CN1875431A - 静电耗散增塑溶胶 - Google Patents

静电耗散增塑溶胶 Download PDF

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CN1875431A
CN1875431A CNA2004800326496A CN200480032649A CN1875431A CN 1875431 A CN1875431 A CN 1875431A CN A2004800326496 A CNA2004800326496 A CN A2004800326496A CN 200480032649 A CN200480032649 A CN 200480032649A CN 1875431 A CN1875431 A CN 1875431A
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S·D·霍顿
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Abstract

揭示了一种固有导电聚合物与增塑溶胶的混合物。由该混合物制造的制品可用作静电耗散(ESD)制品。

Description

静电耗散增塑溶胶
优先权要求
本申请要求2003年11月14日提交的美国临时专利申请系列号60/520,040的优先权，其代理人编号为12003026。
发明领域
本发明涉及具有静电耗散性质的增塑溶胶。
发明背景
对于易受静电影响的电子元件(例如磁盘驱动器、半导体、带盘组件和电子组件封装)的制造来说，静电耗散(ESD)制品是极为重要的。
已经发现固有导电聚合物(固有导电聚合物)(ICP)可非常有效地用于许多种电活性材料，例如防污船舶涂料；抗静电纤维，涂料和封装；电池；导电油墨；导电粘合剂；EMI/RFI屏蔽制品，雷达或微波吸收制品和传感器。
固有导电聚合物可以是涂料的基质。由于成本方面的原因，更优选将固有导电聚合物分散在惰性粘合剂中作为涂料的基质或连续相。
                           发明简述
本领域需要的是固有导电聚合物在惰性粘合剂中的分散体，所述惰性粘合剂在涂敷或模塑到制品表面上之后也可作为阻挡层(barrier)。这种惰性粘合剂的一个例子是乙烯基增塑溶胶，该增速溶胶可容易地用于许多种也需要ESD性质的制品，该制品是环境友好的，比较便宜，易于使用，而且具有良好的性能。
本发明通过提供固有导电聚合物在乙烯基增塑溶胶中形成的混合物解决了本领域的这个问题。
本发明一个方面涉及包含固有导电聚合物和增塑溶胶的混合物。较佳的是尽管该混合物包含固有导电组合物，但是它像任何其它增塑溶胶一样是可涂敷和可模塑的。
本发明一个优点是，由于ICP不会显著地增大增塑溶胶的粘性，当然不会像导电炭黑那样增加增塑溶胶的粘性，因此该混合物便于处理。
参照本发明的实施方式，本发明的其他优点将是显而易见的。
本发明的实施方式
固有导电聚合物
适用于本发明的固有导电聚合物包括具有以下重复单体单元的聚合物：苯胺，噻吩，吡咯，苯基硫醇等。其他例子包括选自以下的导电聚合物：取代和未取代的聚对苯亚甲基亚乙烯基，取代和未取代的聚苯胺，取代和未取代的聚吖嗪，取代和未取代的聚噻吩，取代和未取代的聚对亚苯，取代和未取代的聚对苯硫醚，取代和未取代的聚呋喃，取代和未取代的聚吡咯，取代和未取代的聚硒吩，取代和未取代的聚乙炔(polyacetylene)，它们的混合物以及它们的共聚物。在多种专利中揭示了这些导电聚合物，这些专利包括美国专利第5,069,820号(Jen等人)；第5,160,457号(Elsenbaumer)；第5,185,100号(Han等)；第5,281,363号(Shacklette等)；第5,378,403号(Shacklette)；第5,422,423号(Shacklette等)；第5,456,862号(Kwan-Yue等)；第5,567,355号(Wessling等)；第5,700,398号(Angelopoulos等)和第5,911,918号(Shacklette等)。如这些专利所述，在固有导电聚合物中经常掺杂有酸，例如盐酸或对甲苯磺酸。
特别优选取代的聚苯胺，例如美国专利第5,968,417号(Visawanathan)所揭示的，更优选PolyOne公司所销售的TeslartTM固有导电聚合物。这种取代的聚苯胺是木质素磺酸接枝的聚苯胺。
增塑溶胶
聚合物处理领域与乙烯基增塑溶胶特别类似。这些增塑溶胶由分散级(dispersion-grade)的聚氯乙烯(PVC)树脂(均聚物和共聚物)和增塑剂形成的。在美国专利第4,581,413号；第4,693,800号；第4,939,212号；和第5,290,890号中，以及许多其他专利，例如上述四个专利中揭示了示例性的分散级PVC树脂。
用来由分散级乙烯基树脂制备流体增塑溶胶的原液体(primary liquid)增塑剂是各种酸的有机酯，这些酸是例如邻苯二甲酸、磷酸、己二酸、癸二酸等。其中邻苯二甲酸酯最经常用作分散体类氯乙烯树脂的主要增塑剂。当以合适的比例使用包含中等长度烷基(例如长度约为6-12个碳原子)的邻苯二甲酸二烷基酯时(每100重量份喷雾干燥的氯乙烯树脂粉末中约含5-120重量份)，能够使增塑溶胶的性质获得良好的平衡。有用的液体增塑剂的具体例子包括邻苯二甲酸二辛酯，邻苯二甲酸丁基苄酯，己二酸二辛酯，癸二酸二丁酯，邻苯二甲酸二壬酯和硬脂酸甘油酯。
PolyOne公司( www.polyone.com)是每个消费市场的乙烯基增塑溶胶的商业来源。通过加入热稳定剂或光稳定剂、彩色颜料、阻燃剂、发泡剂和预计产品所需的其他添加剂，可以增强这些PVC树脂在增速液中的分散体。
乙烯基增塑溶胶在室温下通常是液体，可根据所述化合物将其倒入、用泵抽入、喷入或浇注入其中。这些化合物的硬度可变化，从硬度计肖氏硬度A为8的假鱼饵增塑溶胶到硬度计肖氏硬度D为65的旋转浇注(rotocast)增塑溶胶(大部分为PVC)。乙烯基增塑溶胶在涂料和模塑应用中的优点包括使用方便和价格经济。
或者也可将聚(甲基丙烯酸甲酯)及其共聚物和增塑剂用作本发明的增塑溶胶。
固有导电聚合物和增塑溶胶的混合
使用常规的混合设备将固有导电聚合物充分混入增塑溶胶中。
以混合物的总量为基准计，加入增塑溶胶的固有导电聚合物的量可约为1-50重量％，优选约为5-25重量％。
任选的组分
涂料工业中通常使用的各种组分可包含在本发明的混合物中。这些任选的添加剂的非限制性例子包括滑爽剂，防粘剂，抗氧化剂，紫外光稳定剂，猝灭剂，增塑剂，脱模剂，润滑剂，抗静电剂，阻燃剂，以及玻璃纤维、滑石、白垩或粘土之类的填料。在这些填料中，纳米粘土的性质可为阻燃剂增加刚性、韧性和炭化性质。在本发明的混合物中，这些任选添加剂的含量可约为0-95重量％，优选约为0.1-50重量％。最优选其含量约占混合物的1-40重量％。
任何用于涂料和油漆的常规着色剂均可用于本发明。可使用的常规着色剂包括无机颜料，例如二氧化钛、氧化铁、氧化铬、铬酸铅、炭黑、二氧化硅、滑石、高岭土、金属氧化物、硅酸盐、铬酸盐等；以及有机颜料，例如酞菁蓝、酞菁绿、咔唑紫、蒽素嘧啶黄、黄烷士酮黄、异吲哚啉黄、靛蓝、喹吖啶酮紫、苝红、重氮红等。以混合物为基准计，着色剂的量可从0至约为40重量％，优选约为1.5-20重量％。
石墨也可用作混合物中任选的组分。石墨可以是天然或合成得到的，可为常规尺寸的可在市场上购得的片状形式。混合物中石墨的量可从0至约35重量％，优选约为10-20重量％。石墨片沿其平坦表面具有极低的表面电阻率，与固有导电聚合物的微粒性质互补，便于这两种材料在增塑溶胶形成的膜中形成密堆积。
本发明的实用性
本发明的混合物具有上面三个美国专利所揭示的乙烯基增塑溶胶所有的优点和实用性。但是固有导电聚合物增强了这些性质，因为它使该混合物获得电活性，而且能够作为静电耗散剂。
使用四点探针测试(ASTM D-257-99)测得的表面电阻率可约为1×103至约1×1012欧姆/平方。
使用乙烯基增塑溶胶制造ESD制品不会受到所存在的ICP的负面影响。实际上，所有用于乙烯基增塑溶胶的常规涂敷技术也可用于本发明。如果通过加入导电炭黑或其他静电耗散固体使乙烯基增塑溶胶具有静电耗散性，则不会具有这种多用性。由这些静电耗散固体造成的粘度增大会使以下的一些或所有用来处理增塑溶胶的常规制造技术的可用性降低或不可用。
浸涂：当增塑溶胶涂层成为模具本身的功能部份时，该方法被称为浸涂。金属配件可需要粘合剂底漆也可不需要底漆。通常的应用包括工具手柄和夹具；纺织品；线栅和篮；电镀架；传输机钩等。浸涂可以是热浸或冷浸。
热浸：迄今为止最广泛的浸涂处理技术，热浸需要首先对物体进行加热，然后将其浸入增塑溶胶中。热量使得增塑溶胶涂料在热模(hot form)上胶凝。
冷浸：不需要对金属部件进行预热；所获得的量很大程度上取决于增塑溶胶的粘性和触变性。
模塑：一些种类的模塑是施涂增塑溶胶时常用的。可使用薄壳模塑(slushmolding)来制造空心的挠性物品，该方法的步骤是在模具中填入增塑溶胶，充分加热使得模具内表面附近的层发生胶凝，然后排去过量的增塑溶胶。然后使胶凝的层与模具完全融合，然后从模具剥离。旋转模塑包括具有复杂形状的空心挠性或刚性的形式。其过程如下：使用预定重量的增塑溶胶填充两部分的模，将其插入加热的炉内，然后在两个平面上同时旋转。浸渍模塑表示浸渍固体模；胶凝、融合和剥离空心部件的过程。敞口模塑是直接模塑汽车的空气过滤器之类最终制品的方法。
其他涂敷：一些种类的涂敷使增塑溶胶相对于物品运动或使物品相对于增塑溶胶运动。本领域技术人员可以参照百科全书、其他技术文献或专利文献的描述，不需过度试验而简便地进行刮涂，辊涂，逆转辊涂等方法。本发明的混合物可如此方便地用于常规的增塑溶胶涂敷的原因是固有导电聚合物的存在不会对混合物的粘度造成负面影响，粘度当然不会像含有导电炭黑的增塑溶胶那么高。
乙烯基增塑溶胶可用于终端汽车，FDA，UL，ASTM，NSF，USDA，军事，医学或客户特需用途。
可由乙烯基增塑溶胶制备的任何需要ESD性质的制品均可通过本发明制造。由ESD增塑溶胶制造的制品的非限制性例子包括带材、地板、手套、盘衬里和电子元件生产过程中使用的任何其他制品。其他用途包括用于医学和药学净室以尽可能减少尘土和其他污染物聚积；用于制造或贮存爆炸材料的环境，以尽可能减少静电放电，以免产生火花引燃爆炸材料；用于其他低湿度环境的工作场所，以免静电冲击造成安全、健康或舒适方面的问题；用于涂敷的纺织物(纺织织物和无纺织物)；用于传送带和其它自动传送设备，以免静电放电对其中输送的电子器件或用来控制输送过程的电子器件造成负面影响(包括在消费品上的所谓″智能标签(smart tag)″)。
在以下实施例中描述了其它的实施方式。
实施例
表1显示了用于实施例1-5和比较例A的购得的组分
                              表1-组分的来源
  组分名   目的   商品名   通用名   商业来源   供应商的位置
  乙烯基增塑溶胶   成膜剂   150-255Natural   fPVC   PolyOne公司   AvonLake，OH
  固有导电聚合物   静电耗散   TeslartTM   木质素磺酸接枝的聚苯胺   PolyOne公司   AvonLake，OH
  石墨   静电耗散   5026   石墨   SuperiorGraphite公司   Chicago，IL
表2显示了本发明实施例1-3中混合物的配方、制备方法和所得的性质。
                                       表2
                                 配方、制备和性质
  组分名  实施例1  2  3
                                   配方单位：份)
  150-255乙烯基增塑溶胶  100.00  100.00  100
  TeslartTM  17.19  17.19  8.59
  石墨  0  4.17  17.19
                                        制备
  混合设备  Cowels  Cowels  Cowels
  混合温度  保持低于35℃  保持低于35℃  保持低于35℃
  混合速度  200-500RPM  200-500RPM  200-500RPM
  组分加入次序  制备的增塑溶胶，然后混合在Teslart中，然后是石墨  制备的增塑溶胶，然后混合在Teslart中，然后是石墨  制备的增塑溶胶，然后混合在Teslart中，然后是石墨
  混合之后产物的形式  液体分散体  液体分散体  液体分散体
                                        性质
  Brookfield粘度(ASTM D 1824-95)20RPM，6号轴，厘泊  16,000   22,000  11,500
  表面电阻率(ASTM D257-99)表面电阻，欧姆/平方  5.0*10E6   2.1*10E4  8.7*10E9
实施例1-3说明，与实施例3相比，较高的固有导电聚合物含量(实施例1和2)会降低表面电阻率。加入该混合物的石墨降低了表面电阻，但是增大了粘度(实施例1与实施例2相比)。因此，通过这些数据，本领域技术人员不需要进行过度的试验便可根据具体用途的需要，使表面电阻率与粘度达到平衡。
本发明并不限于以上实施方式。以下是权利要求书。

Claims (10)

1.一种混合物，该混合物包含：
固有导电聚合物，
增塑溶胶。
2.如权利要求1所述的混合物，其特征在于，所述增塑溶胶包含聚氯乙烯。
3.如权利要求1或2所述的混合物，其特征在于，所述增塑溶胶包含聚(甲基丙烯酸甲酯)。
4.如权利要求1-3中任一项所述的混合物，该混合物还包含石墨。
5.如权利要求1-4中任一项所述的混合物，其特征在于，所述固有导电聚合物是聚苯胺。
6.如权利要求5所述的混合物，其特征在于，所述固有导电聚合物是木质素磺酸接枝的聚苯胺。
7.一种涂料，由权利要求1-6中任一项所述的混合物制成。
8.一种模塑制品，由权利要求1-6中任一项所述的混合物制成。
9.一种制品，被权利要求1-6中任一项所述的混合物涂层保护。
10.一种使用权利要求1-6中任一项所述混合物的方法，该方法包括将所述混合物施涂到制品上。
CNA2004800326496A 2003-11-14 2004-11-10 静电耗散增塑溶胶 Pending CN1875431A (zh)

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