CN86102214A - 抗静电组合物及其制品 - Google Patents
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Abstract
一种抗静电聚合物共混组合物及其制品被公开 了。组合物包括(重量份数计):(a)聚氯乙烯100份, (b)羧基丁腈三聚体30-40份,(c)非离子型抗静电 剂5-8份,(d)金属稳定剂2-5份,(e)环氧化油 5-10份,(f)主增塑剂50-90份,和(g)润滑剂 1-2份。也公开了应用本发明的组合物制成的制品 而防止抗静电的影响或增长的方法。
Description
本发明涉及一种柔软抗静电组合物及其制品,更特别是本发明涉及抗静电鞋袜、压延片和其它需要抗静电的成形制品。在制品整个使用期间,这种抗静电性质基本保持不变,而且制品和产品也具有耐油和防尘性质。
已有各种方法来制成抗静电的聚合物组合物,例如在聚合物配方中掺入离子型或非离子型抗静电剂、金属粉或结构碳等。然而,由此而制成的组合物或产品存在某些不足:(1)为了要给予产品抗静电性。需要比较大量的金属粉掺入塑料基质中;(2)结构碳由于反复曲挠使石墨结构破裂而变成导电性很少;(3)需要比较大量抗静电剂。大量使用抗静电剂后,由于聚合物的混溶性所限制,在整个使用期内这些抗静电剂开始渗透出来,结果失去抗静电性。
用抗静电剂对产品进行表面处理通常不能持久,在一定时间内就要磨耗掉,所以需要经常或反复处理。
可是,本发明的组合物改进了配方,其中含有金属稳定剂,并具有以往已知产品的一切优点。同时又有满意的商业和工业前景,特别有关抗静电性质。
本发明的目的之一是提供一种聚合物共混组合物,它能消除静电并防止由静电产生的不希望的影响(例如电击或事故)。
本发明的目的之一是提供一种聚合物共混组合物,由它做成的产品,在整个使用期间始终保持抗静电性质,基本上没有损失。
本发明的目的之一是提供一种应用由本发明组合物做成的产品和装置而防止静电产生不希望影响的方法。
本发明的目的之一是提供持久、防尘、柔软及抗静电的产品。这种产品在高温、低温和室温时以及在湿度下能保持这些性质。
其它目的和优点在详细叙述本发明方法时将会看得更明显。
本发明的目的和优点通过一种热塑性聚合物共混组合物体现出来,该组合物由羧基丁腈共聚物(XNBR)与聚氯乙烯树脂(PVC)、非离子型抗静电剂和金属稳定剂相结合而成。
虽然,能使用与本发明的配方相混溶的任何适宜的树脂,而聚氯乙烯(PVC)树脂为最好。聚氯乙烯树脂应是一种均聚体(本体或悬浮),其K值约为65-75(Fikentscher方法)。
为了制备本发明共混物所需的羧基丁腈共聚物(XNBR)可从加拿大萨尼亚的波里萨公司购买。用于制备本共混物的XNBR在美国专利第4,271,052号和第4,438,230号中有更准确地叙述,这二篇专利被收入本发明的参考文献中。
必须注意,XNBR的各种所需要的性质与通常的丁腈橡胶是完全不同的,例如:XNBR在模制温度时,挤出较快,流动更迅速;具有更硬、更坚韧的硫化胶以及抗张强度等。因此,应该注意到XNBR是一种三聚体,而通常的丁腈橡胶是一种共聚体,因此在化学结构上是截然不同的。各种有用的XNBR之中,以波里萨公司(Polysar.Supra)生产的Krynac221属最好。
任何适合的非离子型抗静电剂都可以应用于本发明的配方中,然而最好的是烷基乙氧基化物的共混物,例如阿古斯(Argus)化学公司(纽约,布鲁克林)制造的Markstat AL-15。离子型抗静电剂不能应用于本发明的配方中。
与某些现有技术相反,本发明特别采用商业上可购到的一般金属稳定剂。适宜的金属稳定剂的例子是锡、钡-镉-锌(Ba-Cd-Zn)络合物等。
如果需要也可在本发明的共混物中加入添加剂如增塑剂、偶联剂、润滑剂、阻燃剂、着色剂等,以使产品有所希望的柔性和软度、易加工性和其它要求的特性。
最好的增塑剂主要是邻苯二甲酸酯,如邻苯二甲酸二-2-乙基己基酯。也可以用部分己二酸酯增塑剂代替邻苯二甲酸酯增塑剂。偶联剂的一个例子是有机钛酸酯。环氧化豆油或树脂酸酯是最好的环氧增塑剂。水和三氧化铝为最好的增强阻燃剂。使加工容易的最好润滑剂的例子是低分子量的聚乙烯、硬脂酸和硬脂酸钙。
本发明的组合物也是热塑性的,能够采用一般的挤出、注塑和压延等方法进行加工。当然,本发明的组合物也能由一般的化学方法进行交联。
本发明的一个优点是能够通过添加适宜的颜料(如有机或无机颜料)做成任何颜色的产品,着色后的颜色在正常使用期内和暴露在环境条件下稳定不变色。
此处所用“稳定”一词的含义是组合物或产品在通常条件和产品正常使用下保持它原来性质(如颜色、抗静电和防尘特性)。基本上没有变化。“基本上”这一词意思是比预料在正常条件下产生的变化更好。
低温、高温和室温所指明的是在世界各地各个季节中通常能遇到的温度条件。例如室温可能指大约20℃到30℃,低温可能是5℃到-10℃,高温可以是35℃到45℃,尤其在柏油铺设的人行道以及公路等地方所遇到的。
由本发明的组合物制成的产品包括对静电电击是安全的或是抗静电的制品。“抗静电”一词意味着不会获得、累积、保持或构成在工业和商业中通常不希望存在的一定程度的静电。例如一双抗静电鞋为了防止产生静电荷必须具有一定程度的导电性。然而,为了允许电荷的消散,防止有毛病的电装置或设备产生电击,这种导电率必须是极小的。这些制品的例子是抗静电鞋袜(鞋、鞋底等)、抗静电地板覆盖物、抗静电室内装璜品、抗静电密封环和抗静电的绝缘体、耐油、耐热以及耐尘灰的制品、电子计算机内终端连接件、电器设备元件等,它们都特别希望防止静电。
本发明的聚合物组合物可由下列各种组份共混而制备(其中各组份的量都以100份PVC树脂为基准):(a)PVC树脂100份,(b)XNBR10-50份,最好是30-40份,(C)非离子型抗静电剂3-10份,最好为5-8份,(d)金属稳定剂1-10份,最好为2-5份,(e)增塑剂10-120份,最好为20-90份,(f)环氧增塑剂3-15份,最好为5-10份,(g)偶联剂0.2-0.5份,最好为0.025-0.4份,(h)润滑剂0.5-5.0份,最好为0.5-2.0份,和(i)阻燃剂为2-10份,最好为3-6份。加入着色剂的量足以使产品产生所希望的颜色。
聚合物组合物及其产品的最优实施例列举于下面表1-3中,表1表明一种白色聚合物共混物,表2为一种黑鞋帮,表3为灰鞋底。
这些产品的物性列在表1-3和表4中。测定物理性能所采用的方法为已知技术,已在标准文献(ASTM)中叙述,引证在表4中并以参考文献收入于此。某些试验参数列在表5中。
表1
聚合物树脂共混组合物
白色抗静电PVC
组分 PHR*
PVC树脂 100.0
Al2O3·3H2O Hydral 710B-(阻燃剂) 5.0
Jay Flex 77-(二异庚基增塑剂) 77.0
DHP(邻苯二甲酸二异己酯) 8.5
环氧化豆油 12.0
锡 2.0
KR-55(钛酸酯) 0.05
硬脂酸锌 0.10
硬脂酸 0.50
二氧化钛(白色) 2.2
Krynac 221(羧基丁腈) 30.0
Markstat AL-15(非离子型抗静电剂) 5.0
群青色(增白剂) 0.005
*PHR=为每100份树脂(PVC)的份数
表2
聚合物树脂共混组合物
AWS-60抗静电黑色Welpak鞋帮
组分 PHR*
PVC树脂 100.0
Al2O3·3H2O Hydral 710B-(阻燃剂) 6.0
Jay Flex 77-(二异庚基增塑剂) 84.0
DHP(邻苯二甲酸二异己酯) 10.0
环氧化豆油 10.0
锡 2.0
KR-55(钛酸酯) 0.030
硬脂酸 1.0
Krynac 221(羧基丁腈) 30.0
Markstat AL-15(非离子型抗静电剂) 6.0
一次碳黑 2.5
硬脂酸钙 0.2
*PHR=份数/100份树脂(PVC)的份数
表3
聚合物树脂共混组合物
AWS-25抗静电灰色Welpak鞋底
组分 PHR*
PVC树脂 100.0
Al2O3·3H2O Hydral 710B-(阻燃剂) 6.0
Jay Flex 77-(二异庚基增塑剂) 71.7
DHP(邻苯二甲酸二异己酯) 8.5
环氧化豆油 8.5
锡 1.7
KR-55钛酸酯 0.026
硬脂酸 1.0
二氧化钛(白色) 2.0
Krynac 221(羧基丁腈) 30.0
Markstat AL-15(非离子型抗静电剂) 6.0
一次碳黑 0.05
硬脂酸钙 0.2
*PHR=为每100份树脂(PVC)的份数
表5
全部试验样品为6毫米厚浸没试验(72小时)
初始电阻 72小时后的电阻
水 1.6×107欧姆 1.1×107欧姆
液压油 1.5×107欧姆 1.9×107欧姆
ASTM油#3 1.6×107欧姆 8.0×106欧姆
初始电阻 1.2×107欧姆
24小时以后 2.5×107欧姆
暴露在紫外线下
初始电阻 1.6×107欧姆
6小时以后 2.5×107欧姆
所考虑抗静电为1×105到1×108欧姆之间
试验都在由BTR SilVer town公司(Horninylow Road Barton-on Trcnt,Staffs DE130SN)生产的抗静电和导电鞋试验机上完成的。
Claims (7)
1、一种聚合物共混组合物,其特征在于它基本上由一列组份组成(都是以重量份数计):(a)聚氯乙烯100份,(b)羧基丁腈共聚物30-40份,(c)非离子型抗静电剂5-8份,(d)金属稳定剂2-5份,(e)环氧化油5-10份,(f)主邻苯二甲酸酯或已二酸酯增塑剂50-90份,和(g)由硬脂酸、硬脂酸锌、硬脂酸钙和低分子量聚乙烯等组成的一类物质中任选取的润滑剂1-2份。由此而得到的聚合物共混物是抗静电和柔软的。
2、根据权利要求1所述的组合物,也包括金属偶联剂0.3-0.4份。
3、根据权利要求2所述的组合物,还包括颜料,其量足以提供组合物有所希望的颜色。
4、根据权利要求1所述的组合物,在低温、室温或较高温度时,它能保持抗静电性质,所述的性质实际上没有损失,并在常温和低温时是柔软的。
5、由权利要求1所述组合物所制成的一种抗静电制品。
6、根据权利要求5所述的制品是鞋、鞋底或其它部件。
7、包括使用由权利要求1所述的组合物制成制品的防止静电影响的方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/718,441 | 1985-04-01 | ||
US06/718,441 US4594367A (en) | 1985-04-01 | 1985-04-01 | Antistatic composition and articles made therefrom |
Publications (1)
Publication Number | Publication Date |
---|---|
CN86102214A true CN86102214A (zh) | 1987-01-14 |
Family
ID=24886095
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN86102214A Pending CN86102214A (zh) | 1985-04-01 | 1986-04-01 | 抗静电组合物及其制品 |
Country Status (11)
Country | Link |
---|---|
US (1) | US4594367A (zh) |
EP (1) | EP0216866B1 (zh) |
JP (1) | JP2562443B2 (zh) |
CN (1) | CN86102214A (zh) |
AU (1) | AU578884B2 (zh) |
BR (1) | BR8606736A (zh) |
CA (1) | CA1255418A (zh) |
IN (1) | IN164509B (zh) |
MY (1) | MY100099A (zh) |
NZ (1) | NZ215508A (zh) |
WO (1) | WO1986005662A1 (zh) |
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CN100340627C (zh) * | 2005-03-11 | 2007-10-03 | 华南理工大学 | 聚合物基抗静电剂及其制备方法 |
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US20050203259A1 (en) * | 2004-03-09 | 2005-09-15 | Poliafico Kristen K. | Method for reducing static charge and reactor fouling in a polymerization process |
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SU891713A1 (ru) * | 1979-06-12 | 1981-12-23 | Всесоюзный Научно-Исследовательский Институт Пленочных Материалов И Искусственной Кожи | Полимерна композици дл получени пленочного материала |
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JPS59145234A (ja) * | 1983-02-09 | 1984-08-20 | Mitsui Toatsu Chem Inc | 低毒性農業用塩化ビニルフイルム |
JPS6157441A (ja) * | 1984-08-30 | 1986-03-24 | Nippon Seiki Co Ltd | 警告表示装置 |
-
1985
- 1985-04-01 US US06/718,441 patent/US4594367A/en not_active Expired - Fee Related
-
1986
- 1986-03-18 NZ NZ215508A patent/NZ215508A/xx unknown
- 1986-03-20 IN IN231/CAL/86A patent/IN164509B/en unknown
- 1986-03-27 WO PCT/US1986/000631 patent/WO1986005662A1/en active IP Right Grant
- 1986-03-27 JP JP61501973A patent/JP2562443B2/ja not_active Expired - Lifetime
- 1986-03-27 CA CA000505415A patent/CA1255418A/en not_active Expired
- 1986-03-27 EP EP86902249A patent/EP0216866B1/en not_active Expired - Lifetime
- 1986-03-27 AU AU56663/86A patent/AU578884B2/en not_active Ceased
- 1986-03-27 BR BR8606736A patent/BR8606736A/pt unknown
- 1986-04-01 CN CN86102214A patent/CN86102214A/zh active Pending
-
1987
- 1987-09-09 MY MYPI87001612A patent/MY100099A/en unknown
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CN1067037C (zh) * | 1998-03-02 | 2001-06-13 | 北京四元特种防护技术开发公司 | 防静电水磨石及其制造方法 |
CN100340627C (zh) * | 2005-03-11 | 2007-10-03 | 华南理工大学 | 聚合物基抗静电剂及其制备方法 |
CN1295289C (zh) * | 2005-03-30 | 2007-01-17 | 上海永利带业制造有限公司 | 一种输送带打底贴合材料及其制备方法和用途 |
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Also Published As
Publication number | Publication date |
---|---|
EP0216866A4 (en) | 1987-11-30 |
AU5666386A (en) | 1986-10-23 |
EP0216866A1 (en) | 1987-04-08 |
WO1986005662A1 (en) | 1986-10-09 |
JPS63500177A (ja) | 1988-01-21 |
BR8606736A (pt) | 1987-08-11 |
IN164509B (zh) | 1989-04-01 |
JP2562443B2 (ja) | 1996-12-11 |
US4594367A (en) | 1986-06-10 |
CA1255418A (en) | 1989-06-06 |
NZ215508A (en) | 1988-08-30 |
AU578884B2 (en) | 1988-11-03 |
EP0216866B1 (en) | 1991-12-18 |
MY100099A (en) | 1989-10-10 |
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