CN100509928C - 聚丙烯吹塑薄膜 - Google Patents

聚丙烯吹塑薄膜 Download PDF

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CN100509928C
CN100509928C CNB2004800260802A CN200480026080A CN100509928C CN 100509928 C CN100509928 C CN 100509928C CN B2004800260802 A CNB2004800260802 A CN B2004800260802A CN 200480026080 A CN200480026080 A CN 200480026080A CN 100509928 C CN100509928 C CN 100509928C
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A·沃尔夫比尔格
J·沃尔夫施温格
P·尼德尔苏斯
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Abstract

本发明涉及具有优良的光学性能和机械性能特征的聚丙烯吹塑薄膜。用于该薄膜的聚丙烯组合物含有成核剂。

Description

聚丙烯吹塑薄膜
本发明涉及一种包含聚丙烯组合物的吹塑薄膜。特别地，本发明涉及具有优良的光学性能以及机械性能的聚丙烯吹塑薄膜。
技术背景
现今，用于薄膜的聚丙烯几乎被专门用于流延薄膜。在流延薄膜工艺中，为了将聚丙烯潜在的优良光学性能和机械性能用于薄膜应用，借助于骤冷辊来实现非常迅速的熔体冷却。
直到现在，仅仅当可以采用水接触冷却以实现与流延薄膜工艺中同样迅速的冷却时才可以将聚丙烯用于吹塑薄膜工艺。
在采用空气冷却的常规吹塑薄膜工艺中，聚丙烯熔体和由其制得的薄膜仅仅缓慢地冷却。这导致了不充足的光学参数和机械参数，因为缓慢的冷却过程造成不可控制的晶体和球粒结构的生长。采用空气冷却制得的聚丙烯吹塑薄膜混浊并且易碎。
已经尝试通过采用丙烯无规共聚物与无机成核剂或基于山梨糖醇的成核剂的结合来改进聚丙烯吹塑薄膜的混浊性和脆性问题。但仅仅可以非常有限的程度来改进光学参数和机械参数。
WO 03040202公开了一种用于吹塑薄膜生产的共混研究的基础树脂，其中使用亚甲基-双(4，6-二叔丁基苯基)磷酸酯钠盐作为成核剂。其中公开的所制得的吹塑薄膜作为比较例显示出比WO 03040202请求保护的含有特殊的P/E共聚物的共混物更不利的性能。
发明目的
因此，本发明的目的是提供一种具有可与采用流延薄膜获得的光学参数相比的优良光学参数以及良好平衡的劲度/可拉伸性比例的聚丙烯吹塑薄膜。
[解决方案]
通过这样一种吹塑薄膜实现了以上目的：该吹塑薄膜包括含有丙烯均聚物或者丙烯与乙烯和/或另一种α-烯烃的共聚物的聚丙烯组合物，该聚丙烯组合物含有包括α-成核剂铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]和/或选自乙烯基环烷烃聚合物和乙烯基烷烃聚合物的聚合物α-成核剂的澄清剂。
令人惊奇的是，可以在采用空气冷却的常规吹塑薄膜装置上制得具有优良的光学参数、良好的劲度(拉伸模量)和可拉伸性(断裂伸长率)的聚丙烯吹塑薄膜。
这是特别令人惊奇的，因为对于大多数包括吹塑、注塑以及流延的薄膜的其它应用而言，基于山梨糖醇的成核剂都产生了最好的或者可以比较的光泽度和雾度。
该丙烯共聚物可以是多相的或者无规的，后者是优选的。其含有乙烯和/或另一种α-烯烃，该α-烯烃可以是C4-C10，优选C4-C6的α-烯烃。
该共聚物的乙烯含量可以多至10wt％，或者多至8wt％。优选的含量为小于5wt％，例如为0.3wt％-4.8wt％。
另外，该组合物可以含有其它聚合物，比如HDPE、LDPE、LLDPE、VLDPE、ULDPE或者其它含有乙烯和另一种α-烯烃的聚合物或共聚物。
可用于本发明的吹塑薄膜的α-成核剂包括铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]和/或选自乙烯基环烷烃聚合物和乙烯基烷烃聚合物的聚合物α-成核剂。采用这些聚合物成核剂的成核或者通过特殊的反应器技术(其中催化剂与单体比如乙烯基环己烷(VCH)预聚合)、或者通过将丙烯聚合物与乙烯基(环)烷烃聚合物共混而完成。这些方法更详细地描述于例如EP0316187A2和W099/24479中。
在上述所有α-成核剂中，优选铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]。
我们发现当使用这类α-成核剂时，预期的效果(即，提高的光泽度、降低的雾度和改进的劲度)尤其显著。
用于本发明的吹塑薄膜的聚丙烯组合物优选含有从0.001wt％、优选从0.01wt％至5wt％的α-成核剂。
少于0.001wt％的量的α-成核剂通常不会产生所希望程度的效果，而采用大于5wt％的量尽管产生了所希望的效果，但由于高价格的成核剂，制得的吹塑薄膜因此变得太昂贵。
本发明的另一方面涉及其中至少一层包含根据本发明的聚丙烯吹塑薄膜的多层吹塑薄膜。
当采用借助于基于山梨糖醇的成核剂成核的聚丙烯时，不可能在没有问题的情况下将这种多层吹塑薄膜共挤出，因为基于山梨糖醇的成核剂的挥发性在另一些层(一层或多层)所必需的加工温度范围内已经非常的高。这使得成核剂的沉积物在挤塑模头的周围迅速生长。必须定期地除去这些沉积物，为此必须中止整个生产。
因此，本发明的另一方面涉及这样的多层吹塑薄膜：其中至少一层包含含有澄清剂(该澄清剂包括一种或多种基于磷酸盐的α-成核剂)的聚丙烯吹塑薄膜，和至少另一层包含具有比聚丙烯更高的熔融温度的聚合物。
除了由该聚丙烯层的改进的光学性能和机械性能获得的益处之外，这种多层吹塑薄膜还可以通过共挤出来制得，而不会在挤塑模头的周围产生沉积物。
用于多层吹塑薄膜的共挤出且具有比聚丙烯更高的熔融温度的聚合物优选是聚酰胺、聚乙烯基醇和聚对苯二甲酸乙二酯的任意一种或多种。
根据本发明的另一个实施方案，多层吹塑薄膜包括至少两层，其中至少一层包含根据本发明的聚丙烯组合物，和至少另一层包含乙烯聚合物。
在需要非常低的密封引发温度(seal initiation temperature，SIT)以及优良的光学性能的领域中已经发现将聚丙烯与聚乙烯(例如，C4-LLDPE或LDPE)相结合是有利的。与PE相比，PP具有耐高温性而PE具有低的SIT。为了包装生产线上快速的密封过程，必须具有尽可能高的密封温度。因此，这需要一种薄膜：该薄膜带有具有高的熔体温度的顶层(与熔接棒直接接触的层)以承受高的密封温度和具有非常低的熔融温度的密封层以在最低的可能温度下开始密封并且提供优良的缝合强度。这种薄膜性能可以通过将透明PP用于顶层和将PE用于密封层的组合来实现。
根据另一个方面，该多层吹塑薄膜包括粘合层，该粘合层介于包含根据本发明的聚丙烯组合物的层与另一个包含乙烯聚合物的层之间并且与这两个层相邻。
在常规的PE的情况下，由于PP和常规的PE具有不同的极性并且因此不能充分粘合，因此在那些层之间需要粘合层以在PP与PE层之间产生足够的粘合强度。
根据仍然另一个实施方案，包含根据本发明的聚丙烯组合物的层与另一个包含乙烯聚合物的层彼此相邻，并且选择该另一个层以对包含聚丙烯组合物的层具有优良的粘合性。
粘合层的存在需要这种薄膜可以通过采用至少3层的共挤出薄膜而制得。因此当中间的粘合层可以省略并且为了提供给PP层充足的粘合强度而选择另一个层本身的时候是有利的。
根据一个有利的实施方案，该另一个层的乙烯聚合物是单点催化剂聚乙烯(SSC-PE)。
通过使用特征为低密度(低于0.920g/cm3)的单点催化剂PE(SSC-PE)来代替标准的PE，实现了对PP的优良粘合性并且在PP层与PE层之间不需要额外的粘合层。
可用于本发明的薄膜的聚丙烯组合物可以含有各种通常用于聚丙烯组合物的添加剂，例如稳定剂、抗氧化剂、酸中和剂、润滑剂、紫外线吸收剂、防粘连剂、抗静电剂、消雾剂等。
优选的抗氧化剂是酚类抗氧化剂，例如，2-叔丁基-4，6-二甲基苯酚、2，6-二叔丁基-4-甲基苯酚、2，6-二叔丁基-4-异戊基苯酚、2，6-二叔丁基-4-乙基苯酚、2-叔丁基-4，6-二异丙基苯酚、2，6-二环戊基-4-甲基苯酚、2，6-二叔丁基-4-甲氧基甲基苯酚、2-叔丁基-4，6-二(十八烷基)苯酚、2，5-二叔丁基氢醌、2，6-二叔丁基-4，4-十六烷基氧基苯酚、2，2′-亚甲基-双(6-叔丁基-4-甲基苯酚)、4，4′-硫代双(6-叔丁基-2-甲基苯酚)、十八烷基-3(3，5-二叔丁基-4-羟基苯基)丙酸酯、1，3，5-三甲基-2，4，6-三(3′，5′-二叔丁基-4-羟基苄基)苯和季戊四醇基-四-3-(3，5-二叔丁基-4-羟基苯基)丙酸酯。
优选的稳定剂是基于亚磷酸盐的稳定剂，例如三-(2，4-二叔丁基苯基)亚磷酸盐。
酸中和剂和/或润滑剂优选是其中金属选自周期表的第1或第2族或者选自过渡金属(比如，锌)的羧酸盐。也可以使用合成的水滑石或氧化镁。优选的羧酸盐是硬脂酸锂、硬脂酸钠、硬脂酸钾、肉豆蔻酸锂、肉豆蔻酸钠、肉豆蔻酸钾、硬脂酸钙、硬脂酸镁、12-羟基硬脂酸钙、12-羟基硬脂酸镁、肉豆蔻酸钙、棕榈酸钙、月桂酸钙、肉豆蔻酸镁、棕榈酸镁、月桂酸镁和硬脂酸锌。
测量方法的描述
MFR
在230℃下采用2.16kg的负荷测量熔体流动速率。熔体流动速率是以ISO 1133为标准的试验装置在230℃的温度下在2.16kg的负荷下在10分钟内挤出的以克计的聚合物的量。
共聚单体含量
借助于用13C-NMR校准的傅里叶变换红外光谱(FTIR)测量共聚单体含量(乙烯)。
光泽度
根据DIN 67530在20°角度下在流延薄膜(厚度50μm)上和在吹塑薄膜(厚度40μm)上测量光泽度。
雾度
根据ASTM D 1003-92在注塑的试片(60 x 60 x 2mm)上、在流延薄膜(厚度50μm)上和在吹塑薄膜(厚度40μm)上测量雾度。
拉伸试验
根据ISO 527-3在流延薄膜(厚度50μm)上和在吹塑薄膜(厚度40μm)上进行拉伸试验。
Elmendorf
根据ISO 6383/2(1983)在流延薄膜(厚度50μm)上和在吹塑薄膜(厚度40μm)上测量Elmendorf。
实施例
以下聚合物被用于实施例和比较例。
表1
Figure C200480026080D00081
Milla d3988...1，3：2，4双(3，4-二甲基-苯亚甲基)山梨糖醇
NA21...可以名称“ADK STAB NA21E”从Asahi Denka Kogyo(日本)商购获得。NA21含有铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]。
聚合物1-4带有常规的稳定剂(即，0.15wt％的三-(2，4-二叔丁基苯基)亚磷酸盐、0.1wt％的季戊四醇基-四-[3-(3，5-二叔丁基-4-羟基苯基)丙酸酯])和加工助剂(即，0.05wt％的硬脂酸钙)。
在带有70mm的机筒直径和1mm模口间隙的200mm圆形截面模头以及单冷却圈和内膜泡冷却(IBC)的单螺杆挤出机上制造吹塑薄膜。模头中的熔体温度为210℃；将冷却空气的温度保持在15℃并且将吹胀比(BUR)保持在3:1。通过挤出机产量、引出速度与BUR之间的比例将薄膜厚度调节至40μm。
在带有52mm的机筒直径和800 x 0.5mm的缝口模头以及骤冷辊和引出(takeup)辊的单螺杆挤出机上制造流延薄膜。模头中的熔体温度为240℃；将骤冷辊保持在15℃并且将引出辊保持在20℃。通过挤出机产量与引出速度之间的比例将薄膜厚度调节至50μm。
如上所概述和描述的那样测试和分析这些薄膜。结果示于表2中。
实施例E1是根据本发明，实施例C1-C3为比较例。
表2
 
实施例 E1 C1 C2 C3
材料 聚合物1 聚合物2 聚合物3 聚合物4
吹塑薄膜 吹塑薄膜 吹塑薄膜 流延薄膜
拉伸试验纵向 拉伸模量屈服应力屈服伸长率拉伸应力断裂伸长率 MPaMPa％MPa％  925.726.812.5450.21581.32 912.525.5512.4752.84656.75 144036.388.560681   67018.76.633.8715.6
拉伸试验横向 拉伸模量屈服应力屈服伸长率拉伸应力断裂伸长率 MPaMPa％MPa％  972.524.428.7534.31665.07 911.223.9710.3539.04728.21 138035.457.732.19.71  69318.86.431.8730 
Elmendorf 纵向横向 N/mmN/mm 3.369.95 3.949.64 1.812.3 7.825.5
光泽度 外部内部 ％％ 70.865.3 16.330   11 120115
雾度 ％ 3.96 10.33 64 2.2
得自于实施例E1的薄膜具有优良的劲度，即，两个方向上的拉伸模量高于C2。可拉伸性(断裂伸长率)可与比较例的可拉伸性相比，并且肯定的是，均聚物的吹塑薄膜在横向上的可拉伸性实际上不存在。与C1相比，E1的光学性能--光泽度和雾度明显改进。

Claims (7)

1.一种吹塑薄膜，其包括含有丙烯均聚物或者丙烯与乙烯和/或另一种α-烯烃的共聚物的聚丙烯组合物，特征在于该聚丙烯组合物含有包括α-成核剂铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]的澄清剂。
2.根据权利要求1的吹塑薄膜，特征在于该聚丙烯组合物含有0.001-5wt％的α-成核剂。
3.一种其中至少一层包含聚丙烯组合物的多层吹塑薄膜，其中至少另一层包含具有比聚丙烯更高的熔融温度的聚合物，该聚丙烯组合物含有丙烯均聚物或者丙烯与乙烯和/或另一种α-烯烃的共聚物，特征在于该聚丙烯组合物含有包括α-成核剂铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]的澄清剂。
4.根据权利要求3的多层吹塑薄膜，特征在于该具有比聚丙烯更高的熔融温度的聚合物选自聚酰胺、聚乙烯基醇和聚对苯二甲酸乙二酯。
5.一种多层吹塑薄膜，其中至少一层包含聚丙烯组合物，和至少另一层包含乙烯聚合物，该聚丙烯组合物含有丙烯均聚物或者丙烯与乙烯和/或另一种α-烯烃的共聚物，特征在于该聚丙烯组合物含有包括α-成核剂铝-羟基-双[2，2′-亚甲基-双(4，6-二叔丁基苯基)磷酸酯]的澄清剂。
6.根据权利要求5的多层吹塑薄膜，特征在于其包括粘合层，该粘合层介于该包含聚丙烯组合物的层与另一个包含乙烯聚合物的层之间并且与这两个层相邻。
7.根据权利要求5的多层吹塑薄膜，特征在于该包含聚丙烯组合物的层与另一个包含乙烯聚合物的层彼此相邻，并且选择该另一个层以对该包含聚丙烯组合物的层具有优良的粘合性，所述优良的粘合性通过选择该另一个层的乙烯聚合物是单点催化剂聚乙烯来实现。
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