CN1244836A - 阻挡性能增强的真空金属化薄膜 - Google Patents

阻挡性能增强的真空金属化薄膜 Download PDF

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CN1244836A
CN1244836A CN98802072A CN98802072A CN1244836A CN 1244836 A CN1244836 A CN 1244836A CN 98802072 A CN98802072 A CN 98802072A CN 98802072 A CN98802072 A CN 98802072A CN 1244836 A CN1244836 A CN 1244836A
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polyethylene layer
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E·M·芒特第三
J·R·小瓦格纳
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ExxonMobil Oil Corp
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Abstract

提供一种对氧气和水汽阻挡性能增强了的多层薄膜。该多层薄膜包括聚丙烯基层,在该聚丙烯基层的至少一侧上的高密度聚乙烯层。所述聚乙烯层包含经羟基供体材料(如甲醇)等离子体处理的表面。该薄膜还包括沉积在经等离子体处理的表面上的金属层,如真空沉积的铝层。本发明多层薄膜特别适合作为用于食品的包装薄膜。

Description

阻挡性能增强的真空金属化薄膜
本发明涉及阻挡特性被增强了的并带有经等离子体处理的聚乙烯层的真空金属化的包装薄膜。
塑料材料(如聚合物薄膜)已被广泛用于包装各种食品和非食品产物。为了确保包装在这种聚合物薄膜中产物的保藏，需要使这种薄膜具有对空气、水汽、有害气体等的阻挡性能。但是，未改性的聚合物薄膜通常缺乏正确包装所需的足够的气体和水汽阻挡性能。例如，聚丙烯薄膜由于成本低且容易制造而被偏爱用于制造包装薄膜。但是这种薄膜本身会使氧气和水汽从薄膜的外面渗透至薄膜包装的内部。本领域的普通技术人员可知氧气和水汽渗入食品包装会促使该包装内食品的变质。
业已开发了多层聚合物薄膜它改进了对气体和水汽的阻挡特性。例如，带有乙烯-乙烯醇共挤出涂层的薄膜具有改进了的氧气和水汽阻挡性能。美国专利5,192,620公开了一种取向的聚丙烯基层，在其一个表面上带有乙烯醇均聚物或共聚物与乙烯-丙烯酸共聚物的共混物涂层，该涂层上再带有一层金属层。但是，带有乙烯-乙烯醇共挤出层或涂层的薄膜难以制造并且价格高昂。
还提出了使用带金属层的多层薄膜以获得改进的阻挡性能。美国专利5,194,318(在此引为参考)公开了一种金属化的取向热塑性复合薄膜，它具有丙烯均聚物或共聚物基层，在基层的至少一侧带有高密度聚乙烯表层。所述高密度聚乙烯表层还包括通过蒸气沉积于其上的金属薄层。在一个较好的例子中，该高密度聚乙烯表层经火焰或电晕放电处理并随后在该火焰或电晕放电处理过的层上沉积金属涂层。尽管带有高密度聚乙烯表层的薄膜无金属剥落这种不利影响，这种薄膜仍不能满足各种包装所需的最佳氧气和水汽阻挡性要求。
已提出了用烃类对聚合物薄膜进行等离子体处理，以改进金属涂层对薄膜的粘性。例如，美国专利4,897,305公开了一种聚烯烃基层(如聚丙烯)包装薄膜，所述基层上具有低分子量烃和金属层的薄层。该薄膜是通过将聚丙烯基层进行脂族烃蒸气等离子体处理，随后再蒸气沉积金属层后制得的。但是，通过含脂族烃的等离子体处理制得的薄膜的制造成本高，并且认为烃层不会明显增加薄膜的阻挡性能。
尽管现有技术公开了各种包装薄膜，但是这种薄膜通常难以制造，其难点在于使用高成本的材料和方法，并且对随后的蒸气沉积金属层粘性不够。因此，需要一种包装薄膜，它价廉且便于制造，并能够提供增强的氧气和水汽阻挡性能。
本发明的一个目的是提供一种包装薄膜，它具有改进的氧气和水汽阻挡性能。
本发明另一个目的是提供一种具有改进的阻挡性能的包装薄膜，它价廉且易于制造。
本发明实现了上述和其它目的，提供一种带有聚丙烯基层的多层薄膜，所述基层的至少一个表面上具有高密度聚乙烯层，所述聚乙烯层的一个表面用羟基供体材料(如甲醇)进行过等离子体处理。所述薄膜还包括沉积在聚乙烯层经等离子体处理的表面上的金属层(如蒸气沉积的铝)。结果，形成了具有优良氧气和水汽阻挡性的多层薄膜。
本发明涉及由聚丙烯基层和粘合在该基层的至少一个表面上的高密度聚乙烯层构成的多层薄膜。对聚丙烯基层上的高密度聚乙烯层的露出表面进行羟基供体材料等离子体处理。随后在经如此处理的聚乙烯层上沉积金属层。本发明制得的薄膜具有优良的对氧气和水汽的阻挡性能。
本发明聚丙烯基层可以是适用于制造热塑性薄膜的任何合适的聚丙烯聚合物，如丙烯均聚物和共聚物。特别适用的丙烯均聚物包括80-100％全同立构聚丙烯，最好为95-96％全同立构聚丙烯。较好的是，丙烯均聚物的熔体流动指数为2-10g/10分钟，熔体流动指数最好为3.5-6g/10分钟。较好的丙烯共聚物包括98-93/2-7丙烯/乙烯共聚物，50/50丙烯/1-丁烯共聚物，95/5丙烯/1-戊烯共聚物，90/10丙烯/1-己烯共聚物，80/20丙烯/4-甲基-1-戊烯共聚物。
在聚丙烯基层的至少一个表面上包含有聚乙烯层或表层。该聚乙烯层可以是涂覆在聚丙烯层上的整体层，或者与聚丙烯层共挤出。在本发明中用作聚乙烯层或表层的聚乙烯包括中密度或高密度聚乙烯，最适用的是高密度聚乙烯。确信高密度聚乙烯所具有的高结晶度和光滑性能改进与沉积金属层的粘性。具有密度为0.960或更高的聚乙烯最合适。
高密度聚乙烯可包括单一的高密度聚乙烯树脂、高密度聚乙烯树脂的混合物，或者含10％(重量)少量微晶蜡的高密度聚乙烯。
出于本发明的目的，可将上面带有聚乙烯层的聚丙烯基层视为中间薄膜结构。这种中间薄膜结构可包括粘合在聚丙烯基层的一个或两个表面上的聚乙烯层。在本发明中特别适用的中间薄膜结构包括聚丙烯和高密度聚乙烯的复合物(参见美国专利5,194,318)。如下面将详细描述的那样，较好的中间薄膜结构包括共挤出的聚丙烯和高密度聚乙烯，并且所述中间薄膜结构经双轴取向。
对带聚丙烯基层和聚乙烯层的中间薄膜结构进行羟基供体材料等离子体处理。出于本发明的目的，将羟基供体材料限定为在等离子体环境下能将羟基(-OH)官能度赋予薄膜表面的材料。较适用的是具有小于5个碳原子的低链醇。下面将详细描述的这些材料在等离子体环境下能分解成游离羟基，并重新连接在薄膜表面上。
如上所述，中间薄膜结构可包括聚丙烯基层的一个或两个表面上的聚乙烯层。在本发明中，对上面将沉积金属层的聚乙烯层露出表面进行等离子体处理。如此，在聚丙烯层的两个表面上具有聚乙烯层的中间薄膜结构的情况下，根据金属层是沉积在一层聚乙烯层还是分别沉积在两层聚乙烯层上，可对一层聚乙烯层或两层聚乙烯层进行羟基供体材料等离子体处理。
如下面将详细描述的那样，可使用任何已知的方法进行等离子体处理。尽管未完全了解羟基供体材料等离子体处理的确切化学问题，但是相信在羟基供体材料的存在下产生等离子体导致羟基供体材料分解并重新化合。将中间薄膜结构的聚乙烯表面层置于羟基供体材料的等离子体中，相信羟基供体材料分解成-OH自由基，该自由基重新化合在中间薄膜结构的聚乙烯表面上。该聚乙烯层表面因此变成含-OH基团的富醇表面。相信这种富醇表面具有类似乙烯-乙烯醇本体层表面的阻挡特性及随后的金属化效果，而没有将这种本体层共挤出或涂覆在中间薄膜结构上所带来的困难和成本。
特别适用于本发明的羟基供体材料包括具有小于5个碳原子的低链醇。特别好的例子包括甲醇、乙醇、丙醇和丁醇，尤其是甲醇。
相信用羟基供体材料进行等离子体处理使高密度聚乙烯表面具有-OH官能度，其效果类似于乙烯-乙烯醇本体层的阻挡特性，而无施加或共挤出单独的乙烯-乙烯醇层时的附加处理和成本。尽管未完全了解用羟基供体材料进行等离子体处理确切的表面化学，但是相信在使聚乙烯层表面具有高表面能方面羟基供体材料的含氧量起重要的作用。如上所述，经羟基供体材料等离子体处理的中间薄膜结构的聚乙烯层表面含有-OH基团。这种-OH基团使中间薄膜结构具有高的表面能，这改进了随后沉积的金属层的粘性。尽管已知共挤出或涂覆在中间薄膜结构上的乙烯-乙烯醇本体层能改进中间薄膜结构的阻挡质量，但是本发明人相信高表面能聚合物和随后沉积的金属层之间的界面能对气体和水汽产生高的阻挡。因此，由聚集在其上的-OH基团形成的中间薄膜结构的聚乙烯层的高能表面与随后沉积的金属层之间的界面向薄膜提供了增强的阻挡性能。
另外，-OH基团使中间薄膜结构的聚乙烯表面具有一定的极性。相信这种极性能增强与随后沉积的金属层的粘性。通常，聚烯烃薄膜本身是非极性的。为了与沉积的金属层具有良好的金属粘性，相信至少需要稍许的极性。美国专利4,897,305试图用脂族烃进行等离子体处理以便使聚烯烃薄膜具有粘性。应注意在该专利中这种处理改进了金属与聚烯烃的粘性，但未改变薄膜的非极性性能。相反，在本发明中，可改变中间薄膜结构的高密度聚乙烯层的表面特性以形成稍许的极性，而不会对薄膜的总体性能或金属粘性有不利影响。
如上所述，相信羟基供体材料的含氧量对薄膜的阻挡性能起了重要的作用，这里羟基供体材料分解为-OH基团并复合到薄膜表面上使薄膜表面具有高表面能。为了确保羟基供体材料中存在足够的氧，可在等离子体处理前或在处理过程中向羟基供体材料加入氧。这种加入的氧能改进等离子体处理过程中羟基的浓度，从而有助于保持所需的羟基浓度。尽管未很好地了解羟基表面基团的产生机理，但是认为通过等离子体化在聚乙烯层露出的表面上直接形成了自由基，并且有两种机理在表面上产生羟基表面基团发生作用。第一种，认为通过等离子体化产生羟基部分，该羟基部分与薄膜表面上形成的自由基点重新化合形成羟基表面基团。第二种，在表面上的自由基点能与例如在等离子体化中加入的氧以及在等离子体化中形成的游离氢原子反应，直接在表面上形成羟基表面基团。
随着氧的加入，可以预期可将某些较长链的醇用于本发明中，只要在羟基供体材料中存在足够的氧，以保持适当的自由基浓度以便能在聚乙烯层上形成富醇表面。
还可向等离子体中加入惰性气体(如氦和氩)，以形成高能物质，促进醇分解、形成自由基并随后在薄膜表面上的重新化合。
带有经醇-等离子体处理的聚乙烯表面层的中间薄膜结构还包括沉积在经处理的聚乙烯层上的金属层。这种沉积的金属层是本领域已知的，并可使用任何已知的方法(如真空沉积、电镀、阴极溅射等)进行沉积。较好的是，该金属层是真空沉积的铝、铜、银、铬、金及其混合物中的一种，最好是真空沉积的铝。
可选择地在薄膜中加上热粘聚合物。如本领域已知的那样，这种热粘聚合物可以是能将薄膜自己热粘在一起或与某些其它表面热粘的任何层或涂层。较好的是，中间薄膜结构包括聚丙烯基层，该基层的一侧具有一层聚乙烯层而另一侧具有一层可热粘的层。较好的热粘聚合物是例如乙烯-丙烯(PE)共聚物或乙烯-丙烯-1-丁烯(EPB)三聚物。乙烯/丙烯/1-丁烯的含量以0-15％乙烯、70-100％丙烯和0-15％1-丁烯为较好，最好乙烯-丙烯共聚物含有2-7％(重量)乙烯和93-98％(重量)聚丙烯。
或者，可使用可印刷的表面层，例如中间薄膜结构可包括聚丙烯基层，其一侧上带有聚乙烯层，在其另一侧上带有可印刷的表面层。所述可印刷的表面可以是上面能接受印刷图象的任何聚合物，如聚烯烃均聚物、共聚物或三聚物，聚碳酸酯，聚酯，高密度聚乙烯等。
另外，可将聚合物薄膜层压在多层薄膜的金属层上。这种聚合物薄膜能改进最终薄膜(overall film)的厚度、刚性和抗刺穿性，并能进一步增强薄膜的阻挡性能。该聚合物薄膜可以是取向的、未取向的、透明的或非透明的。较好的是，该聚合物薄膜是聚丙烯或聚乙烯，最好是取向的聚丙烯(OPP)。
可使用任何合适的粘合剂将这种附加的聚合物薄膜层压在金属层上。较好的粘合剂是热熔低密度聚乙烯，施加的量约为10磅/令。
本发明多层薄膜的总厚度一般为0.55-2.0mil。高密度聚乙烯层以0.02-0.08mil较好。
本发明多层薄膜对水汽的渗透和氧气的渗透具有优良的阻挡性能。例如，本发明多层薄膜的水汽渗透率小于0.01g/100英寸2-24小时。氧气渗透率小于1.0-2.0cc/100英寸2-24小时。
本发明还涉及具有优良的氧气和水汽防渗性能的多层薄膜的制备方法。在该方法中，在至少一侧上粘有高密度聚乙烯层的聚丙烯基层作为中间薄膜结构。较好的是该中间薄膜结构由高密度聚乙烯表层和所选的丙烯均聚物或共聚物基层通过共挤出制得。随后可将中间薄膜结构在纵向和/或横向进行取向，最好在纵向和横向同时进行双轴取向。
随后对中间薄膜结构的高密度聚乙烯层进行羟基供体材料(如甲醇)等离子体处理。可使用本领域已知的任何方法进行这种等离子体处理。较好的是，在真空室中使用连续处理薄膜的连续辊处理法进行这种等离子体处理，例如，可参见美国专利4,897,205所述的方法，该专利在此引为参考。
等离子体处理是在负压下，可取20-3000毫乇压力，最好在30-300毫乇下进行。等离子体处理时的温度以保持在20-60℃为佳。
在真空室中，将片状的薄膜置于气态的羟基供体材料中。较好的是，气态的羟基供体材料约以0.1-4SCCM气体/英尺2加工薄膜/分钟的流量流入等离子体室中。
接着用合适的等离子体发生电极(如平面阴极)在真空室中产生等离子体。通过施加电场，等离子体激发羟基供体材料分子，使之分解并以-OH基团的形式重新化合在薄膜聚乙烯层的表面上。较好的是，在约2-4瓦/英尺2加工薄膜/分钟的能量密度下进行等离子体处理。
等离子体处理进行5-60毫秒。薄膜穿过等离子区以后，在其聚乙烯表面上具有-OH自由基的中间薄膜结构准备沉积金属层。在将中间薄膜结构保持在真空室中的同时，将中间薄膜结构转移或传输至金属层沉积区。可使用任何合适的方法进行这种金属沉积，如热蒸发铝，随后该铝冷凝在正卷绕在一激冷辊上的薄膜表面上。
如上所述，通过在羟基供体材料存在下进行等离子体处理，形成了高密度的羟基自由基并在薄膜表面上形成高密度的羟基基团。等离子体处理过的材料一般具有过量的自由基，这种自由基在空气的存在下快速氧化。通过在同一真空室中的自由基产生步骤(即置于羟基供体材料等离子体中)和金属层沉积步骤，使得中间薄膜结构未暴露在空气中，否则对金属层的粘结和薄膜的阻挡性能都有不利影响。因此，等离子体处理和金属化最好依次在同一真空室中进行。
尽管使用具体实例对本发明进行了描述，但是本领域的普通技术人员可理解在不偏离本发明精神和范围的前提下可对本发明进行各种变化和改进。认为这种变化和改进包括在所附的权利要求范围内。

Claims (10)

1.一种多层薄膜，它包括：
一层聚丙烯基层；
一层粘合在所述聚丙烯基层的至少一侧上的高密度聚乙烯层，所述聚乙烯层具有一个露出的表面，在该露出的表面上所述聚乙烯层被施以羟基等离子体层；和
沉积在所述聚乙烯层上的金属层。
2.如权利要求1所述的薄膜，其特征在于所述聚丙烯基层和所述聚乙烯层是共挤出的。
3.如权利要求1所述的薄膜，其特征在于所述聚丙烯基层和所述聚乙烯层是双轴取向的。
4.如权利要求1所述的薄膜，其特征在于所述金属层选自铝、铜、银、铬、金及其混合物。
5.如权利要求1所述的薄膜，它还包括在聚丙烯基层的至少一侧上的热粘聚合物层。
6.如权利要求1所述的薄膜，它还包括层压在所述金属层上的聚合物薄膜。
7.一种多层薄膜的形成方法，它包括：
提供聚丙烯基层，该基层的至少一侧上粘有高密度聚乙烯层；
用羟基供体材料等离子体处理所述聚乙烯层的露出表面；和
在所述等离子体处理的聚乙烯层上沉积金属层。
8.如权利要求7所述的方法，其特征在于所述羟基供体材料能分解成羟基自由基，并重新化合在所述聚乙烯层上。
9.如权利要求7所述的方法，其特征在于所述羟基供体材料选自甲醇、乙醇、丙醇、丁醇及其混合物。
10.如权利要求7所述的方法，其特征在于所述沉积步骤和所述等离子体处理步骤依次在同一真空室中进行。
CN98802072A 1997-01-29 1998-01-19 阻挡性能增强的真空金属化薄膜 Pending CN1244836A (zh)

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CN103937099A (zh) * 2014-04-12 2014-07-23 安徽江威精密制造有限公司 一种无卤阻燃耐高温电容器金属化薄膜及其制备方法

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AU718552B2 (en) 2000-04-13
AU5920598A (en) 1998-08-18
EP0956194A4 (en) 2002-04-10
JP2001509101A (ja) 2001-07-10
CA2278791A1 (en) 1998-07-30
EP0956194A1 (en) 1999-11-17
WO1998032597A1 (en) 1998-07-30
US5981079A (en) 1999-11-09
AR011587A1 (es) 2000-08-30
ID22742A (id) 1999-12-09
KR20000070550A (ko) 2000-11-25

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