Nut Screen Screen Filling Spinning head 11 12 Double filament component 2 2 points Dess yarn Melting point Nylon coated yarn 143877.doc -29-
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| TWI631243B (en) * | 2013-05-29 | 2018-08-01 | 英威達技術有限公司 | Fusible bicomponent spandex |
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| JP5676456B2 (en) * | 2009-03-11 | 2015-02-25 | インヴィスタ テクノロジーズ エスアエルエル | Fusion two-component spandex |
| EP2920343B1 (en) * | 2012-11-16 | 2017-01-11 | Basf Se | A bicomponent fiber, the preparation process and the use thereof, and the fabrics comprising the same |
| EP3237662B1 (en) * | 2014-12-24 | 2021-04-21 | INVISTA Textiles (U.K.) Limited | Easily settable stretch fabrics including low-melt fiber |
| CN113403709B (en) * | 2019-02-12 | 2023-05-16 | 华峰化学股份有限公司 | Composite spandex and preparation method thereof |
| BR112022017945A2 (en) * | 2020-03-11 | 2022-11-29 | The Lycra Company Uk Ltd | ELASTOMERIC FIBER WITH REDUCED ELASTANE SLIDING, ELASTIC COMPOSITE YARN, STRETCHABLE FABRIC AND ARTICLE OF MANUFACTURING |
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| JPH06146112A (en) * | 1992-04-28 | 1994-05-27 | Nisshinbo Ind Inc | Double-layer spandex yarn |
| JP3266222B2 (en) * | 1993-09-02 | 2002-03-18 | 東洋紡績株式会社 | Polyester coated elastic yarn |
| JP2001140127A (en) * | 1999-11-08 | 2001-05-22 | Asahi Kasei Corp | Polyurethane fiber and flexible fabric having dimensional stability |
| CN1555432B (en) * | 2001-07-17 | 2010-10-13 | 陶氏环球技术公司 | Elastic, heat and moisture resistant bicomponent and biconstituent fibers |
| JP2003119632A (en) * | 2001-10-10 | 2003-04-23 | Du Pont Toray Co Ltd | Covered yarn and method for producing the same |
| JP4345084B2 (en) * | 2004-05-20 | 2009-10-14 | オペロンテックス株式会社 | Manufacturing method of stretchable fiber structure with excellent anti-slip-in property |
| JP2006124841A (en) * | 2004-10-26 | 2006-05-18 | Fujibo Holdings Inc | Polyurethane polyurea elastic yarn for thermobonding |
| JP4860261B2 (en) * | 2005-12-27 | 2012-01-25 | 旭化成せんい株式会社 | Polyurethane elastic fiber |
| US20090269582A1 (en) * | 2006-04-21 | 2009-10-29 | Aichi Prefecture | Process for producing core/sheath conjugate elastomer fiber |
| US8920922B2 (en) * | 2006-07-04 | 2014-12-30 | Asahi Kasei Fibers Corporation | Polyurethane urea elastic fiber |
| JP4867907B2 (en) * | 2007-12-12 | 2012-02-01 | 東レ・オペロンテックス株式会社 | Polyurethane yarn and method for producing the same |
| JP5676456B2 (en) * | 2009-03-11 | 2015-02-25 | インヴィスタ テクノロジーズ エスアエルエル | Fusion two-component spandex |
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| TWI631243B (en) * | 2013-05-29 | 2018-08-01 | 英威達技術有限公司 | Fusible bicomponent spandex |
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| JP5676456B2 (en) | 2015-02-25 |
| JP6151233B2 (en) | 2017-06-21 |
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| JP2012520397A (en) | 2012-09-06 |
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| WO2010104531A1 (en) | 2010-09-16 |
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