CN1377432A - 纺丝油剂 - Google Patents

纺丝油剂 Download PDF

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CN1377432A
CN1377432A CN00813545A CN00813545A CN1377432A CN 1377432 A CN1377432 A CN 1377432A CN 00813545 A CN00813545 A CN 00813545A CN 00813545 A CN00813545 A CN 00813545A CN 1377432 A CN1377432 A CN 1377432A
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R·克莱恩
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Abstract

本纺丝油剂组合物包含以纺丝油剂组合物为基准计至少约10重量%具有通式R1－(CO)x－O－(CH(R2)－CH2－O)y－(CO)z－R3的组分(a)和(b),其中R1和R3的每一个均选自氢或具有1～22个碳原子的烷基基团或具有1～22个碳原子的亚烷羟基基团,x为零或1,R2在组分(a)或组分(b)中可以变化并选自氢或具有1～4个碳原子的烷基基团,y为零,或1～25,和z为零或1,在组分(a)中,x和z等于零,组分(a)的平均分子量小于或等于1,900,如果R2变化,则组分(a)是无规共聚物;和在组分(b)中,x或z至少之一等于1,或组分(b)是具有10个以上聚氧乙烯单元的含聚氧乙烯甘油酯的复合化合物;以纺丝油剂组合物为基准计至多约5重量%组分(c)乙氧基化聚硅氧烷;和以纺丝油剂组合物为基准计至少约1重量%通式为R4(CH2O(CO)aR5)b的组分(d),其中R4是－C－或－COC－;a是0或1;R5是－H,自－CH3至－C18H37,或CH(R6)－CH2O;b为4或6;和R6为－H或－CH3或者为－H和－CH3,两者比例为10∶90至90∶10。本纺丝油剂组合物可以应用于工业纱上。

Description

纺丝油剂
本专利申请要求1999年7月30日提交的待审的美国临时专利申请系列号60/146,487的利益。
本发明涉及用于合成纤维的纺丝油剂。
                      发明背景
许多合成纤维在从喷丝板冒出时需要施加纺丝油剂，以便对所纺的丝进一步加工。因为纺丝油剂可以在纤维上以极薄的层存在，所以纺丝油剂充当了纤维和金属表面之间的界面，所述金属表面例如是诸如拉伸或松弛等加工期间与纤维接触的诸如导纱器和辊等。
现有技术涉及用于传统工业纱、地毯纱和纺织品纱的许多纺丝油剂。例如，包含分子量为300～1,000的聚亚烷基二醇润滑剂和第二组分的纺丝油剂叙述在美国专利4,351,738(见比较例)以及共同转让的美国专利3,940,544、4,019,990和4,108,781。美国专利4,340,382叙述了一种包含聚亚烷基二醇嵌段共聚物非离子表面活性剂的油剂。
包含分子量1,000以上的聚亚烷基二醇润滑剂和其它组分如酯、阴离子化合物或聚环氧烷改性的聚硅氧烷的纺丝油剂，叙述在美国专利3,338,830、4,351,738和5,552,671以及研究公开(ResearchDisclosures)19432(1980年6月)和19749(1980年9月)。也可参见1987年1月23日发表的日本公开专利出版物15319。
不幸的是，包含优选的或作为例子的最低分子量为≥2,000的聚亚烷基二醇的纺丝油剂，可以沉积在制造期间所接触的金属表面上。
美国专利5,507,989叙述了一种其中边界润滑剂为分子量≥9,000的聚亚烷基二醇的纺丝油剂。
美国专利4,442,249叙述的一种纺丝油剂，包含分子量大于1,000的环氧乙烷/环氧丙烷嵌段共聚物、三至六甘醇的烷基酯或二烷基酯或多烷基酯润滑剂、以及中和了的脂肪酸乳化剂。不幸的是，包含这些嵌段共聚物的纺丝油剂也会在制造期间其接触的金属表面上形成沉积物，还有这些纺织用纺丝油剂组合物会不适于工业纤维生产所用的较严酷的条件。
共同转让的美国专利3,681,244、3,781,202、4,348,517、4,351,738(15摩尔或更少的聚氧乙烯)和4,371,658叙述了聚氧乙烯蓖麻油在纺丝油剂中的应用。
用于传统工业纱的另一种纺丝油剂叙述在共同转让的美国专利3,672,977中，其中作为例子的纺丝油剂包含椰子油、乙氧基化的月桂醇、石油磺酸钠、乙氧基化的牛脂胺、磺化的丁二酸酯和矿物油。也可参见共同转让的美国专利3,681,244、3,730,892、3,850,658和4,210,710。
多年以来，对制造工业纱的方法一直有较多的需求。参见例如共同转让的美国专利5,132,067、5,397,527和5,630,976所叙述的制造二维聚酯短纤维的方法。另外，在纱线加工工业中所存在的一般趋势是倾向于直接并捻机，以降低加工成本。获得成本降低的部分原因在于：直接并捻机与传统环锭捻线机比较，前者操作速度相当高(高30～50％)，并且同时完成两步操作。但是，对于直接并捻机而言，为维护纱线机械性能对纱线整理的要求更高。因此，本领域需要提高纱线加工性能和赋于改善的纱线性能的纺丝油剂。
                        发明概述
我们开发了一种符合本领域前述要求的纺丝油剂。本纺丝油剂组合物包含以纺丝油剂组合物为基准计至少约10重量％的通式为
          R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3的组分(a)和(b)，其中R1和R3选自氢或具有1～22个碳原子的烷基基团或具有1～22个碳原子的亚烷羟基基团，
x为零或1，
R2在组分(a)或组分(b)中可以变化，选自氢或具有1～4个碳原子的烷基基团，
y为零，或1～25，和
z为零或1，
在组分(a)中，x和z等于零，组分(a)的平均分子量小于或等于1,900，如果R2变化，则组分(a)是无规共聚物；和
在组分(b)中，至少x或z等于1，或组分(b)是具有10个以上聚氧乙烯单元的含有聚氧乙烯甘油酯的复合化合物；
以纺丝油剂组合物为基准计最高5重量％的组分(c)烷氧基化的聚硅氧烷；和
以纺丝油剂组合物为基准计至少约1重量％通式为
                   R4(CH2O(CO)aR5)b的组分(d)，其中R4是-C-或-COC-；a是0或1；R5是-H，自-CH3至-C18H37，或-CH(R6)-CH2O；b为4或6；和R6为-H或-CH3或者为-H和-CH3，两者比例为10∶90至90∶10。
本发明油剂施加于工业纱线上优于传统纺丝油剂，原因在于本纺丝油剂提高了纱线可加工性，这可由低发烟、在每根纱纺丝油剂量较少下具有改善的机械性能、在较高拉伸比下具有改善的机械性能以及微小的沉积所证明，还有其改善了纱线的性能，这由强度的改善和芯吸作用所证明。
本发明的其它优点将表现自以下叙述和附属权利要求。
                     附图简述
图1示出已知纺丝油剂和本发明实施例1的热重分析图。
图2举例说明已知纺丝油剂和本发明实施例1在给定量纺丝油剂下的质量。
图3举例说明已知纺丝油剂和本发明实施例1在给定拉伸比下的性能。
图4示出已知纺丝油剂和本发明实施例1在直接并捻机上的强度变化改善。
图5示出已知纺丝油剂和本发明实施例1的芯吸长度。
                   优选实施方案详述
本纺丝油剂组合物的组分(a)具有下述通式，
          R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3其中R1和R3每一个选自氢或具有1～22个碳原子的烷基基团；x和z为零；R2可以变化，选自氢或具有1～4个碳原子的烷基基团；和y为零，或为1～25。组分(a)的平均分子量小于或等于1,900。
优选，组分(a)的平均分子量大于500。更优选组分(a)的平均分子量小于约1,500。
优选，在组分(a)中，R1和R3每一个均选自氢或具有1～10个碳原子的烷基基团，R2变化并选自氢和具有1或2个碳原子的烷基基团，和y为零或1～20。术语“R2变化”意指R2可以是氢和甲基、氢和乙基、或甲基和乙基。更优选地，在组分(a)中，R1和R3的每一个选自氢或具有1～5个碳原子的烷基基团，R2选自氢和具有1个碳原子的烷基基团，和y为零或1～16。
优选的组分(a)是所谓的无规共聚物，和更优选，无规共聚物制自环氧乙烷和环氧丙烷。环氧乙烷、环氧丙烷和醇同时反应形成具有醇终端的混合聚亚烷基二醇化合物。优选的化合物是约30％至约70重量％环氧乙烷和约30％至约70重量％环氧丙烷的缩合产物，并用具有1～4个碳原子的醇终止。有用的无规共聚物是市售可得的。
优选，组分(a)的存在量以纺丝油剂组合物为基准计至少约10重量％。更优选组分(a)的存在量以纺丝油剂组合物为基准计至少约20重量％。
本纺丝油剂的组分(b)具有下述通式，
          R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3其中R1和R3的每一个均选自氢或具有1～22个碳原子的烷基基团或具有1～22个碳原子的亚烷羟基基团，x为零或1，R2可以变化并选自氢或具有1～4个碳原子的烷基基团；z为零或1；并且至少x或z等于1。组分(b)可以是组分混合物，或者可以是具有10个以上聚氧乙烯单元的含有聚氧乙烯甘油酯的复合化合物。
优选，在组分(b)中，R1和R3的每一个选自氢或具有1～18个碳原子的烷基基团或具有1～18个碳原子的亚烷羟基基团，R2不变化并选自氢或具有1或2个碳原子的烷基基团；和y为5～25。更优选，在组分(b)中，x为1和z为零。
有用的复合酯是市售可得的。
最优选的组分(b)是具有10个以上聚氧乙烯单元的含有聚氧乙烯甘油酯的化合物，而最优选的具有10个以上聚氧乙烯单元的含有聚氧乙烯甘油酯的化合物是乙氧基化的蓖麻油。
优选，组分(b)的存在量至少为以纺丝油剂组合物为基准计约5重量％。
组分(c)是烷氧基化的聚硅氧烷。优选，烷氧基化的聚硅氧烷具有带有机聚环氧烷侧链的聚硅氧烷主链。有用的烷氧基化的聚硅氧烷是市售可得的。烷氧基化的聚硅氧烷用量最高为以纺丝油剂组合物为基准计约5重量％。
本纺丝油剂的组分(d)具有下述通式，
                 R4(CH2O(CO)aR5)b其中，R4是-C-或-COC-；a为0或1；R5为-H，-CH3至-C18H37，或-CH(R6)-CH2O；b为4或6；和R6为-H或-CH3或者为-H和-CH3，两者比例为10∶90至90∶10。有用的组分(d)的实例包括二季戊四醇六庚酸酯，二季戊四醇三庚酸酯三壬酸酯，二季戊四醇三庚酸酯三异壬酸酯，二季戊四醇一元羧酸(C5-9)脂肪酸六酯，二季戊四醇庚酸酯、油酸酯，戊酸、己酸、庚酸、丙烯酸、壬酸和2-甲基丁酸的二季戊四醇的混合酯，季戊四醇四壬酸酯以及二季戊四醇六壬酸酯。有用的组分(d)是市售可得的。
优选，组分(d)的存在量至少为以纺丝油剂组合物为基准计约1重量％。
本纺丝油剂可以用于任何合成纤维。有用的合成材料包括聚酯和聚酰胺。有用的聚酯包括线性对苯二甲酸酯聚酯，即，含有2～20个碳原子的二醇和含有至少约75％对苯二甲酸的二羧酸组分的聚酯。二羧酸组分的其余部分，如果有，可以是任何适宜的二羧酸，如癸二酸、己二醇、间苯二甲酸、磺酰基-4，4’-二苯甲酸或2，8-二苯并呋喃二羧酸。所述二醇可以在其链中含有两个以上碳原子，例如二甘醇、1，4-丁二醇、1，10-癸二醇和双-1，4-(羟甲基)环己烷。线性对苯二甲酸酯聚酯的例子包括聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚(对苯二甲酸乙二酯/5-氯间苯二甲酸乙二酯)(85/15)、聚(对苯二甲酸乙二酯/5-[磺基钠]间苯二甲酸乙二酯)(97/3)、聚对苯二甲酸环己烷-1，4-二亚甲酯和聚(对苯二甲酸环己烷-1，4-二亚甲酯/六氢对苯二甲酸环己烷-1，4-二亚甲酯)。这些起始合成材料是市售可得的。
其它有用的聚合物是共同转让的美国专利5,869,582所叙述的共聚物。所述共聚物包括：(a)第一嵌段芳香族聚酯，其具有(i)特性粘度至少约0.6分升/克，在60/40(重量)苯酚和四氯乙烷的混合物中测定；(ii)牛顿熔体粘度280℃下至少约7,000泊，采用毛细管流变仪测定；和(b)第二嵌段内酯单体。优选的芳香族聚酯的例子包括聚对苯二甲酸乙二酯(“PET”)、聚萘二甲酸乙二酯(“PEN”)、聚对苯二甲酸双羟甲基环己二醇酯、聚萘二甲酸双羟甲基环己二醇酯、其它聚萘二甲酸亚烷基二醇酯或聚萘二甲酸亚环烷基二醇酯，以及混合聚酯，其除了对苯二甲酸乙二酯单元之外，还含有诸如间苯二甲酸乙二酯、己二酸乙二酯、癸二酸乙二酯、对苯二甲酸1，4-环己二甲醇酯或其它对苯二甲酸亚烷基二醇酯单元等成分。也可以使用芳族聚酯的混合物。可以使用市售可得的芳香族聚酯。优选的内酯包括ε-己内酯、丙内酯、丁内酯、戊内酯和高级环内酯。可以同时使用两种或多种类型的内酯。
有用的聚酰胺包括尼龙6、尼龙66、尼龙11、尼龙12、尼龙6，10、尼龙6，12、尼龙4，6，其共聚物和其混合物。
合成纤维可以通过制造工业纤维的已知方法生产。例如：共同转让的美国专利5,132,067和5,630,976叙述的制造二维PET短纤维的方法。在合成纤维自喷丝板冒出之后，可以将本纺丝油剂通过任何已知设备包括浴、喷洒、浸轧和给油辊等给油设备施加到合成纤维上。优选，本纺丝油剂施加到合成纤维上的量为合成纤维纱线重量的约0.1％～约1.5重量％。
使用下述试验方法分析在其上具有本纺丝油剂组合物的纤维。
1.热重分析：热重分析采用敞口铂盘于Seiko RTG 220U仪上进行。重量为5～8mg的试样在200ml/min的空气吹扫下以10℃/min自30℃加热至300℃。
2.擦伤计数：纱线疵点数采用Enka Tecnica FR-20型Fraytec装置在线检测。疵点计数传感器安装在位于混合喷嘴和卷绕张力检测器之间的压实板上。保持弯曲角为2°以上。在每进行另一次落纱期间均清洁传感器，以保证精确地进行测定。
3.断裂强度：断裂强度按照ASTM D885(1998)进行测定。对于每个测试纱线，进行十次试验，报告十次试验的平均值。
4.帘子线芯吸试验方法：该试验方法涉及未处理或处理过的帘子线的浸渍芯吸能力的测定。纱线或帘子线垂直浸渍在以浸渍液填充的容器中。然后，通过追踪染色的浸渍液的垂直前进，测定在二分钟内浸渍液通过纤维毛细管的渗透性。
所用设备包括两个环状架用于固定试验帘子线，1英寸直径和1英寸深的浸渍容器以及控制马达(1/8Hp，具有手动转数控制器)以喂入试验纱线经过设备。
正如ASTM D1776所指出的，所有试样均必须在70°F和65％相对湿度下调节至少24hr。
关于试验步骤，步骤1是将三滴红色染料均匀地与浸渍溶液混合。步骤2是使试验帘子线穿过样品固定器，依次为第一环状架、浸渍容器、和第三环状架至控制马达。将帘子线卷绕在控制马达的滑轮上。最后，将20g预拉重物施加在第一环状架和划线板之间的帘子线上。步骤3是用染色的浸渍液充满浸渍容器。确保浸渍液面在浸渍容器顶沿，并与划线板上的“0”相齐。步骤4是转动马达，将一段纱线喂入通过浸渍液。停止马达，开始试验。步骤5是浸渍试样芯吸2min。随着着色浸渍液爬上试样，测定并报告着色浸渍液位置。每根纤维重复步骤4和5九次。计算十个芯吸读数的平均和标准偏差。
以下实施例用来进行举例说明，并不作为限制。
比较例A和发明实施例1
比较例A是共同转让的美国专利3,672,977所叙述的工业纱纺丝油剂组合物，其包含30重量％椰子油、13重量％乙氧基化月桂醇、10重量％石油磺酸钠、5重量％乙氧基牛油脂肪胺、2重量％磺化丁二酸酯和40重量％矿物油。
对于发明实施例1，使用下表I所描述的通式如下的市售可得组分(a)，其用量为65重量％。
       R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3
                          表I
    MW     R1     X        R2     Y     Z     R3
    950     C4     0     50％H/50％CH3     4-16     0     H
在表I中，MW表示分子量。组分(b)是含有诸如下述组分的市售可得乙氧基化蓖麻油，
Figure A0081354500121
   其中R4是
Figure A0081354500122
组分(b)用量为25重量％。对于组分(c)，聚硅氧烷用量为5重量％。对于组分(d)，二季戊四醇六壬酸酯用量为5重量％。
在图1中，划出了发明实施例1(“IE1”)和比较例A(“CA”)的热重分析曲线图，说明随着温度升高，发明实施例1产生较少的烟。
在图2中，划出了擦伤数或质量随聚酯工业纱上的纺丝油剂量而变化的曲线图，所用纱为1,000旦，有384根。有600个以上擦伤时质量是不可接受的，因此在纱线上需要至少0.35重量％的比较例A(“CA”)的纺丝油剂。具有发明实施例1(“IE1”)纺丝油剂的纱线，在纱线具有至少0.35重量％发明实施例1纺丝油剂时，具有可接受的质量，换句话说擦数在600以下，而当纱线具有0.35％以下直至0.15重量％发明实施例1纺丝油剂时，其质量不可接受。许多最终应用要求减低上油量。
在图3中，划出了擦伤数或质量随聚酯工业纱的最大拉伸比而变化的曲线图，所用工业纱为1000旦，有384根，用于比较例A(“CA”)和发明实施例1(“IE1”)。
聚酯工业纱的纺丝油剂施加量，每种均为0.5重量％。
对于图4，将1100dtex二维聚酯短纤纱拧成绳，其公称捻度为470×470tpm，这是轮胎应用的标准结构。该纱线须经以9500rpm运转的现有技术直接并捻机。三个样品在两台不同机器上拧成绳，以将并捻机的特定性能减至最小。在图4中，将比较例A(“CA”)设定在100％，发明实施例1(“IE1”)则相对于比较例A进行报告。发明实施例1说明，在聚酯工业纱上存在本纺丝油剂使强度至少高约3％。纤维强度在设计纤维复合系统如应用于轮胎者中是主要因素。增加强度提高性能，而且也能考虑通过减少材料降低成本。
在图5中，示出了比较例A(“CA”)和发明实施例1(“IE1”)的芯吸效果。这种改进的芯吸使浸渍附着量改善，这样得到改善的橡胶内性能。
发明实施例2
对于发明实施例2，使用在表II中所描述的具有下通式的市售可得组分(a)，用量为5重量％。
       R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3
                         表II
    MW     R1     X     R2     Y     Z     R3
    950     C4     0   50％H/50％CH3     4-16     0     H
在表II中，MW表示分子量。组分(b)是季戊四醇酯，用量为85重量％。关于组分(c)，聚硅氧烷应用量为5重量％。关于组分(d)，二季戊四醇六壬酸酯用量为5重量％。聚酯工业纱的纺丝油剂施用量为0.6重量％。纱线强度为9g/d。

Claims (20)

1.一种纺丝油剂组合物，其包含以所述纺丝油剂组合物为基准计至少约10重量％具有通式
          R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3的组分(a)和(b)，其中所述R1和所述R3的每一个均选自氢或具有1～22个碳原子的烷基基团或具有1～22个碳原子的亚烷羟基基团，
所述x为零或1，
所述R2在所述组分(a)或所述组分(b)中可以变化并选自氢或具有1～4个碳原子的烷基基团，
所述y为零，或1～25，和
所述z为零或1，
在所述组分(a)中，所述x和z等于零，所述组分(a)的平均分子量小于或等于1,900，如果R2变化，则组分(a)是无规共聚物；和
在所述组分(b)中，所述x或所述z至少之一等于1，或所述组分(b)是具有10个以上聚氧乙烯单元的含聚氧乙烯甘油酯的复合化合物；
以所述纺丝油剂组合物为基准计至多约5重量％组分(c)乙氧基化的聚硅氧烷；和
以所述纺丝油剂组合物为基准计至少约1重量％通式为
                   R4(CH2O(CO)aR5)b的组分(d)，其中R4是-C-或-COC-；a是0或1；R5是-H，自-CH3至-C18H37，或-CH(R6)-CH2O；b为4或6；和R6为-H或-CH3或者为-H和-CH3，两者比例为10∶90至90∶10。
2.权利要求1的纺丝油剂组合物，其中所述组分(a)的存在量以所述纺丝油剂组合物为基准计为至少约20重量％。
3.权利要求2的纺丝油剂组合物，其中在所述组分(a)中，所述R1和R3每一个选自氢和具有1～22个碳原子的烷基基团。
4.权利要求3的纺丝油剂组合物，其中在所述组分(a)中，所述R1和R3每一个选自氢或具有1～10个碳原子的烷基基团；所述R2变化并选自氢和具有1或2个碳原子的烷基基团；和所述y为零或1～20。
5.权利要求4的纺丝油剂组合物，其中所述组分(a)的平均分子量小于约1,500。
6.权利要求5的纺丝油剂组合物，其中所述组分(a)是无规共聚物。
7.权利要求1的纺丝油剂组合物，其中所述组分(b)的存在量为以所述纺丝油剂组合物计的至少约10重量％。
8.权利要求1的纺丝油剂组合物，其中在所述组分(b)中，所述R1和R3的每一个选自氢或具有1～22个碳原子的烷基基团或具有1～22个碳原子的亚烷羟基基团，所述R2可以变化并选自氢或具有1～4个碳原子的烷基基团，和至少所述x或z等于1。
9.权利要求1的纺丝油剂组合物，其中所述组分(b)是具有10个以上聚氧乙烯单元的含有聚氧乙烯甘油酯的复合化合物。
10.权利要求9的纺丝油剂组合物，其中所述含有聚氧乙烯甘油酯的复合化合物是乙氧基化的蓖麻油。
11.权利要求11的纺丝油剂组合物，其中所述组分(d)是二季戊四醇六壬酸酯或季戊四醇四壬酸酯。
12.在其上具有权利要求1的纺丝油剂组合物的纱线。
13.在其上具有权利要求1的纺丝油剂组合物的工业纱。
14.在其上具有权利要求1的纺丝油剂组合物的聚酯工业纱。
15.由权利要求14的纱制造的轮胎帘子线。
16.一种制造纱线的方法，其包括下述步骤：
A.挤出聚合物制造纱线；
B.向所述纱线施加纺丝油剂，所述纺丝油剂包含以所述纺丝油剂组合物计至少约10重量％的通式为
         R1-(CO)x-O-(CH(R2)-CH2-O)y-(CO)z-R3的组分(a)和(b)，其中R1和R3的每一个选自氢或具有1～22个碳原子的烷基基团或具有1～22个碳原子的亚烷羟基基团，
x为零或1，
R2在所述组分(a)或所述组分(b)中可以改变并选自氢或具有1～4个碳原子的烷基基团，
y为零，或1～25，
z为零或1，
在所述组分(a)中，x和z等于零，所述组分(a)的平均分子量小于或等于1,900，和如果R2改变，则组分(a)是无规共聚物；和
在所述组分(b)中，至少所述x或z之一等于1或组分(b)是具有10个以上聚氧乙烯单元的含有聚氧乙烯甘油酯的复合化合物；
以纺丝油剂组合物为基准计至多约5重量％组分(c)乙氧基化的聚硅氧烷；和
以纺丝油剂组合物为基准计至少约1重量％通式为
                   R4(CH2O(CO)aR5)b的组分(d)，其中R4是-C-或-COC-；a是零或1；R5是-H，-CH3至-C18H37，或-CH(R6)-CH2O；b为4或6；和R6为-H或-CH3或者为-H和-CH3，两者比例为10∶90至90∶10；和
C.拉伸所述纱。
17.权利要求16的方法，其中在所述步骤A中，所述聚合物是聚酰胺。
18.权利要求16的方法，其中在所述步骤A中，所述聚合物是聚酯。
19.权利要求16的方法，其中在所述步骤B中，所述纺丝油剂施加到所述纱线上的量为所述纱线重量的约0.2～约1.5重量％。
20.权利要求16的方法，其中在所述步骤B中，在所述组分(a)中，所述R1和R3的每一个选自氢或具有1～22个碳原子的烷基基团，所述x和z为零，所述R2可以变化并选自氢或具有1～4个碳原子的烷基基团，和所述y为零或为1～25。
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US6712988B2 (en) 2004-03-30
US6908579B2 (en) 2005-06-21
KR20020033161A (ko) 2002-05-04
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US7021349B2 (en) 2006-04-04
US20050142360A1 (en) 2005-06-30
WO2001009427A1 (en) 2001-02-08
AU765393B2 (en) 2003-09-18
CN1195919C (zh) 2005-04-06
US6426142B1 (en) 2002-07-30
US20040144951A1 (en) 2004-07-29
CA2380484A1 (en) 2001-02-08
AU6362600A (en) 2001-02-19
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US20030035952A1 (en) 2003-02-20
JP2003526020A (ja) 2003-09-02
EP1200666B1 (en) 2006-09-20

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