CN1222884A - 用于可灭菌处理的液体容器的共挤压多层膜 - Google Patents

用于可灭菌处理的液体容器的共挤压多层膜 Download PDF

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CN1222884A
CN1222884A CN199898800500A CN98800500A CN1222884A CN 1222884 A CN1222884 A CN 1222884A CN 199898800500 A CN199898800500 A CN 199898800500A CN 98800500 A CN98800500 A CN 98800500A CN 1222884 A CN1222884 A CN 1222884A
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P·布兹奥
I·因科林戈
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Baxter Biotech Technology SARL
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Abstract

柔性且透明的完全由聚烯烃形成的膜、箔、片材等,通过成型、灌装和封口的方法,特别适合于制造注入液容器,它包括两个具有不同的聚合物组成的端层(A)和(C),以及“n”个中间基层B1,B2…Bi…Bn,这些基层具有乙烯含量和软化温度梯度。

Description

用于可灭菌处理的液体容器的共挤压多层膜
发明背景
发明的领域
本发明是关于膜，片材，箔和类似的柔性透明复合材料，它们是由具有较高层间相容性和粘着性的多个共挤压层组成，特别适合于通过成型-灌装-封口方法(F-F-S)生产容器，尤其是流体(特别是注入液)的袋，该容器必须在大约121℃或者更高温度下，用水蒸气在高压灭菌器中进行杀菌消毒，该容器除了透明度和良好的接触焊(welding resistance)外还必须具有较高的耐穿破性和耐跌落性，所说的膜至少包括：
-外层(A)，该层在所说的F-F-S加工过程中要与焊接装置形成接触且其熔融温度至少为130℃并且要有高机械强度在杀菌消毒阶段能支撑填充的容器；
-内层(C)，该层将会与所说的液体形成接触，一旦容器形成并填充液体，它经受焊接热封或冷封；以及
-在(A)和(C)层之间的复合中间层(B)，该层对于粘着性，透明性，抗机械性能，吸震性等是特别重要的，所说的层在没有粘合剂和交联化合物的情况下，基本上由烯烃聚合物组成。
现有技术的说明
在专利申请(瑞士专利申请号为3771/93，对应于EP-A-0658421)中描述了基本为上述类型的多层共挤压膜，即具有在本说明书序言和相关的权利要求1中作为现有技术所说明的特征。在所说的申请中(在这里将引入对该申请的描述)，外层(A)和内层(C)具有相同的对称成分(即相同的无菌聚烯烃PO-STERI)，而中间层(B)(不可灭菌，其熔点低于121℃，厚度为50～200微米)是由聚烯烃构成的，该聚烯烃选自热塑性聚烯烃，密度低于0.9g/m3的乙烯-丁烯共聚物和相关的混合物。层(A和C)(其厚度为10～80微米)的材料选自丙烯聚合物和丙烯与乙烯和/或丁烯的共聚物；乙烯聚合物或乙烯与具有六个碳原子的α烯烃的共聚物；带有或不带有少量弹性体的相关混合物。在下面使用的符号表示：PP是丙烯聚合物，PE是乙烯聚合物，该聚合物可能是线性(L)的并具有低密度(L)中密度(M)或高(H)密度(D)。
在实施例中，层(A)和(C)两者可同时是PP或C8-LLDPE(线性的具有少量辛烯的低密度聚乙烯(8))而(B)也可以是回收的材料和重新造粒的聚烯烃材料。类似的在EP-A-0216506(归类为X即在所说的EP-A-0658421的检索报告中被认为是相关的文件)中描述了一种医疗袋，该袋是通过层压形成的，它是由层(A)和(C)组成的，这两层是相同的并选自LDPE，HDPE或乙烯-α烯烃的共聚物，其密度至少为0.920g/cm3，而(B)是乙烯-α烯烃的共聚物，其密度低于0.935g/cm3。具有对称成分的层(A)和(C)的必要性一般基于这样的事实：在这样做时可减少中间层(B)在所说的层(A)和(C)之间赋予充分的相容性和粘着性的难度，仅仅因为它们具有相同的成分，所以层(A)和(C)是可共存的。
可是经验证明，使单层(即使很厚)材料(B)特别是在杀菌消毒后使层(A)和(C)具有充分的粘着性既不容易也不是很有把握，尽管它们具有相同的成分。实际上在注入液袋的情况下要面临双倍的问题，不仅要考虑例如依据粘度来评价和选择(A)和(C)层以使它们配合得更合适，而且还要依据(例如)由“药典(PHARMACOPEA)”的可接受性来考虑问题，对于“药典(PHARMACOPEA)”将要考虑中间层的附着系数，该附着系数必须很高并且要求很严，对于保证结构达到可接受的状态是不可缺少的。而且现在要求袋要能装更多的液体，所以就必须具有足够高的性能。
发明概述
本发明的主要目的是提供共挤压膜以及相关的容器，该容器具有“最大的maximorum”性能，特别是极佳数值的最佳组合：不同组成的端层(A)和(C)之间的粘着性的最佳组合；在没有溶液中分解产物转移的情况下，相容性，透明性，柔软度，抗跌落性，密封强度的最佳组合，等等。
本发明的这一目的和其它目的可用膜和相关容器(该容器具有的特征列举在权利要求中)来实现。实际上已发现通过有利地使用不同组成的层(A)和(C)以及在它们之间的一系列基层B1,B2…Bn，这些基层的组合单体乙烯(E)单元的含量以及它们的熔融(软化)温度严格地呈梯度分布，得到能满足(甚至例如在最苛刻条件下)稳定性(resistance)，可加工性，外观等以及药典(Pharmacopea)特殊要求的膜和袋是可能的。
附图的简要说明
本发明的各个方面和优点将从下面参考两个实施例和附图的描述而变得一目了然。
图1是根据本发明多层膜的示意截面图，图2和3是一曲线图，它象征性的表示出在各层中各自熔融温度、乙烯含量的空间变化。
优选实施方案的说明
仅仅是出自立即固定的想法，根据本发明的第一个特征，在图1中所显示的复合材料膜包括非对称的两个端层(A)和(C)，即具有不同组成(和特征)的端层(A)和(C)以及一定数量的“n”个中间基层B1,B2…Bi…Bn-1,Bn，它们的乙烯含量和熔融温度或软化温度(Tfr)呈梯度分布。
根据本发明的其它优选的特征：
-实际形成中心层或芯CO的中央基层B1…Bmc的下标号“mc”具有最小的软化温度并且E-含量和软化温度的梯度最小或者甚至为零；
-实际形成上部中心层Bs的B1～Bms基层的下标号“ms”表示出乙烯含量的增加和熔融温度从(A)(大约140℃)的最高温度(Tmax)到低于杀菌消毒温度(121℃Tster)的最低温度的降低；
-位于芯CO基层下面的基层的下标号“mi”显示出乙烯含量的仍在增加并且软化温度也从上面提及的最低温度(Tmin；低于121℃)到层(C)温度(Tc至少等于杀菌消毒温度Tster即121℃)增加。显然，ms+mc+mi=n。
图2表示的是端层(A),(C)以及由一系列子层(B1,B2…Bn)组成的中间层(B)。
层(A)基本上由可带有少量乙烯的丙烯组合单体单元组成；优选(A)选自具有低含量PE的PP均聚物；在分界线的情况下，还可能是HDPE，其中混有PP-PE嵌段共聚物；层C基本上由可具有少量α-烯烃的乙烯组合单元组成；优选C选自：LLDPE，优选为与α-烯烃共聚物的形式，α-烯烃主要为辛烯，次要为丁烯，己烯；所说的LLDPE和LDPE的共混料可用高压加工的方法制备。
中央层B，即一系列子层(B1,B2…Bn)必须与端层(即A和C)有较高的亲合性以保证在高温以及在环境温度下整个结构具有良好的相容性和粘着性。只有通过使所有的层，特别是在变形时都具有支持和吸收应力的功能，才可能使结构机械特性(包括耐穿破性和耐跌落性)达到最大。
根据本发明的另一特征，基层的数量要尽可能的高，但是它们优选要形成连续的最佳相容性配合对；这通过保持最佳的粘着性和透明性以使其从PP类似面(A)到PE类似面(C)形成连续的层。
在实际的经验当中现已弄清，一方面“n”不可能是无限的，另一方面，仅有一个基层(B)对于保证所要求的特征的最佳组合是不够的，特别满意的结果是在将两个、最好为三个基层可能重复多次后才开始出现；按这样的重复过程就可成功的产生出一系列适合于优化中间层的粘着性和结构一致性的特性。
在所说的结构中(这里用一般的用语进行描述)，即使其它的基本特征(结晶度，在固体状态下的形态，接触角等)是十分重要的，但表示连续层中材料亲合性的参数是乙烯的含量(CE)和软化点。实际上，对特别适合于形成基层的PP-PE共聚物而言，选择具有增加的乙烯含量的产品，而对于线性PE，为了在两个端层间达到最佳的粘着性优选具有增加的共聚物含量的产品。现已惊奇的发现，在乙烯较丰富的无规共聚物和所谓的具有很低密度的聚乙烯(VLLDPE)之间具有良好的相容性，并且这些共混料可产生通过类似PP和更类似于PE结构的通道。通过简单的物理混合和连续挤出得到的这些共混料可进一步通过在熔融物质混合中初始阶段的混合得到改进，这些共混料如果加入合成的弹性体例如SBS,SEBS等聚合物或者加入聚烯烃橡胶例如PP-PE-EPDM共聚物可变得更加适合于上述使用。在实施例中揭示了一些这样的结构，其有助于在软包装的特殊用途上有要求的层间粘着性和密封强度，耐跌落和耐穿破性，在水蒸气消毒后的透明性以及可加工性达到所要求的性能。
本发明的又一目的是关于共挤多层结构，下面实施例所揭示的结构适合于称为“流延挤出”的平面机头共挤出。不管怎样本发明不会限于此项技术，它还能通过吹胀共挤出再加上管式急冷或从各机头中连续共挤出来体现，各分开的机头可使不同的材料以连续的步骤挤出，一旦这些材料被冷却，它就会缠绕在一起成为单个片材。
实验部分
在一特别简单的实施方案中，本发明的结构在一个由五台单螺杆挤出机(各挤出机可单独控制，能熔融并准确喂入最多达五种具有所要求的往复流的不同材料)组成的流延共挤出线上实现，熔融的材料然后被送到具所有希望顺序的平行和稳定的系统层，该系统层然后喂到一扁平模头中在熔融状态下最终形成片材。
在螺杆口模的出口处，片材通过与一旋转圆柱体(内部流有冷却液)接触而进行冷却，相对于从螺杆口模输出的熔融物质的速度，圆柱体的线性速度允许根据多层结构的厚度进行控制。更外层可以提供有传统的润滑剂(sliding agent)或防粘剂以提高袋的机械性能。用实施例的膜样品，袋可用传统的方式形成并填充满注入液，然后在121℃和2巴的反压下，在高压灭菌器中进行杀菌消毒每60分钟为一完整周期(加热，消毒和冷却)。下面的结构(特别是那些总结在表1中简单的结构)以相同的挤出速度并通过保持200微米不变的总厚度来制造。如此获得的膜的主要性能可根据传统的方法在挤出后72小时内进行测试和确认。在表中所引用的简单材料相当于下面的类型和性能：
A)PP COPO：具有乙烯含量为3～3.5的PP-PE无规共聚物，在230℃测量的MFI(熔体流动指数)在9和12之间；熔点为148～152℃。典型的商用聚合物是BOREALIS RE764或DAPLEN KFC2004；
B1)高乙烯(含量)的PP COPO：无规的PP-PE共聚物具有较高含量的乙烯(7～10％)，在230℃的MFI为12，熔点为132℃。典型的商用制品是DAPLEN MFC 2110 SB；
B2)PP化合物：具有较低乙烯含量(低于15％)的无规共聚物，该乙烯与类型为SEBS、EPDM的嵌段共聚物混合均匀。弹性体含量在20％和30％之间，在230℃的MFI在2和8之间。在聚合阶段完全可以得到与由MONTELL公司生产的称为ADFLEX C 200 F特征性能相似的种类。
B3)VLLDPE：具有很低密度(大约0.900g/cm3)的线性聚乙烯，它一般是由乙烯与共聚单体例如丁烯、己烯或其它α-烯烃在立构有规催化剂存在的条件下进行共聚得到。在这些试验中使用的产品是由“POLIMERI EUROPA”公司商品化的“CLEARFLEX”CLDO，其共聚单体含量低于20％，在190℃的MFI为3，熔点为115℃。
C)LLDPE：线性聚乙烯(类似于上面的VLLDPE)可通过乙烯与少量(低于10％)的α-烯烃型共聚单体立构有规聚合来制备。在优选的实施方案中，可按下面的方式加入另两个基层B4和B5：
B4)MDPE：用传统的方法(高压)在压力釜中制备的中密度聚乙烯，其特征在于相对高的密度(d=0.933g/cm3)，该密度会使膜具有特别的劲度，在190℃的MFI=2.5-3.5。
B5)LDPE：在所有其它的条件相同的情况下，与丁烯或己烯的共聚物。
所期望的最佳结果可通过重复象B1-B2,B2-B3,B3-B4等两层组成的基层或象B1-B2-B3,B2-B3-B4,B3-B4-B5等三层组成的基层几次来得到。
比较例
除了根据本发明的实施例外，在表中还披露了两种产品，它们所具有的结构与本发明的那些产品的结构是不一致的(实施例4和5)，因而性能很差，这就证实需要一种特殊的成分以达到在袋的特殊应用中需要的性能。
图2和3的曲线图象征性的表示出随着乙烯组合单体单元的含量(在图2中在X轴上的E)以及各熔融-软化温度(图3中在X轴上的Tfr)的空间的变化(Y轴)。这两个重要参数的改变在芯CO的上面和下面的两个主要段A-As和C-Ci中更明显(更强烈)，相反在芯CO中，E和Tfr的变化甚至可以忽略不计。E和Tfr的梯度一般存在在所说的主要段A-As和C-Ci中，但它们在中心段CO中可能是最小的或者可忽略不计。在所说的图中，odashed曲线代表其它可能的E和Tfr变化的规律。
在图2的中心段BC中，乙烯的含量E可能是一定的(曲线2，零梯度=GR=0)或呈线性变化(曲线3，恒定梯度GR=常数)或不呈线性变化(变化的梯度GR=变数)。由上述可以看出，各种变化和改进都可以被实现而没有脱离本发明新颖想法的精神和范围。
表1
 试验 外层A 中间层B1 中间层B2 中间层B3 内层C 密封强度kg/15mm 层脱力kg/15mm 透明度
  1 PP Copo高55my PP     Copo高乙烯15my PP化合物/VLLDPE15my VLLDPE20my LLDPE95my     4.5     2.1    好
  2 PP Copo60my PP化合物25my PP化合物/VLLDPE25my MDPE10my LLDPE80my     4.9     2    好
  3 PP Copo55my PP     Copo高乙烯25my PP化合物20my VLLDPE15my LLDPE70my     4     2    好
  4 PP Copo55my PP     Copo高乙烯25my PP化合物20my MDPE20my LLDPE80my     2.7     0.5   不好
  5 PP Copo55my     PP化合物65my LLDPE80my     2.6     1.1   不好

Claims (7)

1．膜、片材、箔和类似的柔性透明复合材料，它们是由具有高层间相容性和粘着性的多个共挤压层组成，特别适合于通过成型-灌装-封口方法(F-F-S)生产容器，尤其是流体袋，该流体特别是注入液，该容器必须在大约121℃或者更高温度下，用水蒸气在高压灭菌器中进行杀菌消毒，该容器除了透明度和良好的接触焊外还必须具有高耐穿破性和耐跌落性，所说的膜至少包括：
-外层(A)，该层在所说的F-F-S加工过程中要与焊接装置形成接触且其熔融温度至少为130℃并且要有高机械强度以在杀菌消毒阶段能支撑填充的容器；
-内层(C)，该层将会与所说的液体形成接触，一旦容器形成并填充，它经受焊接热封或冷封；以及
-在(A)和(C)层之间的复合中间层(B)，该层对于粘着性、透明性、抗机械性能、吸震性等是特别重要的，所说的层在没有粘合剂和交联化合物的情况下，基本上由烯烃聚合物组成，其特征在于：
层(A)和(C)具有不同的成分；层(A)基本上由聚合物组成，该聚合物由可含有少量乙烯或α-烯烃的组合单体单元的丙烯组合单体单元形成；层(C)基本上由可具有少量α-烯烃的乙烯组合单元组成；层(B)基本上由一定数量(n)的聚合物层组成，它包括在(A)附近上部(A-AS)中“ms”数量的基层，“mc”数量的中央基层，该基层形成在(A)和(C)之间的中间层(B)的中央层或芯(BB)，和包含在所说的集合体B-B和C-Ci之间的下部C-Ci中“mi”数量的层，其中ms+mi+mc=n，至少上部(A-As)和下部(C-Ci)的层或基层“ms”和“mc”分别具有乙烯组合单体单元的含量梯度和软化温度的梯度。
2．根据权利要求1的膜，其特征在于外层(A)基本上由可带有不高于4％的少量乙烯组合单元的丙烯组合单体单元形成；层(C)基本上由可带有少量α-烯烃的乙烯组合单体单元形成；在层(B)的A-As和C-Ci段中的所有“ms”和“mc”基层显示出乙烯单体单元含量的增加，但在A-As中软化温度从(A)的最高软化温度(Tmax)降到在芯(CO,BB)中的最低温度(Tmin)，分别地，在C-Ci段软化温度从层C的所说的芯的最低温度增加到至少121℃的杀菌消毒温度。
3．根据权利要求2的膜，其特征在于“mc”是在6和8之间，“ms”至少等于2,“mi”是在2和10之间。
4．根据前述权利要求中至少之一的膜，其特征在于层(A)选自具有乙烯含量低于3.5％的丙烯聚合物，其厚度在10～80微米之间，层(C)选自具有α-烯烃含量低于10％的乙烯聚合物，所说的“ms”上部基层的熔融温度从140℃降低到大约90℃，所说的“mi”下部基层的温度从90℃增加到至少121℃。
5．根据前述权利要求中至少之一的膜，其特征在于：层(A)是由具有PE(聚乙烯)含量低于3.5的PP(聚丙烯)无规共聚物形成的；层(C)是具有α-烯烃含量低于10％的LLDPE(线性低密度聚乙烯)；层(B)包括由无规的PP共聚物和弹性体改良剂的混合物构成的至少第一基层B2，该弹性体改良剂选自乙烯-丙烯-单体二烯的三元共聚物EPDM或SEBS；以及基层B3,B4,B5,B6,B7等，它们是由聚乙烯形成的，该聚乙烯选自具有少量α-烯烃和MDPE的聚合物型的VLLDPE和LDPE。
6．主要根据表1的复合多层膜。
7．容器，特别是盛液体，尤其是盛医用液体的袋，可在121℃或者更高的温度下用水蒸气在高压灭菌器中进行消毒，它们是由聚烯烃共挤压多层膜组成，至少在共挤压多层膜中的一层上要有软化温度低于121℃的基层，其特征在于外层(A)和内层(C)(在121℃或者更高的温度下消毒期间，即当中间层(B)的“n”个基层中的至少大部分处在部分熔融的条件下并且使容器具有耐机械性能)的厚度随着含在袋中液体重量和(B)的总厚度的增加而增加，并且当(B)的总厚度是在50微米之上时是在40微米之上，并且，对于至少1升的液体量，(B)基层的数量“n”也要随着所说的最后液体量的增加而增加。
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HUP0002055A2 (hu) 2000-10-28
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AR015366A1 (es) 2001-05-02
AU735409B2 (en) 2001-07-05
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AU5875798A (en) 1998-09-09
CA2252585A1 (en) 1998-08-27
US6528173B1 (en) 2003-03-04
EP0923451A1 (en) 1999-06-23
CO4761091A1 (es) 1999-04-27
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BR9805902A (pt) 2000-01-25
CH692846A5 (it) 2002-11-29

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