CN104802481A - 多层膜和其制造方法 - Google Patents

多层膜和其制造方法 Download PDF

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Publication number
CN104802481A
CN104802481A CN201510144196.6A CN201510144196A CN104802481A CN 104802481 A CN104802481 A CN 104802481A CN 201510144196 A CN201510144196 A CN 201510144196A CN 104802481 A CN104802481 A CN 104802481A
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Prior art keywords
layer
film
aforementioned
specifically
thermoplastic
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H·施米特
C·赫斯
J·玛萨
R·哈克福特
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BioTec Biologische Naturverpackungen GmbH and Co KG
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BioTec Biologische Naturverpackungen GmbH and Co KG
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Wrappers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

本发明描述了一种多层膜，具体用于包装，所述膜包括至少一个第一层A和至少一个第二层B，其中层A含有热塑性聚酯，层B含有热塑性淀粉。本发明多层膜的特征是出色的阻挡性能、对水汽敏感性低和良好的机械强度。

Description

多层膜和其制造方法
本申请是国际申请号为PCT//EP2007/053518，国际申请日为2007年4月11日的PCT国际专利申请进入中国阶段后的国家申请号为200780020730.6，发明名称为“多层膜和其制造方法”的中国专利申请的分案申请。
技术领域
本发明涉及多层膜，具体涉及用于包装的多层膜，其包含至少两层A和B。本发明还涉及制造所述多层膜的方法和由其制造的包装材料。
背景技术
序言中提到的多层膜类型通常是已知的，并可用于包装食品和其它商品。在包装对氧敏感的食品时，该膜还需要具有低氧渗透性。这类膜也被称为“阻挡膜”。它们可用于包装新鲜肉类或水果和蔬菜，通过具体调整气体阻挡作用，具体是氧气和/或水蒸汽阻挡作用，可显著延长其储藏时间。目前，包装工业中使用的绝大部分屏障膜由基于石油化学获得的塑料组成。
由于经济和生态学上的考虑，对可再生原料制成和/或可生物降解的合适膜的需求越来越大。
发明内容
因此，本发明的目的是提供序言中提到的多层膜类型，其具有良好的阻挡特性，由可再生原料制成和/或可生物降解。而且，该膜应具有足够的机械强度、对水汽不敏感且经济。根据其目标用途，如果需要，该膜应具有良好的透光性。
本发明的目的可通过多层膜实现，特别是包装目的，所述多层膜包含至少一个第一层A和至少一个第二层B，其中层A含有至少一种热塑性聚酯，层B含有热塑性淀粉。
从属权利要求中描述了本发明的优选实施方式。
本发明多层膜的主要特征是它的层结构一方面含有热塑性聚酯(层A)，另一方面含有热塑性淀粉(层B)。令人惊讶地发现，含有这种材料组合的多层膜作为包装膜时具有非常良好的特性。
本发明膜的特征是出色的阻挡特性，具体是氧和二氧化碳渗透性低。该膜还具有出色的机械强度，对水汽敏感性低。如果需要，可以制备具有本发明层结构的膜，它能够深冲压且具有优良的透光性。
具体实施方式
本发明多层膜的特征是优良的机械强度，并且在制造包装元件时可进行出色地加工。因此，例如，具有本发明层结构时，根据DIN 53455的抗张强度值范围可能达到10-40N/mm2，具体是15-30N/mm2。
本发明多层膜的特征还在于出色的阻挡特性。因此，例如，在23℃、50％相对湿度和400μm膜厚度时，按照ASTM F 1927-98，本发明多层膜的氧渗透性优选为1-50cm3/m2d，优选1.5-20cm3/m2d，更优选2-10cm3/m2d。另外，在23℃、75％相对湿度和400μm膜厚度时，按照ASTM F 1249，本发明多层膜的水蒸汽渗透性优选为1-100cm3/m2d，具体是2-10cm3/m2d。最后，在23℃、50％相对湿度和400μm膜厚度时，按照ASTM D 1434，本发明多层膜的二氧化碳渗透性优选为0.5-5cm3/m2d，具体是1-2.5cm3/m2d。由于上述阻挡特性，本发明多层膜特别适合用作包装目的的阻挡膜。
本发明多层膜可具有任何所需厚度，其中所述膜的厚度在很大程度上取决于所需应用目的和所需膜特性。出于包装目的，该膜的总厚度优选为10-2000μm，具体是100-2000μm，更优选200-800μm，其中单独各层的厚度优选为5-1000μm，具体是10-1000μm，优选为20-700μm，更优选为10-700μm。吹制多层膜的总厚度优选为30-100μm。
由本发明多层膜制造的包装元件可具有任何所需厚度。用于包装食品的本发明多层膜制成的托盘的总厚度优选为350-400μm，相应的覆盖膜的厚度优选为30-100μm。
本发明多层膜包含至少一个层A和至少一个层B。除此之外，本发明膜可包含任意数量的其它层。按照本发明的具体优选的实施方式，本发明多层膜包含至少两个层A和一个层B，其中层B优选安置在两个层A之间。这种多层膜具有以下层结构：层A–层B–层A。
采用这种层结构时，层A可紧邻层B。然而，也可提供一层或多层其他层用作中间层，例如一个或多个结合层(tie layer)H。本领域技术人员了解这类结合层H，优选由嵌段共聚物组成。结合层H在一侧表面优选直接与层A接界，另一侧表面直接与层B接界，用于提高层A和B之间的粘结性。作为含有粘结层的本发明多层膜的例子，可指出以下层结构：层A–结合层H–层B–结合层H–层A。
根据所需应用，该膜可进一步包含层A和/或B。也可能是具有(例如)以下层结构的多层膜：层A–层B–层A–层B–层A。因为提供了两个层B，所以这种膜的阻挡性能更好。此外，结合层H也可安置在单个层之间。
按照本发明，多层膜的层A含有至少一种热塑性聚酯。在这种情况下，热塑性聚酯的选择不受限制。可能是脂族和芳族聚酯及其共聚物和/或混合物。
热塑性聚酯通常是本领域已知的，参见例如，Oberbach等，“Saechtling Kunstoff Taschenbuch”，第29版，翰塞出版社(Hanser publishing house)，慕 尼黑(2004)。
按照本发明的优选实施方式，层A中所含的热塑性聚酯是按照EN13432可生物降解的热塑性聚酯。
具体说，热塑性聚酯可以是基于一种或多种羟基羧酸的生物聚合物。
特别适合本发明的热塑性聚酯是聚羟基烷酸酯(PHA)，聚丁二酸亚烷基二醇酯(PAS)如聚丁二酸丁二醇酯(PBS)，聚对苯二甲酸亚烷基二醇酯(PAT)如聚对苯二甲酸乙二醇酯(PET)，脂族-芳族共聚酯和/或聚对二氧环己酮(poly[p-dioxanon],PPDO)，以及它们的共聚物和混合物。也考虑单独或与其它热塑性聚酯联合使用生物丙二醇(生物-PDO)聚酯。
按照本发明的特别优选的实施方式，层A含有至少一种聚羟基烷酸酯(PHA)作为热塑性聚酯。合适的聚羟基烷酸酯的例子是聚羟基乙酸酯如聚羟基乙酸(PGA)、聚羟基丙酸酯如聚乳酸或聚丙交酯(PLA)、聚羟基丁酸酯如聚羟基丁酸(PHB)、聚羟基戊酸酯(poly[hydroxypentanoate])如聚羟基戊酸酯(poly[hydroxyvalerate],PHV)和/或聚羟基己酸酯如聚已内酯(PCL)，以及它们的共聚物和混合物。
本发明特别合适的热塑性聚酯是聚乳酸或聚丙交酯(PLA)。PLA是可通过多步合成由糖制备的可生物降解聚酯。在这类多步合成中，糖一般发酵成乳酸，然后通过二丙交酯(dilactide)的中间阶段聚合成PLA。PLA是透明的刚性晶体，其机械强度高，并可通过常规热塑方法进行加工。基于PLA的合适聚合物参见例如US 6 312 823、US 5 142 023、US 5 274 059、US 5 274 073、US 5 258 488、US 5 357 035、US 5 338 822和US 5 359 026。按照本发明，PLA可以是新原料和回收料的形式。
特别合适的热塑性聚酯是聚羟基丁酸(PHB)。在天然情况下，PHB由多种细菌产生用作贮存和储藏物质。因此，可通过细菌技术制造PHB。基于PHB的合适聚合物参见例如，US 4 393 167、US 4 880 592和US 5 391 423。
作为本发明层A的材料，特别考虑了US 6 312 823中所述的“脂族聚酯聚合物”，在本文中明确参考其说明书并使其成为本发明对象。
所述热塑性聚酯的合适的共聚物或混合物是，例如，聚己内酯/聚丁二酸丁二醇酯混合物或共聚物(PCL/PBS)、聚羟基丁酸/聚羟基戊酸酯共聚物(PHB/PHV)、聚羟基丁酸戊酸酯(PHBV)、聚丁二酸丁二醇酯/聚己二酸丁二醇酯混合物或共聚物(PBS/PBA)、聚对苯二甲酸乙二醇酯/聚丁二酸乙二醇酯共聚物(PET/PES)和/或聚对苯二甲酸丁二醇酯/聚己二酸丁二醇酯共聚物(PBT/PBA)。
除热塑性聚酯外，层A还可含有其它组分。具体说，层A可由不同聚合物的混合物组成。此外，层A还可含有常规添加剂，如加工助剂、增塑剂、稳定剂、阻燃剂和/或填充剂。也可将粘合剂加入层A，其具体用于改善层A和B之间的粘合性。优选地，层A含有热塑性聚酯，以层A总重计热塑性聚酯含量为至少20重量％，具体为至少30重量％，或至少40重量％，更优选至少50重量％或至少60重量％，更优选至少80重量％，最优选至少90重量％，或至少95重量％。更优选地，层A基本上由热塑性聚酯组成。
本领域技术人员通常了解可用于本发明的加工助剂。原则上，在这种情况下，所有加工助剂均可考虑用于改善所用聚合物的工艺特性，尤其是其在挤塑机中的流动特性。
按照本发明，特别合适的加工助剂是聚合物主链被反应性基团官能化或修饰的聚合物。这类聚合物也称为“官能化聚合物”。本发明所用的加工助剂的分子量优选最高为200,000，具体为最高100,000。
作为加工助剂的聚合物主链，原则上可考虑与多层膜至少一层(如层A)的至少一种聚合物组分(如PLA)可混溶的所有聚合物。合适的加工助剂的聚合物主链是，例如，乙烯乙酸乙烯酯(EVA)，聚乙烯(PE)，聚丙烯(PP)，丙烯酸亚乙酯，聚酯(如PLA)，以及它们的混合物和/或共聚物(如聚乙烯丙烯酸甲酯共聚物或聚乙烯丙烯酸丁酯共聚物)。
作为本发明所用的加工助剂的反应性基团，原则上可考虑适合与多层膜至少一层(如层B)的至少一种聚合物组分(如TPS)发生化学反应的所有反应性基团。合适的反应性基团是，例如，马来酸酐和/或其它合适羧酸或二羧酸或其它多元(multibase)酸的酸酐。
优选地，以加工助剂的总重计，用0.01-7重量％，具体是0.1-5重量％，更优选是0.3-4重量％的反应性基团修饰聚合物主链。优选地，将反应性基团嫁接到聚合物主链上。
这种类型的加工助剂可以以下商品名购得，例如和(美国澳柯玛公司(Arkema Inc.，USA))，、Biomax和(美国杜邦公司(DuPont，USA))以及(美国艾奎斯化学品公司(Equistar Chemical Company，USA))。
以单层总重计，加工助剂的用量优选为至多5重量％，具体是0.01-2重量％，更优选0.1-1.5重量％，更优选0.2-1重量％，最优选<1重量％。根据本发明特别优选的实施方式，马来酸酐修饰的乙烯基聚合物，具体是马来酸酐修饰的聚乙烯/丙烯酸烷基酯共聚物，用作层A的加工助剂。
按照本发明可发现，使用上述加工助剂时，不仅可提高所用聚合物的加工能力(挤塑机中的流动特性，熔体均一性)，而且显著提高各层之间的粘结力。
按照本发明，多层膜的层B含有热塑性淀粉。
热塑性淀粉或热塑可加工性淀粉(TPS)通常是已知的，详见EP 0 397 819 B1、WO 91/16375 A1、EP 0 537 657 B1和EP 0 702 698 B1。热塑性淀粉的市场占有率约为80％，它是最重要和最广泛使用的代表性生物塑料。热塑性淀粉通常由天然淀粉，如马铃薯淀粉制得。为了制备能够进行热塑性加工的天然淀粉，可加入增塑剂如山梨糖醇和/或甘油。热塑性淀粉的特征是含含水量低，以热塑性淀粉总重计，其含量优选小于6重量％。热塑性淀粉的特征也在于，它优选基本上是无定形结构。
按照本发明的优选实施方式，层B至少部分地由热塑可加工性淀粉制成，以淀粉总重计，其含水量小于6重量％，优选小于4重量％，具体是小于3重量％。
已发现，使用具有所示含水量(<6重量％)的热塑可加工性淀粉时，可以改善挤塑机中的流动特性，并减少层中形成微泡。
然而，所用的热塑可加工性淀粉的含水量优选为至少1重量％，具体是至少1.5重量％，因为否则便可容易地发生热诱导氧化过程，从而使产品变成令人不快的颜色。相反，含水量大于约6重量％时，可容易地发生微泡形成增加，这同样是不合需要的。
层B中所含的热塑性淀粉的优选特征是，由该热塑性淀粉制成的膜按照DIN 53455的抗张强度为2-10N/mm2，具体是4-8N/mm2，和/或按照DIN53455断裂伸长率为80-200％，具体是120-180％。
按照本发明的另一个优选实施方式，可通过以下步骤获得热塑性淀粉：(a)将淀粉和/或淀粉衍生物与至少15重量％的增塑剂，如甘油和/或山梨糖醇混合；(b)施加热和/或机械能量，和(c)至少部分去除淀粉或淀粉衍生物中的天然水分，使含水量小于6重量％。
除热塑性淀粉外，层B还可含有其它组分。具体说，层B可由不同聚合物的混合物组成。此外，层B还可含有常规添加剂，如增塑剂、加工助剂、稳定剂、阻燃剂和/或填充剂，如上述有关层A所述。具体说，层B可含有合适的加工助剂，详情如上文层A中所述。也可将粘合剂加入层B，其具体用于改善层B和A之间的粘合性。
优选地，层B含有热塑性淀粉，以层B总重计热塑性淀粉含量为至少20重量％，具体为至少30重量％，或至少40重量％，更优选至少50重量％或至少60重量％，更优选至少80重量％，最优选至少90重量％，或至少95重量％。更优选地，层B基本上由热塑性淀粉组成。
按照本发明的一个实施方式，层A和层B分别主要由热塑性聚酯和热塑性淀粉组成。
更具体说，层B主要由含有热塑性淀粉和至少一种其它热塑性材料，具体是热塑性聚酯的共混聚合物组成。作为另一种热塑性材料，具体可能加入的是可生物降解的聚合物，如聚酯、聚酯酰胺、聚酯型聚氨酯(polyesterurethane)和/或聚乙烯醇。共混聚合物中还可包含多层膜回收料形式的其它热塑性材料，具体是热塑性聚酯。因此，可由热塑性淀粉和特定比例的多层膜回收料生产层B，其中该回收料可获自(例如)本发明膜生产过程中的切削残料。共混聚合物中含有其它热塑性材料，具体是热塑性聚酯，以共混聚合物总重计其含量优选为1-80重量％，具体是5-30重量％。
本发明特别优选的多层膜是A-B-A型三层膜，其中层A由基于PHA(具体是PLA)的聚合物组成，层B由基于热塑性淀粉的聚合物组成(或含有热塑性淀粉的共混聚合物)。
可按照任何期望的制备方法，如压延、挤塑或铸塑来制造本发明多层膜。本领域技术人员通常了解这类制备方法，参见例如，J.Nentwig，“Plastic Films”(塑料膜)，第2版，汉森公司(Hanser Verlag)，柏林(2000)，第39-63 页。
优选地，本发明多层膜通过挤塑，具体是吹膜挤塑、平膜挤塑、平挤薄膜挤塑和/或吹塑形成。本领域技术人员通常了解这些制备方法。这些制备方法的详述可参见例如J.Nentwig,“Plastic Films”(塑料膜)，第2版，汉 森公司(Hanser Verlag)，柏林(2000)，第45-60页，明确参考该文献并使其成为本发明对象。可将该文献所述的制备实施例转用来制造本发明多层膜。在这种情况下，可通过挤塑形成该膜的单个层或所有层。优选通过挤塑形成该膜的所有层。
按照本发明特别优选的实施方式，通过共挤塑形成本发明多层膜。本领域技术人员通常了解这类共挤塑或多层挤塑方法。所述共挤塑方法的描述可参见例如J.Nentwig,“Plastic Films”(塑料膜)，第2版，汉森公司(Hanser Verlag)，柏林(2000)，第58-60页，明确参考该文献并使其成为本发明对象。可将该文献所述的制备实施例转用来制造本发明多层膜。
因此，本发明还涉及制备多层膜的方法，其中所述多层膜包括至少一个层A，至少一个层B，如果合适还包括其它层；具体说，如果合适，还包括至少另一个层A，其特征是以下步骤：
(a)挤塑含有至少一种热塑性聚酯的材料形成膜，从而形成至少一个层A；
(b)挤塑含有热塑可加工性淀粉的材料形成膜，从而形成至少一个层B；和
(c)使单个层的表面至少部分地粘结，从而形成多层膜。
在共挤塑过程中，单独的方法步骤(a)-(c)优选同时进行，具体是通过吹膜挤塑、平膜挤塑、平挤薄膜挤塑和/或吹塑进行。
制成后，可根据具体应用将多层膜切成具有所需尺寸的部件。可以将大小切削期间累积的切削残料至少部分地加入步骤(b)中挤塑层B所用的材料中，因此可用作回收料。
最后，本发明涉及用于食品，具体是新鲜肉类、奶酪、新鲜水果或蔬菜、烘烤商品、饮料和/或咖啡的包装元件，其含有本发明多层膜。
下文中，根据代表本发明实施方式的实施例更详细地描述了本发明。
附图简要说明
单一附图以举例方式显示层结构类型为A-B-A的本发明多层膜的剖面图。
实施例1
制备用于中层(层B)的热塑性淀粉。
将天然马铃薯淀粉(63重量％)、甘油(23重量％)和山梨糖醇(14重量％)的混合物填充到双螺杆(twin-shaft)挤塑机中。在挤塑机中，130-160℃的温度下充分混合该混合物，熔体同时脱气，以去除混合物中的水。这产生可排出和成粒的均一熔体。以所述方式均一化的热塑可加工性化合物的含水量为3-4重量％。
由于天然淀粉与甘油和山梨糖醇的混合和均一化，破坏了淀粉的晶体结构，使得所产生的热塑性淀粉大部分为无定形状态。与其相反，由天然淀粉(例如)在水中加热制备的变性淀粉仍然具有一定程度的结晶性。
实施例2
制造三层膜(平膜)。
制备由聚乳酸(PLA)/热塑性淀粉(TPS)/PLA组成的三层膜(A-B-A)。将实施例1中制备的热塑性甘油/山梨糖醇淀粉用作淀粉，其含水量为3-4重量％。所用聚乳酸(PLA颗粒，Nature Works)的D含量为1.4％。
两种材料(PLA和TPS)在共挤塑机中同时运行，以形成三层膜。为了达到此目的，在L/D比为33、温度范围是140-190℃的单螺杆挤塑机中熔化TPS。挤塑机以100转/分的速度运行，产生的熔体压力为130巴，通量为25kg/h。在平行试验中，在第二单螺杆挤塑机(L/D＝30，温度200℃，速度20转/分，熔体压力100巴，通量10kg/h)中熔化PLA(熔化温度177℃)。在共同外部接套(coex-adapter)中混合两种熔体，其中PLA熔体流被分成两半，各自流向淀粉层上方和下方(->外层A)。通过缝模(T＝190℃)，借助温度可控辊(T＝25℃，V＝3m/分)拉出以此方式产生的三层系统，切出所需宽度，绕成卷。
如此产生的三层膜的总厚度为400μm，由2x 50μm(外层A)和300μm(中层B)组成。
测定所述三层膜的气体渗透性：
氧气(O2)：       15.5cm3/m2d
二氧化碳(CO2)：  2.1cm3/m2d
实施例3
按照实施例2用预混的中层(层B)制造三层膜。
类似于实施例2所述方法，用PLA作为外层(A)制造三层膜A-B-A。就中层(B)而言，由按照实施例1制备的TPS颗粒(90重量％)和PLA颗粒(10重量％)制备预混物，加入单螺杆挤塑机，在150-190℃熔化。以100转/分、通量25kg/h和熔体压力120巴运行中层挤塑机。在平行试验中，在第二个单螺杆挤塑机(温度185–200℃，速度20转/分，熔体压力130巴，通量10kg/h)中熔化PLA(熔化温度175℃)。在共同外部接套中混合两种熔体，其中如实施例2所述，PLA熔体流被分成两半，各自流向淀粉层上方和下方(->外层A)。通过缝模(T＝190℃)，借助温度可控辊(T＝25℃，V＝3m/分)拉出以此方式产生的三层系统，切出所需宽度，绕成卷。
如此产生的三层膜的总厚度为400μm，由2x 50μm(外层A)和300μm(中层B)组成。
与实施例2相比，这种三层膜的浊度明显较高，但与实施例2相比外层(A)和中层(B)之间的粘结更稳定。
实施例4
制备用于中层(层B)的改性热塑性淀粉。
将天然马铃薯淀粉(56.5重量％)、甘油(20.5％)、山梨糖醇(13％)和PLA(10％)的混合物填充到双螺杆挤塑机中。在挤塑机中，130-160℃的温度下充分混合该混合物，熔体同时脱气，以去除混合物中的水。以类似于实施例1的方式，产生可拉出和造粒的均一熔体。以所述方式均一化的热塑可加工性化合物的含水量为3-4重量％。
实施例5
按照实施例2在中层(层B)中使用改性热塑性淀粉制造三层膜。
类似于实施例2和3所述方法，用PLA作为外层(A)制造三层膜A-B-A。就中层(B)而言，将实施例4所述的热塑可加工性淀粉/PLA化合物加入挤塑机中，在140-195℃熔化。以90转/分、通量25kg/h和熔体压力115巴运行制备中层的挤塑机。
在平行试验中，在第二单螺杆挤塑机(温度190-200℃，速度25转/分，熔体压力120巴，通量10kg/h)中熔化PLA(熔化温度180℃)。
在共同外部接套中混合两种熔体，其中如实施例2和3所述，PLA熔体流被分成两半，各自流向淀粉层上方和下方(->外层A)。通过缝模(T＝185℃)，借助温度可控辊(T＝25℃，V＝3.1m/分)拉出以此方式产生的三层系统，切出所需宽度，绕成卷。
如此产生的三层膜的总厚度为400μm，由2x 50μm(外层A)和300μm(中层B)组成。
与按照实施例2和3制备的样品相比，这种三层膜的浊度明显较高，但与实施例2和3相比外层(A)和中层(B)之间的粘结更稳定。
实施例6
如实施例2所述，只是向聚乳酸(PLA)中加入用约3重量％马来酸酐官能化的乙烯/丙烯酸甲酯聚合物来形成外层，以PLA层总重计加入的量约为1重量％。与实施例2所述产品相比，以此方式获得的三层膜，各层之间的粘结力增强。
实施例7
制造三层膜(吹膜)。
制备由聚乳酸(PLA)/热塑性淀粉(TPS)/PLA组成的三层膜(A-B-A)。将实施例1中制备的热塑性甘油/山梨糖醇淀粉用作淀粉，其含水量为3-4重量％。所用聚乳酸(PLA颗粒，Nature Works)的D含量为1.4％。
两种材料(PLA和TPS)在共挤塑机中同时运行，以形成三层膜。为了达到此目的，在单螺杆挤塑机(科林博士(Dr.Collin)，直径45x 25D)中、140-160℃的温度下熔化TPS。挤塑机以20转/分的速度运行，产生的熔体压力为130巴，通量约为7kg/h。在平行试验中，在第二个单螺杆挤塑机(科林博士(Dr.Collin)，直径30x 25D，温度160-190℃，速度60转/分，熔体压力140巴，通量约为15kg/h)中熔化PLA。在环形模具(三层吹膜模具，直径80mm，环形缝隙1.1mm)中混合两种熔体，其中PLA熔体流被分成两半，各自流向淀粉层上方和下方(->外层A)。以吹胀比3.5和速度约4.5m/分将如此产生的三层体系拉成长筒状，总的膜厚度约为50μm，在镀铬辊和橡胶辊(各自的宽度为400mm)上各膜的铺展宽度为325mm，绕成卷。经测定，所得多层膜A-B-A中各层的厚度百分比为20-60-20。
实施例8
类似于实施例7，只是向聚乳酸(PLA)中加入用约3重量％马来酸酐官能化的乙烯/丙烯酸甲酯聚合物以形成外层，以PLA层总重计加入的量约为1重量％。与实施例7所述产品相比，以此方式获得的三层膜，各层之间的粘结力增强。
实施例9
类似于实施例8，但加入聚乳酸(PLA)中形成外层的是脂族/芳族共聚酯(购自BASF公司的)，以PLA层总重计加入的量约为5重量％。与实施例7的配方相比，如此获得的体系的加工性能较好。
实施例10
类似于实施例7，但采用按照实施例1所述制备的热塑性甘油/山梨糖醇淀粉，其含水量约为2.5重量％。与实施例7相比，以此方式获得的体系在挤塑机中的加工性能得到改进，并且在中层中形成的气泡较少。
至此，已经根据实施例描述了本发明。应理解，本发明不受所述实施例的限制。但是，本领域技术人员在本发明框架内能想到多种可能的改变或修饰，本发明的保护范围具体受所附权利要求书的限制。

Claims (29)

1.一种多层膜，具体用于包装目的，其包括至少一个第一层A和至少一个第二层B，其中层A含有热塑性聚酯，层B含有热塑性淀粉。
2.如权利要求1所述的多层膜，其特征在于，所述层A中包含的热塑性聚酯是按照EN 13432可生物降解的热塑性聚酯。
3.如前述任一项权利要求所述的多层膜，其特征在于，所述热塑性聚酯是基于一种或多种聚羟基羧酸的生物聚合物。
4.如前述任一项权利要求所述的多层膜，其特征在于，所述热塑性聚酯选自下组物质：聚羟基烷酸酯(PHA)，聚丁二酸亚烷基二醇酯(PAS)如聚丁二酸丁二醇酯(PBS)，聚对苯二甲酸亚烷基二醇酯(PAT)如聚对苯二甲酸乙二醇酯(PET)，脂族-芳族共聚酯和聚对二氧环己酮(PPDO)，以及它们的共聚物和混合物。
5.如权利要求4所述的多层膜，其特征在于，所述聚羟基烷酸酯(PHA)选自下组物质：聚羟基乙酸酯(如聚羟基乙酸，PGA)、聚羟基丙酸酯(如聚乳酸或聚丙交酯，PLA)、聚羟基丁酸酯(如聚羟基丁酸，PHB)、聚羟基戊酸酯(如聚羟基戊酸酯，PHV)和聚羟基己酸酯(如聚已内酯，PCL)，以及它们的共聚物和混合物。
6.如前述任一项权利要求所述的多层膜，其特征在于，所述层B至少部分地由热塑可加工性淀粉制成，以所述淀粉的总重计，所述热塑可加工性淀粉的含水量小于6重量％，优选小于3重量％。
7.如前述任一项权利要求所述的多层膜，其特征在于，所述层B含有热塑性淀粉，所述热塑性淀粉的特征是由所述热塑性淀粉制备的膜按照DIN53455的抗张强度为2-10N/mm2，具体是4-8N/mm2，和/或按照DIN 53455断裂伸长率为80-200％，具体是120-180％。
8.如前述任一项权利要求所述的多层膜，其特征在于，所述热塑性淀粉可通过以下步骤获得：(a)将淀粉和/或淀粉衍生物与至少15重量％的增塑剂，如甘油和/或山梨糖醇混合；(b)施加热和/或机械能量，和(c)至少部分地去除所述淀粉或淀粉衍生物中的天然水分以使含水量小于6重量％。
9.如前述任一项权利要求所述的多层膜，其特征在于，所述层A基本上由热塑性聚酯组成，和/或所述层B基本上由热塑性淀粉组成。
10.如前述任一项权利要求所述的多层膜，其特征在于，所述层B基本上由共混聚合物组成，其含有热塑性淀粉和至少一种其它热塑性材料，具体是热塑性聚酯。
11.如权利要求10所述的多层膜，其特征在于，所述其它热塑性材料包含在所述共混聚合物中，以所述共混聚合物的总重计，其含量为1-80重量％，具体是5-30重量％。
12.如权利要求10或11所述的多层膜，其特征在于，所述其它热塑性材料以多层膜回收料的形式包含在所述共混聚合物中。
13.如前述任一项权利要求所述的多层膜，其特征在于，所述膜的总厚度为100-2000μm，具体是200-800μm。
14.如前述任一项权利要求所述的多层膜，其特征在于，所述单独层的厚度为10-1000μm，具体是10-700μm。
15.如前述任一项权利要求所述的多层膜，其特征在于，所述膜是具有层A-层B-层A结构的三层膜。
16.如前述任一项权利要求所述的多层膜，其特征在于，在层A和层B之间提供至少一个结合层H，具体是由嵌段共聚物制成的结合层H。
17.如前述任一项权利要求所述的多层膜，其特征在于，所述膜是具有层A-结合层H-层B-结合层H-层A结构的三层膜。
18.如前述任一项权利要求所述的多层膜，其特征在于，所述膜按照DIN53455的抗张强度为10-40N/mm2，具体是15-30N/mm2。
19.如前述任一项权利要求所述的多层膜，其特征在于，按照ASTM F1927-98，所述膜在23℃、50％相对湿度和400μm膜厚度时的氧渗透性为1-50cm3/m2d，具体是1.5-20cm3/m2d。
20.如前述任一项权利要求所述的多层膜，其特征在于，按照ASTM F1249，所述膜在23℃、75％相对湿度和400μm膜厚度时的水蒸汽渗透性为1-100，具体是2-10cm3/m2d。
21.如前述任一项权利要求所述的多层膜，其特征在于，按照ASTM D1434，所述膜在23℃、50％相对湿度和400μm膜厚度时的二氧化碳渗透性为0.5-5cm3/m2d，具体是1-2.5cm3/m2d。
22.如前述任一项权利要求所述的多层膜，其特征在于，所述膜中至少一层是通过挤塑，具体是吹膜挤塑、平膜挤塑、平挤薄膜挤塑和/或吹塑形成的。
23.如前述任一项权利要求所述的多层膜，其特征在于，所述膜中所有层是通过挤塑，具体是吹膜挤塑、平膜挤塑和/或吹塑形成的。
24.如前述任一项权利要求所述的多层膜，其特征在于，所述膜是通过共挤塑形成的。
25.一种制造前述任一项权利要求所述的多层膜的方法，其中所述多层膜包括至少一个层A，至少一个层B，如果合适还包括其它层，具体说，如果合适，还包括至少另一个层A，其特征是：
(a)挤塑含有至少一种热塑性聚酯的材料形成膜，从而形成至少一个层A；
(b)挤塑含有热塑可加工性淀粉的材料形成膜，从而形成至少一个层B；和
(c)使单个层的表面至少部分地粘合，从而形成多层膜。
26.如权利要求25所述的方法，其特征在于，所述方法步骤(a)-(c)在所述共挤塑过程中同时进行，具体是通过吹膜挤塑、平膜挤塑、平挤薄膜挤塑和/或吹塑进行。
27.如权利要求25或26所述的方法，其特征在于，根据具体应用，在制造后将所述多层膜切成具有所需尺寸的部件。
28.如权利要求27所述的方法，其特征在于，可以将大小切削期间累积的切削残料至少部分地加入在步骤(b)中挤塑层B所用的材料中。
29.一种用于食品，具体是新鲜肉类、烘烤商品、奶酪、新鲜水果或蔬菜、饮料和/或咖啡的包装元件，其含有权利要求1-24中任一项所述的多层膜。
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