CN1745139A - 静电分散树脂组合物及其制造方法 - Google Patents
静电分散树脂组合物及其制造方法 Download PDFInfo
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- CN1745139A CN1745139A CNA2003801095297A CN200380109529A CN1745139A CN 1745139 A CN1745139 A CN 1745139A CN A2003801095297 A CNA2003801095297 A CN A2003801095297A CN 200380109529 A CN200380109529 A CN 200380109529A CN 1745139 A CN1745139 A CN 1745139A
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Abstract
一种实质上透明的抗静电、耐冲击的模塑组合物，其中包含聚碳酸酯树脂和脂环族聚酯树脂以及抗静电聚合材料的可混溶混合物，其中所述聚碳酸酯和脂环族聚酯树脂的混合物以适当比例存在，以与抗静电聚合材料的折射率基本相匹配。
Description
相关申请的交叉文献
本申请要求保护于2002年12月18日提出的U.S临时申请序号60/434855的优先权，该申请作为参考文献全文引入本文。
发明领域
本发明涉及具有实质上透明性的热塑性永久的静电分散组合物。
发明背景
本发明涉及具有优异透明性和耐冲击性的永久的静电分散组合物。由于聚合树脂的强度-重量比高并易于加工，所以适合于许多用途。然而，聚合树脂就其性质来说是绝缘的，因此当受摩擦力如摩擦时，塑料上产生静电荷。它们不能分散这样的静电荷，因而导致它们吸收灰尘和外来的颗粒，由此损坏了由该树脂制成的模塑部件的外观。另外，静电荷的积累使聚合树脂不能在某些电器和电子用途中使用。因此，人们希望聚合树脂具有抗静电性(即，静电传导性)，并且在加工这些材料所用的升温情况下，仍能保持这些性能。
具有抗静电性的聚合树脂和制品，代表性的制备方法是在混合过程中使抗静电剂直接与聚合树脂掺合。不幸的是，抗静电剂随时迁移至制品的表面层上，由于表面层的磨耗而降低了抗静电性。因此，一直保留对稳定的抗静电组合物的需求，组合物中的抗静电剂在高温加工和其使用过程中，在整个聚合树脂中均能保持良好的分散状态。另外，人们希望所述抗静电组合物透明，以便能用于重要性在于能看见被包装零件的电子包装中。
发明概述
含有聚合的树脂和静电分散树脂的抗静电组合物经常是不透明的，尤其在电子包装应用中不合乎要求。特别是为了获得透明的产品，往聚碳酸酯树脂中添加静电分散聚合物是非常困难的。
按照一具体实施方案，基本上透明的抗静电、耐冲击的模塑组合物，其中含有的聚碳酸酯树脂、脂环族聚酯树脂以及抗静电聚合材料的可混溶合物占主要的重量百分比，其中，聚碳酸酯和脂环族聚酯树脂的混合物以适当的比例存在，为的是使与抗静电聚合材料的折射率基本匹配。按照另一具体实施方案，组合物可以含有另外的可混溶的树脂，该另外的可混溶树脂与聚碳酸酯和聚酯树脂一起形成与抗静电聚合材料的折射率基本匹配的混合物。按照具体实施方案，人们希望模塑组合物中以不混溶树脂的形式存在的另外组分，具有的折射率与抗静电聚合材料的折射率基本匹配。由于组合物具有优异的抗静电性、耐冲击性和透明性，所以，组合物可以用于电器和电子装置、电子包装和要求抗灰尘性能的用途。
最佳实施方式的详细说明
按照具体实施方案，把约MV2000～约6000泊的各种粘度的脂环族树脂(优选聚(环己烷-1，4-二亚甲基环己烷-1，4二羧酸酯)，以下称PCCD)与具有约1.52～约1.44(RI)折射率的特定的聚合的静电分散材料，优选聚醚酯酰胺一起添加，以及添加具有约22000～约30000重均分子量的芳族聚碳酸酯树脂，制成一种具有高冲击性的清亮、抗静电组合物。合乎要求的脂环族聚酯树脂具有的折射率，低于聚合的抗静电材料的折射率，而合乎要求的聚碳酸酯具有的折射率，大于抗静电材料的折射率。选择脂环族聚酯树脂和聚碳酸酯树脂的比例，以便使所得到的可混溶混合物的折射率与抗静电聚合材料的折射率基本匹配。优选可混溶混合物的折射率不超出所用聚合的抗静电材料约0.005单位，更优选不超出0.003单位。
术语芳族聚碳酸酯树脂，含有芳族碳酸酯链单元并包括具有通式(I)结构单位之组分，所述通式(I)为：
其中，R1基团总数中至少约60％是芳族有机原子团，而其余部分是脂族、脂环族、或芳族原子团。优选的是R1是芳族有机原子团，更优选的是通式(II)的原子团，所述通式(II)为：
-A1-Y1-A2-
(II)其中，每个A1和A2各为单环、二价的芳基原子团，而Y1是具有把A1和A2分开的一个或两个原子的桥联原子团。在举例说明的实施方案中，一个这样的原子能把A1和A2分开。Y1说明性的但非限制性实例是-O-、-S-、-S(O)-、-S(O2)-、-C(O)、亚甲基、环己基-亚甲基、2-[2，2，1]-双环亚庚基、亚乙基、异亚丙基、亚新戊基、环亚己基、环亚戊基、环亚癸基和亚金刚烷基。桥联原子团Y1可以是烃基或饱和的烃基如亚甲基、环亚己基或异亚丙基。
聚碳酸酯树脂是通过碳酸酯前体与二羟基化合物反应产生的。作为用于本发明的术语“二羟基化合物”，包括例如具有下列通式(III)的双酚化合物：
其中，Ra和Rb分别代表卤原子，例如氯或溴，或一价的烃基，优选具有1～10个碳原子，并且可以是相同的或不同的；p和q各任选0～4的整数；优选的是，Xa代表通式(IV)的基团中的一种：
其中，Rc和Rd分别独立地表示氢原子或一价的线性或环状烃基，而Re是二价的烃基。
一些适当的二羟基化合物的说明性、非限制性实例，包括公开在美国专利4,217,438中的二羟基取代的芳族烃，引入本文作为参考。由通式(III)表示的双酚化合物类型的具体实例的非全部目录包括1，1-二(4-羟基苯基)甲烷；1，1-二(4-羟基苯基)乙烷；2，2-二(4-羟基苯基)丙烷(以下称“双酚A”或“BPA”)；2，2-二(4-羟基苯基)丁烷；2，2-二(4-羟基苯基)辛烷；1，1-二(4-羟基苯基)丙烷；1，1-二(4-羟基苯基)正丁烷；二(4-羟基苯基)苯基甲烷；2，2-二(4-羟基-1-甲基苯基)丙烷；1，1-二(4-羟基-t-丁基苯基)丙烷；二(羟基芳基)链烷烃如2，2-二(4-羟基-3-溴苯基)丙烷；1，1-二(4-羟基苯基)环戊烷烃；和二(羟基芳基)环烷如1，1-二(4-羟基苯基)环己烷。也可以使用两种或更多种不同的二元酚。
典型的碳酸酯前体包括羰基卤化物，例如碳酰氯(光气)和碳酰溴；二卤代甲酸酯，例如二元酚如双酚A、氢醌等的二卤代甲酸酯等，以及乙二醇如1，2-亚乙基二醇和新戊二醇的二卤代甲酸酯；和碳酸二芳基酯，如碳酸二苯酯、碳酸二甲苯酯和碳酸二萘酯。
术语“抗静电分散聚合物”(以下称抗静电聚合物)既与熔融加工成聚合树脂的一些材料有关，又与市售聚合物和制品上喷涂以改进传导性和整个物理性能有关。代表性的是，单元的抗静电剂是单硬脂酸甘油酯、二硬脂酸甘油酯、三硬脂酸甘油酯、乙氧化胺、伯、仲和叔胺、乙氧化醇、硫酸烷基酯、烷基芳基硫酸酯、烷基磷酸酯、烷基胺硫酸酯、季铵盐、季铵树脂、咪唑啉衍生物、脱水山梨醇酯、乙醇胺、甜菜碱和上述的混合物。
典型的聚合的抗静电聚合物是：共聚酯酰胺、聚醚-聚酰胺、聚醚酰胺嵌段共聚物、聚醚酯酰胺嵌段共聚物、含聚亚烷基二醇部分的聚氨基甲酸酯、聚醚酯及其混合物。聚合的抗静电材料是合乎要求的，因为它们有典型的良好的热稳定性，并且可以以纯态或与其它聚合树脂的掺合物状态在熔融态下进行加工。聚醚酰胺、聚醚酯和聚醚酯酰胺包括嵌段共聚物和接枝共聚物，这两者都是通过聚酰胺形成化合物和/或聚酯形成化合物以及含聚烯化氧单元的化合物反应获得的。聚酰胺形成化合物包括氨基羧酸，如ω-氨基己酸、ω-氨基庚酸、ω-氨基辛酸、ω-氨基壬酸、ω-氨基癸酸、1，1-氨基十一酸和1，2-氨基十二酸；内酰胺如ε-己内酰胺和庚内酰胺；肼与二元羧酸的盐，如六亚甲基二胺己二酸盐、六亚甲基二胺癸二酸盐和六亚甲基二胺间苯二甲酸盐；以及这些聚酰胺形成化合物的混合物。合乎要求的聚酰胺形成化合物是己内酰胺、1，2-氨基十二酸或六亚甲基二胺与己二酸的混合物。
优选的抗静电材料是聚合的抗静电剂。通常抗静电聚合物的使用量为总组合物的约0.015～约25wt％，优选约5～约20wt％，更优选的是约5～约10wt％。市售的抗静电材料包括来自Sanyo Chemical的Pelestat NC7530(聚醚酯酰胺)，其RI约为1.531；由Atofina(Pebax MV1074)制造的，从CIBASPECIALTY CHEMICALS买到的IRGASTAT P16，其RI＝1.508；PelestatNC632l(由Tomen制造，美国Sanyo Chemical销售，RI＝1.51)；具有与PelestatNC632l相同折射率的Peletat 6500，盐或电解质小分子加往其中能提高其导电性。
脂环族聚酯是脂族二酸或化学等效物(chemical equivaleents)，和脂族二醇或化学等效物的缩合产物。该脂环族聚酯可以由脂族二酸和脂族二醇的混合物制成，但必须含有至少50摩尔％的环二酸和/或环二醇成分，若有剩余部分，则为线性脂族二酸和/或二醇。环状成分对于赋予聚酯以良好的刚性以及允许透明掺合物的形成是必须的，因为其对与聚碳酸酯树脂的相互反应起促进作用。以重量计，脂环族聚合物优选至少8重量％的脂环族二醇和/或脂环族二羧酸或其化学等效物，而其余部分为线性脂族二醇和/或线性脂族二酸或其等效物。
脂环族聚酯中的脂环族原子团优选由1，4-环己二酸衍生，并且优选反式异构体的形式大于70摩尔％。脂环族原子团R来自1，4-环己基一级二醇如1，4-环己基二甲醇，优选反式异构体形式大于70摩尔％。
用于制备本发明脂环族聚酯树脂的其它二醇是脂环族链烷二醇，以及含有2～12个碳原子。所述二醇的例子包括但不限于1，2-亚乙基二醇；丙二醇，即，1，2-和1，3-丙二醇；2，2-二甲基-1，3-丙二醇；2-乙基、2-甲基、1，3-丙二醇；1，3-和1，5-戊二醇；一缩二丙二醇；2-甲基-1，5-戊二醇；1，6-己二醇；二甲醇萘烷，二甲醇(dimethanol)双环辛烷；1，4-环己烷二甲醇，特别是其顺式-和反式-异构体；2，2，4，4-四甲基-1，3-环丁二醇(TMCBD)，三甘醇；1，10-癸烷二醇；以及前述化合物的任意混合物。优选的是脂环族二醇或其化学等效物，特别是1，4-环己烷二甲醇或其化学等效物可作为二醇成分使用。
二醇的化学等效物包括酯，如二烷基酯、二芳基酯等。
用于制备脂族聚酯树脂的二酸优选脂环族二酸。这意指包括具有两个其中之一与饱和碳连接的羧基的羧酸。优选二酸是单环或双环的脂族酸，例如十氢萘二羧酸、降冰片烯二羧酸、双环辛烷二羧酸、1，4-环己烷二羧酸或化学等效物，最优选反式-1，4-环己烷二羧酸或化学等效物。线性二羧酸如己二酸、壬二酸、二羧基十二烷酸和丁二酸也是有效的。
制备环己烷二羧酸及其化学等效物，例如，通过使用合适的催化剂如负载于载体如炭或氧化铝上的铑，在合适的溶剂中如水或乙酸，对环芳族二酸和相应的衍生物如异萘酸、间苯二甲酸、邻苯二甲酸或萘酸进行氢化。见Friefelder等人，有机化学杂志(Journal of Organic Chemistry)，31，3438(1966)；美国专利2,675,390和4,754,064。还可以在反应条件下采用炭或二氧化硅上负载的钯或铑催化剂，使用至少部分溶解苯二甲酸的惰性液体介质制备所述化合物。见美国专利2,888,484和3,444,237。
采用氢化法时，典型的是所获得的两种异构体中羧基处于顺式-或反式位置上。分离顺式-和反式异构体可以借助于结晶法，使用或不用溶剂，例如正庚烷，或者借助于蒸馏法。顺式异构体倾向于更好的掺合；然而，反式异构体具有较高的熔化和结晶温度，因此是优选的。顺式-和反式异构体的混合物在本发明中同样是有效的。
当使用异构体的混合物或者一种以上的二酸或二醇时，可以把共聚酯或两种聚酯的混合物作本发明脂环族聚酯树脂使用。
这些二酸的化学等效物包括酯、烷基酯，例如，二烷基酯、二芳基酯、酐、盐、酰基氯、酰基溴等。优选化学等效物包括脂环族二酸的二烷基酯，最有利的化学等效物包括酸的二甲酯，特别是二甲基-1，4-环己烷-二羧酸酯。
优选的脂环族聚酯是具有通式II重复单元的聚(环己烷-1，4-二亚甲基环己烷-1，4-二羧酸酯)，也称作聚(1，4-环己烷-二甲醇-1，4-二羧酸酯)(PCCD)，所述通式(II)为：
通常聚酯的聚合反应是在适量的合适催化剂如钛酸四(2-乙基己基)酯的存在下以熔融态进行操作，钛基于最终产品，典型为约50～200ppm是合适的量。
用于本发明透明模塑组合物中的优选脂族聚酯，其玻璃化转变温度(Tg)约为50℃，更优选约80℃，最优选约100℃。
另外，本发明期待的上述聚酯，是约1～约50重量％的来自聚合的脂族酸和/或聚合的脂族多元醇单元形成的共聚酯。脂族多元醇包括二元醇，如聚(乙二醇)或聚(丁二醇)。这样的聚酯可以按照例如美国专利2,465,319和3,047,539进行制造。
用于本发明中的聚碳酸酯包括经由碳酸酯链键合的二元酚Art的二价残基，并且优选由下列通式表示：
其中，A是含有1～约15个碳原子的二价烃原子团，或者是含有1～约15个碳原子的取代的二价烃原子团；各X独立地选自氢、卤素和一价的烃原子团如1～约8个碳原子的烷基、6～约18个碳原子的芳基、7～约14个碳原子的芳烷基、1～8个碳原子的烷氧基；而m为0或1，n为0～约5的整数。Art可以是单芳环如氢醌或间苯二酚，或多芳环如双酚或双酚A。
所使用的二元酚是已知的，并且认为反应性基团是酚羟基。所用的一些典型的二元酚是双酚，如双(4-羟基苯基)甲烷、2，2-双(4-羟基苯基)丙烷(也称为双酚-A)、2，2-双(4-羟基-3，5-二溴苯基)丙烷；二元酚醚如双(4-羟基苯基)醚、双(3，5-二氯-4-羟基苯基)醚；p，p′-二羟基二苯基和3，3′-二氯-4，4′-二羟基联苯；二羟基芳基砜如双(4-羟基苯基)砜、双(3，5-二甲基-4-羟基苯基)砜、二羟基苯如间苯二酚、氢醌、卤代-和烷基-取代的二羟基苯如1，4-二羟基-2，5-二氯苯、1，4-二羟基-3-甲基苯；以及二羟基二苯基硫化物和亚砜如双(4-羟基苯基)硫化物、双(4-羟基苯基)亚砜和双(3，5-二溴-4-羟基苯基)亚砜。各种其它的二元酚都是可以得到的，并且公开在美国专利2,999,835、3,028,365和3,153,008中；所有这些专利都作为参考引入本文。当然，使用两种或多种不同的二元酚或二元酚与乙二醇的组合物是可能的。
碳酸酯前体典型的是羰基卤化物、二芳基碳酸酯或二卤代甲酸酯。羰基卤化物包括，例如碳酰溴、碳酰氯及其混合物。二卤代甲酸酯包括二元酚的二卤代甲酸酯，如2，2-二(4-羟基苯基)-丙烷的二氯代甲酸酯、氢醌等，或乙二醇的二卤代甲酸酯等。尽管所有上述的碳酸酯前体都是有用的，但是碳酰氯也称为光气和碳酸二苯酯是优选的。
制造芳族聚碳酸酯可以通过任何方法如通过二元酚与碳酸酯前体，如光气、卤代甲酸酯或碳酸酯以熔融态或溶液进行反应。美国专利4,123,436介绍了用光气的反应，而美国专利3,153,008介绍了酯交换法。
优选的聚碳酸酯是由能导致产生低双折射的树脂的二元酚制成，例如具有侧芳基或杯状芳基的二元酚。
苯基-二(4-羟基苯基)乙烷(乙酰苯双酚)：
二苯基-二(4-羟基苯基)甲烷(二苯甲酮双酚)：
2，2-双(3-苯基-4-羟基苯基)丙烷
2，2-双(3，5-二苯基-4-羟基苯基)丙烷；
双-(2-苯基-3-甲基-4-羟基苯基)丙烷；
2，2′-二(羟基苯基)芴；
1，1-二(5-苯基-4-羟基苯基)环己烷；
3，3′-二苯基-4，4′-二羟基二苯醚；
2，2-二(4-羟基苯基)-4，4-二苯基丁烷；
1，1-二(4-羟基苯基)-2-苯基乙烷；
2，2-二(3-甲基-4-羟基苯基)-1-苯基丙烷；
6，6′-二羟基-3，3，3′，3′-四甲基-1，1′-螺(双)二氢化茚；
其它典型的用于制备聚碳酸酯的二元酚在U.S.2,999,835、3,028,365、3,334,154和4,131,575中已作了介绍。支链聚碳酸酯也是有效的，如美国专利3,635,895和4,001,184中所介绍的那些。聚碳酸酯掺合物包括线性聚碳酸酯和支链聚碳酸酯的掺合物。
还有可能使用两种或多种不同的二元酚，或者二元酚与脂族二羧酸的共聚物；二聚体酸、十二烷二羧酸、己二酸、壬二酸，最终是碳酸酯共聚物或共聚体，而不是制备本发明的聚碳酸酯混合物所希望使用的均聚物。最优选脂族C5～C12的二酸共聚物。
优选的聚碳酸酯最好是具有特性粘数(在25℃于二氯甲烷中测量)范围在约0.30～1.00dl/gm的高分子量芳族碳酸酯聚合物。聚碳酸酯可以是支链的，也可以是非支链的，用凝胶渗透色谱法测量，通常其重均分子量约10,000～约100,000，优选约20,000～约50,000。可以设想聚碳酸酯具有多种已知的端基。
在本发明的实地应用中可以使用任意的抗冲击改良剂。假若抗冲击改良剂与聚碳酸酯/脂环族聚酯的可混溶混合物不混溶，则合乎要求的抗冲击改良剂具有与抗静电聚合材料折射率相匹配的折射率。往本发明组合物中可添加基本上是无定形的抗冲击改良剂共聚物树脂，其数量处于约1和30重量％之间，并且可以包含若干不同的橡胶改性剂中的一种，如接枝或芯壳橡胶或这些改性剂的两种或多种的组合物。合适的改性剂已知有丙烯酸类橡胶、ASA橡胶、二烯橡胶、有机硅氧烷橡胶、EPDM橡胶、SBS或SEBS橡胶、ABS橡胶和缩水甘油酯抗冲击改良剂。
术语丙烯酸类橡胶改性剂指的是具有交联或部分交联的(甲基)丙烯酸酯橡胶芯相的多级、芯-壳、共聚体改性剂，优选丙烯酸丁酯。与这种交联的丙烯酸酯芯有关的是丙烯酸或苯乙烯树脂的外壳，优选互穿橡胶芯相的甲基丙烯酸甲酯或苯乙烯。树脂壳中少量掺入其它单体如丙烯腈或(甲基)丙烯腈，可以另外提供合适的抗冲击改良剂。当形成树脂相的单体进行聚合并在预聚的和交联的(甲基)丙烯酸类橡胶相存在下交联时可以提供互穿网络。
优选的橡胶是具有接枝或芯壳结构的橡胶组分，该组分Tg低于0℃，优选介于-40～-80℃，由聚烷基丙烯酸酯或用PMMA或SAN接枝的聚烯烃构成。优选橡胶含量至少为40wt％，最优选介于约60～90wt％。
典型的市售橡胶是从Rohm & Hass得到的丁二烯芯-壳聚合物，例如Paraloid EXL2600。典型的是，抗冲击改良剂包括具有丁二烯基橡胶芯的两段聚合物，且第二段是单一的甲基丙烯酸甲酯或与苯乙烯的组分一起进行聚合。其它有代表性的橡胶是ABS型Blendex336和415，它是从GESpecialty Chemicals得到的。所使用的合乎要求的橡胶，若与聚碳酸酯/脂环族聚酯掺合物不混溶，则具有与抗静电聚合材料相匹配的折射率，或者，若与聚碳酸酯/脂环族聚酯掺合物可混溶，则以适当比例使用，以便使所获得的混合物具有与聚合抗静电材料相匹配的折射率。
抗冲击改良剂，假若使用的话，应当具有基本上与抗静电聚合物相同的折射率(RI)。还应当与其它组分相容。
本发明优选的聚碳酸酯、脂环族聚酯组合物包含：
(A)以脂环族聚酯树脂(PCCD)与聚碳酸酯树脂的比例为约1.0～约2，优选约1.6～约1.9为条件，20～80重量％的聚碳酸酯和脂环族聚酯树脂的掺合物，其中脂环族聚酯包含(a)至少一种脂环族C2～C12链烷二醇，最好的是C6～C12脂环族二醇或其化学等效物；和(b)至少一种脂环族二酸，最好的是C6～C12二酸或其化学等效物的反应产物；
(B)0.01～约25重量％，优选约5～20重量％，以及更优选的是约5～10重量％的静电分散聚合物；以及任意的
(C)1～30％，优选5～20重量％的包括基本无定形的抗冲击改良剂。
组合物的掺合方法可以通过常规技术来完成。优选的聚酯和聚碳酸酯以选自与静电分散聚合物的折射率相匹配的量进行预混。组分典型的是粉末状或颗粒状，因此先挤压掺合物，再粉碎成颗粒或利于模塑的其它形状。各组分可以采用任意有效的方式混合，例如通过干混合或在挤压机内以熔融态混合或采用其它掺合的方法。
在含有脂环族聚酯树脂和聚碳酸酯树脂的热塑性组合物中，优选的是使用稳定剂或猝灭剂材料。催化剂猝灭剂是能抑制存在于树脂中的任何催化剂活性的试剂。催化剂猝灭剂于美国专利5,441,997中作了详细地介绍。选择恰当的猝灭剂以避免本发明所述组合物着色和透明度下降是人们所要求的。
包括猝灭剂在内的稳定剂种类优选是能提供透明和无色产品的那些。典型的是，所述稳定剂的用量为0.001～约10重量％，优选含量为0.005～约2重量％。优选的稳定剂包括有效量的酸式磷酸盐；具有至少一个酸性氢的酸式、烷基、芳基或混合的亚磷酸盐；IB或IIB族金属的磷酸盐；磷的含氧酸，金属酸式焦磷酸盐或其混合物。用作稳定剂的特殊化合物的适用性和确定作为稳定剂的用量，很容易通过制备聚酯树脂成分和聚碳酸酯的混合物加以确定，并且同时确定对熔融物粘度、气体的产生或颜色的稳定性或共聚体形成的影响。酸式磷酸盐包括磷酸二氢钠、磷酸锌、磷酸氢钾、磷酸二氢钙等。
IB或IIB族金属的磷酸盐包括磷酸锌等。磷的含氧酸包括亚磷酸、磷酸、多磷酸或次磷酸。
最优选的猝灭剂是磷的含氧酸或酸式有机磷化合物。无机酸式磷化合物也可以作猝灭剂使用，但是它们导致光雾或透明度的下降。最优选的是猝灭剂是磷酸、亚磷酸或其部分酯。
实施例
下列实施例用来说明本发明而不是用来限制本发明的范围。在享舍尔高速混合器中通过干混合适当量的物料，制备掺合物。把干掺合物在30mmWerner和Pfleiderer双螺杆挤出机中挤出。静电分散聚合物和含PCCD的聚碳酸酯线材如表所示。实施例中所用的抗静电分散聚合物是具有RI约为1.531的聚醚酯酰胺(来自Sanyo Chemical的Pelestat NC7530)。往本例掺合物中添加分别为0.07和0.1标准稳定量的磷酸单锌和亚磷酸酯。使来自挤出机的含热塑性树脂组合物的透明抗静电线材在水浴中冷却、造粒、干燥，并用85吨Van Dom注塑机进行注塑成型，得到试验样品。
按ASTM D790测定样品的挠曲强度和弯曲模量，按ASTM D638测定拉伸强度和伸长，按ASTM D256进行切口冲击试验。按ASTM D648，在0.5″×0.125″×5″的棒上测定热变形温度(HDT)，测定条件是负荷264磅/英寸2(psi)，于248°F1小时，于554°F完成。光雾用Color-Edge 7000型仪器测定。计算下列样品的掺合物的折射率为～1.535(PC～1.58，PCCD～1.506以及具有RI～1.531的Pelestat NC7530)。表中的PCCD/PC比例为1.8～1。结果如下：
表1实施例
| 实验号 | 抗静电树脂％ | 光雾％ | 缺口冲击试验(/ft lb/”) | FM×103/psi | HDT/°F |
| 1 | 5 | 6.25 | 21.6 | 244.4 | 160 |
| 2 | 10 | 6.58 | 14.1 | 225.8 | 158 |
| 3 | 15 | 7.87 | 19.1 | 204.4 | 153 |
用掺合物生产的透明和无色零件。
下表2示出当PCCD/PC比例处于下表2所示范围时，掺合物的性能。
表2对比例
| 实验号 | ％PCCD | ％PC | 比例PCCD/PC | ％抗静电树脂 | ％光雾 | 缺口冲击试验(/ft lb/”) | FM×10 | HDT°F |
| C4 | 75 | 15 | 5 | 0 | 5.1 | 21.2 | 210.0 | 139 |
| C5 | 75 | 15 | 5 | 10 | 78 | 17.9 | 188.9 | 139 |
| C6 | 65 | 13 | ||||||
| C7 | 67 | 13 | 5 | 20 | 97 | 16 | 134 | |
| C8 | 14 | 71 | 5 | 15 | 92 | 21.9 | 169.8 | 136 |
| C9 | 65 | 25 | 2.6 | 10 | 45 | 21.0 | 203.6 | 143 |
正如上述表2所述，没有抗静电分散聚合树脂的实验C4的％光雾相当低(5.1％)。然而，组合物没有静电分散性能。另外值得注意的是，即使PCCD/PC的比例为2.6时，与PCCD/PC掺合比例1.8～2对比，光雾％特别高。PCCD/PC的比例优选低于约2，更优选约2～约1.6，尤其优选约1.9～约1.7。另外，热变形温度HDT，显著低于本发明的组合物表1的实验1～3。为了降低热变形，上述优选比例同样也是合乎要求的。
尽管本发明是参照最佳实施方案予以说明的，但所属技术领域的技术人员将会理解在不偏离本发明范围的情况下可以作出各种变更和为本发明要素所取代的等效方案。另外，可以作出许多符合本发明教导但不偏离本发明范围的特殊情况或材料的改进方案。因此，可以把本发明延伸至不限于作为完成本发明所预定的最佳方式而公开的特定具体实施方案，但本发明将包括所有附上的权利要求书中所列的范围。
Claims (19)
1.一种透明永久的静电分散组合物，其中包含配合的透明芳族聚碳酸酯树脂、可混溶的透明脂环族共聚酯以及足够量能赋予所述组合物以静电分散性能的静电分散聚合物，所述芳族聚碳酸酯、所述脂环族共聚酯和所述静电分散聚合物，各具有预定的折射率，其中所述静电分散聚合物的所述折射率具有介于所述聚碳酸酯树脂和所述脂环族共聚酯树脂之间的折射率，所述聚碳酸酯树脂和所述脂环族共聚酯树脂在与所述静电分散聚合物的折射率基本匹配的所述静电组合物中存在，所述脂环族共聚酯包含选自下列反应的产物：(1)至少80重量％的脂环族二醇，其余部分则为线性脂族二醇，或组合的线性脂族二醇和线性脂族二酸，或上述的化学等效物；(2)至少80重量％的脂环族二羧酸，其余部分则为线性脂族二酸，或组合的线性脂族二酸和线性脂族二醇，或上述的化学等效物；和(3)至少80重量％的脂环族二醇和至少80重量％的脂环族二羧酸的混合物，其余部分则为线性脂族二醇或线性脂族二酸或这两者的混合物，或上述的化学等效物。
2.按权利要求1所述的组合物，其中，脂环族共聚酯与聚碳酸酯的比例约2.0～约1.6，并且聚碳酸酯和脂环族共聚酯的总重量为组合物总量的20～80％重量。
3.按权利要求1所述的组合物，其中，静电分散聚合物的存在量为组合物总重量的0.01～约25重量％。
4.按权利要求3所述的组合物，其中，静电分散聚合物的存在量为5～15重量％。
5.按权利要求1所述的组合物，其中，脂环族二醇是由2～12个碳原子的脂环族链烷二醇制备的。
6.按权利要求5所述的组合物，其中，脂环族链烷二醇是1，4-环己烷一级二醇。
7.按权利要求1所述的组合物，其中，脂环族二酸是由具有至少两个羧基而其中每一个与饱和碳相连接的二羧酸制备的。
8.按权利要求7所述的组合物，其中，二酸选自十二氢萘二羧酸、降冰片烯二羧酸、二环辛烷二羧酸、1，4-环己烷二羧酸及其化学等效物中的单环和二环脂族酸。
9.按权利要求1所述的组合物，其中，脂环族共聚酯是聚(1，4-环己烷-二甲醇-1，4-二羧酸酯)。
10.按权利要求1所述的组合物，其中，静电分散聚合物选自共聚酯酰胺、聚醚-聚酰胺、聚醚酰胺嵌段共聚物、聚醚酯-酰胺嵌段共聚物、含聚烷基亚烷基二醇部分的聚氨基甲酸酯、聚醚酯及其混合物。
11.按权利要求10所述的组合物，其中，静电分散聚合物是聚酯酰胺。
12.按权利要求10所述的组合物，其中，静电分散聚合物是聚醚酯酰胺。
13.按权利要求1所述的组合物，其中，组合物另外还含有抗冲击改良剂，其中，抗冲击改良剂具有与权利要求1组合物折射率同样的折射率。
14.按权利要求13所述的组合物，其中，抗冲击改良剂是橡胶改性剂。
15.按权利要求14所述的抗冲击改良剂，其中，抗冲击改良剂是具有至少部分交联的(甲基)丙烯酸橡胶芯相和含丙烯酸树脂外壳的芯-壳改性剂。
16.按权利要求1所述的组合物，其中，组合物的折射率为1.52～1.54。
17.一种实质上透明的抗静电、耐冲击的模塑组合物，其包含大部分重量百分比的聚碳酸酯树脂和脂环族聚酯树脂和抗静电聚合物材料的可混溶混合物，其中聚碳酸酯和脂环族聚酯树脂以合适的比例存在，以与抗静电聚合材料的折射率基本匹配。
18.按权利要求17所述的实质上透明的抗静电模压组合物，其中，包括另外的可混溶树脂，而所述可混溶树脂与聚碳酸酯和聚酯树脂一起形成与抗静电聚合材料的折射率基本匹配的混合物。
19.按权利要求17所述的实质上透明的抗静电模压组合物，其中，包括存在于模塑组合物中的另外的不可混溶的树脂，合乎要求的所述另外的不可混溶树脂具有与抗静电聚合材料的折射率基本匹配的折射率。
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2003
- 2003-10-23 US US10/691,686 patent/US7022764B2/en not_active Expired - Lifetime
- 2003-12-08 AT AT03796874T patent/ATE514749T1/de not_active IP Right Cessation
- 2003-12-08 AU AU2003297805A patent/AU2003297805A1/en not_active Abandoned
- 2003-12-08 EP EP03796874A patent/EP1576053B1/en not_active Expired - Lifetime
- 2003-12-08 KR KR1020057011070A patent/KR101015654B1/ko active IP Right Grant
- 2003-12-08 WO PCT/US2003/039203 patent/WO2004060997A1/en active Application Filing
- 2003-12-08 JP JP2004565317A patent/JP4861622B2/ja not_active Expired - Fee Related
- 2003-12-08 CN CN2003801095297A patent/CN1745139B/zh not_active Expired - Fee Related
-
2006
- 2006-02-16 US US11/356,252 patent/US20060135708A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282434A (zh) * | 2010-12-23 | 2013-09-04 | 拜耳知识产权有限责任公司 | 抗静电聚碳酸酯模塑组合物 |
| CN103282434B (zh) * | 2010-12-23 | 2015-11-25 | 拜耳知识产权有限责任公司 | 抗静电聚碳酸酯模塑组合物 |
| CN109651592A (zh) * | 2018-12-21 | 2019-04-19 | 山东诺威聚氨酯股份有限公司 | 本质抗静电热塑性聚氨酯弹性体及其制备方法 |
| CN110564115A (zh) * | 2019-09-12 | 2019-12-13 | 南通协鑫热熔胶有限公司 | 抗静电聚合物组合物 |
| CN110564115B (zh) * | 2019-09-12 | 2022-03-15 | 南通协鑫热熔胶有限公司 | 抗静电聚合物组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20060135708A1 (en) | 2006-06-22 |
| EP1576053A1 (en) | 2005-09-21 |
| AU2003297805A1 (en) | 2004-07-29 |
| CN1745139B (zh) | 2012-09-26 |
| JP2006511668A (ja) | 2006-04-06 |
| ATE514749T1 (de) | 2011-07-15 |
| EP1576053B1 (en) | 2011-06-29 |
| KR101015654B1 (ko) | 2011-02-22 |
| KR20050092709A (ko) | 2005-09-22 |
| US20040122168A1 (en) | 2004-06-24 |
| JP4861622B2 (ja) | 2012-01-25 |
| US7022764B2 (en) | 2006-04-04 |
| WO2004060997A1 (en) | 2004-07-22 |
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