CN102066105A - 玻璃容器盖的密封 - Google Patents

玻璃容器盖的密封 Download PDF

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CN102066105A
CN102066105A CN200980121715XA CN200980121715A CN102066105A CN 102066105 A CN102066105 A CN 102066105A CN 200980121715X A CN200980121715X A CN 200980121715XA CN 200980121715 A CN200980121715 A CN 200980121715A CN 102066105 A CN102066105 A CN 102066105A
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multilayer tablet
container
edge
composite packaging
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A·格雷尔
G·宝伊罗恩
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Amcor Flexibles Selestat SAS
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Abstract

一种通过热封至玻璃容器(10)的边沿(12)而用于封盖该容器的多层片，所述边沿已经金属氧化物和/或金属盐处理，所述多层片至少包含一个支撑层(21)和一个下层(22)，所述下层由其上接枝有不饱和羧酸的可热封聚合物材料制成。

Description

玻璃容器盖的密封
技术领域
本发明涉及玻璃容器的密封，更具体而言，涉及当由玻璃容器和玻璃容器的封堵部件所形成的复合包装的内容物必须在包装内部于高温下消毒时玻璃容器的密封。
更具体而言，本发明涉及一种用于封盖玻璃容器的多层片，一种包含由所述多层片制成的盖(opercule)的复合包装，和一种制造所述包装的方法。
背景技术
玻璃容器是由玻璃制成的中空物件，例如壶、罐、瓶、杯、小瓶等。复合包装的内容物可以是供食用的液态、固态或粉状食物，例如果汁、酸奶、成品菜(plat préparé)等。
其内容物须经高温消毒的包装通常由金属帽(couvercle)部件旋拧于玻璃容器上而制成。这种包装通常难于开启，其原因在于为了获得完全的密封，即避免漏出(特别是在消毒过程中)，封闭时所施加的力要非常大，以使帽的内表面与玻璃容器边沿(buvant)在其整个边缘上压紧。这样的办法也是价格昂贵的。
还已知一种由其上热封有盖的玻璃容器所构成的复合包装，所述盖通常由铝膜和包含一个热塑性材料层的聚合物膜构成。所述热塑性材料起到盖和玻璃容器边沿之间的粘合剂的作用，容器的边沿对应于界定容器开口的容器的周缘区域，更具体而言对应于进行热封的区域。为了获得改进的玻璃与热塑性材料之间的粘合，已知(例如由专利FR 2435439)可向容器的边沿施用一种偶联剂(agent couplant)，该偶联剂对玻璃具有高亲和性，并且具有可与热塑性材料形成强键的自由键，该偶联剂在此处为例如一种硅烷或氧化硅。另一种由专利FR 2723939和FR 2519956已知的改善玻璃与热塑性材料间的粘合的玻璃处理方法为在边沿上沉积一层例如氧化锡或氧化钛，在其上再沉积一种铬复合物，例如DuPont的VolanTM。专利FR 2712583、FR 2723939和EP0620202还公开了所述铬复合物可分别用锆盐、铝盐或铬盐等替代。
然而，用这些金属氧化物和金属盐处理边沿所获得的热塑性材料与玻璃容器间的粘合是不够的，并且当包装进行消毒时不能获得充分的密封。实际上，消毒步骤中包装内容物温度的升高以及由此导致的气体的膨胀会使盖受到较大的压力，并使包装的内部和外部间产生漏洞。
还由专利申请FR 2523112已知一种复合包装，其中玻璃容器的边沿用氧化钛或氧化锡处理、然后用硅烷处理，接着获得一个Dupont公司的“SurlynTM”型乙烯/丙烯酸共聚物层，该共聚物的作用是将盖粘固于边沿上。这种共聚物的使用能够改善玻璃容器和盖之间的粘合，但当包装需要在高于115℃、更特别是高于120℃的温度下消毒时是不适合的，因为“SurlynTM”的熔点为80至95℃，此时已低于消毒温度。因此，在此类包装的消毒过程中，热塑性材料便会熔化而不再能提供密封，尤其是在消毒过程中施加于盖上的压力较大时。
同样的问题也出现在许多以聚乙烯、改性聚乙烯、或含聚乙烯的混合物为主要成分的热塑性材料的使用中，例如专利EP 0620202所提出的，这是因为这些热塑性材料的熔点等于或低于聚乙烯的98至115℃的熔点，因此不能将其用于制造将要在高于115℃、更特别是高于120℃的温度下进行消毒的包装。
本发明的目的是获得一种具有满意的密封的复合包装。
本发明的另一个目的是获得一种其密封可经受消毒步骤的复合包装。
发明内容
为此，本发明的目的是一种通过热封至玻璃容器的边沿而用于封盖该容器的多层片，所述边沿已经金属氧化物和/或金属盐处理，所述多层片至少包含一个支撑层和一个下层，所述下层由其上接枝有不饱和羧酸的可热封聚合物材料制成，其特征在于，所述可热封聚合物材料的熔点高于115℃。已发现，接枝到可热封聚合物材料上的不饱和羧酸可与金属氧化物和/或金属盐形成强键，从而使所述下层与玻璃容器边沿的粘合得以改善，并实现满意的复合包装密封。与许多含溶剂的粘合剂不同，这样的下层还具有低毒性，使得该复合包装可非常好地适用于食品包装。此外，粘合有利地不受水接触的影响，例如位于复合包装内部的水，例如消毒过程中以蒸汽的形式。使用高熔点的可热封聚合物材料有利地可使粘合具有很好的温度耐受性，特别是在产品需要消毒时。
根据本发明的一个优选实施方案，所述多层片设计为将与容器一起经受消毒温度Tst，且可热封聚合物材料的熔点高于所述消毒温度Tst。消毒温度通常随着复合包装内容物及所采用技术的不同而在115℃和135℃之间变化。通过选择熔点高于复合包装及其内容物的消毒温度的可热密封聚合物材料，可确保下层在消毒操作中不熔化，从而使由多层片所制成的盖与玻璃容器间的粘合可保持强力并且坚固。该特征尤其是在包装要进行消毒时是重要的，因为消毒过程中会有自复合包装内部向外的压力施加于盖上--特别是由于包装内气体的膨胀，容易促使漏洞的形成。热塑性聚合物材料的温度耐受性使得下层的密封性能可保持不变。因此，本发明的盖可不同于现有技术的盖而用于消毒应用，对所述现有技术的盖而言，下层密封层会在消毒过程中熔化且会暂时失去其密封性能，使得盖被施加于其上的力抬起，并在盖和边沿之间形成漏洞。
根据本发明的一个优选实施方案，所述可热封的聚合物材料为一种其PP均聚物的熔点约为160℃的聚丙烯。也存在熔点介于120至160℃之间的以丙烯为主要成分的共聚物适用于所述应用。还可使用聚酯，其熔点约为260℃。特别是从成本、市场易得性和共挤出使用的难易考虑，聚丙烯优于聚酯。对于某些应用而言，当消毒温度在上述数值范围的较低部分时，可有利地使用熔点在115℃和130℃之间浮动的高密度聚乙烯(HDPE)作为所述可热封聚合物材料。HDPE牌号的选择取决于使用的消毒温度。
根据一个优选实施方案，所述不饱和羧酸为马来酸酐，这特别是出于成本和市场易得性的考虑，以及还由于其易于接枝。其他的羧酸也可使用，例如富马酸、柠康酐、衣康酸酐、四氢亚甲基马来酸酐(anhydrideméthylène tétrahydro maléique)等。
根据一个优选实施方案，所述不饱和羧酸与所述聚合物材料的质量比为低于2％，优选低于1％。
根据本发明的不同优选实施方案：
-所述支撑层包含铝或为一种半透明的聚合物膜；
-所述下层为一种多层聚合物膜层；
-所述下层通过粘合剂层粘在所述支撑层上；
-所述玻璃的边沿的处理包括沉积铬盐、硅烷、锆盐或铝盐。
本发明还涉及一种包括一个玻璃容器和一个位于所述玻璃容器的边沿上的可热封盖的复合包装，其中所述盖由一种如上所述的多层片制成。该包装可例如进行消毒。也可在容器上旋拧一个塑料或金属材料的帽，以便在所述盖被去除时，能够再次封闭该容器。可利用上述帽来在产品的消毒步骤中提供反压力(contrepression)，以使施加于盖上的压力不会导致盖变形或破裂以及密封带的大的牵引。此外，上述帽也可用来使盖维持在紧贴容器边沿的状态。
本发明还涉及一种制造复合包装的方法，包括以下步骤：
-提供一个带有边沿的玻璃容器，所述边沿已经金属氧化物和/或金属盐处理，
-提供一个至少包括一个支撑层和一个下层的盖，所述下层由其上接枝有不饱和羧酸的可热封聚合物材料制成，
-将所述盖热封在所述容器的边沿上。
根据本发明的一个优选实施方案，所述方法还包括，在热封后进行复合包装的消毒的步骤，该消毒步骤通常包括使复合包装处于115℃至135℃的温度10至60分钟的时间。
根据另一个优选实施方案，所述方法还包括一个将帽旋拧于所述容器上的步骤；可在消毒前或消毒后将所述帽旋拧于所述容器上。
通过以下说明和附图可更好地理解本发明，所述附图以非限制实例方式给出。
附图说明
图1为本发明的一种复合包装的部分截面图。
图2为本发明的另一种复合包装的侧视图。
具体实施方式
图1局部示出由玻璃容器10和盖20构成的本发明复合包装1，其中玻璃容器10仅包含开口11的上部是可见的。进行盖20热封的容器10的边沿12经金属氧化物和/或金属盐处理，并因此包含一种所述金属氧化物和/或金属盐的沉积物13。这种用金属氧化物和/或金属盐对玻璃的处理已被专业文献大量报道，特别是专利文献FR 2435439、FR 2723939、FR 2519956、FR 2712583、FR 2523112、EP 0620202，因此是本领域技术人员已知的。这些金属氧化物和/或金属盐有助于热塑性聚合物材料与玻璃的粘合。它们例如为铬盐、硅烷、锆盐或铝盐等。
盖20通过从一种多层片上裁下而制得，并且包括，如该多层片所包括的，至少一个支撑层21和一个下部热封层22。盖20通过该下部热封层22热封至容器10的边沿12。支撑层21例如为厚度12至300μm的铝层。下部热封层22由其上接枝有不饱和羧酸的可热封聚合物材料制成，且厚度为2至80μm。该不饱和羧酸的接枝使得所述可热封聚合物材料与金属氧化物和/或金属盐之间可形成强的结合，并由此使盖20的下部热封层22与玻璃之间形成强的结合。下层中不饱和羧酸的存在也有助于下层22粘合于铝制的支撑层21上。
可热封聚合物材料优选为聚丙烯，且不饱和羧酸优选马来酸酐。不饱和羧酸与所述可热封聚合物材料的质量比为低于10％，优选低于2％，还优选低于1％。事实上，为了限制成本和防止可热封聚合物材料物理性能的降低--特别是温度性能的降低，接枝少量的不饱和羧酸是有利的。
为使盖与容器的密封质量受温度条件的影响更少，可热封聚合物材料有利地选自高熔点的材料。优选可热封聚合物材料选择为熔点高于115℃。当复合包装及其内容物经受消毒步骤时，确保容器和盖之间的粘合的可热封聚合物材料经受高于115℃的消毒温度，优选高于120℃的消毒温度。
聚丙烯均聚物或共聚物和聚酯由于其熔点显著高于目前介于115℃和135℃之间的消毒温度而非常适合于消毒应用。在某些消毒应用中，当消毒温度保持在上述消毒温度范围的较低部分时，高密度聚乙烯也是适合的。
图2示出了本发明的另一个复合包装1′。容器10′在其上部的外侧面包括凸起14′，用于旋拧包含相应的槽31′的帽30′。由塑料或金属制成的帽30′使得例如当盖20′被移除时容器10′可再次被封闭。也可利用帽30′来在产品的消毒步骤中提供反压力，以使施加于盖20′上的压力不会导致盖20′变形或破裂。此外，帽也可用来使盖维持在紧贴容器边沿的状态。
图2中，盖20′由一个支撑层21′、一个下层22′和一个粘合剂中间层23′构成，下层22′由其上接枝有不饱和羧酸的可热封聚合物材料制成，中间层23′用于将下层22′粘在支撑层21′上。支撑层21′例如为一种聚酯(12μm)/Siox/PP(40μm)多层膜。Siox膜使盖具有氧屏障能力。粘合剂中间层23′例如为一种厚度为2至50μm的PP层。下层22′由其上接枝有不饱和羧酸的可热封聚合物材料制成，更具体地由厚度为2至80μm的其上接枝有马来酸酐的PP制成。如此制得的盖20′是半透明的。下层22′和粘合剂中间层23′可例如以施加于支撑层21′上的多层膜共挤出。
可设计不同的多层膜--包括下部热封层并将固定于支撑层上--以例如方便盖的开启或引入赋予更好的耐油脂性或耐酸性等的功能性屏障。这些多层膜可有利地通过共挤出获得。
本发明显然可延伸到对本领域技术人员而言显而易见的所有复合包装改进方案，例如，使用其他聚合物或除铝之外的其他金属来形成支撑层，或者在支撑层上添加一个带印花(impression)的上层，等等。盖也可例如包括一个突出部(languette)，使盖抓取更容易且可通过剥除复合包装而将其开启。
试验已证明本发明的复合容器具有非常好的耐消毒步骤特性。在150cm3的玻璃容器--其边沿已经氧化锡和铬盐处理--中填充入100ml水，然后盖封，盖由50μm的铝层和55μm的接枝有1％马来酸酐的PP层构成。密封温度为160至180℃。一部分复合包装经过121℃的消毒30分钟。
消毒前后剥离值没有变化，根据边沿的宽度不同介乎8和35牛顿之间。此外，消毒前后复合包装均未显示出任何泄露。
相比之下，现有技术中没有复合包装能够用在消毒应用中。

Claims (17)

1.一种通过热封至玻璃容器(10)的边沿(12)而用于封盖该容器的多层片，所述边沿已经金属氧化物和/或金属盐处理，所述多层片至少包含一个支撑层(21)和一个下层(22)，所述下层由其上接枝有不饱和羧酸的可热封聚合物材料制成，其特征在于，所述可热封聚合物材料的熔点高于115℃。
2.权利要求1的多层片，其中所述多层片设计为将与容器(10)一起经受消毒温度Tst，且所述可热封聚合物材料的熔点高于所述消毒温度Tst。
3.前述权利要求之一的多层片，其中所述可热封聚合物材料为聚丙烯均聚物或共聚物、高密度聚乙烯或聚酯。
4.前述权利要求之一的多层片，其中所述不饱和羧酸为马来酸酐。
5.前述权利要求之一的多层片，其中所述不饱和羧酸和所述可热封聚合物材料的质量比为低于2％、优选低于1％。
6.前述权利要求之一的多层片，其中所述支撑层包含铝或为一种半透明的聚合物膜。
7.前述权利要求之一的多层片，其中所述下层为一种多层聚合物膜层。
8.前述权利要求之一的多层片，其中所述下层通过一个粘合剂层粘在所述支撑层上。
9.前述权利要求之一的多层片，其中所述玻璃的边沿的处理包括沉积铬盐、硅烷、锆盐或铝盐。
10.一种复合包装(1)，包括一个玻璃容器(10)和一个位于所述玻璃容器的边沿的可热封盖(20)，其中所述盖由一种权利要求1至9之一的多层片制成。
11.权利要求11的复合包装，设计为用于消毒。
12.权利要求10和11之一的复合包装，包括一个用于旋拧至所述容器的帽。
13.权利要求12的复合包装，其中所述帽由塑料材料或金属制成。
14.一种制造权利要求10至13之一的复合包装(1)的方法，包括以下步骤：
-提供一个带有边沿(12)的玻璃容器(10)，所述边沿已经金属氧化物和/或金属盐处理，
-提供一个至少包括一个支撑层(21)和一个下层(22)的盖(20)，所述下层由其上接枝有不饱和羧酸的可热封聚合物材料制成，
-将所述盖热封在所述容器的边沿上。
15.权利要求14的方法，还包括一个在热封步骤后进行复合包装的消毒的步骤。
16.权利要求15的方法，其中所述消毒步骤包括使所述复合包装处于115℃至135℃的温度10至60分钟的时间。
17.权利要求14至16之一的方法，包括一个将帽旋拧于所述容器上的步骤。
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* Cited by examiner, † Cited by third party
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CN105745157A (zh) * 2013-07-03 2016-07-06 阿尔费尔德塑料制品赫尔姆迈尔有限公司 用于容器，尤其是瓶的塞盖的密封垫圈
CN105745157B (zh) * 2013-07-03 2019-11-08 阿尔费尔德塑料制品赫尔姆迈尔有限公司 用于容器，尤其是瓶的塞盖的密封垫圈

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PL2303571T3 (pl) 2013-01-31
ES2392801T3 (es) 2012-12-14
BRPI0914986B1 (pt) 2019-08-13
CA2727440A1 (fr) 2010-01-07
EP2303571B1 (fr) 2012-08-08
RU2487064C2 (ru) 2013-07-10
RU2010153907A (ru) 2012-07-20
WO2010000968A1 (fr) 2010-01-07
US20110100949A1 (en) 2011-05-05
US8617674B2 (en) 2013-12-31
MX2010013442A (es) 2011-04-05
EP2303571A1 (fr) 2011-04-06
FR2932169A1 (fr) 2009-12-11
BRPI0914986A2 (pt) 2015-10-27
EP2303571B9 (fr) 2012-10-31

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