CN1867449A - 耐脱层的多层容器、预成型品、制品和制造方法 - Google Patents

耐脱层的多层容器、预成型品、制品和制造方法 Download PDF

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Publication number
CN1867449A
CN1867449A CNA2004800306172A CN200480030617A CN1867449A CN 1867449 A CN1867449 A CN 1867449A CN A2004800306172 A CNA2004800306172 A CN A2004800306172A CN 200480030617 A CN200480030617 A CN 200480030617A CN 1867449 A CN1867449 A CN 1867449A
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China
Prior art keywords
blend
polyamide
evoh
resin
pet
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Pending
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CNA2004800306172A
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English (en)
Inventor
菲利普·D·布儒瓦
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Graham Packaging Pet Technologies Inc
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Graham Packaging Pet Technologies Inc
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Publication of CN1867449A publication Critical patent/CN1867449A/zh
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • B29B11/06—Making preforms by moulding the material
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    • B29B11/14—Making preforms characterised by structure or composition
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)

Abstract

一种塑料容器、预成型品或者制品，包括具有至少一层基质树脂、至少一层防渗透树脂和一种与所述防渗透树脂和/或所述基质树脂掺合的粘着力增强材料，以增强所述防渗透层基质层之间的结合增强。所述基质树脂优选是含酯树脂，最优选是比如PET的聚酯。所述粘着力增强材料包括胺聚合物，优选是具有多个可利用的伯、仲或者叔胺基团的亚胺聚合物。亚烷基亚胺聚合物是优选的，特别是聚亚乙基亚胺聚合物。

Description

耐脱层的多层容器、预成型品、制品和制造方法
本发明涉及多层的塑料容器、预成型品、制品和制造这样的容器、预成型品和制品的方法。
背景和发明内容
多层的塑料容器和预成型品通常包括交替的一种或多种塑料基质树脂层比如聚对苯二甲酸乙二醇酯(PET)层与一种或多种防渗透树脂比如聚酰胺或者乙烯-乙烯醇共聚物(EVOH)以阻挡气体、水蒸气和/或包括香料和香精油的食用香料透过容器壁的层。这种类型容器的重要特性是，在容器制造商和产品包装者填充和操作容器期间，和在消费者使用容器期间，在所述各种各样的层之间保护脱层的层间粘着力，需要增加层间的粘着力而不对其他容器性质比如不透气性和容器透明度产生不利的影响。因此本发明总的目的是提供一种多层容器、容器预成型品、多层制品、制造方法和具有改进预成型品和由其得到的容器层之间粘着力特性的防渗透树脂共混物。
根据本发明一个优选方面的塑料容器包括多层壁，其具有至少一个基质树脂层、至少一个防渗透树脂层，和用以增强防渗透层和基质层之间结合的掺合有防渗透树脂和/或基质树脂的粘着力增强材料。在本发明优选实施方式中，所述粘着力增强材料掺合有防渗透树脂。所述粘着力增强材料是胺聚合物，优选亚胺聚合物，具有多个可利用的伯、仲或者叔胺基。这样的聚胺聚合物优选是亚烷基亚胺聚合物或者亚烷基胺聚合物。亚烷基亚胺聚合物，特别是聚亚乙基亚胺(PEI)聚合物是特别优选的。聚亚乙基亚胺聚合物由Nippon Shokubai有限公司以商品名Epomin销售，由Nippon Shokubai有限公司出版的Epomin说明单引入本发明作为参考。
本发明的多胺是聚合的、均聚或者共聚的多胺，优选是亚烷基胺聚合物或者亚烷基亚胺聚合物，其分子量为约150-2,000,000，优选约150-约400,000，最优选的是约300-约80,000。可用于本发明的多胺的例子包括聚乙烯胺、氨基官能化的聚丙烯酰胺、聚DADMAC、聚乙烯基吡咯烷酮共聚物、聚亚乙基亚胺、聚亚丙基亚氨和乙二胺和氯甲代氧丙环共聚物的反应产物。
可用于实现增强粘着力特性的优选的多胺是称为聚亚烷基亚胺的多胺，比如聚亚乙基亚胺，很宽分子量和不同支化度范围的此类多胺很容易地可以得到。聚亚乙基亚胺由不同分子量和化学修饰度的大量的水可溶多胺组成。通常熟知的是亚乙基亚胺的聚合不能得到完全由具有直链结构的单元组成，而是取决于在聚合期间的酸浓度和温度具有支化度的聚亚乙基亚胺。使用本领域众所周知的方法可以将另外的基团接枝在聚亚乙基亚胺上以改变其他希望的物理的和化学性质。优选的聚亚乙基亚胺的分子量为约150-80,000。出于对材料粘度的考虑聚亚乙基亚胺最优选的分子量为约300-80,000。作为本发明另外的特征，掺合在防渗透层或者基质层中的聚PEI聚合物还可以与酸性气体比如二氧化碳相互作用以提供增强的酸性气体防渗透聚合物，从而提供增强二氧化碳抗渗性能的容器。当得到的容器用于包装充气饮料比如软饮料或者啤酒时，在减少由于包装引起的二氧化碳损耗方面特别有用。
所述基质聚合物优选是含酯聚合物，即在所述聚合物主链上具有酯的聚合物，酯部分接枝到聚合物主链上的聚合物，或者酯部分作为链侧基的聚合物。聚酯树脂是特别优选的。所述聚酯树脂可以是任何适合的在聚合物主链上具有酯的聚酯树脂。适当的聚酯包括聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PPT)、聚萘二甲酸乙二醇酯(PEN)、聚乙醇酸(PGA)、聚碳酸酯纤维(PC)和聚乳酸(PLA)。其他适当的基质聚合物包括聚丙烯酸酯，比如聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸酯亚乙基酯(PEMA)和醋酸乙烯酯。同样可用的是上述的共混物和共聚物，基本上由上述组成的加工和消费后的回收物料，或者上述的共混物或者共聚物。基于PET的树脂、共混物、共聚物和回收物料是特别优选的。其他的基质聚合物包括聚烯烃和聚酰胺。
所述聚PEI聚合物由于它们结合高含量的伯、仲和叔胺官能团，因此熟知具有高的阳离子电荷密度。尽管不束缚于任何特定的理论，似乎是这些胺官能团强烈地与酯或者其他官能团相互作用实现防渗透层和含酯层之间改进的粘着力以减少或者阻止在操作和使用容器期间所述壁层的层离。
所述防渗透树脂优选选自EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺的共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物的共混物、丙烯腈、环状烯烃共聚物、聚偏氯乙烯(PVDC)、聚乙醇酸(PGA)和其共混物。EVOH和间二甲苯二胺(MXD)聚酰胺是特别优选的。因此本发明实现防渗透层和聚酯层之间改进的粘着力从而在操作和使用容器期间减少或者阻止壁层的层离。
根据本发明，本发明其他方面包括塑料容器预成型品、制造塑料容器和预成型品的方法、防渗透树脂共混物、多层制品和制造方法。
附图简述
本发明与其另外的目的、特征、优点和方面一起，从以下的描述、附加的权利要求和附图更好地理解，其中：
图1A和1B是根据本发明一个方面的容器预成型品的示意图，
图2A和2B是根据本发明另外的方面的塑料容器的示意图，和
图3-7是对根据本发明典型实施方式制造的容器的试验结果的图解说明。
优选实施方式的详细说明
本发明容器和预成型品具有多层壁，所述的多层壁具有交替的至少一层基质树脂与至少一层防渗透树脂。(同样可以包括与本发明没有密切关系的另外的层，比如消费后树脂层)例如，三层容器或者预成型品可以具有以聚酯/防渗透层/聚酯顺序的层的壁。五层容器或者预成型品可以具有以聚酯/防渗透层/聚酯/防渗透层/聚酯顺序的壁层。所述防渗透层或者层可以延伸贯穿容器或者预成型品底部壁和侧壁，或者可以被封闭在例如侧壁或者底部的部分。所述阳挡层可以或者不延伸进入容器或者预成型品的面层。图2A和2B是本发明典型实施方式的五层容器的示意图，所述的尺寸和几何结构仅仅是用于说明性目的的举例说明。在该申请中讨论的所有举例说明的试验容器(和预成型品)(除了表1中的容器(1))都是五层容器(和预成型品)。根据本发明的一个方面，粘着力增强材料掺合有防渗透树脂比如EVOH，和/或基质树脂比如聚酯树脂，优选掺合有防渗透树脂，以增强防渗透层和聚酯层之间的粘着力。该粘着力增强材料包括亚烷基胺聚合物，其中亚烷基亚胺聚合物是优选的，特别是聚亚乙基亚胺(PEI)聚合物。特别优选的PEI聚合物是Nippon Shokubai有限公司制造的SP-012等级的EPOMIN(商品名)聚合物。可以使用其他PEI聚合物，包括其他由其他树脂制造商比如BASF以商品名LUPASOL销售的EPOMIN聚合物和PEI聚合物。
所述聚酯树脂优选选自PET、PEN、PET和PEN共混物和共聚物、基本上由PET、PEN或者PET和PEN共混物或者共聚物组成的加工或者消费后回收物料。在本发明申请中讨论的例子中，所述树脂是PET基聚酯。
所述防渗透树脂是具有低气体和/或水蒸汽传递速率，和/或显示对包括香料和香精油的食用香料透过的高防渗透性的热塑性材料。以下的防渗透树脂材料是优选的：EVOH、聚酰胺(包括无定形的聚酰胺和半结晶聚酰胺比如MXD6)、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯(例如PET)和聚酰胺共混物、EVOH和离子聚合物共混物、环状烯烃共聚物、PGA、EVOH或者聚酰胺和粘土的纳米复合材料、聚偏氯乙烯和其共混物。EVOH和聚酰胺是特别优选的。MXD6聚酰胺和EVOH在该申请讨论的例子中用作防渗透树脂。同样可以使用一种或多种其他的防渗透层组合物。
本发明优选的是所述粘着力增强材料掺合防渗透树脂。因为所述防渗透树脂层占总的预成型品或者容器相对小的重量百分率，与如果粘着力增强材料掺合有所述基质树脂的情况相比较，需要更少量的粘着力增强材料。然而，根据本发明最宽广的方面，所述粘着力增强材料可以掺合有基质树脂，或者掺合有基质树脂和防渗透树脂。
所述所述粘着力增强材料通常形式为液态，优选在形成多层预成型品或者容器之前掺合所述防渗透树脂材料。当使用EVOH防渗透树脂时，通过将粘着力增强材料高压液体喷射送入挤出机而实施所述的共混，其中所述防渗透材料流动通过该挤出机，或者通过将所述防渗透材料置于所述挤出机相同的进料注入口，以使所述粘着力增强材料和所述防渗透树脂不接触直到它们靠近挤出机螺杆，从而实现共混。做为选择，可以使用上面描述的将粘着力增强材料引入到所述EVOH防渗透树脂中的高压液体喷射树脂方法或者共用进料口方法，制备粘着力增强材料-EVOH母料，所述的母料随后通过本领域众所周知的方法造粒。这些母料颗粒然后在形成所述多层的预成型品或者容器之前，以适当的稀释比掺合EVOH防渗透树脂。当使用MXD6防渗透树脂时，在将所述共混物加入到挤出机中之前，所述液态的粘着力增强材料添加剂可以在室温下与防渗透材料粒子掺合。
粘着力增强树脂的量通常不大于实现希望粘着力水平的所必须的量，因为增加粘着力增强材料的比例将影响掺合粘着力增强材料树脂的粘度或者其他性能。掺合与所述防渗透树脂或者所述基质树脂掺合的粘着力增强材料的量优选不超过用于形式多层制品的共混物的约10％，优选不超过5wt％。在这方面，所述粘着力增强材料优选掺合防渗透树脂，优选不超过共混物的约10％。更优选粘着力增强材料量不超过用于形式多层制品的含有防渗透树脂的共混物的5wt％。在许多的应用场合，粘着力增强材料的量不超过含有防渗透树脂的共混物的2％或者3wt％。在该申请中所有的共混物百分数是按重量计算，除非另有说明。
制造容器的方法优选包括制造预成型品，随后吹塑预成型品以形成容器。在该申请中讨论的例子中，所述预成型品通过US4,550,043、4,609,516、4,710,118和4,954,376所述的连续的注塑操作中形成。图1A和1B是预成型品的示意图，尺寸和几何结构仅仅是用于说明性目的的举例说明。然而，所述预成型品还可以同时用US4,990,301和5,098,274中所述类型的注塑操作，用US6,428,737所述类型的包覆成型操作，用在US申请公开2002/0098310所述类型的压塑操作，使用包括聚酯树脂和防渗透树脂/粘着力增强材料共混物的模塑进料形成，或者在可产生具有基质树脂和防渗透树脂共混物交替层的中空管的共挤出操作中形成。这些具体的引用仅仅是举例说明。
当所述PEI粘着力增强材料与至少一种材料在高熔融温度下接触时，所述优选的PEI粘着力增强材料可增强基质和防渗透树脂层之间的结合，在预成型品冷却以后很难分离预成型品的层。以上确认的本发明优选的粘着力增强材料很适合用于所述公开的防渗透层和基质树脂的化学作用。本发明可改进所述防渗透层和基质(例如聚酯)层之间的粘着力以减少或者阻止在操作和使用包括预成型品和容器的多层制品期间壁层的层离。
图3-7说明根据本发明构造的各种容器样品的层离试验结果。每一个容器具有PET/MXD6/PET/MXD6/PET构造(图6-7)，或者PET/EVOH/PET/EVOH/PET构造(图3-5)的五层壁。图3试验容器的标称的层厚度为6.5/0.25/11.5/0.25/6.5密耳。这些是在侧壁的宽节间面积的中心测量的平均值。如以下讨论，图4-7试验容器的标称的侧壁厚度为3/0.5/6/0.5/3密耳。在所有的试验中，容器是仅仅用于对比目的构造的实验容器。试验是任意设计的以得到区别数据，并没有反映任何的性能规格或者使用条件。在每一个图中，纵坐标表示作为试验结果的其中通过肉眼观察发生层离的容器百分比，同时横坐标表示容器结构，具体地说是按重量计算的防渗透材料总量和所述使用的粘着力增强材料的量。除粘着力增强材料量和使用的防渗透树脂类型(EVOH或者MXD6)外，在每一试验中所有的容器是相同的。
在该申请中描述的所有试验中，所述粘着力增强材料是NipponShokubai有限公司以商品名EPOMIN销售的SP-012等级PEI材料，根据树脂制造商该材料具有以下性能：
分子量                    1200(近似地)
比重                      1.05@25℃
胺值                      19mg当量/g固体
凝固点                    小于-20℃
分解温度                  290℃
闪点                      260℃
胺比例
伯胺                      35％
仲胺                      35％
叔胺                      30％
化学文摘目录(CAS)No.106899-94-9
制造商声称SP-012等级材料可溶于水和醇，部分可溶于乙酸乙酯、THF和甲苯，在正己烷中不溶解。
图3说明在二十四盎司的具有变圆的长方形横截面的容器上实施坠落试验的结果。容器充满水，其中加入蓝色染料以便于如果发生剥离时的目视判别。(水/染料混合物用于该申请中讨论的所有试验)所述阳挡层共计为按重量计算容器的1.5％，其中图3(和图4-7)中注明的SP-012百分比是总的阳挡层的百分数，例如1.5％防渗透层的2.0％，或者基于容器总重量，0.03％的粘着力增强材料。所述填充的容器从三英尺高度坠落在水泥底部上，使得容器底部受到冲击，然后查看层离。如图3所示，在阳挡层中不含SP-012粘着力增强材料的情况下，84％的容器显示层离。具有与2.0％SP-012掺合的EVOH的容器仅14％的容器显示层离。
图4和5说明在用于充碳酸气软饮料的400ml圆筒形容器上侧冲击试验结果。所述的侧冲击试验包括容器被夹紧在固定的位置，用钢楔单次的撞击容器侧壁。所述冲击能量大约为3.3焦耳。图4说明对于充满非碳酸水容器的试验结果，而图5说明对于充满水和4.2GV(气体容积)的充碳酸气的容器的试验结果。所述防渗透树脂层共计为容器的3wt％。在具有粘着力增强材料的样品中，粘着力增强材料逐渐从0.25％增加，经过0.50％、0.75％、1.0％、1.5％到2.0％的防渗透层重量。如在图4中可见，在所述非充碳酸气的样品中层离的出现逐渐减少，到在2.0％SP-012时没有层离。如图5中所示，在含有SP-012粘着力增强材料的样品中没有发现层离。
图6和7显示在分别与图4和5条件相同的条件下，在400ml CSD容器上侧冲击试验的结果。然而在图6和7的容器中，使用MXD6聚酰胺代替EVOH作为防渗透树脂。在图6中的非充碳酸气的包装中，通过添加0.25％的SP-012，层离出现从约36％减少到约7％，对于0.5％的SP-012没有观察到层离。在图7中充碳酸气的包装中，在含有粘着力增强材料的任何一种样品中都没有观察到层离。
正如以上所指出的，本发明优选作为粘着力增强剂的PEI聚合物同样显示出对于酸性气体比如二氧化碳增强的防渗透效应，除它们的粘着力增强作用之外，还可以用于改善防渗透层的二氧化碳防渗性。当容器用于包装充气饮料比如软饮料和啤酒时，这在降低二氧化碳损失方面是特别有利的。
以下表显示出与PEI聚合物相关的，具体地说在这些试验中的EPOMIN SP-012的防渗透性的增加，其中通过化学碳酸饱和技术在二氧化碳4.0气体容积下填充28mm 400ml的饮料容器，用28mm的封闭物封住。这些封闭物是如公开在US5,306,542公开的具有乙烯-乙酸乙烯酯共聚物(EVA)衬里的聚丙烯封闭物。在68F/50％RH下存储放置平衡14天以后，通过将容器放置在具有已知收集体积的密封容器中测量总的容器二氧化碳渗透率。所述密封容器具有氮载气流动通过的两个端口，所述的氮载气通过一个端口流入，从另一个端口离开容器。所述出口被导入Mocon C-IV CO2试验机，用于检测CO2的量。测量一段时间的二氧化碳量，由此确定二氧化碳的渗透率。
除所述单层的PET容器外，每一容器具有标称厚度分别为3/0.5/6/0.5/3密耳的PET/防渗透层/PET/防渗透层/PET的五层标称13密耳的侧壁。(所述“单层的”PET容器是使用所有的层都是PET的五层方法制造的。)在容器(2)到(9)中，所述两个“防渗透层防渗透”层共计为容器重量的3％，SP-012的百分比是总的防渗透层的百分数-例如3％的阳挡层的1％，或者基于总的容器总重量0.03％的粘着力增强材料。表1的结果是对于每一容器五次的平均值。具有聚苯乙烯“阳挡层”的容器(2)与单层的PET容器(1)相比较显示出差的防渗性。然而，与容器(2)相比较添加PEISP-012显著改进容器(3)和(4)的CO2防渗性。与容器(5)相比较，共混PEI SP-012同样显著含有EVOH阳挡层的容器(7)、(8)和(9)的改进的CO2防渗性，尽管在这些试验中作为PEI-012浓度函数的所述性能似乎是可变的。
表1
  容器构造   渗透率cc-CO2/天
  1   单层的PET   4.55
  2   3％聚苯乙烯   4.81
  3   3％(聚苯乙烯+1％Epomin SP-012)   4.25
  4   3％(聚苯乙烯+2％Epomin SP-012)   3.8
  5   3％EVOH   2.48
  6   3％(EVOH+1％Epomin SP-012)   2.5
  7   3％(FVOH+2％Epomin SP-012)   1.69
  8   3％(EVOH+3％Epomin SP-012)   1.76
  9   3％(EVOH+4％Epomin SP-012)   1.87
在所述举例说明的容器中：
—所述PET树脂是Cleartuf8006，是本征粘度为0.8dl/g的由M&GPolymer USA销售的PET共聚物。
—所述聚苯乙烯是Chevron EA3400，根据ASTM D1238，条件G下熔体流动指数为9g/10分钟。
—所述EVOH是Eval Company of America，等级F 171A，是32mol％乙烯含量的聚(乙烯-乙烯醇)共聚物。
确实，根据本发明一个方面，亚烷基亚胺聚合物可以用于单层的或者多层的制品，比如单层的PET容器，以阻止二氧化碳通过容器壁迁移。在这方面，所述制品可以是一种包装组件，比如容器，或者封闭体，其中所述聚合物包括在封闭体的衬里和/或封闭体的壳中。
本发明因此公开了充分满足上述阐述的所有目标和目的的多层容器、多层预成型品、用于多层容器的防渗透树脂共混物、制造多层预成型品或者容器的方法和制造多层的塑料制品的方法。本发明已经公开了容器、防渗透层共混物和制造方法，同时公开了许多举例说明的实施方式，已经讨论了若干种改性和变化。对于本领域普通技术人员而言，其他的改性和变化是容易想到的。本发明意图是包括所有的属于附加权利要求精神和宽的范围中的如此改性和变化。

Claims (61)

1.一种用于吹塑具有多层壁塑料容器的预成型品，所述的预成型品包括：
至少一层基质树脂，
至少一层防渗透树脂，和
掺合有所述的防渗透树脂和/或所述基质树脂的材料，以增强改进所述的防渗透层和基质层之间的粘着力，所述的材料包括胺聚合物。
2.权利要求1所述的预成型品，其中所述的胺聚合物是亚胺聚合物。
3.权利要求1所述的预成型品，其中所述的胺聚合物是亚烷基胺聚合物。
4.权利要求3所述的预成型品，其中所述的亚烷基胺聚合物是亚烷基亚胺聚合物。
5.权利要求4所述的预成型品，其中所述的亚烷基亚胺聚合物是聚亚乙基亚胺聚合物。
6.权利要求1所述的预成型品，其中所述的基质树脂是含酯树脂、聚烯烃或者聚酰胺。
7.权利要求1所述的预成型品，其中所述的基质树脂是聚酯树脂。
8.权利要求7所述的预成型品，其中所述的聚酯树脂是PET、PEN、PET和PEN的共混物或者共聚物，或者包括PET、PEN或者PET和PEN共混物或者共聚物的回收物料。
9.权利要求1所述的预成型品，其中所述的防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
10.一种用于吹塑具有多层壁的塑料容器的预成型品，包括：
至少一层聚酯树脂，选自PET、PEN、PET和PEN共混物或者共聚物和基本上由PET、PEN或者PET和PEN共混物或者共聚物组成的回收物料，
至少一层防渗透树脂，选自EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺的共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物的共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯和其共混物，和
掺合在至少一层防渗透树脂中的聚亚乙基亚胺，以增强所述的防渗透层和聚酯层之间的粘着力。
11.一种具有多层壁的塑料容器，所述的多层壁包括：
至少一层基质树脂，
至少一层防渗透树脂，和
掺合有所述的防渗透树脂和/或所述的基质树脂的材料，以增强所述的防渗透层和基质层之间的粘着力，所述的材料包括胺聚合物。
12.权利要求11所述的容器，其中所述的胺聚合物是亚胺聚合物。
13.权利要求11所述的容器，其中所述的胺聚合物是亚烷基胺聚合物。
14.权利要求13所述的容器，其中所述的亚烷基胺聚合物是亚烷基亚胺聚合物。
15.权利要求14所述的容器，其中所述的亚烷基亚胺聚合物是聚亚乙基亚胺聚合物。
16.权利要求11所述的容器，其中所述的基质树脂是含酯树脂、聚烯烃或者聚酰胺。
17.权利要求11所述的容器，其中所述的基质树脂是聚酯树脂。
18.权利要求17所述的容器，其中所述的聚酯树脂是PET、PEN、PET和PEN的共混物或者共聚物，或者包括PET、PEN或者PET和PEN共混物或者共聚物的回收物料。
19.权利要求11所述的容器，其中所述的防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物的共混物、丙烯腈、环状的烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
20.一种具有多层壁的塑料容器，所述的多层壁包括：
至少一层聚酯树脂，选自PET、PEN、PET和PEN的共混物或者共聚物和基本上由PET、PEN或者PET和PEN共混物或者共聚物组成的回收物料，
至少一层防渗透树脂，选自EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺的共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物的共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸和其共混物，和
掺合在至少一层防渗透树脂中的聚亚乙基亚胺，以增强所述的防渗透层和聚酯层之间的粘着力。
21.一种用于层化塑料制品的防渗透树脂共混物，所述的防渗透树脂共混物包括：
阻挡气体、水蒸气或者食用香料透过的防渗透树脂，和
包括胺聚合物的材料，以增强多层塑料制品中的所述防渗透树脂和相邻层之间的粘着力。
22.权利要求21所述的防渗透树脂共混物，其中所述的材料是亚烷基亚胺聚合物。
23.权利要求22所述的防渗透树脂共混物，其中所述的材料是聚亚乙基亚胺聚合物。
24.权利要求23所述的防渗透树脂共混物，其中所述的防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
25.一种制造多层的塑料容器的方法，包括：
(a)掺合防渗透树脂、包括亚烷基胺聚合物粘着力增强材料，和
(b)形成预成型品，其中在步骤(a)中形成的共混物在与聚酯树脂层交替的层中，和其中所述的胺聚合物增强所述的防渗透树脂和聚酯树脂之间的粘着力。
26.权利要求25的方法，其中所述的胺聚合物是亚烷基亚胺聚合物。
27.权利要求25的方法，进一步包括：(c)吹塑在步骤(b)形成的预成型品，制成中空的塑料容器。
28.权利要求27所述的方法，其中进行所述的步骤(b)，同时在所述的步骤(a)中形成的所述共混物和所述聚酯树脂的至少一种为熔融相。
29.权利要求28所述的方法，其中通过选自如下的方法进行所述的步骤(b)：同时注塑所述的聚酯树脂和所述的防渗透树脂共混物、顺序注塑所述的聚酯树脂和所述的防渗透树脂共混物、包覆成型连续的聚酯树脂和防渗透树脂共混物层、压塑包括所述的聚酯树脂和防渗透树脂共混物的模塑进料，及挤出包括聚酯树脂和防渗透树脂共混物的交替层的中空管。
30.权利要求29的方法，其中所述的粘着力增强材料是聚亚乙基亚胺聚合物。
31.权利要求30所述的方法，其中所述的聚酯树脂是PET、PEN、PET和PEN的共混物或者共聚物，或者包括PET、PEN或者PET和PEN共混物或者共聚物的回收物料。
32.权利要求25所述的方法，其中所述的防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
33.一种多层制品，其包括：
至少一层基质树脂，
至少一层防渗透树脂，和
掺合有所述的防渗透树脂和/或所述的基质树脂的材料，以增强所述的防渗透层和基质层之间的粘着力，所述的材料包括胺聚合物。
34.权利要求31所述的制品，其中所述的基质树脂是含酯的树脂、聚烯烃或者聚酰胺。
35.权利要求34的制品，其中所述的含酯的树脂是聚酯树脂。
36.权利要求35所述的制品，其中所述的聚酯树脂是PET、PEN、PET和PEN的共混物或者共聚物，或者包括PET、PEN或者PET和PEN共混物或者共聚物的回收物料。
37.权利要求33所述的制品，其中所述的胺聚合物是亚烷基胺聚合物。
38.权利要求37所述的制品，其中所述的亚烷基胺聚合物是亚烷基亚胺聚合物。
39.权利要求38所述的制品，其中所述的亚烷基亚胺聚合物是聚亚乙基亚胺聚合物。
40.权利要求33所述的制品，其中所述的防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
41.一种制造多层塑料制品的方法，包括：
(a)掺合防渗透树脂、包括胺聚合物的粘着力增强材料，和
(b)形成制品，其中在步骤(a)中形成的共混物位于与基质树脂层交替的层中，和其中所述的胺聚合物增强所述的防渗透树脂和基质树脂之间的粘着力。
42.权利要求41所述的方法，其中进行所述的步骤(b)，同时在所述的步骤(a)中形成的所述共混物和所述基质树脂的至少一种为熔融相。
43.权利要求42所述的方法，其中所述的胺聚合物是亚烷基亚胺聚合物。
44.权利要求43所述的方法，其中所述的亚烷基亚胺聚合物是聚亚乙基亚胺聚合物。
45.权利要求41所述的方法，其中所述的基质树脂是含酯树脂、聚烯烃或者聚酰胺。
46.权利要求41所述的方法，其中所述的基质树脂是聚酯树脂。
47.权利要求46所述的方法，其中所述的聚酯树脂是PET、PEN、PET和PEN的共混物或者共聚物，或者包括PET、PEN或者PET和PEN共混物或者共聚物的回收物料。
48.权利要求41所述的方法，其中所述的防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
49.一种具有塑性树脂壁的包装组件，所述的塑性树脂壁包括阻挡二氧化碳迁移通过树脂壁的亚烷基亚胺聚合物。
50.权利要求49所述的包装组件，其中所述壁中的所述亚烷基亚胺聚合物掺合有另外的塑性树脂。
51.权利要求49所述的包装组件，其中所述的壁是具有至少两个塑性树脂层的多层壁，其中所述的亚烷基亚胺聚合物在所述层之一中。
52.权利要求51所述的包装组件，其中在所述一中层中的所述亚烷基亚胺聚合物掺合有另外的塑性树脂。
53.权利要求52所述的包装组件，其中所述的亚烷基亚胺聚合物是聚亚乙基亚胺聚合物。
54.权利要求52所述的包装组件，其中所述的其他塑性树脂是防渗透树脂，所述防渗透树脂为EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
55.权利要求54所述的包装组件，其中所述的至少两层中的另一个包括聚酯树脂。
56.权利要求55所述的容器，其中所述的聚酯树脂是PET、PEN、PET和PEN的共混物或者共聚物，或者包括PET、PEN或者PET和PEN共混物或者共聚物的回收物料。
57.一种制造制品的方法，包括掺合亚烷基亚胺聚合物和另外的塑性树脂以形成所述的阻挡二氧化碳迁移通过所述的侧壁的制品。
58.权利要求57所述的方法，其中所述的其他塑性树脂是防渗透树脂，所述防渗透树脂是EVOH、聚酰胺、丙烯腈共聚物、EVOH和聚酰胺共混物、聚酯和聚酰胺共混物、EVOH或者聚酰胺和粘土的纳米复合材料、EVOH和离子聚合物共混物、丙烯腈、环状烯烃共聚物、聚乙醇酸、聚偏氯乙烯或者其共混物。
59.权利要求58所述的方法，其中所述的壁是具有至少两个塑性树脂层的多层壁，其中所述的亚烷基亚胺聚合物在所述层之一中。
60.权利要求59的方法，其中所述的至少两层的另外一个包括聚酯树脂。
61.权利要求57所述的方法，其中所述的亚烷基亚胺聚合物是聚亚乙基亚胺聚合物。
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