CN1076281C - 多层材料 - Google Patents

多层材料 Download PDF

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CN1076281C
CN1076281C CN96194704A CN96194704A CN1076281C CN 1076281 C CN1076281 C CN 1076281C CN 96194704 A CN96194704 A CN 96194704A CN 96194704 A CN96194704 A CN 96194704A CN 1076281 C CN1076281 C CN 1076281C
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multilayer material
hypochlorite bleaching
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CN1187789A (zh
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M·阿尔瓦内斯埃
M·乔法尼
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Procter and Gamble Co
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Abstract

本发明涉及一种盛装液态产品的多层材料，尤其适用于盛装含次氯酸盐漂白剂的液态产品。这种多层材料包括内层、粘合剂层和外层。根据本发明的多层材料还包括一种防止该多层材料受次氯酸盐漂白剂或其组分侵蚀作用时而老化的部件。特别地，该保护部件防止多层材料的片层之间出现相互脱层现象。

Description

多层材料
                      发明领域
本发明涉及适用于制造柔性容器的多层材料。特别地，本发明涉及耐含有次氯酸盐漂白剂产品的化学侵蚀作用的多层材料。
                      发明背景
已知的包装材料很多。在这些包装材料中，很多是以不同片层构成的。这些不同的片层使获得的复合材料具有所希望的综合性能。而这性能是单一材料的单层所不具备的。
一种市场上能够买得到的花费非常经济的多层材料包含使用粘合剂层合到聚乙烯层的聚对苯二甲酸乙二醇酯(＝PET)。优选地，该聚乙烯层由低密度聚乙烯(＝LDPE)制成。当这种多层材料制备成容器时，优选是制成一种柔性的香袋或小袋时，通常PET作为外层材料，LDPE作为内层材料。一种通常实施中，香袋或小袋具有扁平的、基本平行的、对置的长方形器壁，各器壁通过热封沿其周边彻底地粘接在一起。特别地，由LDPE制成的对置器壁的内层紧密地被密封在一起。由此制得的香袋或小袋是防漏的、完全耐穿刺，因而完全适用于盛装液态产物。
我们发现，当这种容器内盛装含次氯酸盐漂白剂的液态产品时，容器会老化。确实，该次氯酸盐漂白剂或漂白剂的组分通过所说的LDPE层向所说的容器外层，尤其是向所说的容器的粘合剂层的迁移是不可阻止的。从而，介于LDPE层和PET外层间的粘合剂层就会受到漂白剂或其组分的作用。结果，粘合剂可能会分解，从而失去其粘合性能。因而，PET层与LLDPE层间就会发生部分或完全脱层现象。最终，该容器的密封性能(containment properties)即使未完全丧失，也大大降低了。
因而，本发明一个目的是提供一种多层材料，由该材料制成的容器当盛装含有含次氯酸盐漂白剂的液态产品时，该容器的密封性能不会降低。
                      发明概述
本发明是用于盛装含有次氯酸盐漂白剂的液态产品的一种多层材料。这种多层材料包括内层、粘合剂层和外层。所说的内层是由一种可热封的聚烯烃制成，所说的外层由一种可印刷的塑性材料制成。该多层材料还包括一种当其受到次氯酸盐漂白剂或其组分的侵蚀作用时防止该多层材料降解的部件(means)。优选地，按照本发明的多层材料包含阻挡层和/或耐漂白剂侵蚀的粘合剂层。
                        发明详述
在下文中，“侵蚀性”描述由于该次氯酸盐漂白剂的至少一种组分使根据本发明的多层材料的层例如粘合剂层产生的分解作用。此外，下文中“老化”是该次氯酸盐漂白剂的至少一种组分侵蚀根据本发明的多层材料的层的结果，例如外层与内层的脱层。“包装的老化”也可意指该包装由于受该次氯酸盐漂白剂的侵蚀而失去其防漏性能。
按照本发明的多层材料包括外层、内层和粘合剂层。外层应适合于印刷。事实上，当该多层材料制成容器时，所说的外层是该多层材料最外层。因而适于用作外层的材料是可印刷的塑料，例如聚丙烯(＝PP)、聚对苯二甲酸乙二醇酯(PET)、聚酰胺、聚苯乙烯、乙基乙烯醇(＝EVOH)、聚碳酸酯、聚氯乙烯(＝PVC)或赛珞玢。优选地，适于该外层的优选的可印刷塑料为PP或PET。
为了便于印刷过程和/或保证印刷在塑料表面的油墨具有足够的粘结力，可印刷塑料的表面通常采用静电涂布或电晕放电处理进行修饰。静电涂布和电晕放电处理均能使层材外表面的电荷取向。电荷的取向对其后油墨的粘合产生静电吸引力。特别地，静电涂布是含有金属离子的溶液涂在外层的外表面上，而电晕放电处理是作用在外层外表面的一种静电处理方法。
内层是由可热封的聚烯烃制成。可热封的聚烯烃便于容器的成型。事实上，制备一容器，用热封工艺足以使由按照本发明的多层材料制成的第一个片材的内层与第二个片材的内层密封在一起。优选地，该可热封的聚烯烃是聚乙烯，更优选的是低密度聚乙烯(＝LDPE)或线性低密度聚乙烯(＝LLDPE)。作为一种优选方案，醋酸乙基乙烯酯(ethylvinyl acetate)(＝EVA)被加入到所说的内层中，以降低熔点和利于以后的热封过程。优选地，由LDPE或LLDPE制成的该内层，其密度至少为0.9g/cm3(克/立方厘米)，更优选的密度为0.910g/cm3～0.925g/cm3。该内层的厚度优选超过80μm，更优选厚度为95μm～105μm。
在这里，第三层为粘合剂层。该粘合剂层将所说的内层和所说的外层粘接在一起。优选地，该粘合层可以通过层合过程将外层和内层粘接在一起。我们发现，现有技术制作的香袋中的该粘合剂层对于能迁移透过内层的次氯酸盐漂白剂或其组分很敏感。该粘合剂层受到该次氯酸盐漂白剂组分的侵蚀作用而分解。从而，外层与内层发生脱层现象。因此，按照本发明的这种多层材料还包括一种阻止该多层材料由于受到该次氯酸盐漂白剂或其组分的侵蚀作用而老化的部件。
按照本发明，一种阻止该多层材料受次氯酸盐漂白剂或其组分的侵蚀作用而老化的部件是耐次氯酸盐漂白剂侵蚀的粘合剂。优选地，该耐漂白剂侵蚀的粘合剂由聚氨酯制成，更优选的由双组分聚氨酯制成。由聚氨酯制成的这些粘合剂在性能和成本上具有良好的平衡性。该双组分聚氨酯粘合剂中包括作为第一组分的聚氨酯、聚酯和其它少量成分的混合物，第二组分包括异氰酸酯作为其共反应物。这种共反应物在与双组分聚氨酯粘合剂的第一组分混合时作为催化剂。该共反应物与所说的第一组分的上述混合通过聚合物结构的控制交联，提高了该粘合剂的粘合性能。此外，该共反应物与所说的第一组分的混合物提高了粘合剂的柔韧性，减小了粘合层本身断裂的可能性。
优选地，在将双组分聚氨酯粘合剂应用于该多层材料之前，首先将其第一组分与第二组分混合。一旦将其应用到多层材料上，在该多层材料进一步加工和成型为容器之前，该粘合剂通常需要至少10天的时间进行熟化，以使粘合剂组分完全网状化和聚合。我们发现市场上买得到的一种适用的粘合剂的实例是ET-691，它是由Morton GmbH，BeimStruckenberge，11，D-28239不来梅，德国生产的。我们发现这种粘合剂应用在根据本发明的多层材料中足以耐次氯酸盐漂白剂组分的侵蚀作用。
我们发现当该粘合剂用量超过一临界(threshold)表面密度时，其对该次氯酸盐漂白剂或其组分的耐侵蚀的抵抗能够获得进一步提高。该粘合剂的表面密度是单位表面积上粘合剂的量，下文用g/m2表示(克粘合剂/每平方米塑料层)。所以，所说的表面密度也定义了该粘合剂层的厚度；该粘合剂层临界表面密度主要依赖于粘合剂本身类型以及该产品中次氯酸盐漂白剂组分透过内层的扩散系数。例如，采用聚氨酯粘合剂时，内层厚度约为100μm，含有的包含次氯酸盐漂白剂的产品有效氯浓度约高达150g/l(克/升)，我们测定出临界表面密度最低为2.5g/m2，更优选的约为4g/m2。
临界表面密度已被实验测定。实验中，将几种粘合剂层表面密度不同的多层材料浸入含有次氯酸盐漂白剂的产品中，三周以后，具有最低表面密度粘合剂层的多层材料未出现脱层现象，则确定为该粘合剂层的临界表面密度。因而，作为一种进一步提高该多层材料耐次氯酸盐漂白剂优选方案，该粘合剂层的涂布高于该临界表面密度。
此外，我们发现能降低该粘合剂对所说的次氯酸盐漂白剂或其组分侵蚀行为的敏感性的另一改进措施为该粘合剂层达到均一分布。在下文中，均一分布意指层的厚度均匀，允许误差低于50％，更优选的约10％。该粘合剂层的均一性要通过实验来测定。一种可行方法为通过其厚度方向切取该多层材料，获得多层材料沿其厚度方向的截面切片，然后该截面切片采用光学显微镜进行分析。相反，采用共焦激光显微镜可以不用预先通过其厚度方向切取该多层材料，就能分析相同的截面切片。
粘合剂层一般都具有一些缺陷，比如裂纹、空洞和不希望的气孔，在机械或化学应力下此处的粘合性能很容易被破坏。我们发现薄粘合剂层比厚层更易于丧失其粘合性能。实际上，在具有缺陷的薄层中粘合剂基体本身不能完全被周围无缺陷的基体所补偿。相反，厚层就有更多机率以较多基体补偿该缺陷部分，即薄层粘合剂比厚层更易于失去其粘合性能。因而，作为另一种提高该多层材料耐次氯酸盐漂白剂的优选方案，该粘合剂层在多层材料中必须均一分布。
能阻止所说的多层材料受次氯酸盐漂白剂或其组分的侵蚀作用而老化的另一可选择部件为一种阻挡层。该阻挡层位于该内层与该粘合剂层之间。优选地，该阻挡层由聚烯烃材料制成，其密度和厚度应足以阻止漂白剂透过所说的阻挡层向粘合剂层的迁移。优选地，该阻挡层由中密度聚乙烯(MDPE)或高密度聚乙烯(＝HDPE)，或乙基乙烯基醇(＝EVOH)或其混合物所组成。优选地，制备的该阻挡层密度大于0.9g/cm3，更优选的密度为0.926g/cm3～0.97g/cm3，最优选的为0.926g/cm3～0.965g/cm3。优选地，该阻挡层的厚度为5μm～95μm，更优选的30μm～60μm。我们发现含有根据本发明的阻挡层的该多层材料减少了所盛装的次氯酸盐漂白剂或其组分向粘合剂层的迁移。
优选地，该阻挡层与内层共挤出成为一共挤出层，然后外层通过粘合剂与该共挤出层粘合。事实上，由内层制成的相对的面比阻挡层更易于热封，因为内层所需的密封能量较低。为了进一步提高多层材料耐次氯酸盐漂白剂，该粘合剂层可以是一种上述的耐次氯酸盐漂白剂的粘合剂层，和/或粘合剂的应用超过上述的临界表面密度，和/或如上所述该粘合剂具有均一分布。
如前所述，该阻挡层位于该多层材料的内层与粘合剂层之间以保护粘合剂层。特别地，当该多层材料成型为盛装含有次氯酸盐漂白剂的产品的容器时，该阻挡层保护该粘合剂层。事实上，我们发现该产品中含有的次氯酸盐漂白剂或其组分能够迁移通过如上所述的由LDPE制成的内层。相反，阻挡层能显著减弱向粘合剂层的这种迁移。否则，若无阻挡层则该粘合剂层就会受到大量侵蚀性的次氯酸盐漂白剂/次氯酸盐漂白剂组分的作用，它们能够使该粘合剂分解并最终至少部分地破坏该粘合剂的粘合性能。从而，该外层材料就会与共挤出阻挡-内层脱层。例如几天后，相应的容器就会失去其防漏性能。因而，该阻挡层能够显著提高该多层材料耐次氯酸盐漂白剂的侵蚀作用。
按照本发明，作为另一优选方案，可将该阻挡材料夹在所说的内层和一种中间层之间。该中间层优选地由低密度聚烯烃制成。优选地，该中间层由与该内层相同的材料制成。以一种经济的方式，该中间层进一步提高了多层材料的内层和阻挡层的厚度及其阻挡性能。该中间层的厚度为5μm～50μm，更优选的为20μm～40μm。
在另一优选方案中，增加了由LDPE组成的内层厚度。以这种方式，内层透次氯酸盐漂白剂性被进一步降低，从而使渗透性低于使粘合剂层老化的临界极限之下。优选地，该LDPE层的厚度超过100μm，更优选的厚度为150μm～200μm。
本发明的该多层材料是柔性的，这表明该多层材料能够被充分弯曲，而不会引起多层材料本身任何永久性裂纹。不管怎样，我们发现按照本发明的多层材料与现有技术生产的无该阻挡层的多层材料相比，更抗皱和耐刺穿。此外，我们发现按本发明的该多层材料与现有技术生产的无阻挡层的多层材料相比，其透水性降低了。因而，按照本发明的该多层材料与现有技术生产的无阻挡层的多层材料相比，能提供更好的对液态产物的密封性能。
当根据本发明的该多层材料成型为一容器时，该容器能够盛装含有次氯酸盐漂白剂的液态产品。优选地，该次氯酸盐漂白剂有效氯浓度高达150g/l，最优选的次氯酸盐漂白剂有效氯浓度为25g/l～50g/l。优选地，该液态产品可以作为一种洗涤剂组合物。该洗涤剂组合物可以用于衣物、盘子或硬表面物的洗涤。
本发明的多层能成型为容器，该容器通过热封而成型。优选地，根据本发明的该多层材料成型为一容器包括以下步骤：
(A)阻挡层与内层共挤出，或作为一种选择方案，该阻挡层夹在内层和中间层之间共挤出；
(B)通过在外层和(A)的共挤层之间放入粘合剂层，将(A)的共挤层与外层层合成型为根据本发明的多层材料；
(C)(B)经至少10天熟化后，根据本发明的该多层材料被切成为所需尺寸的片材；
(D)将至少两个相同尺寸的片材相互面对面放，以这种方式，使内层相互接触；
(E)通过热封使(D)的片材周边热封连在一起以成型为香袋或小袋，其中装料的周边除外，以便于该香袋或小袋的装料；
(F)该开口的香袋或小袋充装含有次氯酸盐漂白剂的液态产品；
(G)沿该香袋或小袋装料部分周边通过热封将其完全密封。

Claims (15)

1.一种用于盛装含次氯酸盐漂白剂液态产品的多层材料，该多层材料包括内层、粘合剂层和外层，该内层由可热封的聚烯烃制成，和该外层由可印刷材料制成，所述多层材料还包括一种能阻止该多层材料受次氯酸盐漂白剂或其组分的侵蚀作用而老化的部件，其特征在于所述部件包括由耐次氯酸盐漂白剂的粘合剂制备的所说的粘合剂层，该耐次氯酸盐漂白剂的粘合剂为双组分聚氨酯粘合剂。
2.按照权利要求1所述的多层材料，其特征在于，所述部件包含阻挡层，它由聚烯烃材料制成，其密度高于0.9g/cm3而厚度在5μm到95μm之间，能够足以减少所述次氯酸盐漂白剂通过该阻挡层向粘合剂层的迁移，并且该阻挡层位于所述内层和粘合剂层之间。
3.按照权利要求2所述的多层材料，其特征在于，所述阻挡层由选自中密度或高密度聚乙烯、乙基乙烯基醇和它们的混合物的材料制备。
4.按照前述任意一项权利要求所述的多层材料，其特征在于，所述粘合剂层被均匀分布在该粘合剂层中，其厚度的允许偏差低于50％。
5.按照前述任意一项权利要求所述的多层材料，其特征在于，所述粘合剂以超过临界表面密度2.5g/m2涂布。
6.按照权利要求2-5之任一项所述的多层材料，其特征在于，该多层材料还包含一层或多层由聚烯烃制备的中间层，并且该中间层位于所述粘合剂层和阻挡层之间。
7.按照前述任意一项权利要求所述的多层材料，其特征在于，所述外层由可印刷塑料制备。
8.按照权利要求7所述的多层材料，其特征在于，所述可印刷塑料选自聚对苯二甲酸乙二醇酯、聚丙烯、聚酰胺、聚苯乙烯、乙基乙烯基醇、聚碳酸酯、聚氯乙烯和赛珞玢。
9.按照前述任意一项权利要求所述的多层材料，其特征在于，所述内层由低密度聚乙烯制备。
10.按照前述任意一项权利要求所述的多层材料，其特征在于，所述次氯酸盐漂白剂有效氯浓度高达150g/l。
11.按照权利要求10所述的多层材料，其特征在于，所述次氯酸盐漂白剂有效氯浓度为25g/l～50g/l。
12.一种由前述任意一项权利要求所述的多层材料制备的柔性容器，其特征在于，该容器包括至少两片该多层材料，该片材沿其周边被热封在一起。
13.按照权利要求12所述的柔性容器，其特征在于，该容器用于盛装含有含次氯酸盐漂白剂的产品。
14.按照权利要求12所述的柔性容器，其特征在于，所述次氯酸盐漂白剂的有效氯浓度高达150g/l。
15.按照权利要求14所述的柔性容器，其特征在于，该次氯酸盐漂白剂的有效氯浓度为25g/l～50g/l。
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