CN1735726A - 带有导电整理剂的芳族聚酰胺长丝纱线 - Google Patents

带有导电整理剂的芳族聚酰胺长丝纱线 Download PDF

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CN1735726A
CN1735726A CNA2003801081576A CN200380108157A CN1735726A CN 1735726 A CN1735726 A CN 1735726A CN A2003801081576 A CNA2003801081576 A CN A2003801081576A CN 200380108157 A CN200380108157 A CN 200380108157A CN 1735726 A CN1735726 A CN 1735726A
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aramid
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S·威廉森
H·斯图特
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Teijin Aramid GmbH
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Abstract

本发明涉及带有导电整理剂的芳族聚酰胺长丝纱线。该纱线带有包含大于1.5wt.％的有机物质的整理剂并且该纱线的特定电阻率小于2.5×104Ohm.cm，在20℃下作为在水中的50wt.％的整理剂成分测量时该有机物质的电导率大于4mS/cm；本发明还涉及制造该纱线的方法。此外，本发明还涉及该整理剂制造导电电缆，尤其是制造电梯电缆的应用。

Description

带有导电整理剂的芳族聚酰胺长丝纱线
技术领域
本发明涉及一种带有导电整理剂(finish)的芳族聚酰胺长丝纱线、一种制造这种纱线的方法、所述纱线的使用以及一种包含所述纱线的电缆。
背景技术
纱线常见的问题是当在某些场合下应用时纱线会断裂。纱线断裂可能是过载、疲劳或磨损而产生的结果。接地电缆损坏还可能是啮齿动物导致的损坏而产生的结果。在电梯电缆中，电缆的断裂是严重的安全问题。已知的是向芳族聚酰胺加强电梯电缆中加入例如一根或多根碳纱(carbonyarn)或金属线作为断裂(断电)检测器。然而，经过这种处理的芳族聚酰胺加强电缆不再具有与仅由未经处理的芳族聚酰胺纱线制成的电缆相同的机械性能。而且，这种碳纱或金属线的断裂性能与芳族聚酰胺纱线的断裂性能不同，从而妨碍了精确地指示芳族聚酰胺加强电缆的断裂危险。与电缆的主要加强材料相比非芳族聚酰胺纱线的其它机械性能使得预见电缆断裂非常复杂。因此，提供具有充足的导电性能并且具有与电缆中未经处理的芳族聚酰胺纱线相同的机械性能的芳族聚酰胺纱线是有利的。
已经提出了上述问题的一些解决方案。在WO 9748832中，利用酸向纱线涂覆一种金属例如镍。这种处理提供了含金属纱线，其纤维表面可能被酸处理所损坏，导致韧性和/或伸长性能下降。在WO 9325748中，公开了一种利用微粒石墨材料在一种溶胀的溶剂中的扩散处理芳族聚酰胺纤维的方法。使用这种方法同样存在损坏纤维表面的危险。而且，这两种方法都非常复杂、耗时，因而成本很高。
带有抗静电整理剂的芳族聚酰胺纤维和纱线在现有技术中也是已知的。在US 5478648中，公开了带有纺丝整理剂的芳族聚酰胺纤维，该纤维具有适于制造板材的性能。这些纤维包含基于含磷和/或磷酸三乙酯的抗静电整理剂，但是并不具有非常低的特定电阻率，例如小于2.5*104Ohm.cm。类似地，US 5,674,615说明了用于纺织板材的成品芳族聚酰胺纤维，该纤维不具有非常低的特定电阻率；在EP 416486中公开了具有较高特定电阻率的成品芳族聚酰胺纤维，该纤维用于加强弹性体和塑性材料中。在WO 9215747中公开了用一种抗静电整理剂处理的芳族聚酰胺纤维。这些纤维可以用于加强带、绳索光缆、橡胶以及合成物。此处公开的电缆不具有非常低的特定电阻率，也不适于用作电梯电缆中的断裂检测器。
发明内容
因此，本发明提供上述问题的一种解决方案，使用一种不耗时、廉价并且不存在任何损坏纤维的危险的简单的方法，来提供具有非常低的特定电阻率的成品纤维，该纤维尤其用作电梯电缆中的断裂检测器。已经发现，一种带有包含重量百分比(wt.％)大于1.5的有机物质的整理剂并且特定电阻率小于2.5*104Ohm.cm的芳族聚酰胺长丝纱线具有充足的电导率以用作断裂检测器而不影响其机械性能，其中在20℃下作为在水中的50wt.％的整理剂成分(composition)检测时该有机物质的电导率大于4mS/cm。这是优于例如从US 5,834,942中已知的使用例如碳纱或金属线作为芳族聚酰胺加强电梯电缆中的断裂检测器的一个本质的优势。经过处理的有机物质和损坏的纱线的电导率会由于磨损或疲劳导致的断裂而减小，并向使用者提供有关电缆的剩余寿命的信息。纱线或电缆的电导率可以利用电阻计或万用表测定。当包含导电的有机物质(COS)的整理剂被施加到芳族聚酰胺长丝纱线上时，纱线的电阻减小。根据整理剂的量和所施加的有机物质的电导率，经过处理的纱线可以单独或与未经处理的芳族聚酰胺长丝纱线结合用作(电梯、承载部件、接地)电缆中的早期断裂检测器，或者由于其电阻低而用作在例如唱机、磁带、光盘等中必须提供或用以消除静电的附件(电刷、辊子)。
导电的有机物质可以在纺丝工序或单独的工序步骤中以较高的纱线线速度作为纺丝整理剂(这样或利用溶剂例如水稀释，在烘干之前或之后)施加到湿的或干的纱线上。
优选利用大于2wt％的电导率大于30mS/cm的导电的有机物质处理的芳族聚酰胺长丝纱线。更优选利用大于2wt％的电导率大于41mS/cm的导电的有机物质处理的纱线。纱线的特定电阻率优选小于2*103Ohm.cm，更优选小于103Ohm.cm。尤其合适的COS的量在3至12wt％的范围内，更优选在4至9wt％的范围内。wt％是相对于不带整理剂的纱线的总重量。
适于在本发明中使用的合适的有机物质为盐或具有可静电充电的酸基或碱基的材料。具有酸基的材料优选地具有羧酸、膦酸或磺酸基。具有碱基的材料优选地具有胺基。
尤其优选的材料为脂肪酸、碳酸、(环)烷基磷酸酯、(环)烷基膦酸酯、(环)烷基硫酸酯、(环)烷基磺酸酯、咪唑啉衍生物和聚合物例如聚二烯丙基二甲基氯化铵poly(diallyldimethylammonium chloride)等。
芳族聚酰胺纱线优选由聚对苯二甲酰对苯二胺(PPDT)制成，但是也可以包含少量的其它单体。
COS通过本领域中已知的常规方法施加到纱线上。COS能够在溶液中施加。溶剂可以为任何合适的溶剂，例如乙醇、醚、四氢呋喃、丙酮、苯、甲苯、乙酸乙酯、二氯甲烷等。最优选的是，COS作为水溶液而施加。一些COS作为可以这样施加的含水产品而购买。
要施加的COS的合适量可以通过如本领域中已知的简单电导率测量方法容易地测定。当COS或COS溶液的电导率测定之后，本领域中的技术人员能够容易地根据特定用途施加要求量的整理剂。
本发明还涉及这些纱线在电缆中的应用以及包含所述纱线的电缆，该电缆具有与由未经处理的芳族聚酰胺纱线制成的电缆相同的机械性能。本发明在电梯电缆中尤其有用，电梯电缆中通常包含不同材料例如碳纤维的断裂检测器，从而导致电缆的机械性能改变。本发明能够制造类似纱线——即包括未经处理的纱线和根据本发明用整理剂处理过的相同或类似纱线的纱线——的电缆尤其是电梯电缆。
测定整理剂的电导率的工序
根据本发明测定整理剂成分的电导率的合适的工序如下。
将足够量的待测试的整理剂水溶液(50wt.％的水和50wt.％的COS)倾注到一烧杯中。然后，在20℃温度下根据DIN标准38404 Teil 8(9.1985)测定该溶液的电导率。
当包含COS的整理剂中水的含量低于或高于50wt.％时，应该分别通过加入软化水或通过在低于100℃的高温下在一加热板上加热并搅拌水使之蒸发而将整理剂溶液的浓度调整到50wt.％。使用Wissenschaftlich-Technische Werksttten GmbH，Weilheim，Germany的LF 537型电导率计来测量电导率。
整理剂溶液的水含量通过Karl Fischer方法测定。1984年Springer-Verlag出版社出版的Eugen Scholz所著的“Karl FischerTitration，Methoden zur Wasserbestimmung”一书中给出了通过KarlFischer试剂测定水(含量)的确切说明。
测定特定电阻率的工序
为了测定芳族聚酰胺纱线的特定电阻率，使用一包括由两个聚四氟乙烯棒隔开的两个铜棒的样品保持架。这些棒相互之间的距离为52mm。待测试的纱线环绕两个铜棒缠绕数圈(优选地在3与7之间)，该两个铜棒与一高压直流电源和一Keithley静电计相连。在20℃的温度和65％的相对湿度下给铜棒施加500V的电压之后，利用Keithley静电计测定电流。根据欧姆定律、铜棒之间的纱线长度、纱线接头的数量以及纱线的截面积计算出纱线的特定电阻率。
具体实施方式
利用下面的非限定性示例进一步说明本发明。
示例1
本示例示出了在与纺丝工序一体的操作中将包含导电的有机物质(COS)施加到没有预先烘干的湿纱线上的工序。通过混合浓(99.8wt.％)硫酸雪(snow)与粉末状的聚对苯二甲酰对苯二胺制备纺丝物质(spinningmass)。该纺丝物质被除去空气、在一双螺杆挤出机中加热至90℃并经由一过滤器和一纺丝泵供给至一喷丝板。该喷丝板具有1000个直径为59微米的喷丝孔。纺丝物质通过该喷丝孔被挤出，然后相继穿过一长度为8mm的空气带和一凝固浴(纺丝浴)。该浴为温度为5℃的硫酸与水(按重量计算大约为19％)的稀溶液。这样形成的长丝束相继穿过一包含稀碳酸钠溶液的中和浴和一洗涤浴，长丝在该洗涤浴内被大约75℃的水彻底冲洗。借助于一对挤出辊去除过度粘附的水。然后，借助于一液体涂抹器和一供给泵向未烘干的长丝束提供包含COS的含水整理剂。然后，纱线经过一连串3个烘干滚筒(6卷(warp)，160℃；6卷，180℃；4卷，200℃)。纱线与滚筒的表面总共接触5-6秒。然后，纱线经过一输送滚筒(4卷，约20℃)并以400m/min的速度绕成一卷。所得纱线的线密度为1610dtex。以下工艺条件变化(表A和B)：
a)包含COS的整理剂的成分
b)纱线上的COS量
表A包含导电的有机物质的含水整理剂
整理剂的浓度(wt.％)             整理剂成分代号
    a120   b120   c120   d120
溶液中的COS(％)Afilan V4855(37.6％)Afilan PTUPolyDADMAC(42.4％)Tallopol ACF(50.5％)软化水 53.246.8 37.26.056.8 47.152.9 39.660.4
Afilan V4855为Clariant GmbH，Frankfurt，Germany的链烷膦酸酯钾盐。
Afilan PTU为Clariant GmbH，Frankfurt，Germany的CH3-capped的乙氧基和丙氧基油酸。
PolyDADMAC为catalog nr.52237-6，supplier Aldrich ChemicalCompany，Inc.，Milwaukee，USA的低摩尔质量的聚二烯丙基二甲基氯化铵的缩写。
Tallopol ACF为Stockhausen，Krefeld，Germany的碳酸钾盐和碳酸钠盐的产品混合物。
表B特定电阻率
试验号   1A   1B   1C   1D   1E
用涂抹器施加的整理剂成分纱线上的COS量(wt.％)20℃下50wt.％的整理剂成分的电导率(mS/cm)纱线的特定电阻率(Ohm.cm)   a13.042.63.5E+03   b13.043.76.5E+03   b14.043.72.8E+03   c14.045.42.8E+03   d14.0215.05.8E+02
比较示例1
该比较示例涉及其中示例1中的纱线带有0.9％的通常用于Twaron纱线的纺丝的非离子型整理剂的试验。整理剂溶液(50wt.％)的电导率为0.009mS/cm。所得纱线的特定电阻率为7.2E+07Ohm.cm。
示例2
该示例示出在与纺丝工序一体的操作中将包含导电的有机物质(COS)的整理剂施加到烘干的纱线上的工序。示例1中的纺丝物质通过具有2000个直径为59微米的喷丝孔的喷丝板被挤出，然后相继穿过与示例1中所述相同的空气带、凝固浴、中和浴和冲洗浴。借助于一对挤出辊去除过度粘附的水。然后，纱线经过一连串3个烘干滚筒(6卷，160℃；6卷，180℃；4卷，250℃)。纱线与滚筒的表面总共接触大约7秒。然后借助于一液体涂抹器和一供给泵为完全烘干的长丝束提供包含COS的含水整理剂。然后，纱线经过一输送滚筒(4卷大约20℃)并以300m/min的速度绕成一卷。所得纱线的线密度为3220dtex。以下工艺条件变化(表C和D)：
a)包含COS的整理剂的成分
b)纱线上的COS量
c)整理剂溶液的浓度
表C包含导电的有机物质的含水整理剂
整理剂的浓度(wt.％)        整理剂成分代号
  a237.6   b246.3   d250
溶液中的COS(％)Afilan V4855(37.6％)Afilan PTUTallopol ACF(50.5％)软化水 100 86.113.9 99.01.0
表D特定电阻率
试验号   2A   2B    2C
用涂抹器施加的整理剂成分纱线上的COS量(wt.％)20℃下50wt.％的整理剂成分的电导率(mS/cm)纱线的特定电阻率(Ohm.cm)   a23.042.67.8E+03   b23.543.77.2E+03    d22.5215.09.6E+02
示例3
该示例示出将包含导电的有机物质(COS)的整理剂施加到一没有直接与纺丝工序连接的烘干的纱线上。可以通过商业途径获得的Twaron2200(1610dtex/f 1000)纱线经受下面的处理。纱线卷被转动展开同时使纱线相继经过一液体涂抹器，通过一蒸气箱(温度240℃，停留8秒时间)，最后以75m/min的速度绕成一卷。利用液体涂抹器和供给泵，纱线被涂覆表E和F中所提到的整理剂。以下工艺条件变化：
a)包含COS的整理剂的成分
b)纱线上的COS量
c)整理剂溶液的浓度
表E包含导电的有机物质的含水整理剂
整理剂的浓度(wt.％)              整理剂成分代号
   a315    d310    d415    d120
溶液中的COS(％)Afilan V4855(37.6％)Tallopol ACF(50.5％)软化水 40.060.0 19.880.2 29.770.3 39.660.4
表F特定电阻率
试验号   3A   3B   3C    3D
用涂抹器施加的整理剂成分纱线上的COS量(wt.％)20℃下50wt.％的整理剂成分的电导率(mS/cm)纱线的特定电阻率Ohm.cm   a32.542.63.9E+03   d32.0215.02.9E+03   d43.0215.01.8E+03    d14.0215.08.8E+02
示例4
该示例示出将包含导电的有机物质(COS)的整理剂施加到一没有直接与纺丝工序连接的烘干的纱线上。可以通过商业途径获得的Twaron2200(3220dtex/f 2000)纱线经受下面的处理。纱线卷被转动展开同时使纱线相继经过一双转动式单面给液辊并通过一热空气箱(温度180℃，停留18秒时间)，最后以100m/min的速度绕成一卷。利用该双转动式单面给液辊，纱线被涂覆表G和H中所提到的整理剂。以下工艺条件变化：
a)包含COS的整理剂的成分
b)纱线上的COS量
c)整理剂溶液的浓度
表G包含导电的有机物质的含水整理剂
整理剂的浓度(wt.％)   整理剂成分代号
   a120    d415
溶液中的COS(％)Afilan V4855(37.6％)Tallopol ACF(50.5％)软化水 53.246.8 29.770.3
表H特定电阻率
试验号   4A   4B
用涂抹器施加的整理剂成分纱线上的COS量(wt.％)20℃下50wt.％的整理剂成分的电导率(mS/cm)纱线的特定电阻率(Ohm.cm)   a110.342.63.5E+03   d45.6215.01.2E+03
示例5
该示例示出将包含导电的有机物质(COS)的整理剂施加到一没有直接与纺丝工序连接的烘干的并且无整理剂的纱线上。无整理剂的Twaron(1610dtex/f 1000)纱线卷经受下面的处理。纱线卷被展开并使纱线相继经过一液体涂抹器，通过一热空气箱(温度90℃，停留32秒时间)，最后以50m/min的速度绕成一卷。利用液体涂抹器和供给泵，纱线被涂覆表K和L中所提到的整理剂。以下工艺条件变化：
d)包含COS的整理剂的成分
e)纱线上的COS量
f)整理剂溶液的浓度
表K包含导电的有机物质的含水整理剂
整理剂的浓度(wt.％)          整理剂成分代号
   e120     f132     g120
溶液中的COS(％)Leomin ANLeomin ORAtlas G3634a软化水 20.080.0 16.016.068.0 20.080.0
Leomin AN为Clariant GmbH，Frankfurt，Germany的辛烷膦酸乙酯钾盐。
Leomin OR为Clariant GmbH，Frankfurt，Germany的脂肪酸聚乙二醇酯。
Atlas G3634a为Uniqema，Middlesbrough，England的咪唑啉季铵化衍生物。
表L特定电阻率
试验号   5A   5B   5C
用涂抹器施加的整理剂成分纱线上的COS量(wt.％)20℃下50wt.％的整理剂成分的电导率(mS/cm)纱线的特定电阻率(Ohm.cm)   e15.040.82.2E+03   f18.015.25.6E+03   g15.04.72.2E+04

Claims (10)

1、一种芳族聚酰胺长丝纱线，该纱线带有包含大于1.5wt.％的有机物质的整理剂并且该纱线的特定电阻率小于2.5*104Ohm.cm，在20℃下作为在水中的50wt.％的整理剂成分测量时该有机物质的电导率大于4mS/cm。
2、根据权利要求1所述的芳族聚酰胺长丝纱线，其特征在于，该纱线带有包含大于2wt.％的有机物质的整理剂并且该纱线的特定电阻率小于2*103Ohm.cm，在20℃下作为在水中的50wt.％的整理剂成分测量时该有机物质的电导率大于30mS/cm。
3、根据权利要求1或2所述的芳族聚酰胺长丝纱线，其特征在于，该纱线带有包含大于2wt.％的有机物质的整理剂并且该纱线的特定电阻率小于103Ohm.cm，在20℃下作为在水中的50wt.％的整理剂成分测量时该有机物质的电导率大于41mS/cm。
4、一种制造权利要求1所述的特定电阻率小于2.5*104Ohm.cm的纱线的方法，它包括将有机物质溶液施加到芳族聚酰胺纱线上使得所述有机物质的质量百分比相对于不带整理剂的纱线的总重量大于1.5wt.％，其特征在于，在20℃下作为在水中的50wt.％的整理剂成分测量时，该有机物质的电导率大于4mS/cm。
5、根据权利要求1至3中任一项所述的纱线的用于输送电流的应用。
6、根据权利要求5所述的应用，其特征在于，该纱线用于在包含芳族聚酰胺的材料中输送电流。
7、根据权利要求5所述的应用，其特征在于，该纱线用于在电梯电缆中输送电流。
8、根据权利要求5所述的应用，其特征在于，该纱线用于在基本由芳族聚酰胺纱线构成的电梯电缆中输送电流。
9、一种基本由芳族聚酰胺纱线构成的电缆，至少一芳族聚酰胺长丝纱线带有包含大于1.5wt.％的有机物质的整理剂并且该纱线的特定电阻率小于2.5*104Ohm.cm，在20℃下作为在水中的50wt.％的整理剂成分测量时该有机物质的电导率大于4mS/cm。
10、根据权利要求9所述的电缆，其特征在于，所述电缆为电梯电缆。
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CN101929073A (zh) * 2009-06-23 2010-12-29 东丽纤维研究所（中国）有限公司 一种抗静电性聚酰胺纤维纺织品的加工方法
CN101929073B (zh) * 2009-06-23 2013-07-17 东丽纤维研究所（中国）有限公司 一种抗静电性聚酰胺纤维纺织品的加工方法
CN105189854A (zh) * 2013-03-15 2015-12-23 帝人芳纶有限公司 芳族聚酰胺纱的高速搓捻法

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EP1435407A1 (en) 2004-07-07
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