CN1926186B - 包含热塑性弹性体的间规聚丙烯组合物 - Google Patents

包含热塑性弹性体的间规聚丙烯组合物 Download PDF

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CN1926186B
CN1926186B CN200580003741.4A CN200580003741A CN1926186B CN 1926186 B CN1926186 B CN 1926186B CN 200580003741 A CN200580003741 A CN 200580003741A CN 1926186 B CN1926186 B CN 1926186B
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P·卡斯滕
E·穆尔肯斯
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Renolit SE
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Abstract

包含热塑性弹性体和间规聚丙烯(s-PP)的聚合物组合物，该热塑性弹性体包括苯乙烯和异戊二烯和/或乙烯基异戊二烯单元(SI)。

Description

包含热塑性弹性体的间规聚丙烯组合物
本发明涉及包括热塑性弹性体的聚合物组合物；涉及包含此类组合物的膜或管，和涉及其专门应用。 
为医药用途设计的制品必须不仅符合常规的要求，如良好机械强度或低成本，而且在专用领域的应用有着极其严格的要求，例如，关于所述制品的生物相容性性能、它们的经受灭菌处理的能力、它们的挠性、它们的透明度、它们的可焊性、它们的抗冲击强度(包括关于装满液体的容器)、物质转移量(例如在医用(脂肪)液体中)或能被萃取(例如用己烷和/或净化水)以及有时候对它们阻隔性能的要求。 
迄今，市场上可买到的医用制品，例如灌注袋或血袋以及为保护医用相关液体而设计的袋子均为基于氯乙烯聚合物，例如基于PVC的制品。 
尽管这类聚合物具有几个优点，然而，同时具有一定的缺点，例如需要掺入大量的稳定剂以改进其热稳定性或掺入大量的增塑剂以获得足够的挠性。因此市场需要无氯化聚合物的医用制品。 
为了获取此类制品，公知的由聚烯烃基膜开始，并将其焊接一起(或焊接本身)以便制造袋或盒。更具体地说，使用基于聚丙烯(PP)的膜是公知的，它包括添加剂以便改进一些上述的性能。此类添加剂是通常用于改进PP树脂透明度和挠性的弹性体。此类弹性体的实例包括氢化或非氢化的苯乙烯和异戊二烯和/或乙烯基异戊二烯单元(此后称为“SI”树脂)。其中，苯乙烯-乙烯基异戊二烯-苯乙烯嵌段共聚物(SVIS)和苯乙烯-异戊二烯-丁二烯-苯乙烯(SIBS)是优选的，因为它们具有经改进的与PP树脂的相容性，特别地当它们被至少部分氢化时。然而，不久(或热处理之后，如热灭菌)之后，用PP和SI树脂制造的膜看起来放松了其透明性，这指示长期使用/储存后出现一些相分离。 
申请人意外地发现，当选择间规聚丙烯树脂(s-PP)时，这些长期相分离易于消失。 
使用s-PP相比“常规的”i-PP的另一个优点是熔点降低(130℃相对165℃)，这容许在较低温度下焊接，同时容许在121℃的常规温度蒸汽灭菌。 
因此，本发明涉及包含SI和s-PP的聚合物组合物。 
在用于根据本发明的组合物中的SI树脂一般具有两个聚苯乙烯外部嵌段和包括异戊二烯的中部嵌段以及最终的其它单体的三嵌段共聚物，并且它可以被部分地或充分地氢化。术语“部分地氢化”意思是还有一些不饱和异戊二烯单元留在结构中。通常，在商品的氢化SI树脂中，约有5wt％或更少的二烯(不饱和度)留下，优选1wt％或更少，和最优选0.5wt％或更少。由于稳定性的原因，充分地或几乎充分地氢化的树脂是优选的。 
此类树脂的实例是那些可由KURARAY商购、商品名为HYBRAR的树脂。这些树脂包括至多约40％(重量)的苯乙烯，所述苯乙烯形成通过由乙烯基-异戊二烯-共-聚异戊二烯形成的嵌段连接在一起的嵌段。等级5127和5125是非氢化的，而等级7125是氢化的。氢化的SVIS树脂，如HYBRAR7125是优选的。 
此类SI树脂的其它实例是苯乙烯-异戊二烯-丁二烯-苯乙烯树脂(SIBS)。获得良好结果的此类树脂的实例是那些以商品名 G-1730，RP-6924和RP-6917商购的。 
这些树脂被充分地或几乎充分地氢化(即它们具有低于0.2wt％的不饱和度留下)。 
根据本发明的s-PP可以是丙烯均聚物或丙烯与至多30％的C2-C8共聚单体(优选乙烯)的共聚物。它们优选是如WO00／61062描述的控制结晶度的聚烯烃。其优选显示软化点(或“维卡点”)低于121℃(根据ASTM标准D1525测量)，至少在合适的条件(描述于WO00／061062，其内容在此引入作为参考)下可被加工，即使树脂生产者宣布了更高的价值。根据本发明的s-PP因此优选显示出区别特征：它们的结晶度在其加工中容易降低。容易控制的结晶度在本发明内容中是有益的，只要它可以提供在s-PP树脂中结晶度的降低，条件是使用合适的加工条件，因此提高整个结构的透明度和挠性。 
根据本发明的s-PP的多分散性有利地低于8，并优选低于4。该特性反映了分子质量的低分散性，提高在熔化温度范围和软化温度范围之间的分离，因此加工过程中可以对结晶度有更有效的作用。 
此外，使用的s-PP熔体流动指数有利地低于12g／10分钟，优选低于10g/10分钟，和最优选低于8g／10分钟(根据ASTM标准D1238测量，在190℃/2.16kg条件下对于乙烯聚合物和丁烯的共聚物测量，和在230℃/2.16kg条件下对丙烯聚合物和丁烯均聚物测量)。 
在根据本发明的组合物中，s-PP一般存在量为30％或更多，或甚至为40％或更多(与共混物的总重量相比较的重量)。另一方面，共混物中SVIS含量一般为5％或更多，或甚至为10％或更多。一般，s-PP存在量为95％或更少，或甚至为90％或更少，而另一方面，SVIS一般存在量为70％或更少，或甚至为60％或更少。 
根据本发明的组合物可以包括其它聚合物和/或常见的添加剂，如颜料、稳定剂等。特别地，当打算焊接时，可以包含至少一种非结晶的或无定形的聚烯烃，该聚烯烃选自乙烯-乙酸乙烯基酯(EVA)、乙烯-丙烯酸甲酯(EMA)、乙烯-丙烯酸乙酯(EEA)或乙烯-丙烯酸丁酯(EBA)共聚物。在以上提到的共聚物中，只有显示至少9％的共聚单体含量的共聚物被考虑作为另外的组分。这些共聚物的浓度一般等于或高于0.05％(相对于全部组合物的重量)，和优选高于0.1％。它一般等于或低于15％，优选低于10％和最优选低于5％。EVA和EMA的混合物，优选为总量的至少0.1％，或甚至至少1％，而不大于5％的EVA得到良好的结果。也就是说，它可以采用完全可再现的剥离强度焊接，这对制造具有可剥离密封的制品是非常有用的，如多腔袋或包括永久的外部密封和至少一个可剥离密封的盒。 
根据本发明的组合物容易被加工成任何类型物件，从扁平物(如膜或薄片)到三维物(如容器或管)，以及将这二种加工入单层结构中或加工入多层结构中。 
优选，本发明涉及包含至少一个层的膜或管，该层包括以上描述的组合物。 
术语“膜”用来表示薄的层状结构(例如流延薄膜的情况)或管状物(例如吹膜情况)，它一般具有1000μm或更小的厚度，优选500μm或更小，或更优选250μm或更小。实际上，90μm或更大，或甚至140μm或更大的厚度是适合的。术语“管”用来表示管状结构，它一般具有200μm或更大，优选500μm或更大的壁厚。实际上，这些厚度常常低于2500μm。此类管可以作为端口元件用于医用包装单元(例如容器、盒、袋子等)。 
优选，如上所述的组合物用于多层结构(膜或管)，它包括几个提供 特定性能的层。例如阻隔性能、密封性等。在优选的实施方案中，组合物被包括在该结构(膜或管)的封闭层中。“封闭层”意味着当焊接时实际上熔化的层(永久的或可剥离的密封)，它通常是表面层并通常具有该结构的最低熔点。也就是说，SI树脂(例如是玻璃化转变温度低于0℃的热塑性弹性体)在环境温度或以上软化，而且s-PP具有相当低的熔点以便于它们的混合物显示优异的密封性。在该实施方案中，如以上解释，封闭层优选另外地包含EVA和/或EMA，以上述列举的量存在，但是为了不放松透明度，优选等于或低于5重量％。 
根据本发明的多层结构(如膜或管)可以包括至少一个含有树脂，例如EVOH、PA、聚酯、LCP(液晶聚合物)等或它们的混合物的阻隔层。在优选的实施方案中，纯EVOH被用作阻隔树脂，更具体地说是乙烯含量在20～45mol％之间，优选在25～40mol％之间，和最优选约30mol％的EVOH，以经受住在121℃/250的蒸汽灭菌。适合的工业级EVOH是Kuraray EVALTM 101B(27mol％乙烯)。在另一个优选实施方案中，EVOH与聚酰胺(PA)混合/共混以改进在较高的湿度下的阻隔性能。此类PA树脂的实例是PA 11或PA 12(例如商购自Atofina的RilsanB或RilsanA)，PA 6/66(例如购自BASF的Capron
Figure 058037414_4
CF120 ZI)或FDA 21 CFR 177.1500和EU directive2007/72/Eccompliant PA6(例如购自BASF的Capron
Figure 058037414_5
，购自Bayer的DurethaneT40)或PA6/12(购自Dupont的Zytel
Figure 058037414_7
)。具有约为200℃的熔点的这些树脂是优选的(根据DSC{吸热峰温度}测定)。具有低于150℃的维卡软化温度的那些树脂是优选的(ISO306 50N；120℃/小时)，同时获得一些挠性。在还有另一个优选实施方案中，EVOH层与至少一个如上所述的适合的PA层(PA 11、12、6、6/66、612等)组合一起以便获取与高阻隔性能结合的最大透明度。可以包括适合的PA(PA 11、12、6、6/66、612等)的介质阻隔膜层。     
为了将该含有聚烯烃的层粘着到此类阻隔层上，使用连系层，例如马来酸化的热塑性树脂(购自Dupont的Bynel
Figure 058037414_8
，购自Mitsui的Admer，购自Atofina的Orevac
Figure 058037414_10
，购自Solvay的Priex等)和/或热塑性弹性体(Kraton
Figure 058037414_12
FG 1901，FG 1921，FG 1924)。特别感兴趣的是最终与马来酸化的热塑性弹性体共混/混合的马来酸化的s-PP。 
根据一个实施方案，所述膜包括阻隔层，该层包括环烯烃树脂 (COP)，它可以是热塑性塑料或弹性体或两者的混合物。这容许获得更好的针对醇、酸和水(或蒸气)的转移阻隔性能。 
术语“COP”应理解为C5～C12环状单体和/或二-环状单体(二聚物)的均聚物或共聚物，它可以带有侧链使得达到总计5～30个C。一般说来环烯烃共聚物由除了C2～C10烯烃单体之外还由环状单体组成。它们通常为无定形或半结晶塑料，其软化点和玻璃化转变温度(Tg)可以在较宽温度范围内通过变化共聚单体部分而调节。那些具有高于约20wt％的环状单体含量的共聚物是相对脆性的并具有室温以上的Tg。那些具有低于约20wt％的环烯烃含量共聚物具有室温以下的Tg，并因此本质上具有弹性(具有至少50％的断裂伸长率)。特别感兴趣的是具有至少40wt％，优选50wt％或更多的环烯烃含量，和最优选60wt％或更多的具有环烯烃含量和具有20wt％或更少，或2％或更多的环烯烃含量的那些。特别感兴趣的是当它们可被蒸汽灭菌时具有121℃或更大的Tg，以及它们具有低于20wt％的环烯烃含量，同时它们显示一些结晶性并因此具有熔点，这有益于密封和其它热处理。申请人意外地发现，当混合高Tg的COP与低Tg的COP时，某些医用领域最想要的挠性、透明度、灭菌性和密封性的性能可以被组合一起。 
基本的环状单体单元可以是环戊烯、环己烯、降冰片烯、二环戊二烯、四环十二碳烯或甲基四环十二碳烯。优选降冰片烯： 
二环[2.2.1]庚-2-烯 
最终带有可以是线性的侧链： 
二环[2.2.1]庚-2-烯 
Rl，R2(＝CxHy+1，x，y＝0，1，2，...) 
或环状的，例如在二环戊二烯(它实际上是带有环戊二烯侧链的降冰片烯)中： 
烯烃有利地为乙烯。COP优选是带有或不带有侧链的降冰片烯的均聚物或共聚物；更优选为降冰片烯(带有或者不带有侧链，但是优选带有环戊二烯作为侧链，即优选二环戊二烯的均聚物)的均聚物或者降冰片烯(带有或者不带有侧链)与乙烯的共聚物。在后一种情况中，乙烯的含量在80～98wt％之间或低于60wt％是有益的。 
根据此实施方案，COP可以同另一种聚合物或氢化的烃共混。有益地，COP与s-PP共混以便制造更具挠性、延展性、抗冲击以及抗刺痕的膜/管，便于焊接和蒸汽灭菌，而其它热塑性聚合物/弹性体和烃也可以被用来较好地稀释/共混该COP。这些有利地选自不完全结晶或无定形的聚烯烃或烃，例如如上所述的或下列类型的SI树脂： 
-烯属共聚物，由至少两种C2～C10烯烃组成，包含至少60wt％的乙烯和/或丙烯和/或丁烯，但不包含大于90重量％的同样共聚单体，或 
-烯属共聚物，包含乙烯和/或丙烯和/或丁烯和10～40wt％的一种或多种不同的共聚单体，该单体优选选自C5～C10烯烃[例如乙烯和1-辛烯的共聚物，其数量使得具有线性低密度聚乙烯(LLDPE)、极低密度聚乙烯(VLDPE)或超低密度聚乙烯(ULDPE)]和羧酸或酯，例如乙酸乙烯酯、丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯和甲基丙烯酸甲酯，或一氧化碳，或 
-含有苯乙烯嵌段和一种或多种烯烃嵌段的弹性体的共聚物或三元共聚物(例如，苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)或苯乙烯-乙烯-丙烯-苯乙烯型(SEPS)等的共聚物)，或 
-高支化的均聚物[例如，低密度聚乙烯(LDPE)或中密度聚乙烯 (MDPE)]或 
-氢化的烃，例如链烷烃或石蜡油。 
有益地，该包含COP的层包括至少一种选自SI树脂，苯乙烯-乙烯-丁烯-苯乙烯(SEBS)，最终包括苯乙烯-乙烯-丁烯(SEB)，苯乙烯-乙烯-丙烯-苯乙烯(SEPS)，最终包括苯乙烯-乙烯-丙烯(SEP)和乙烯-1-辛烯共聚物(优选通过金属茂技术制得)的树脂。SI树脂、SEBS和/或SEPS是优选的，因为它们都容许制造永久的密封和可剥离的密封(在较低温度下)，并且因为它们改进了树脂的抗冲击强度。这些树脂的总浓度一般等于或高于1％(相对于全部层组合物的重量)，和优选等于或高于5％。它一般等于或低于39％，优选低于30％。 
因为COP树脂对油脂敏感，即使以较低的量，例如当接触或操纵油脂时，根据本发明优选实施方案的包含COP的层作为内层被包含在两个其它的层之间是有益地。这些层之一可以是包含SI和s-PP的层。 
根据本发明的膜/管也可以包括具有高熔体温度(＞130℃)、挠性的透明外层(即在该结构之外的层，位于封闭层的另一面)。该层可以包括热塑性聚酯弹性体(TPE)和/或PEBA(聚酯嵌段酰胺共聚物)。TPE树脂由交替的硬聚1，4-丁二醇和/或聚(氧化烯)乙二醇、对苯二甲酸或1，4-环己烷-二羧酸酯和由醚和酯键连接的1，4-环己烷-二甲醇嵌段共聚物组成。此类TPE的实例是ECDEL树脂(PCCE或聚环己烷二羧酸-环己烷二甲醇-弹性体或基于1，4-环己烷二羧酸、1，4-环己烷二甲醇和商购自Eastman的聚(氧化四亚甲基)乙二醇)的共聚酯、商购自Dupont的HYTREL
Figure 058037414_14
树脂、商购自GE的LOMOD
Figure 058037414_15
和购自Celanese的RITEFLEX
Figure 058037414_16
树脂。PEBA树脂由聚酰胺嵌段和至少一个聚(氧化烯)嵌段组成。此类树脂例如商购自Atofina chemicals PEBAX
Figure 058037414_17
的树脂。 
根据本发明，上述的外层膜也可以包含SI或SEBS、SBS等树脂(即具有苯乙烯外部嵌段和包含至少一种聚烯烃或异戊二烯中部嵌段的嵌段共聚物，如上所述)以减少膜储藏(折叠或卷起)和/或包装时，其本身的粘连。 
除了上述的封闭层、阻隔层和外层外，根据本发明的膜/管还可以包括至少一个另外的内层，其具有融化点在密封和外层之间，并包括相似的聚合物(在一种或多种SI树脂、s-PP、其它PP树脂、弹性体...之间选择)。例如，从经济观点考虑包括由碎片(即根据本发明的膜/管 的生产废料)制造的层作为如上所述膜/管的内层是有意义的。无论什么数目的层，一般在结构中具有熔点梯度是令人感兴趣的，其中具有最低熔点的层是封闭层。 
根据本发明的实施方案，如上所述的多层结构(膜或管)包括大于40重量％的金属茂技术PO树脂，其中至少30wt％PP树脂(或者间同立构或者全同立构，或者均聚物或者共聚物，例如与乙烯的共聚物)。 
选择通过金属茂催化剂技术获得的PO树脂改进了全部结构的纯度(可萃取的催化量残基的含量)。这些金属茂PP树脂优选是s-PP和/或i-PP。 
根据本发明的膜可以由任何已知的技术充分地或部分地(部分地意味着具有窗口)被饰以浮饰(即可以载有浮雕图形)，以免结块。 
根据本发明的膜非常易于焊接，因此可以非常方便地用来制造袋子。因此，本发明也涉及通过焊接如上所述的膜而制得的袋子。优选地，这些袋子是多腔袋子，包括至少一个永久的外部密封和至少一个可剥离的密封。永久的密封意思是不容易手工剥离的密封，并且它一般显示出至少2000N/m的剥离强度(根据ASTM/ISO F88)，或甚至至少3000N/m，而可剥离的密封是易于用手工剥离的密封，并且它一般显示低于2000N/m的剥离强度。要获得具有给定的结构的永久的和可剥离的密封的分别的最佳温度、压力和焊接时间的范围可以由本领域技术人员使用一些实验非常容易地确定。一般地，永久的和可剥离的密封使用热气或热的工具焊接制造，而热的工具焊接是优选的。 
根据本发明的膜、管和袋子可以用于任何应用，在该应用中它们上述的性能是有价值的。医用领域就是如此一个应用领域。根据本发明的袋子实际上特别适合于含有医用液体的袋子，例如透析、灌输、营养溶液。 
最后，根据本发明的聚合物组合物还可以有益地用于注塑制品。即在上述的膜和袋子的大多数的应用领域，后者必须与某种装置(例如灌注或透析装置)连接并且要进行这种连接，常常使用连接部件，连接部件一般通过注塑法制得。为了具有完整的由同样的聚合物成分组成的体系和利用其如上所述的优点，这些注塑制品有益地包括与如上所述的聚合物组成相同的聚合物组成。 
下列的实施例用来说明本发明。在这些实施例中，使用下列聚合 物等级(s意思是间同立构；i意思是全同立构)： 
*s-PP是商购自Totalpetrochemicals的等级1251，根据ASTMD1238其MFI为2，并使用金属茂催化剂制得。 
*氢化的SI嵌段共聚物是商购自Kuraray的等级Hybrar 7125。 
*EVA1具有约为3的MFI和约18wt％的VA。 
*EVA2具有根据ASTM D1238在190℃、2.16kg下测得的为2的MFI，和18％的VA。 
*EMA具有16％MA，根据ASTM D1238在190℃、2.16kg下测得的MFI为0.3。 
*i-PP1是来自Borealis的等级HD601CF。 
*i-PP2具有约为5.6MFI，使用金属茂催化剂制得。 
*i-PP3具有的MFI为5，根据ASTM D 1238测得。 
*i-PP4具有约为2的MFI。 
*i-PPE1无规挠性共聚物是商购自Borealis的等级SD233CF。 
*i-PPE2无规挠性共聚物弹性体是商购自Exxonmobile的等级Vistamaxx1100，使用金属茂催化剂制得。 
*i-PPE3无规挠性共聚物弹性体是商购自Dow的等级Versify 2300。 
*i-PP共聚物是来自Borealisis的等级RD208CF。 
*COP1具有的MFI为30(ISO 1133，260℃，2,16kg) 
*COP2具有的MFI为13(ISO 1133，260℃，2,16kg) 
*COP3具有至少80wt％的乙烯。 
膜的光雾值和透明度根据ASTMD 1003以总的光透射率形式被测量。 
膜是通过共挤压(扁平模头和进料模块)方式制得的，每一层具有其自己的独立的单螺杆挤出机(直径为60和45mm并且圆筒的长度为25D)。设置在模头、进料模块和管接头上的温度为约210℃。根据所使用的聚合物，圆筒的温度设置在约150～210℃。单层管是使用45mm单螺杆挤出机进行制造的。使用环形模头制造该管。挤出温度为约210℃。袋子是通过在下列条件下热工具焊接这些膜与管的方式而制得的：温度在120℃至最高150℃，压力为6巴，环形焊接的焊接时间为1.4秒，将该管在80℃预热。在121℃进行蒸汽灭菌30分钟，按照可 应用的USP和/或EP指南中描述的方式可应用蒸汽压力釜。 
对比实施例1： 
共挤压包括下列层的多层膜：包括50wt％i-PP1与50wt％i-PP2的共混物的层A(外层40微米)、由i-PP75wt％无规挠性的i-PPEl共聚物和25wt％i-PP2组成的层B(中间层110微米)、和由75wt％的i-PP共聚物和25wt％的SEBS的共混物组成的层C(密封层40微米)。膜的总厚度为190微米。该膜的袋子在148℃焊接温度下显示永久环形密封。   
在使用蒸汽灭菌后，膜的光雾值为23％。 
对比实施例2： 
共挤压包括下列层的多层膜：层A(外层)：90wt％i-PP1和10wt％SEBS的共混物； 
层B1：i-PP3(100wt％)； 
层B2：由75wt％i-PP3和25wt％SEBS制得的共混物； 
层C(封闭层)：由75wt％i-PP3和22wt％SEBS以及2wt％EVA1和1wt％EMA制得的共混物。 
膜的总厚度为200微米，层B1为40微米。在灭菌后，其光雾值为26％。 
对比实施例3： 
共挤压包括下列层的多层膜：包含100wt％的i-PP1的层A(外层40微米)、由50wt％的无规挠性i-PPEl共聚物和50wt％的i-PP4组成的层B(封闭层)。该膜的总厚度为200微米。该膜的袋子在148℃的焊接温度下显示出永久的环形密封。使用蒸汽灭菌后，膜的光雾值为30％。 
实施例4： 
共挤压包括下列层的根据本发明的膜：包含50％i-PPl与50％i-PP2的共混物的层A(外层40微米)、由75wt％的无规挠性i-PPEl共聚物和25wt％i-PP2组成的层B(中间层110微米)、由75wt％s-PP和25 wt％的氢化SI嵌段共聚物的共混物组成的层C(封闭层40微米)。膜的总厚度为190微米。该膜的袋子在135℃的焊接温度下显示出永久的环形密封。在使用蒸汽灭菌后，膜的光雾值为14％。 
实施例5： 
根据本发明，共挤压包括下列层的多层膜：层A(外层)：90wt％i-PP1和10wt％SEBS的共混物； 
层B1：i-PP3(100wt％)； 
层B2：由75wt％的s-PP和25wt％的氢化SI嵌段共聚物制得的共混物； 
层C(封闭层)：由75wt％的s-PP3和22wt％的氢化SI嵌段共聚物以及2wt％EVA1和1wt％EMA制得的共混物。 
膜的总厚度为200微米，层A和B1两个均为40微米。灭菌后的光雾值是5％。该膜的袋子在135℃焊接温度下显示出永久的环形密封。 
实施例6： 
根据本发明，共挤压包括下列层的多层膜：层A(外层)：90wt％的i-PP1和10wt％的SEBS的共混物； 
层B1：45wt％COP1和40wt％COP2以及15wt％s-PP的共混物； 
层B2：由75wt％的s-PP和25wt％的氢化SI嵌段共聚物制得的共混物； 
层C(封闭层)：由75wt％的s-PP3和22wt％的氢化SI嵌段共聚物以及2wt％EVA2和1wt％EMA制得的共混物。 
膜的总厚度为200微米，层A和B1两个均为40微米。灭菌后的光雾值是6％。该膜的袋子在135℃的焊接温度下显示出永久的环形密封。 
实施例7： 
根据本发明，共挤压包括下列层的膜：包含100wt％的i-PP1的层A(外层40微米)、由50wt％的s-PP和50wt％的氢化SI嵌段共聚物的 共混物组成的层B、由50wt％的无规挠性的i-PPE1共聚物和50wt％的i-PP4组成的层C(封闭层)。膜的总厚度为200微米。该膜的袋子在148℃的焊接温度下显示出永久的环形密封。蒸汽灭菌后，膜的光雾值为25％。 
实施例8： 
根据本发明，共挤压包括下列层的膜：包含100wt％的i-PP1的层A(外层40微米)、由50wt％的s-PP和50wt％的氢化SI嵌段共聚物的共混物组成的层B、由50wt％的无规挠性的i-PPEl共聚物和50wt％的i-PP4组成的层C(封闭层)。膜的总厚度为200微米。该膜的袋子在148℃的焊接温度下显示出永久的环形密封。蒸汽灭菌后，膜的光雾值为15％。 
实施例9： 
根据本发明，共挤压包括下列层的膜：包含100wt％的i-PP1的层A(外层40微米)。由50wt％的s-PP和50wt％的氢化SI嵌段共聚物的共混物组成的层B。由50wt％的无规挠性的i-PPE3共聚物和50wt％的i-PP4组成的层C(封闭层)。膜的总厚度为200微米。该膜的袋子在148℃的焊接温度下显示永久的环形密封。蒸汽灭菌后，膜的光雾值为19％。 
实施例10： 
根据本发明，共挤压包括下列层的膜：包含100wt％的i-PP1的层A(外层40微米)、由25wt％的s-PP和25wt％的氢化SI嵌段共聚物以及25wt％的无规挠性的i-PPE2共聚物和25wt％的i-PP4的共混物组成的层B、由70wt％的无规挠性的i-PPE2共聚物和30wt％的i-PP4组成的层C(封闭层)。膜的总厚度为200微米。该膜的袋子在142℃的焊接温度下显示出永久的环形密封。蒸汽灭菌后，膜的光雾值为19％。 
对比实施例11： 
共挤压包括下列层的多层膜：包含50％的i-PPl与50％的i-PP的共混物的层A(外层40微米)； 
层B：75wt％的i-PPE1和25wt％的氢化SI嵌段共聚物。 
层C：包括如WO03/097739描述的由85wt％的COP3和15wt％的s-PP组成的共混物。灭菌后，光雾值是17％。 
实施例12： 
根据本发明，共挤压包括下列层的膜。层A(外层40微米)：包含50％i-PPl与50％i-PP的共混物。层B：层B由25wt％的s-PP和25wt％的氢化SI嵌段共聚物以及25wt％的无规挠性的i-PPE2共聚物和25wt％的i-PP4的共混物组成。层C：包括如WO03/097739描述的由85wt％的COP3和15wt％的s-PP组成的共混物。灭菌后，光雾值是6％。 
实施例13： 
根据本发明，共挤压包括下列层的膜。层A(外层40微米)：包含50％i-PPl与50％i-PP的共混物。层B：层B由75wt％的s-PP和25wt％的氢化SI嵌段共聚物的共混物组成。层C：包含COP3。在灭菌之前，光雾值是4％。 

Claims (15)

1.包含间规聚丙烯和热塑性弹性体的聚合物组合物，该热塑性弹性体选自包括至多40重量%苯乙烯的树脂和苯乙烯-异戊二烯-丁二烯-苯乙烯，其中，所述树脂中的所述苯乙烯形成通过由乙烯基-异戊二烯-共-聚异戊二烯形成的嵌段连接在一起的嵌段。
2.根据权利要求1的聚合物组合物，其中所述热塑性弹性体是至少部分氢化的。
3.多层结构，至少一层包括根据权利要求1或2所述的聚合物组合物。
4.根据权利要求3所述的多层结构，它是多层膜或管，并且其中包括根据权利要求1或2所述聚合物组合物的层是封闭层。
5.根据权利要求4所述的多层结构，为膜或管形式，其中封闭层包括另外的乙烯-乙酸乙烯基酯和/或乙烯-丙烯酸甲酯。
6.根据权利要求4或5所述的多层结构，为膜或管形式，具有至少一个包含树脂的阻隔层，树脂选自乙烯-乙烯醇共聚物、聚酰胺、聚酯、液晶聚合物或它们的混合物，或环烯烃聚合物。
7.根据权利要求4或5所述的多层结构，为膜或管形式，具有包含热塑性聚酯弹性体和/或聚酯嵌段聚酰胺的外层。
8.根据权利要求6所述的多层结构，为膜或管形式，具有包含热塑性聚酯弹性体和/或聚酯嵌段聚酰胺的外层。
9.根据权利要求4或5所述的多层结构，为膜或管形式，其包含大于40wt%的金属茂技术聚烯烃树脂，其中包含至少30wt%的聚丙烯树脂。
10.根据权利要求6或7所述的多层结构，为膜或管形式，其包含大于40wt%的金属茂技术聚烯烃树脂，其中包含至少30wt%的聚丙烯树脂。
11.通过熔焊根据权利要求3、4或5所述的多层结构而制得的袋子，其中所述多层结构为膜形式。
12.通过熔焊根据权利要求6所述的多层结构而制得的袋子，其中所述多层结构为膜形式。
13.通过熔焊根据权利要求7所述的多层结构而制得的袋子，其中所述多层结构为膜形式。
14.通过熔焊根据权利要求8所述的多层结构而制得的袋子，其中所述多层结构为膜形式。
15.包含根据权利要求1或2所述的聚合物组合物的注塑制品。
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EP1711558B1 (en) 2008-06-11
CN1926186A (zh) 2007-03-07
JP5075412B2 (ja) 2012-11-21
KR20070017318A (ko) 2007-02-09
BRPI0507323A (pt) 2007-07-03
CA2554909C (en) 2014-03-25
US20070142557A1 (en) 2007-06-21

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