CN1075088C - 用于液体容器的模制密封塞 - Google Patents

用于液体容器的模制密封塞 Download PDF

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CN1075088C
CN1075088C CN94192354A CN94192354A CN1075088C CN 1075088 C CN1075088 C CN 1075088C CN 94192354 A CN94192354 A CN 94192354A CN 94192354 A CN94192354 A CN 94192354A CN 1075088 C CN1075088 C CN 1075088C
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L·D·布尔恩斯
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Abstract

一种用于液体容器的模制密封塞，它含有热塑弹性体和发泡剂。该模制密封塞尤其适于用作酒瓶的合成塞。该模制密封塞不允许氧气进入容器中，也不从容器的内含物中吸收氧，可用开塞钻开启而本身不会膨胀、破碎或开裂，不污染容器中的液体，使容器在塞紧密封塞后可立即水平放置，且可在其表面上长时间保持印制标记。

Description

用于液体容器的模制密封塞
相关申请互相参照
本申请是于1993年5月5日申请并仍在进行中的美国专利申请08/058,914的部分继续申请。
技术领域
本发明涉及用于液体容器的模制密封塞和制造该密封塞的组合物及方法。本发明一方面涉及由热塑弹性体和发泡剂混合而成的、用于制造瓶类、尤其是酒瓶类的模制塞的组合物和由该组合物制造的产品；另一方面涉及模制密封塞如酒瓶塞的制造方法以及一种紧塞的酒瓶的制造方法。
发明背景
最普通的用于制造瓶塞的材料是天然软木，但采用软木对瓶塞的生产和销售都有许多明显的不利。就颜色、干燥状况、收缩性或扩张性、脆性、对容器的粘附以及密封性等而言，软木塞具有易变性，这对其生产，价格和产品的性能都会有不利的影响。当作为酒瓶的密封塞时，软木可能会带入一种异味，使消费者拒绝接受酒产品，而且有近10％的瓶装酒因模制天然软木带来的意想不到的污染而被废弃。另外，木材供应的急剧减少使采用软木制造瓶塞正变得越来越昂贵。
目前已有各种努力在寻找天然软木瓶塞的替代品。其中酒类容器的螺旋盖因不具备传统软木瓶塞的外观、礼仪或传奇气氛而被认为是很不合适的替代品。一些人工软木塞业已被开发。近来以注模泡沫热塑塑料开发密封塞的努力产生了许多问题，尤其是在产品的成本、性能和消费者的接受方面。有些这种密封塞显示出明显的污染产品和(或)低的抗氧渗透的倾向，而且在产品的大小、外观、重量上具有很差的均一性，在其它对生产、销售和性能很重要的因素方面，由泡沫热塑塑料制造的合成密封塞也较差。
在一特定的用于液体容器的泡沫热塑塑料密封塞的注射模塑过程中，热塑性组合物被注射到一较冷的模具中，使在塞子表面形成一致密的“外皮”和一多孔的泡沫状内部结构。密封塞的组成与其外皮和多孔内部的结构关系可能对终产品的密封能力是至关重要的。一些泡沫热塑密封塞就面临因起皱的外皮而带来的塞子与容器之间产生裂隙的问题。其它先有技术合成塞也有各种不同的密封问题，例如受压后不能很快恢复正常大小，因而在塞子塞进之后容器必须朝上放置一段时期才能获得可靠的密封效果。另外，以往的人工合成塞不能在特定的时间内有效地保持住其上的印迹。
美国专利4,363,849公开了一种具有天然软木塞外观的热塑密封塞的制备方法，但它采用了特殊的模塑设备并需要将冷模腔中的空气逐步排除，代之以注射入的热塑性树脂状材料，通过控制最小排气量或其它方法来维持模中的高压，如约110MPa。美国专利4,188,457公开了一种用于制造酒瓶塞的热塑性组合物。该组合物含有二氧化硫和水，二氧化硫被认为是氧气净化剂。但该方法并不可取，因为二氧化硫或其生成的偏二亚硫酸盐会使封闭容器中的液体着色。
本发明的目的和概述
本发明的目的在于提供一种用于液体容器的模制密封塞，它包括一种热塑弹性体(“TPE”)和一种发泡剂，装于液体容器上时，它具有强的抗氧渗透能力，对液体产品很少或不产生污染。该模制密封塞也适用于非液体的容器。
本发明的另一目的在于提供一种易于制成液体容器如酒瓶的合适密封塞的组合物。
本发明的另一目的在于提供制造用于液体容器、具有天然软木塞的优良特性同时最好没有软木塞各种缺陷的密封塞的一种组合物。
本发明的另一目的在于提供用于液体容器的密封塞的注射模塑方法。
本发明的另一目的在于提供用于制造插入后可立即可靠地密封液体容器和/或可保持印刷标记的密封塞的一种新型组合物和方法。
本发明的模制密封塞最好模塑成大小适于酒瓶的木塞形状，它具有大小、外观和重量的均匀性以及符合审美要求。它的人工颜色、仿大理石表面质地和表面上尤其是其一端或两端上能够压花标记，使其在外观上和天然软木塞明显区别开来。此外，该密封塞可用标准的装瓶设备方便地插入液体容器中，并可用传统的开塞钻开启而不发生粘附、破碎或膨胀。由于开启后不发生膨胀，本发明的密封塞可重新插入液体容器中，在容器未完全空时将其重新密封。该模制密封塞在插入容器中后可以立即与内含液体接触，因此在水平放置容器之前不需为使塞与容器之间良好密封而等待一段时间。该模制密封塞也可长期地保持其上的印刷标记。
参照以下的详细说明和附图，本发明的各个方面将会更为明白。
对附图的简要说明
图1描绘的是用于酒瓶的一种模制密封塞，其明显具有一仿大理石表面质地，一端压花标记，侧部印制图案和径向边缘。
本发明的详细说明
本发明一方面提供了一种用于液体容器的模制密封塞，它可作为天然软木塞的合适替代品，并可控制其大小、形状、表面纹理、表面润滑性、回弹性、伸缩性、密度分布和美观的外形。
因此本发明提供用于液体容器特别是酒瓶的一种模制密封塞，它包括使用适当比例的一种热塑弹性体和一发泡剂，制造可以密封酒瓶的模制塞，防止泄漏和空气中氧气进入酒中，同时也基本不从酒中或塞子与酒之间的空气中吸收氧。该模制密封塞能够用一开塞钻开启而不引起塞自身的膨胀、破碎或开裂(这种扩张、破碎或开裂会使酒变得不可口或使塞子无法使用)。
该模制密封塞可以印上标记，包括在其与容器接触的表面上，而且插入塞子的容器可以立即水平放置。该模制密封塞可经长时间之后使用以适应酒类需经一定的时间(比如可以是两年或两年以上)才达到合适的口感的需要，而且它具有对醇、酸或碱的耐溶解性，因而可使酒不被污染。该模制密封塞最好还包括一种或多种润滑剂、颜料、填料或其它可提高其性能和/或产量的添加剂。该模制密封塞不包括过去用来提高合成塞的抗渗透性但对酒类有污染的氧气净化剂，如二氧化硫。
本发明的另一方面在于，该模制密封塞是由包括一种或多种热塑弹性体和一种或多种发泡剂的组合物形成的。该模制密封塞的硬度，可作为热塑弹性体硬度的间接表征，一般是为约60A至约90A，特别是约70A至约85A，优选为约71A或75A至约80A。热塑弹性体在组合物中的含量一般为从约70％至约97％，特别是约80％至约95％，优选为约90％至约95％(除非特别指出，本文的百分比值均为体积百分比)。热塑弹性体对酒类液体很少有或没有任何污染作用，具有适合的压缩力以提高其密封能力和耐久力，易于加工，能加速生产周期和提高生产速率。另外，选择的热塑弹性体符合美国食品医药管理局(FDA)关于间接的食物添加剂与食物相接触时的要求。
在优选的实施方案中，该热塑弹性体包含苯乙烯嵌段共聚物，进一步优选还包含一种或多种苯乙烯-乙烯-丁烯-苯乙烯(“SEBS”)共聚物、苯乙烯-乙烯-丁烯共聚物、苯乙烯-丁二烯-苯惭烯共聚物、苯乙烯-丁二烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、苯乙烯-异戊二烯共聚物、苯乙烯-乙烯-丙烯-苯乙烯共聚物和苯乙烯-乙烯-丙烯共聚物。包含有苯乙烯嵌段共聚物、特别是SEBS对模制密封塞是特别有利的(尤其当密封塞作为酒瓶塞时)，因为和其它热塑弹性体比较，这类共聚物具有优越的性能。许多这种共聚物的商品名为KRATON。在更优选的实施方案中，这种苯乙烯嵌段共聚物是SEBS，其示例包括J-VONR、DYNAFLEXGS6771-000和DYNAFLEX GX6768-1000，它们具有抗臭氧、耐热和耐久性，而且耐水、碱、酸和醇。J-VONR为J.Von Ltd.Partnership,Leominser,Massach-usetts的产品，DYNAFLEXGS6771-000和GS6768-1000为CC&P Porland,Oregon产品。
组合物中发泡剂的含量一般大于1％，特别是至少为约1.3％或1.5％或2.0％，不超过约9.0％或5.0％或4.0％或3.0％。复合物中发泡剂的含量优选为约1.3％至约3％、特别是约1.5％至2.5％，更优选含量为约2％。发泡剂的精确含量是本领域专业人员综合考虑具体的聚合物、发泡剂、其它组份以及模塑条件后可确定的。过多的发泡剂一般会使模制塞内部结构产生太多的大孔，造成模塞本身具有多孔结构和其生产制造中均匀性差。使用发泡剂过少会使模制塞的孔目不足或孔的尺寸不足，这样会给使用开塞钻开启模制塞造成困难并带来其它问题。
在一优选实施方案中，发泡剂Quantum Chemical Corp.,USI Division,Cincinnati,Ohio的商品SpectratechTMFM1150H，它是基于聚烯烃的组合物，组分包括有低密度聚乙烯基的吸热性泡沫浓缩物、以CH3-(CH2)n-CH3为结构的树脂占50％，另外50％为碳酸氢钠(NaHCO3)和柠檬酸的混合物。该发泡剂具有快速排气、增加连续运转次数、改善密度分布和模制品表面质量的优点。其它合适的发泡剂有偶氮二酰胺、Ozodecarbonoxide和碳酸氢钠。在不超出本发明的实质和范围之内，其它发泡剂亦可采用。
在另一实施方案中，一种或多种填料可与热塑弹性体和其他原料并且。填料例如包括碳酸钙。如果使用这种填料，其在组合物中的用量可达20％甚至以上，但最好至多约5％。该填料可节省原料的消耗。其它填料为本领域专业人员所熟知的。
在本发明的另一具体实施方案中，热塑弹性体和其它原料的混合物中加入了粉末状或液态颜料。颜料在总组合物中的含量一般小于约1％。在加入到热塑弹性体和其他的主要原料中之前，颜料最好先和热塑性树脂状材料如聚丙烯和/或部分热塑弹性体进行预混。
在一优选实施方案中，本发明组合物包含约96％的热塑弹性体、约2％的发泡剂、约2％的低密度聚丙烯和少量所需的颜料。在另一优选实施方案中，颜料、聚丙烯和约2％的热塑弹性体先进行预混，然后以均相混合物的形式加入到余下的热塑弹性体和发泡剂中。在组合物还含有填料的另一实施方案中，本发明组合物包含约75％至约95％的热塑弹性体、约1.5％至约2.5％的发泡剂以及至多约20％的填料。
在另一优选实施方案中，在模塑成型工艺之前或之后，加入了润滑剂如脂肪酸、聚硅氧烷、醇或水(包括矿质水)，它可以使密封塞较方便地插入容器。该润滑剂优选是一脂肪酸，在总的组合物中的含量小于约0.5％。
本发明另一方面提供了一具有圆边的模制密封塞，该圆边优选是凸起的，该圆边位于密封塞的上下两端。这一点尤其是对含有热塑弹性体的模制密封塞有用，但也可适于由非热塑弹性体的传统热塑性树脂制造的密封塞。这种圆边可允许密封塞方便而有效地塞入容器中(尤其是酒瓶中)，使密封塞在塞入容器内时可保持一均匀的边界面，据信这样有助于使容器在塞入密封塞后能够立即被平置侧放。
本发明的一个特点是模制密封塞能够在其与容器接触的表面上长久地保持所印的标记。模制密封塞的表面一般非常光滑，无法在其上印制或保持住印刷标记。为了能够保持标记，虽然本发明也使用热塑性树脂，但所用的组合物最好包括热塑弹性体，优选是苯乙烯嵌段共聚物，特别是SEBS共聚物。模制密封塞在经模塑之后，其表面经一处理工艺以便印刷标记。这种处理工艺包括将密封塞加高强度的电磁辐射，范围最好是可见光或近可见光(比如紫外光)区域。处理工艺的一个示例是印刷工业中标准的电晕预处理工艺。这种处理优选在印刷之前进行，但也可在印刷之后进行。
本发明的又一特征在于液体容器如酒瓶在塞入本发明的模制密封塞之后，一般可在约4小时之内，特别是在约1小时之内，优选可马上被水平放置。模制密封塞具有这样的性能是因为本发明的组合物可使模制密封塞获得一内部孔径，从而使其在从压力状态下被释放的约4至5秒之内恢复到其原有尺寸的至少约90％。模制密封塞具有的圆边据信也利于它的这种性能。
因此，当模制密封塞被压入容器之后，它在约4至5秒之内恢复到大约其原有的尺寸，从而使容器可以立刻被水平放置而不会使内装液体泄露，也不会影响塞与容器之间的密封。例如，当容器为酒瓶时，在它们装架之前不需要一段使其立着的时间。
本发明的又一实施方案中在总的组合物中还可加入一种或多种其它原料，包括化学发泡活化剂和可提高密封塞产量和/或性能的其它添加剂。例如，如果需要的话，可加入一种增加容器中液体芳香和/或味道的原料。
本发明进一步的特征在于该模制密封塞可用标准的注射模塑工艺来制造。
在一模塑成型工艺的示例中，将构成组合物的本体原料完全混合均匀，然后经进一步处理使之适于注射到一注塑模具中。在另一容器中，将颜料、聚丙烯和少量的热塑弹性体(最好为SEBS共聚物)混合成均相。然后将准备好的原料和带有颜料的混合物一般在约0.02秒至约6秒、特别是在约0.03秒至约2秒、最好在约0.04秒至约1秒的时间内注射到模具中。该模具具有所需的形状，最好是酒瓶塞的形状。模塑成型的压力一般为约1.34MPa至约6.2MPa，特别是为约2.07MPa至约5.51MPa，优选为约2.76MPa至约4.82MPa。模塑成型的温度一般为约149℃至约288℃，特别是为约163℃至约218℃，优选为约177℃至约221℃，更优选为约190.6℃。混合物在模具中停留的时间一般为约20秒至约90秒，特别是为约30秒至80秒，优选为约35秒至60秒。模塑成型的过程越快越好，且其中不需特殊的排气过程。
在一优选实施方案中，组合物以一定的速率和温度注射到模具中，使软化或熔化的组合物在模具中无规地盘绕起来，就如线料自由地落在瓶中一样，这样就在沿模制密封塞成品的表面产生可见的无规卷曲线，如图1所示。在另一实施方案中，组合物以一定速率和温度注射到模具中，不产生任何无规的盘绕。
此外，在一个模塑循环周期的开始阶段，模具中的空气优选被协同组合物的注射步骤的真空辅助装置从模中抽出。抽真空步骤可在注射阶段的最后时刻或在注射期完成后马上进行。在注射阶段过早使用真空辅助装置会使模制密封塞内部产生过大的孔容积而使塞子本身过于松软。不使用真空辅助装置则会延长模塑循环的周期。
经过一段足够长的时间，组合物在模中已有效地固化后，打开模具将模制密封塞移去。
模塑成型的时间、压力、排气状况、冷却过程、真空辅助、成品取出以及其它与注射模塑有关的因素，取决于总的组合物中各原料的具体组合情况、模具的大小和形状以及其它为普通专业人员所熟知的因素。
本发明的一个特点是所用模具上，最好是在其一端或两端，能够雕饰一个所需的标记，比如酒窖的象征或字母，该标志将会转印到所制的塞子上。
以上的各个实施方案总的说来是作为说明例证的，是非限制性的，本发明的范围将在所附的权利要求中说明，而且所有符合本发明的实质和范围的变动，都应包括在本发明的范围之中。

Claims (15)

1．一种用于可开启地塞住酒瓶的模制瓶塞，它可由含有热塑性弹性体和发泡剂的组合物制得，其中，所述热塑性弹性体是选自苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物和苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物的至少一种苯乙烯嵌段共聚物。
2．权利要求1的模制瓶塞，其特征在于，所述热塑性弹性体是苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物。
3．权利要求1的模制瓶塞，其特征在于，所述模制瓶塞含有填料。
4．权利要求3的模制瓶塞，其特征在于，所述填料占模制瓶塞的5％至20％重量。
5．权利要求1的模制瓶塞，其特征在于，所述模制瓶塞包括颜料。
6．权利要求1的模制瓶塞，其特征在于，所述模制瓶塞包括润滑剂。
7．权利要求6的模制瓶塞，其特征在于，所述润滑剂选自脂肪酸、聚硅氧烷、醇和水。
8．权利要求7的模制瓶塞，其特征在于，所述润滑剂为脂肪酸。
9．权利要求1的模制瓶塞，其特征在于，所述模制瓶塞具有圆边。
10．权利要求9的模制瓶塞，其特征在于，所述圆边是凸起的。
11．权利要求1的模制瓶塞，其特征在于，所述模制瓶塞具有大理石表面纹理。
12．权利要求1的模制瓶塞，其特征在于，所述模制瓶塞上具有印刷标记。
13．权利要求1的模制瓶塞，其特征在于，所述发泡剂是偶氮二酰胺或碳酸氢钠。
14．权利要求1的模制瓶塞，其特征在于，所述发泡剂占树脂组合物的1％-5％重量。
15．一种制造带有印制标记的权利要求1的模制瓶塞的方法，它包括：
(a)将热塑性弹性体和发泡剂混合成为一适于注射到一注塑模具中的混合物；
(b)．将所述混合物注射到一注塑模具中；
(c)．将所述混合物在所述注塑模具中维持成型直至其有效地固化成为模制瓶塞；
(d)．将所述模制瓶塞从所述注塑模具中取出；
(e)．将所述模制瓶塞进行包括高强电磁辐射的处理，以及
(f)．在所述模制瓶塞的表面印制标记，以得到所述带有印制标记的模制瓶塞。
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