TWI646231B - Bicomponent fiber, preparation method and use thereof, and fabric containing the same - Google Patents
Bicomponent fiber, preparation method and use thereof, and fabric containing the same Download PDFInfo
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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
- 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
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Abstract
本發明係關於一種雙成份纖維，包含i)第一熱塑性聚胺基甲酸酯成份；及ii)第二熱塑性聚胺基甲酸酯成份，其與成份i)可能相同或不同，其中成份i)及ii)中之至少一者藉由交聯劑發生交聯從而形成聚合物i)及聚合物ii)中之至少一種聚合物，其中聚合物i)之熔點比聚合物ii)之熔點高至少10℃，且纖維尺寸在8丹尼爾(denier)與300丹尼爾之間，更佳在10丹尼爾與100丹尼爾之間。本發明之雙成份纖維具有優良的熱黏合性質及恢復率，且可具有可染性及耐化學性。 The present invention relates to a bicomponent fiber comprising i) a first thermoplastic polyurethane component; and ii) a second thermoplastic polyurethane component, which may be the same as or different from component i), in which component i ) And at least one of ii) is cross-linked by a cross-linking agent to form at least one polymer of polymer i) and polymer ii), wherein the melting point of polymer i) is higher than the melting point of polymer ii) At least 10°C, and the fiber size is between 8 denier and 300 denier, more preferably between 10 denier and 100 denier. The bicomponent fiber of the present invention has excellent thermal bonding properties and recovery rate, and can have dyeability and chemical resistance.
Description
本發明係關於一種雙成份纖維、其製備方法與用途，以及包含其之織物。 The invention relates to a bicomponent fiber, its preparation method and use, and the fabric containing it.
顯示各種特性之多成份纖維經歷了大力開發並獲得了廣泛應用。其重要用途在於針織或編織織物。與非編織織物相反，針織或編織織物具有相對較高的彈性及恢復特性，使得最終產品耐用且容易順應使用或穿戴此等產品之個體。 Multi-component fibers showing various characteristics have undergone vigorous development and have been widely used. Its important use is in knitted or woven fabrics. In contrast to non-woven fabrics, knitted or woven fabrics have relatively high elasticity and recovery characteristics, making the final product durable and easy to adapt to individuals who use or wear these products.
當前，多成份或雙成份纖維一般藉由溶液紡絲方法製得。然而，此方法導致最終纖維中包含對纖維之機械特性或耐久性或人類健康有負面影響的雜質，諸如溶劑、單體及寡聚物。舉例而言，溶液紡絲方法中通常使用DMF(二甲基甲醯胺)作為溶劑，但其包含於最終纖維中會引起健康上的擔憂。熔融紡絲方法通常用於製備聚酯、耐綸及聚烯烴纖維，其可用於生產服裝，但很少用於製備由熱塑性聚胺基甲酸酯製成的纖維。隨著對多樣化針織或編織產品之需求增大，不斷地需要開發用於製造針織或編織物品(諸如女士內衣及褲襪)的高彈性纖維，其中溶劑含量為零且單體及寡聚物之含量較低。 Currently, multi-component or bi-component fibers are generally produced by solution spinning. However, this method results in the final fiber containing impurities such as solvents, monomers, and oligomers that negatively affect the fiber's mechanical properties or durability or human health. For example, the solution spinning method generally uses DMF (dimethylformamide) as a solvent, but its inclusion in the final fiber may cause health concerns. The melt spinning method is generally used to prepare polyester, nylon and polyolefin fibers, which can be used to produce clothing, but is rarely used to prepare fibers made of thermoplastic polyurethane. As the demand for diversified knitted or knitted products increases, there is an ongoing need to develop highly elastic fibers for the manufacture of knitted or knitted items (such as women's underwear and pantyhose), where the solvent content is zero and monomers and oligomers The content is lower.
US2011/0275262揭示一種雙成份斯潘德克斯彈性纖維(spandex)，其橫截面之至少一個區域中包含聚胺基甲酸酯-尿素組合物。其 應用於諸如服裝、泳裝及襪類之產品。其中所揭示之雙成份斯潘德克斯彈性纖維藉由溶液紡絲技術製備。 US2011/0275262 discloses a two-component spandex with a polyurethane-urea composition in at least one region of its cross-section. its Used in products such as clothing, swimwear and socks. The bicomponent spandex elastic fibers disclosed therein are prepared by solution spinning technology.
US 6,773,810 B2揭示具有核心/外鞘構造之彈性雙成份纖維，特別是其中形成外鞘之聚合物之熔點比形成核心之聚合物低的纖維。其亦揭示核心包含熱塑性彈性體，較佳為熱塑性聚胺基甲酸酯(TPU)，且外鞘包含均勻分枝的聚烯烴。 US 6,773,810 B2 discloses elastic bicomponent fibers with a core/sheath configuration, especially fibers in which the sheath-forming polymer has a lower melting point than the core-forming polymer. It also reveals that the core contains a thermoplastic elastomer, preferably a thermoplastic polyurethane (TPU), and the outer sheath contains a uniformly branched polyolefin.
US 7,740,777 B2揭示一種用於生產包括多種聚合物成份的聚合物纖維及非編織織物的方法及裝置。 US 7,740,777 B2 discloses a method and apparatus for producing polymer fibers and non-woven fabrics including multiple polymer components.
EP 1,944,396 Al揭示一種藉由熔融紡絲方法所得之用於可拉伸衣物的彈性核心-外鞘結合物纖維，其中用於核心與外鞘之材料均可為TPU。然而，其未揭示使用交聯劑來製備纖維。 EP 1,944,396 Al discloses an elastic core-sheath conjugate fiber for stretchable clothing obtained by a melt spinning method, in which both the core and the sheath material can be TPU. However, it does not disclose the use of cross-linking agents to prepare fibers.
因此，本發明之一個目的為提供一種包含熱塑性聚胺基甲酸酯(TPU)成份且藉由熱塑性胺基甲酸酯預聚物至少部分交聯的雙成份纖維，該纖維具有優良的高恢復率、熱黏合性質、可染性及耐化學性。 Therefore, an object of the present invention is to provide a bicomponent fiber comprising a thermoplastic polyurethane (TPU) component and at least partially crosslinked by a thermoplastic polyurethane prepolymer, the fiber having excellent high recovery Rate, thermal bonding properties, dyeability and chemical resistance.
特定而言，根據本發明之雙成份纖維包含i)第一熱塑性聚胺基甲酸酯成份；及ii)第二熱塑性聚胺基甲酸酯成份，其與成份i)可能相同或不同，其中成份i)及ii)中之至少一者藉由交聯劑發生交聯從而形成聚合物i)及聚合物ii)中之至少一種聚合物，其中聚合物i)的熔點比聚合物ii)之熔點高至少10℃，且纖維尺寸介於8丹尼爾與300丹尼爾之間，更佳介於10丹尼爾與100丹尼爾之間。 Specifically, the bicomponent fiber according to the present invention comprises i) a first thermoplastic polyurethane component; and ii) a second thermoplastic polyurethane component, which may be the same as or different from component i), where At least one of components i) and ii) is cross-linked by a cross-linking agent to form at least one polymer of polymer i) and polymer ii), wherein the melting point of polymer i) is higher than that of polymer ii) The melting point is at least 10°C higher, and the fiber size is between 8 denier and 300 denier, more preferably between 10 denier and 100 denier.
在一個特定具體實例中，成份i)與成份ii)相同。 In a specific embodiment, component i) is the same as component ii).
根據本發明之第二態樣，雙成份纖維藉由熔融紡絲方法製 備，其中將交聯劑分別添加至TPU成份i)之熔體與TPU成份ii)之熔體之任一者或兩者中。 According to the second aspect of the present invention, the bicomponent fiber is produced by the melt spinning method Preparation, wherein the crosslinking agent is added to either or both of the melt of the TPU component i) and the melt of the TPU component ii).
根據本發明之另一個態樣，提供使用本發明之雙成份纖維製得的具有優良彈性伸展性的針織或編織織物，從而為具有高支撐性之時髦、可拉伸衣物(諸如女士內衣、長襪及褲襪)提供材料。 According to another aspect of the present invention, a knitted or woven fabric having excellent elasticity and stretchability obtained by using the bicomponent fiber of the present invention is provided, so as to be fashionable, stretchable clothing (such as women's underwear, long Socks and tights) provide materials.
本發明之另一個態樣係關於本發明之纖維用於生產針織或編織織物的用途。 Another aspect of the invention relates to the use of the fibers of the invention for producing knitted or woven fabrics.
圖1為顯示本發明方法之一個具體實例的示意圖。 FIG. 1 is a schematic diagram showing a specific example of the method of the present invention.
圖2a為根據本發明之一個具體實例之核心-外鞘雙成份纖維的示意圖，其中聚合物i)用於核心且聚合物ii)用於外鞘。 2a is a schematic diagram of a core-sheath bicomponent fiber according to a specific example of the present invention, where polymer i) is used for the core and polymer ii) is used for the outer sheath.
圖2b為根據本發明之一個具體實例之並排式雙成份纖維的示意圖。 FIG. 2b is a schematic diagram of side-by-side bicomponent fibers according to a specific example of the present invention.
圖3為根據本發明之一個具體實例之核心-外鞘(50%/50%)雙成份纖維的顯微照片。纖維尺寸為30丹尼爾。 3 is a photomicrograph of a core-sheath (50%/50%) bicomponent fiber according to a specific example of the present invention. The fiber size is 30 denier.
在第一態樣中，本發明提供一種雙成份纖維，其包含i)第一熱塑性聚胺基甲酸酯成份；及ii)第二熱塑性聚胺基甲酸酯成份，其與成份i)可能相同或不同，其中成份i)及ii)中之至少一者藉由交聯劑發生交聯從而形成聚合物i)及聚合物ii)中之至少一種聚合物，其中聚合物i)的熔點比聚合物ii)之熔點高至少10℃，且纖維尺寸介於8丹尼爾與300丹尼爾之間，更佳介於10丹尼爾與100丹尼爾之間。 In the first aspect, the present invention provides a bicomponent fiber comprising i) a first thermoplastic polyurethane component; and ii) a second thermoplastic polyurethane component, which is compatible with component i) Same or different, wherein at least one of components i) and ii) is cross-linked by a cross-linking agent to form at least one polymer of polymer i) and polymer ii), wherein the melting point ratio of polymer i) The melting point of polymer ii) is at least 10° C., and the fiber size is between 8 denier and 300 denier, more preferably between 10 denier and 100 denier.
如本文所用，「雙成份纖維」意謂包含至少兩種成份(亦即，具有至少兩種不同聚合區域)的纖維。為了簡化起見，本發明之雙成份纖維可描述為核心/外鞘結構；然而，纖維亦可具有任一種組態之結構，諸如對稱(同心)核心/外鞘、不對稱(偏心)核心/外鞘、並排式、扇形區(pie section)、娥眉月及其類似組態。較佳地，本發明之雙成份纖維由兩種聚合物組成，該兩種聚合物各自衍生自相同或不同TPU成份且已藉由相同或不同交聯劑至少部分交聯，限制條件為該等聚合物具有至少10℃之熔融溫度差。熔融溫度差較佳為至少15℃。 As used herein, "bicomponent fiber" means a fiber containing at least two components (ie, having at least two different polymerized regions). For the sake of simplicity, the bicomponent fiber of the present invention can be described as a core/sheath structure; however, the fiber can also have any configuration, such as a symmetric (concentric) core/sheath, an asymmetric (eccentric) core/ Sheath, side-by-side, pie section, Emeiyue and similar configurations. Preferably, the bicomponent fiber of the present invention is composed of two polymers, each of which is derived from the same or different TPU components and has been at least partially crosslinked by the same or different crosslinking agent, the limiting conditions are these The polymer has a difference in melting temperature of at least 10°C. The difference in melting temperature is preferably at least 15°C.
TPU成份i)與TPU成份ii)可能相同或不同，其由(a)異氰酸酯與(b)可與異氰酸酯反應且具有400g/mol至8000g/mol之數目平均分子量之化合物及(c)具有50g/mol至500g/mol之數目平均分子量之鏈伸長劑，視情況在(d)催化劑及/或(e)慣用助劑及/或(f)添加劑存在下反應而製備。 TPU component i) and TPU component ii) may be the same or different. It consists of (a) isocyanate and (b) a compound that can react with isocyanate and has a number average molecular weight of 400g/mol to 8000g/mol and (c) has 50g/ The number average molecular weight chain extender from mol to 500 g/mol is prepared by reacting in the presence of (d) catalyst and/or (e) conventional auxiliary agent and/or (f) additive.
可使用之有機異氰酸酯(a)為通常已知之脂族、環脂族、芳脂族及/或芳族異氰酸酯，較佳為二異氰酸酯，例如三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、五亞甲基二異氰酸酯、六亞甲基二異氰酸酯、七亞甲基二異氰酸酯及/或八亞甲基二異氰酸酯、2-甲基五亞甲基1,5-二異氰酸酯、2-乙基伸丁基1,4-二異氰酸酯、五亞甲基1,5-二異氰酸酯、伸丁基1,4-二異氰酸酯、1-異氰酸酯基-3,3,5-三甲基-5-異氰酸酯基甲基環己烷(異佛爾酮二異氰酸酯，IPDI)、1,6-六亞甲基二異氰酸酯(HDI)、2,4-四亞甲基二甲苯基二異氰酸酯(TMXDI)、1,4-雙(異氰酸酯基甲基)環己烷(HXDI)及/或1,3-雙(異氰酸酯基甲基)環己烷(HXDI)、環己烷1,4-二異氰酸酯、1-甲基環己烷2,4-二異氰酸酯及/或1-甲基環己烷2,6-二異氰酸酯，及/或二環己基甲烷4,4'-二異氰酸酯、二環己基甲烷2,4'-二異氰酸酯及二環己基甲烷2,2'-二異氰酸酯、二苯基甲烷2,2'-二異氰酸酯、二苯基甲烷2,4'-二異氰酸酯及/或二 苯基甲烷4,4'-二異氰酸酯(MDI)、伸萘基1,5-二異氰酸酯(NDI)、伸甲苯基2,4-二異氰酸酯及/或伸甲苯基2,6-二異氰酸酯(TDI)、3,3'-二甲基二苯基二異氰酸酯、1,2-二苯基乙烷二異氰酸酯及/或伸苯基二異氰酸酯，或其混合物。 Organic isocyanates (a) that can be used are generally known aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates, preferably diisocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, penta Methylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylidene butyl 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butyl 1,4-diisocyanate, 1-isocyanate group-3,3,5-trimethyl-5-isocyanate group methyl ring Hexane (isophorone diisocyanate, IPDI), 1,6-hexamethylene diisocyanate (HDI), 2,4-tetramethylene xylyl diisocyanate (TMXDI), 1,4-bis( Isocyanatomethyl) cyclohexane (HXDI) and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2 ,4-diisocyanate and/or 1-methylcyclohexane 2,6-diisocyanate, and/or dicyclohexylmethane 4,4'-diisocyanate, dicyclohexylmethane 2,4'-diisocyanate and diisocyanate Cyclohexyl methane 2,2'-diisocyanate, diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate and/or di Phenylmethane 4,4'-diisocyanate (MDI), naphthyl 1,5-diisocyanate (NDI), tolyl 2,4-diisocyanate and/or tolyl 2,6-diisocyanate (TDI ), 3,3'-dimethyldiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylenediisocyanate, or a mixture thereof.
在一個特別較佳具體實例中，有機異氰酸酯為包含至少90重量%、更佳至少95重量%、尤其較佳至少99重量%之二苯基甲烷二異氰酸酯(MDI)的異氰酸酯。 In a particularly preferred embodiment, the organic isocyanate is an isocyanate containing at least 90% by weight, more preferably at least 95% by weight, and particularly preferably at least 99% by weight of diphenylmethane diisocyanate (MDI).
通常已知之可與異氰酸酯反應的化合物可用作多羥基化合物(b)，例如聚酯醇、聚醚醇及/或聚碳酸酯二醇，其一般亦彙總於「多元醇(bl)」項下，其具有400至8000g/mol、較佳500g/mol至6000g/mol、尤其1000g/mol至4000g/mol之數目平均分子量，且較佳具有1.8至2.3、較佳1.9至2.2、尤其2之平均官能度。亦可使用多元醇(bl)混合物。 Generally known isocyanate-reactive compounds can be used as the polyhydroxy compound (b), such as polyester alcohol, polyether alcohol, and/or polycarbonate diol, which are generally summarized under the "polyol (bl)" It has a number average molecular weight of 400 to 8000 g/mol, preferably 500 g/mol to 6000 g/mol, especially 1000 g/mol to 4000 g/mol, and preferably has an average of 1.8 to 2.3, preferably 1.9 to 2.2, especially 2 Functionality. Mixtures of polyols (bl) can also be used.
多元醇(bl)在此項技術中通常已知，且已描述於「Polyurethane Handbook，第2版.Gunter Oertel」,Carl Hanser Verlag,Munich 1994，第3.1章中。 Polyols (bl) are generally known in the art and have been described in "Polyurethane Handbook, 2nd Edition. Gunter Oertel", Carl Hanser Verlag, Munich 1994, Chapter 3.1.
可使用的鏈伸長劑(c)為通常已知的脂族、芳脂族、芳族及/或環脂族化合物，其具有50至500之分子量，較佳為雙官能化合物，例如伸烷基中具有2至10個碳原子之二胺及/或烷二醇，尤其1,4-丁二醇、1,6-己二醇，及/或具有3至8個碳原子之二伸烷基、三伸烷基、四伸烷基、五伸烷基、六伸烷基、七伸烷基、八伸烷基、九伸烷基及/或十伸烷基二醇，較佳為相應的寡丙二醇及/或聚丙二醇，亦可使用鏈伸長劑混合物。特別較佳之鏈伸長劑為1,4-丁二醇。 Useful chain extenders (c) are generally known aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds with a molecular weight of 50 to 500, preferably bifunctional compounds such as alkylene Diamines and/or alkanediols having 2 to 10 carbon atoms, especially 1,4-butanediol, 1,6-hexanediol, and/or dialkylene groups having 3 to 8 carbon atoms , Tri-alkylene, tetra-alkylene, penta-alkylene, hexa-alkylene, hepta-alkylene, octa-alkylene, nona-alkylene and/or deca-alkylene glycol, preferably corresponding Oligopropylene glycol and/or polypropylene glycol can also be used as a chain extender mixture. A particularly preferred chain extender is 1,4-butanediol.
特別適合於使二異氰酸酯(a)之NCO基團與成份(b)及(c)之羥基及/或胺基之間的反應加速的催化劑(d)為根據先前技術已知的慣用三級胺，諸如三乙胺、二甲基環己胺、N-甲基-嗎啉、N,N'-二甲基哌嗪、 2-(二甲基胺基乙氧基)乙醇、二氮雜雙環-(2,2,2)辛烷及其類似物；及金屬化合物，諸如鈦酸酯、鐵化合物(例如乙醯丙酮酸鐵(III))、錫化合物(例如二乙酸錫、二辛酸錫、二月桂酸錫或脂肪族羧酸之二烷基錫鹽，諸如二乙酸二丁基錫、二月桂酸二丁基錫或其類似物)。以100重量份之多羥基化合物(b)計，催化劑用量一般為0.0001至0.1重量份。 The catalyst particularly suitable for accelerating the reaction between the NCO group of the diisocyanate (a) and the hydroxyl and/or amine groups of the components (b) and (c) (d) is a conventional tertiary amine known according to the prior art , Such as triethylamine, dimethylcyclohexylamine, N-methyl-morpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo-(2,2,2)octane and its analogues; and metal compounds such as titanate, iron compounds (eg acetopyruvate) Iron (III)), tin compounds (such as tin diacetate, tin dioctoate, tin dilaurate or dialkyl tin salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate or the like) . The amount of the catalyst is generally 0.0001 to 0.1 part by weight based on 100 parts by weight of the polyhydroxy compound (b).
除催化劑(d)之外，亦可向成份(a)至(c)中添加慣用助劑(e)及/或添加劑(f)，包括表面活性物質、無機及/或有機填料、增強劑、增塑劑、耐火劑、成核劑、氧化穩定劑、潤滑劑及脫模劑、染料及色素、適當時除根據本發明之穩定劑混合物之外之另外的穩定劑例如水解、光或熱穩定劑或防止褪色之穩定劑。在一個較佳具體實例中，成份(e)亦包括水解穩定劑，諸如聚合及低分子量碳化二亞胺。成份(f)可包括其他熱塑性材料，諸如聚碳酸酯(PC)、聚氯乙烯(PVC)、聚甲基丙烯酸甲酯(PMMA)、聚醯胺(PA)、聚對苯二甲酸伸丁酯(PBT)、聚苯乙烯(PS)、熱塑性聚酯彈性體(TPEE)等。 In addition to the catalyst (d), conventional additives (e) and/or additives (f), including surface active substances, inorganic and/or organic fillers, reinforcing agents, can be added to components (a) to (c) Plasticizers, refractory agents, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments, and other stabilizers other than the stabilizer mixture according to the present invention as appropriate, such as hydrolysis, light or heat stability Agent or stabilizer to prevent discoloration. In a preferred embodiment, component (e) also includes hydrolysis stabilizers, such as polymerization and low molecular weight carbodiimides. Component (f) may include other thermoplastic materials, such as polycarbonate (PC), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyamide (PA), polybutylene terephthalate (PBT), polystyrene (PS), thermoplastic polyester elastomer (TPEE), etc.
除該等成份(a)、(b)及(c)及適當時(d)、(e)及(f)之外，亦可使用一般具有31至499之分子量的鏈長調節劑。此等鏈長調節劑為僅具有一個可與異氰酸酯反應之官能基的化合物，諸如單官能醇、單官能胺及/或單官能多元醇。藉助於此等鏈長調節劑，可以控制方式建立流動行為，特別是在TPU情況下。以100重量份之組分b)計，鏈長調節劑用量一般可為0至5重量份，較佳為0.1至1重量份，且根據定義包括於成份c)下。 In addition to these components (a), (b) and (c) and, where appropriate, (d), (e) and (f), chain length regulators generally having a molecular weight of 31 to 499 can also be used. These chain length regulators are compounds having only one functional group reactive with isocyanate, such as monofunctional alcohols, monofunctional amines, and/or monofunctional polyols. With the help of these chain length regulators, flow behavior can be established in a controlled manner, especially in the case of TPU. Based on 100 parts by weight of component b), the amount of chain length regulator can be generally 0 to 5 parts by weight, preferably 0.1 to 1 part by weight, and is included under component c) according to the definition.
除非另有定義，否則本文提及之所有分子量以g/mol之度量單位呈現。 Unless otherwise defined, all molecular weights mentioned herein are presented in units of g/mol.
或者，本發明所用之TPU之製備方法可見於EP1078944B1中。根據本發明之一個具體實例，所用TPU可具有20,000至1,000,000、較 佳40,000至500,000且更佳50,000至300,000之重量平均分子量。本發明中可使用一些商業化產品作為TPU成份，諸如BASF之商標為Elastollan®之TPU。最佳使用BASF之Elastollan® 2200、1100或600系列產品。 Alternatively, the preparation method of the TPU used in the present invention can be found in EP1078944B1. According to a specific example of the present invention, the TPU used may have 20,000 to 1,000,000 Preferably the weight average molecular weight is 40,000 to 500,000 and more preferably 50,000 to 300,000. In the present invention, some commercial products can be used as TPU components, such as BASF under the trademark Elastollan® TPU. It is best to use BASF's Elastollan® 2200, 1100 or 600 series products.
本發明所用之TPU較佳彼此獨立地具有根據DIN 53505所量測如下之蕭氏A硬度(Shore A hardness)：65蕭氏A至98蕭氏A，更佳為70蕭氏A至95蕭氏A，甚至更佳為75蕭氏A至90蕭氏A，對於兩種TPU成份而言，其可能不同或相同。若硬度太低，則纖維強度極低；另一方面，若硬度太高，則纖維彈性極低。 The TPU used in the present invention preferably independently have Shore A hardness measured according to DIN 53505 as follows: 65 Shore A to 98 Shore A, more preferably 70 Shore A to 95 Shore A, or even more preferably 75 Shore A to 90 Shore A, may be different or the same for the two TPU ingredients. If the hardness is too low, the fiber strength is extremely low; on the other hand, if the hardness is too high, the fiber elasticity is extremely low.
根據本發明，將交聯劑添加至至少一種TPU中以改良雙成份纖維之機械性質。在本發明之一個具體實例中，交聯劑僅添加至TPU成份i)中，此可形成聚合物i)用於提供雙成份纖維之高恢復率。在本發明之另一個具體實例中，一或多種交聯劑添加至TPU成份i)與ii)中，分別產生聚合物i)及聚合物ii)。 According to the present invention, a crosslinking agent is added to at least one TPU to improve the mechanical properties of bicomponent fibers. In a specific embodiment of the present invention, the crosslinking agent is only added to the TPU component i), which can form the polymer i) to provide a high recovery rate of the bicomponent fiber. In another embodiment of the present invention, one or more cross-linking agents are added to TPU components i) and ii) to produce polymer i) and polymer ii), respectively.
在核心-外鞘型雙成份纖維中，具有較高熔點之聚合物i)用於核心且具有較低熔點之聚合物ii)用於外鞘，諸如圖2(a)中所示。對於並排型雙成份纖維而言，諸如圖2(b)中所示，具有較高熔點之聚合物i)可使纖維具有捲曲性質且具有較低熔點之聚合物ii)可使纖維具有熱黏合性質。 In the core-sheath type bicomponent fiber, the polymer having a higher melting point i) is used for the core and the polymer having a lower melting point ii) is used for the outer sheath, such as shown in FIG. 2(a). For side-by-side bicomponent fibers, such as shown in Figure 2(b), polymers with higher melting points i) polymers with crimping properties and polymers with lower melting points ii) fibers with thermal bonding nature.
在本發明纖維之製備方法中，如下文定義之交聯劑添加至熔融成份i)與ii)之任一者或兩者中。添加時，交聯劑添加量以用於聚合物ii)之TPU重量計，為約0%至約15%，較佳為1%至10%，更佳為2%至8%，且以用於聚合物i)之TPU重量計，為約5%至25%，較佳為8%至20%，且更佳為10%至15%。 In the preparation method of the fiber of the present invention, the crosslinking agent as defined below is added to either or both of the melting components i) and ii). When added, the amount of the crosslinking agent added is about 0% to about 15%, preferably 1% to 10%, more preferably 2% to 8%, based on the weight of the TPU used in the polymer ii), and is used The weight of TPU of polymer i) is about 5% to 25%, preferably 8% to 20%, and more preferably 10% to 15%.
本發明中所用之交聯劑為NCO封端預聚物，其官能度為1.5至3，較佳為1.5至2.5，且更佳為1.6至2.1。在本發明之一個具體實例中，所用交聯劑為NCO含量為3重量%至20重量%，較佳為4重量%至10重量 %且更佳為5重量%至8重量%的預聚物。 The crosslinking agent used in the present invention is an NCO-terminated prepolymer, and its functionality is 1.5 to 3, preferably 1.5 to 2.5, and more preferably 1.6 to 2.1. In a specific embodiment of the present invention, the crosslinking agent used has an NCO content of 3% to 20% by weight, preferably 4% to 10% by weight % And more preferably 5% to 8% by weight of the prepolymer.
交聯劑可由異氰酸酯與可與異氰酸酯反應之化合物反應來製備，該等化合物之數目平均分子量為200g/mol至10000g/mol，較佳為250g/mol至8000g/mol，且更佳為500g/mol至6000g/mol。 The crosslinking agent can be prepared by reacting an isocyanate with a compound that can react with the isocyanate. The number average molecular weight of these compounds is 200g/mol to 10000g/mol, preferably 250g/mol to 8000g/mol, and more preferably 500g/mol To 6000g/mol.
在本發明之一些具體實例中，交聯劑添加至TPU成份之熔體中。在一些其他具體實例中，交聯劑添加至TPU成份中，隨後熔融。添加預聚物之時間無限制，且其可由熟習此項技術者根據實際方法確定。交聯劑可呈固體或液體狀態。 In some embodiments of the present invention, the crosslinking agent is added to the melt of the TPU component. In some other specific examples, the crosslinking agent is added to the TPU component and then melted. The time for adding the prepolymer is unlimited, and it can be determined by those skilled in the art according to actual methods. The cross-linking agent may be in a solid or liquid state.
適當交聯劑以及其製造及加工描述於例如EP2139934A1中。交聯劑可基於脂族及/或芳族異氰酸酯，較佳基於芳族異氰酸酯。本發明所用交聯劑較佳可為商業化產品，諸如BASF之商標為Elastollan®之預聚物。最佳可使用BASF之PLP9302或CR-1型產品。 Suitable cross-linking agents and their manufacture and processing are described in, for example, EP 2139934A1. The crosslinking agent may be based on aliphatic and/or aromatic isocyanates, preferably based on aromatic isocyanates. The crosslinking agent used in the present invention is preferably a commercial product, such as a prepolymer of BASF under the trademark Elastollan®. It is best to use BASF's PLP9302 or CR-1 products.
在本發明之一個具體實例中，聚合物i)之熔點比聚合物ii)高至少10℃，較佳至少15℃，更佳至少20℃。較佳地，在本發明之雙成份纖維中，聚合物i)之熔點比聚合物ii)高至多80℃，更佳至多60℃且甚至更佳至多40℃。 In a specific embodiment of the present invention, the melting point of polymer i) is at least 10°C higher than that of polymer ii), preferably at least 15°C, more preferably at least 20°C. Preferably, in the bicomponent fiber of the present invention, the melting point of polymer i) is higher than polymer ii) by at most 80°C, more preferably at most 60°C and even more preferably at most 40°C.
在雙成份纖維中，以雙成份纖維之總重量計，聚合物ii)(例如用於外鞘)之存在量為5重量%至80重量%，較佳為8重量%至50重量%，更佳為10重量%至40重量%。 In the bicomponent fiber, based on the total weight of the bicomponent fiber, the polymer ii) (for example, used in the outer sheath) is present in an amount of 5% to 80% by weight, preferably 8% to 50% by weight, more It is preferably 10% by weight to 40% by weight.
雙成份纖維可具有外鞘-核心型(同心或偏心)或並排型橫截面。較佳為外鞘-核心型(同心或偏心)結構。較佳地，在外鞘/核心結構中，纖維含有用於核心之聚合物i)及用於外鞘之聚合物ii)，其中聚合物i)具有較高熔點，諸如超過170℃，且聚合物ii)可具有較低熔點，諸如低於170℃，更佳低於160℃且甚至更佳低於150℃。另一方面，聚合物i)一般具有比聚合物ii)高之彈性，從而使最終纖維之超過80%具有300%恢復率。 根據DIN 53835測試300%恢復率。在此情況下，纖維同時具有良好彈性及熱黏合性質，此特別適合於生產女士內衣、褲襪等。 Bicomponent fibers can have a sheath-core type (concentric or eccentric) or side-by-side cross-section. It is preferably a sheath-core type (concentric or eccentric) structure. Preferably, in the outer sheath/core structure, the fiber contains a polymer i) for the core and a polymer ii) for the outer sheath, wherein the polymer i) has a higher melting point, such as exceeding 170°C, and the polymer ii) may have a lower melting point, such as below 170°C, more preferably below 160°C and even more preferably below 150°C. On the other hand, polymer i) generally has a higher elasticity than polymer ii), so that more than 80% of the final fiber has a recovery rate of 300%. Test 300% recovery rate according to DIN 53835. In this case, the fiber has good elasticity and thermal bonding properties, which is particularly suitable for the production of women's underwear, pantyhose and so on.
在其他具體實例中，纖維可另外於兩種成份之一或兩者中包括添加劑。舉例而言，在核心-外鞘型纖維中，外鞘包括可改良纖維之耐化學性或可染性之添加劑。 In other specific examples, the fiber may additionally include additives in one or both of the two components. For example, in core-sheath fibers, the outer sheath includes additives that can improve the chemical resistance or dyeability of the fiber.
驚人的是，已發現由於纖維中之兩種成份均為TPU，因此與由不同類型聚合物製成之習知雙成份纖維相比，根據本發明之兩種聚合物之相容性可得以改良。因此，即使根據DIN 53835多次反覆拉伸之後，根據本發明之雙成份纖維仍具有出色的恢復率，例如超過75%、更佳超過80%且甚至更佳超過88%具有300%恢復率。 Surprisingly, it has been found that since both components in the fiber are TPU, the compatibility of the two polymers according to the invention can be improved compared to conventional bicomponent fibers made from different types of polymers . Therefore, even after repeated drawing repeatedly according to DIN 53835, the bicomponent fiber according to the present invention still has an excellent recovery rate, such as more than 75%, more preferably more than 80%, and even more preferably more than 88% having a 300% recovery rate.
在本發明之第二態樣中，雙成份纖維由包括以下步驟之方法製成：(1)使成份i)及ii)在不同擠壓機中、在160至230℃溫度下熔融，(2)在熔融製程(1)中，將交聯劑添加至TPU之任一者或兩者中，(3)使用具有兩個或兩個以上噴嘴的紡絲頭將成份i)及ii)之熔體擠出，熔體在160至230℃下加熱以獲得雙成份纖維，(4)使纖維通過輥以100m/min至1000m/min之紡絲速率捲繞。 In the second aspect of the present invention, the bicomponent fiber is made by a method including the following steps: (1) The components i) and ii) are melted at 160 to 230°C in different extruders, (2 ) In the melting process (1), the crosslinking agent is added to either or both of the TPU, (3) using a spinning head with two or more nozzles to melt the components i) and ii) The body is extruded, and the melt is heated at 160 to 230°C to obtain bicomponent fibers. (4) The fibers are wound through a roll at a spinning rate of 100 m/min to 1000 m/min.
熟習此項技術者會瞭解，具有兩個或兩個以上噴嘴之紡絲頭具有使得所產生雙成份纖維具有核心/外鞘結構或具有任一組態(諸如對稱(同心)核心/外鞘、不對稱(偏心)核心/外鞘、並排式、扇形區、娥眉月及其類似組態)之結構的組態。 Those skilled in the art will understand that a spinning head with two or more nozzles has a bicomponent fiber with a core/sheath structure or any configuration (such as a symmetric (concentric) core/sheath, (Asymmetric (eccentric) core/sheath, side-by-side, fan-shaped area, Emeiyue and similar configurations).
纖維以拉伸狀態通過一或多個導絲輥捲繞，且藉由捲繞機之旋轉捲繞於捲線軸上。較佳將紡絲油(諸如基於聚矽氧之油或礦物油)施加(較佳噴霧)於纖維上以促進捲繞。 The fiber is wound through one or more godets in a stretched state, and is wound on the spool by the rotation of the winding machine. Preferably, spinning oil (such as silicone-based oil or mineral oil) is applied (preferably sprayed) to the fibers to promote winding.
在製程中，如上文定義之預聚物作為交聯劑添加至熔融成份 i)與ii)之任一者或兩者中。在本發明之一個具體實例中，預聚物添加量以用於聚合物ii)之TPU重量計，為約0%至約15%，較佳為1%至10%，更佳為2%至8%，且以用於聚合物i)之TPU重量計，為約5%至25%，較佳為8%至20%，且更佳為10%至15%。 In the process, the prepolymer as defined above is added as a cross-linking agent to the molten component Either one or both of i) and ii). In a specific embodiment of the present invention, the prepolymer is added in an amount of about 0% to about 15% based on the weight of the TPU used in the polymer ii), preferably 1% to 10%, more preferably 2% to 8%, and based on the weight of the TPU used for the polymer i), about 5% to 25%, preferably 8% to 20%, and more preferably 10% to 15%.
諸位發明人已發現，在纖維用於特定用途的情況下，諸如用於需要高恢復率及彈性以及舒適皮膚觸感的女士內衣或褲襪，拉製纖維之輥較佳具有200m/min至800m/min且甚至更佳300m/min至700m/min之速度。 The inventors have found that in the case where the fiber is used for a specific purpose, such as lingerie or pantyhose requiring high recovery rate and elasticity and comfortable skin touch, the roller for drawing the fiber preferably has a length of 200m/min to 800m /min and even better 300m/min to 700m/min speed.
較佳使用2至5個導絲輥；更佳使用2至4個，最佳3個導絲輥。在本發明之一個具體實例中，使用2至4個導絲輥以300m/min至700m/min之速度拉製纖維，從而製得在適當尺寸與高恢復率之間達成完美平衡的纖維。 Preferably, 2 to 5 godet rollers are used; more preferably, 2 to 4 goddess rollers are used. In a specific example of the present invention, 2 to 4 godet rollers are used to draw fibers at a speed of 300 m/min to 700 m/min, thereby producing fibers that achieve a perfect balance between appropriate size and high recovery rate.
根據本發明製得之雙成份纖維用於生產編織或針織織物。在具有外鞘-核心結構之纖維中，具有相對較低熔融溫度的外鞘聚合物具有良好的黏合能力，而核心聚合物使得纖維具有高恢復率。經針織形成產品之後，可向該產品施加另外的加熱步驟，使得外鞘聚合物部分熔融，以便在兩種纖維連接處形成黏合位點。由此便避免由高彈性纖維製成之物品的運作問題。此在生產女士內衣或褲襪時特別有利。 The bicomponent fiber prepared according to the present invention is used to produce woven or knitted fabrics. Among the fibers with sheath-core structure, the sheath polymer with relatively low melting temperature has good adhesion, and the core polymer makes the fiber have a high recovery rate. After knitting to form a product, an additional heating step can be applied to the product to partially melt the sheath polymer to form a bonding site at the junction of the two fibers. This avoids the operational problems of articles made of highly elastic fibers. This is particularly advantageous when producing lingerie or pantyhose.
實施例 Examples
以下方法及準則用於測定及評估各參數。 The following methods and guidelines are used to determine and evaluate various parameters.
拉伸強度 Tensile Strength
拉伸強度根據DIN 53834測定。 The tensile strength is measured according to DIN 53834.
斷裂伸長率 Elongation at break
斷裂伸長率根據DIN 53834測定。 The elongation at break is measured according to DIN 53834.
300%恢復率 300% recovery rate
300%恢復率根據D1N53835測定，其中在伸長率為300%、拉伸速度為100mm/min的連續5次負載-恢復循環之後測試恢復率。提供以下準則來評估結果(「+」意謂良好，且「-」意謂不良)。 The 300% recovery rate was determined according to D1N53835, where the recovery rate was tested after 5 consecutive load-recovery cycles with an elongation rate of 300% and a tensile speed of 100 mm/min. Provide the following criteria to evaluate the results ("+" means good, and "-" means bad).
熔點Tm Melting point T m
在30kg力、1mm模內徑、10mm模長度及3℃/min加熱速率之條件下由毛細管流變儀測試之流動開始溫度(FBT)視為Tm。提供以下準則來評估測試結果(「+」意謂良好，且「-」意謂不良)。 The flow start temperature (FBT) measured by the capillary rheometer under the conditions of 30 kg force, 1 mm mold inner diameter, 10 mm mold length, and 3° C./min heating rate is regarded as T m . Provide the following criteria to evaluate the test results ("+" means good, and "-" means bad).
纖維尺寸藉由顯微鏡量測。 The fiber size is measured with a microscope.
實施例1 Example 1
使用兩種商業化TPU E1180A及E2280A(獲自BASF，兩者均具有80A蕭氏A硬度；其重量平均分子量分別為130,000及210,000)製備單成份纖維。使用商業化預聚物PLP9302(獲自BASF，分子量為約2500)作為交聯劑(PLP9302官能度為2.0且NCO%為約5.3)。 Two commercial TPUs E1180A and E2280A (available from BASF, both with 80A Shore A hardness; their weight average molecular weights were 130,000 and 210,000, respectively) were used to prepare single component fibers. A commercial prepolymer PLP9302 (available from BASF with a molecular weight of about 2500) was used as a crosslinking agent (PLP9302 functionality is 2.0 and NCO% is about 5.3).
亦使用E1180A、E2280A及PLP9302製備雙成份纖維。特定而言，藉由以下步驟製備纖維：(1)使E1180A及E2280A分別在不同擠壓機中、在200℃及210℃溫度 下熔融，(2)使PLP9302分別以相應基質TPU重量之2%及10%之量混合於所熔融E1180A及E2280中，(3)用具有兩個同心排列之噴嘴的紡絲頭將兩個熔體擠出，熔體在210℃下加熱以獲得具有核心-外鞘結構的雙成份纖維，(4)纖維在通過獲自Takemoto Oil & Fat有限公司之紡絲油噴霧之後，通過三個導絲輥捲繞且以300m/min之紡絲速率捲繞。 E1180A, E2280A and PLP9302 are also used to prepare bicomponent fibers. Specifically, the fibers are prepared by the following steps: (1) E1180A and E2280A are in different extruders at 200°C and 210°C respectively Lower melting, (2) Mix PLP9302 in the melted E1180A and E2280 in the amount of 2% and 10% of the weight of the corresponding matrix TPU, (3) Use the spinning head with two concentrically arranged nozzles to melt the two Body extrusion, the melt is heated at 210°C to obtain a bicomponent fiber with a core-sheath structure, (4) the fiber is sprayed through spinning oil obtained from Takemoto Oil & Fat Co., Ltd., and then passed through three guide wires The roll is wound and wound at a spinning rate of 300 m/min.
如自表1可見，在添加交聯劑的情況下，單組分纖維恢復率變得更高，此有利於最終使用；纖維之熱黏合溫度(Tm)亦變得更高，此不利於最終使用。亦即，使用單成份纖維難以同時達成良好恢復率及良好熱黏合性質。 As can be seen from Table 1, in the case of adding a crosslinking agent, the recovery rate of the single-component fiber becomes higher, which is beneficial to the final use; the thermal bonding temperature (T m ) of the fiber also becomes higher, which is not conducive to End use. That is, it is difficult to achieve a good recovery rate and good thermal bonding properties at the same time using single-component fibers.
如自表2可見，對於核心-外鞘雙成份纖維而言，即使外鞘使用大量聚合物ii)，纖維仍顯示良好恢復率。結合外鞘所提供之良好熱黏合性質，如此形成之纖維有利於最終使用。 As can be seen from Table 2, for the core-sheath bicomponent fiber, even if the outer sheath uses a large amount of polymer ii), the fiber still shows a good recovery rate. Combined with the good thermal bonding properties provided by the outer sheath, the fibers so formed are beneficial for end use.
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| CN108277554A (en) * | 2017-12-21 | 2018-07-13 | 苏州浩洋聚氨酯科技有限公司 | A kind of new polyurethane fiber |
| DE102018110246B4 (en) * | 2018-04-27 | 2020-12-31 | Johann Borgers GmbH | Nonwoven molded part |
| WO2019213932A1 (en) * | 2018-05-11 | 2019-11-14 | Covestro Deutschland Ag | Thermoplastic polyurethane composition and use thereof |
| WO2020178417A1 (en) * | 2019-03-07 | 2020-09-10 | Adient Engineering and IP GmbH | Method for producing a luggage compartment covering and luggage compartment covering for vehicles |
| KR20220027161A (en) * | 2019-07-03 | 2022-03-07 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Bicomponent thermoplastic polyurethane fibers and fabrics made therefrom |
| KR20220034027A (en) * | 2019-07-15 | 2022-03-17 | 프리마로프트, 인크. | Recycled Polyester Binder Fiber |
| JP2023532196A (en) * | 2020-06-15 | 2023-07-27 | 東レ繊維研究所（中国）有限公司 | Knitted fabric and its use |
| TWI775508B (en) * | 2021-06-30 | 2022-08-21 | 三芳化學工業股份有限公司 | Elastic fiber, elastic fiber covered yarn and reeling manufacturing methods thereof |
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