CN101068975A - 用于提高芳族聚酰胺纱束的束粘结性的方法 - Google Patents
用于提高芳族聚酰胺纱束的束粘结性的方法 Download PDFInfo
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Abstract
本发明涉及一种用于提高芳族聚酰胺纱束的束粘结性和降低其摩擦系数的方法，其包括基于纱的重量，向纱束加入0.1－3.0重量％的水可溶性或水可分散性膜形成粘结剂，随后用具有低于100mm2/s(25℃)的特性粘数的油处理纱束。
Description
本发明涉及一种用于提高芳族聚酰胺纱束的束粘结性的方法，一种用于针织、缝纫或编织所述的芳族聚酰胺纱束的方法，以及包含用于汽车应用的所述的束的针织管(knitted tube)。
短纤纱(spun yarn)或牵引纱(stretch broken yarn)的芳族聚酰胺线(aramid cord)经常在橡胶、热塑性材料或热固性材料中用作加强材料。芳族聚酰胺线由两根或多根绞合成线的扭绞的短纤纱或牵引纱组成。该线这样即使用或在适宜的设备上处理后用作针织品、编织品或纤维。然而，在机器上加工这样的芳族聚酰胺丝是有问题的，并且经常导致断裂或所使用的针织、编织、缝纫机或编织机的反复停机。此外，在加工期间这样的芳族聚酰胺线容易丢丝且聚合物部分容易从单独的丝脱出并在机器部件上和机器部件里形成沉积物。特别地，用于针织或编织的针的堵塞导致在强化最终形式中的不规则性。作为这些不规则性的结果，基质(matrix)中的线加强失效且加强材料的寿命大幅度降低。
芳族聚酰胺纤维束已用多种成分处理。例如在JP10158939中用油处理包含芳族聚酰胺的多丝纱束以在修整加工期间防止起毛。在JP09041274中用水可溶性聚脂处理芳族聚酰胺纤维束以提高成束力(bundlingpower)，但该材料用于完全不同的应用，即用于水泥材料的加强材料。
当芳族聚酰胺纱束用于针织、编织和缝纫时，已知的束具有上述的缺点。尚不知道适宜用于这样的目的的芳族聚酰胺纱(纤维)。因此本发明的目的是提供具有优异束粘结性并同时具有低摩擦系数以便易于针织、编织与缝纫的芳族聚酰胺纱束。术语“芳族聚酰胺纱束”包括至少两根单独的纱，特别是由芳族聚酰胺制成的纱。
在US4455341中，提供了一种具有水可溶性胶的芳族聚酰胺、特别是聚-对-亚苯基对苯二酰胺的多丝纱。除了胶还可以对纱提供非离子蜡。该上胶的纱在纺织工业中用作经向和纬向纱。现已发现(见实施例3)如此非离子蜡处理过的纱的摩擦力对于这些纱在线针织机中的最佳适用还是太高。因此，还需要获得一种具有低摩擦系数同时具有良好束粘结性的纱。
现发现了一种方法可以满足这些要求。为此，本发明涉及一种提高聚酰胺纱束束粘结力和降低其摩擦系数的方法，包括向纱束加入以纱重量为基准0.1-3.0重量％的水可溶性或水可分散性膜形成粘结剂，随后用具有低于100mm2/s(25℃)特性粘数的油处理纱束。
芳族聚酰胺纱束，比如线，根据本发明用膜形成粘结剂和覆盖涂层处理。该粘结剂提高丝间和纱的粘结并且应该是膜形成聚合物。优选地该粘结剂是水可溶性的或水可分散性的聚氨基甲酸酯和/或磺化聚酯树脂。
适宜的聚酯的例子是磺化二羧酸，二羧酸和二元醇衍生的聚合物。优选衍生自二甲基磺基间苯二甲酸钠、间苯二甲酸和乙二醇的聚酯。这种产品以商品名Eastman LB-100提供。
适宜的聚氨基甲酸酯的例子是聚醚-聚氨基甲酸酯或聚酯-聚氨基甲酸酯分散体，分别以商品名Alberdingk U400N和Imprani DLF提供。
覆盖涂层是减少线的纱对金属摩擦力的具有低特性粘数的油。优选覆盖涂层是一种酯油。这些线特性导致无故障的针织、缝纫和编织行为。
适宜的油的例子是硬脂酸2-乙基己酯、棕榈酸2-乙基己酯、月桂酸正丁酯、辛酸正辛酯，硬脂酸丁酯或者其混合物。更优选的酯油是以商品名LW245提供的硬脂酸2-乙基己酯和棕榈酸2-乙基己酯的混合物。
上述胶料的这样的使用可以从US4,455,341中知道。然而，本发明涉及为提高纤维中纤丝粘结性对各根纤维上胶，而不是为提高各根纱而不是纤丝的粘结性对纱束上胶。此外，本发明要求使用当在编织设备中使用纱束时其使用有害的非离子蜡。
可根据本方法处理的纱束包括任何芳族聚酰胺纱，包括短纤纱和牵引纱。牵引纱(也称为精纺纱(spunnized yarn))特别适用于使用本方法。适宜的芳族聚酰胺包括间和对芳族聚酰胺纱，比如Teijinconex纱[聚-(间-亚苯基间苯二酰胺)；MPIA]，Twaron纱[聚(对-亚苯基对苯二酰胺)；PPTA]和Technora纱[共聚-(对亚苯基/3，4’-氧二亚苯基对苯二酰胺)]。
最后，本发明的目的还在于为芳族聚酰胺纱束的针织、缝纫或编织提供一种方法，其包括使用加入以纱重为基准0.1-3.0重量％的水可溶性或水可分散性膜形成粘结剂和此后使用具有小于100mm2/s特性粘数的油的纱束。
根据本发明的方法处理的纱显示了强的粘合性质，即含有这种纱的线不易于分成单独的纱。而且束(线)显示了提高的摩擦性能。本发明的纱束因此适宜于应用于针织、缝纫或编织的方法中，和应用于制造用于汽车应用的编织管。
本发明在下面的非限制性的说明性例子中进一步说明并且优势得到了进一步显示。
(纱-金属)摩擦系数(f)的确定
为了确定线的摩擦系数，线由线轴穿过磁力拉伸装置。然后它通过张力测量头(预张力T1)，摩擦力针(包角90℃)，第二张力测量头(后张力T2)和导丝辊。最后将线缠绕。在确定的过程中测量了后张力(T2)。摩擦系数在以下条件下计算：
人工气候室条件： 20℃/65％RH
线/导丝辊速度； 50米/分钟
预张力(T1)： 用磁性拉伸装置固定为50cN
摩擦针： 光滑的镀铬钢
摩擦针直径： 32mm
计算摩擦系数(f)： f＝1/α*ln(T2/T1)
其中α＝包角弧度(1/2π)
切割测试
100厘米长的线试样垂直悬挂在桌子上。它的头端用夹子固定。试样的自由低端加上使线张力为0.15cN/dtex的重量。应防止悬挂线自由端的旋转。然后，用剪刀在悬挂点以下75cm处剪断。接下来，对剩余悬挂线试样的四分之三部分，从线切断点形成的新的张开的末端测量长度。在上述拉伸下线切断导致的径向打开程度表明了纱的粘结力程度。本实验进行5次，平均值(cm)作为切割测试值。本测试是纱束中各根纱粘结性的指示。
实施例1(实验1A-1J，2A-2J，3A-3J，4)
本实施例说明粘结剂和覆盖涂层在3-股Teijinconex KB线中的应用。该线由Teijinconex KB牵引纱(100dtex X 3Z80)生产并经过如下处理。
线包滚动解绕，同时使线依次穿过液体施涂器A，蒸汽室(温度240℃，停留时间10秒)，使线穿过液体施涂器B，最后以60m/min的速度缠绕成包。
线用表I中描述的粘结剂水溶液用液体施涂器A和管式泵处理。，线用表II中描述的覆盖涂层(净油)用液体施涂器B和注射器泵处理。
改变下面的处理条件：
a)粘结剂的组成
b)粘结剂的剂量
c)覆盖涂层的剂量
测量产品线的纱-金属摩擦系数和根据切割测试的束粘结性。此外测定了某些线的机械特性和含湿量。作为参考，测试了未处理的TeijinconexKB线。结果如表III所示。
实验2B和1E的线在卢卡斯圆形针织机上表现出极好的针织性能，而未处理的线(实验4)在同样的机器上显示出差的针织性能(停机和失效)。
表I 水性聚酯和聚氨基甲酸酯粘结剂
| 树脂组成代码 | a1 | a2 | a3 | b1 | b2 | b3 | c1 | c2 | c3 |
| 树脂浓度(重量％) | 1.0 | 2.0 | 3.0 | 1.0 | 2.0 | 3.0 | 1.0 | 2.0 | 3.0 |
| Eastman LB-100(100％) | 1.0 | 2.0 | 3.0 | ||||||
| Alberdingk U 400N(40％) | 2.5 | 5.0 | 7.5 | ||||||
| ImpranilDLF(40％) | 2.5 | 5.0 | 7.5 | ||||||
| 软化水 | 99.0 | 98.0 | 97.0 | 97.5 | 95.0 | 92.5 | 97.5 | 95.0 | 92.5 |
Eastman LB-100是一种水可分散性的聚酯聚合物，美国Kingsport的Eastman ChemialCompany提供
Alberdingk U 400N(40％)是一种聚酯-聚氨基甲酸酯水分散体，德国Krefeld的AlberdingkBoley GmbH提供
ImpranilDLF(40％)是一种聚酯-聚氨基甲酸酯水分散体，德国Leverkusen的Bayer AG，提供
表II 覆盖涂层
| 覆盖涂层代码 | d |
| 以重量％计的浓度 | 100 |
| LW 245 | 100 |
LW 245是一种低粘度酯油(硬脂酸2-乙基己酯和棕榈酸2-乙基己酯的混合物)，25℃时的粘度为14.6mm2/sec，德国Düsseldorf的Cognis提供
表III 实施例1结果
| 实验序号 | 粘结剂 | 覆盖涂层TretN81 | 含湿量 | 强度N | 线性密度dtex | 伸长％ | 摩擦系数f | 切割实验值cm | |
| 纱上的量％ | 代号 | ||||||||
| 1A*1B1C | 0.30.30.3 | a1a1a1 | 无0.30％0.50％ | 4.13.94.0 | 131 | 3563 | 12.1 | 0.500.380.38 | 7.76.59.2 |
| 1D*1E1F | 0.60.60.6 | a2a2a2 | 无0.30％0.50％ | 3.7 | 139 | 3556 | 12.2 | 0.510.390.39 | 2.21.91.9 |
| 1G*1H1J | 0.90.90.9 | a3a3a3 | 无0.30％0.50％ | 3.7 | 133 | 3632 | 12.1 | 0.520.370.36 | 1.61.21.4 |
| 2A*2B2C | 0.30.30.3 | b1b1b1 | 无0.30％0.50％ | 4.6 | 135 | 3486 | 12.3 | 0.500.440.43 | 4.46.15.8 |
| 2D*2E2F | 0.60.60.6 | b2b2b2 | 无0.30％0.50％ | 4.1 | 130 | 3526 | 12.0 | 0.500.430.43 | 1.72.41.7 |
| 2G*2H2J | 0.90.90.9 | b3b3b3 | 无0.30％0.50％ | 3.9 | 129 | 3641 | 11.3 | 0.520.460.45 | 1.21.41.1 |
| 3A*3B3C | 0.30.30.3 | c1c1c1 | 无0.30％0.50％ | 3.9 | 133 | 3570 | 11.4 | 0.500.430.42 | 4.16.55.3 |
| 3D*3E3F | 0.60.60.6 | c2c2c2 | 无0.30％0.50％ | 3.8 | 122 | 3527 | 10.3 | 0.490.430.43 | 2.41.82.7 |
| 3G*3H3J | 0.90.90.9 | c3c3c3 | 无0.30％0.50％ | 3.7 | 141 | 3537 | 11.9 | 0.490.430.41 | 1.41.21.5 |
| 4* | 未处理的TeijinConex KB线 | 4.0 | 135 | 3478 | 11.9 | 0.52 | 28.4 | ||
*比较实施例
实施例2(实验5，6)
由TeijinconexKB短纤纱(1100dtex X 2Z120)生产的线经过如以上实验1E描述的同样处理。作为参考，测试了未处理的TeijinconexKB线。结果如表IV所示。根据本发明处理过的线显示出极好的束粘结性和低的摩擦系数。
表IV 实验5和6的结果
| 实验序号 | 粘结剂 | 覆盖涂层Tret N81 | 含湿量 | 强度N | 线性密度dtex | 伸长％ | 摩擦系数f | 切割实验值cm | |
| 纱上的量％ | 代号 | ||||||||
| 5 | 0.6 | a2 | 0.30％ | 1.8 | 97 | 2352 | 12.1 | 0.35 | 0.6 |
| 6* | 未处理的TeijinConex KB线 | 3.7 | 96 | 2270 | 12.2 | 0.44 | 12.1 | ||
*比较实施例
图1是显示了本发明方法影响的照片。在照片中比较显示了切割测试后的未处理的线(A)(3×1100dtex)和经过本发明处理的线B。
实施例3
在本实施例中显示了了25℃下具有低于100mm2/s的低特性粘数的油与和一种非离子型腊相比较的影响。
线由Teijinconex KB短纤纱(1100dtex X 2Z120)生产。该线经过以下处理。线包解绕，同时使线依次穿过液体施涂器A，穿过热空气炉(温度240℃，停留时间10秒)，使线穿过液体施涂器B(在油的情况下)或加热的金属给油辊C(在蜡的情况下)，并最后以36m/min的速度缠绕成包。用液体施涂器A和管式泵，对线用来自2.0重量％的水溶液中的0.6重量％的粘结剂Eastman LB 100(水可分散性的聚酯聚合物，美国Kingsport的Eastman Chemical Company提供)处理。
用液体施涂器B和注射器泵用LW245油(25℃时的粘度为14.6mm2/sec)处理线。
作为比较该线用加热的金属给油锟C用熔融的蜡Bevaloid 256处理。Bevaloid 256是一种非离子蜡(由法国Lauterbourg的Kemira Chimie SA提供)，它被Kemira推荐作为已不再供应的非离子蜡Sopromine CF的替代品。
经过处理的线的摩擦(纱-金属)系数按照上述方法处理。
结果如表V所示。
表V 经过处理的Teijinconex KB线的摩擦系数
| 线上的Eastman LB100粘结剂(重量％)1 | 覆盖涂层1 | 摩擦系数f | |
| 线上的LW 245(油)(重量％) | 线上的Bevaloid256(重量％) | ||
| 0.6* | 无 | 无 | 0.36 |
| 0.6 | 0.5 | 0.24 | |
| 0.6 | 1.0 | 0.24 | |
| 0.6* | 0.5 | 0.28 | |
| 0.6* | 1.0 | 0.31 | |
1剂量
2为了应用正确量的蜡，首先绘制了标准曲线(蜡的吸收对给油锟速度)
*参考实施例
显然使用油(25℃时粘度＜100mm2/s)作为覆盖涂层时，得到Teijinconex KB线的最低纱-金属摩擦系数。使用非离子蜡作为覆盖涂层较不有效因此导致例如在线针织机上的前期过程停止和和断裂。
Claims (6)
1.一种用于提高芳族聚酰胺纱束的束粘结性和降低其摩擦系数的方法，该方法包括，基于纱的重量，向纱束加入0.1-3.0重量％的水可溶性或水可分散性膜形成粘结剂，随后用在25℃具有低于100mm2/s的特性粘数的油处理纱束。
2.如权利要求1所述的方法，其中膜形成粘结剂是水可分散性的聚氨基甲酸酯和/或磺酸聚酯，或它们的混合物。
3.如权利要求1或2所述的方法，其中的纱是牵引纱。
4.如权利要求1到3中任意一项所述的方法，其中纱是聚-(间-亚苯基间苯二酰胺)纱。
5.一种用于针织、缝纫或编织芳族聚酰胺纱束的方法，其包括使用，基于纱的重量，加入0.1-3.0重量％的水可溶性或水可分散性膜形成粘结剂、随后加入具有低于100mm2/s的特性粘数的油的纱束。
6.用于汽车应用的针织管，其包括由权利要求1-4中任意一项所述的方法得到的纱的针织的束。
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| EP0052897B1 (en) * | 1980-11-24 | 1984-11-07 | Akzo N.V. | A sized multifilament yarn of an aromatic polyamide, a yarn package, a woven fabric and a process for making said yarn |
| JPH0781234B2 (ja) * | 1988-08-30 | 1995-08-30 | 帝人株式会社 | 表面変性全芳香族ポリアミド繊維 |
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