CN102006992B - 包装膜中的可剥离的复合热塑性密封剂 - Google Patents

包装膜中的可剥离的复合热塑性密封剂 Download PDF

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Publication number
CN102006992B
CN102006992B CN2009801139381A CN200980113938A CN102006992B CN 102006992 B CN102006992 B CN 102006992B CN 2009801139381 A CN2009801139381 A CN 2009801139381A CN 200980113938 A CN200980113938 A CN 200980113938A CN 102006992 B CN102006992 B CN 102006992B
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sealant
organic clay
peelable seals
sealing
thermoplastic polymer
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CN102006992A (zh
Inventor
P·基尼加基斯
K·波库萨
G·阿尔鲍姆
A·琼斯
E·弗里德里克森
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Intercontinental Great Brands LLC
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Kraft Foods Global Brands LLC
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/76—Making non-permanent or releasable joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D33/00—Details of, or accessories for, sacks or bags
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract

本发明公开一种可剥离密封结构，其包括密封层和一个或多个任选的额外层。该可剥离密封结构包括密封表面，在可剥离密封温度范围内的所有温度下，所述密封表面一旦与密封基底接触可形成可剥离密封。而且，可剥离密封结构包含热塑性聚合物和分散在至少一部分热塑性聚合内的添加剂，所述可剥离密封结构界定出密封表面。

Description

包装膜中的可剥离的复合热塑性密封剂
相关申请的交叉引用
本申请是2008年2月14日提交的、系列号为12/031,450的美国申请的继续申请并要求该美国申请的优先权，通过引用将该美国申请的全部内容合并至本文中。
发明的背景
1.发明领域
本发明涉及包括可剥离密封(peelable seal)的包装系统，特别地，本发明涉及用于形成这种可剥离密封的组合物和方法。
2.背景技术
包装在销售和营销多数产品时是重要的特性。特别地，食物产品具有相当严格的包装要求，以保持新鲜和提高货架寿命。某些医疗器械也提出了严格的包装要求以保持这种器械的无菌性。在这些应用中，包装体通常为真空包装或被气驱(gas-flushed)，随后被气密密封。虽然产品的有效包装是强制性的，但是产品包装体的各种美学性质也是重要的。例如，产品的外表在吸引消费者方面是重要的。而且，在许多应用中，特别是对于食物产品而言，包装体的可再利用性和容易打开也是重要的考虑事项。在许多应用中，易于打开包装体的性能将取决于密封的机械性质。
一种特别重要的包装结构利用可剥离的密封。在至少一个现有的包装系统中，可剥离的密封是通过将可热封的聚合材料覆盖在金属箔上而形成的。因为具有这种密封的包装通常不让空气和污染物进入，因此可剥离的密封必须也不让这些物质进入。当具有可剥离的密封的包装体被打开时，可将密封层从基底剥离开。期望的是，这种剥离可通过微弱的且相对恒定的剥离力来完成。可剥离密封的弹性性质使得不会由于包装体的弯曲和正常操作而导致密封失效。在一些现有包装中，可剥离密封是由多层片材构成的。具有这种密封的包装系统的例子包括托盘式(tray-type)食品包装体、瓶子、泡罩包装体(blister package)等等。虽然一些现有可剥离密封包装体用得较好，但一直难以构建出始终形成既阻止泄漏同时又易于被最终用户打开的气密密封的包装系统。而且，这种现有的可剥离包装系统往往在相对窄的范围内(特别是窄的温度范围内)起作用。窄的密封温度范围往往导致包装缺陷。例如，在可用温度范围的下限值时，可能形成泄漏的密封(不是气密密封的)。在可用温度范围的上限值时，形成非可剥离的密封，当打开时其被撕裂。
因此，需要一种改进的可剥离包装系统，其阻止泄漏、提供气密密封并且容易打开。
发明概述
本发明通过在至少一个实施方式中提供一种可剥离密封结构来解决现有技术的一个或多个问题。该实施方式的可剥离密封结构有利地包括密封表面，在可剥离密封温度范围的所有温度下，当与密封基底接触时，该密封表面可形成可剥离密封。而且，该实施方式的可剥离密封结构包括热塑性聚合物，以及被分散在至少一部分热塑性聚合物内的添加剂。
在本发明的另一种实施方式中，可剥离密封结构用于形成位于容器开口处的可剥离密封。该实施方式的可剥离密封结构包括密封层和一个或多个任选的额外层。有利地，密封层包括用热塑性聚合物分散的官能化的有机粘土。已发现，官能化的有机粘土颗粒被加入到常用的可热封热塑性聚合物中会在热封条件的宽广范围内提供稳定的(consistent)剥离强度。而且，可商购的有机粘土聚合物浓缩物与多种聚烯烃密封树脂的混合物有利地表现出与有机粘土装载百分数(percent load)成反比例的剥离强度。虽然利用该密封层的密封界面以稳定的模式剥离，但是即使当在各种包/袋包装体类型中密封样品包括细纹、褶皱和衬料(gusset)结构时，密封的气密完整性也不受损害。
在本发明的另一种实施方式中，提供一种包含本发明的可剥离密封结构的包装系统。本发明的包装系统包括容器部分和附着至容器部分的可剥离密封部分。密封部分包括上述本发明的密封层。
附图简述
图1A是粘合剂A型失效的示意图；
图1B是粘合剂B型失效的示意图；
图1C是分层C型失效的示意图；
图1D是破裂D型失效的示意图；
图1E是破裂E型失效的示意图；
图1F是伸长F型失效的示意图；
图1G是剥离+伸长G型失效的示意图；
图2A是单层密封结构的示意性截面图；
图2B是双层密封部分的示意性截面图；
图2C是三层密封层的示意性截面图；
图3A是包含本发明的可剥离密封结构的实施方式的袋状包装系统的示意性截面图；
图3B是图3A的袋状包装系统的侧视图；
图4A是改进品(refinement)的示意性截面图，其中密封基底包括第二密封层；
图4B是改进品的示意性截面图，其中密封基底160包括第二密封层170，可剥离密封162形成在第一密封层152和第二密封层186之间；
图5A是利用了本发明的可剥离密封结构的杯状包装系统的示意性截面图；
图5B是利用了本发明的可剥离密封结构且包含多个杯状容器的泡罩包装系统的示意性截面图；
图6是展示形成本发明的包装系统的方法的图表。
图7A提供由具有5wt％和6wt％有机粘土的密封层形成的顶部密封的剥离力与温度的曲线图；
图7B提供由HDPE、EVOH和LLDPE与EVA的混合物(添加或未添加有机粘土)三层共挤压制成的密封的剥离力与温度的曲线图；
图7C提供由层压至密封膜的箔制成的密封的剥离力与密封形成温度的曲线图；
图8是用于确定熔化温度(“Tm”)的一系列曲线图；
图9是用于确定结晶温度(“Tc”)的一系列曲线图；
图10A是一组x射线衍射图，其显示来自Nanoblend 2001的有机粘土在包含聚乙烯的密封层中的分散；
图10B是一组x射线衍射图，其显示来自Nanoblend 2101的有机粘土在包含聚乙烯的密封层中的分散；
图11提供由高频熔接机制造的密封的密封强度与密封形成温度的曲线图；
图12A提供由聚乙烯或聚乙烯与EVA的混合物通过传导密封法(conduction sealing method)制成的密封的密封强度与密封形成温度的曲线图；
图12B提供下述密封的密封强度与密封形成温度的曲线图，在该密封中至少一个密封层包括聚乙烯、EVA和有机粘土的混合物；
图13A提供表6，其总结了图12A和12B的密封强度数据；
图13B是图13A的续篇；
图14A是具有一个或多个折叠的可剥离密封的示意性截面图；
图14B是具有一个或多个折叠的可剥离密封的示意性截面图；
图15是在密封中具有折叠或弯曲的包装系统的俯视图。
优选实施方式的详细描述
现将详细参考本发明目前优选的组成、实施方式和方法，它们构成目前为发明人所知的实践本发明的最佳方式。附图并非必然按比例绘制。但要理解的是，所公开的实施方式仅为本发明示例性的，且本发明可以不同的和替代性的形式来实施。因此，本文公开的具体细节不应解释为限制性的，而仅作为本发明的任何方面的代表性的基本原则和/或仅作为教导本领域技术人员以各种方式利用本发明的代表性的基本原则。
除非在实施例或其他地方明确说明，本说明书中表示物质的量或反应条件和/或使用条件的所有数字数量在描述本发明的最大范围时要理解为被词语“大约”修饰。在所述的数字限值内实施通常是优选的。而且，除非另有说明，百分数、“份”和比例值都是以重量计；术语“聚合物”包括“低聚物”、“共聚物”、“三元共聚物”等。关于一群或一类物质对于本发明的给定目的是适合的或优选的描述暗指该群或该类物质的成员的任何两个或多个的混合物是同等适合的或优选的；以化学术语对组分的描述是指在添加至说明书中指定的任何组合物(combination)中时的组分并且不是必然地排除一旦混合时混合物的组分之间的化学相互作用；首字母缩写词或其他缩写词的第一次定义适用于相同缩写词在本文中的所有后续使用并且比照最初定义的缩写词的正常语法变化应用；而且，除另有说明，性质的测量是由与之前或之后为相同性质所提及的相同技术来确定的。
还要理解的是，本发明不限于下述的特定实施方式和方法，因为具体的成分和/或条件当然可变化。而且，本文使用的术语仅用于描述本发明的具体实施方式，而并不有意以任何方式限制本发明。
还须注意的是，如用在说明书和所附权利要求中的，除另有明确说明，单数形式“一个(a)”、“一个(an)”和“所述(the)”包括复数指代物。例如，以单数形式提及一个成分意在包括许多个这个成分。
在本申请中，当提及公开文献时，通过引用将这些文献的公开内容以它们的整体形式合并至本申请中，以更加完全地描述本发明所属的现有技术。
用在本文中的术语“有机粘土”是指有机改性的粘土。通常，这种改性使得粘土更具相容性，因而可与聚合物混合。
用在本文中的术语“平均粗糙度”(“Ra”)是指根据ANSI B46.1在整个测量长度或面积上计算的表面的平均高度。平均粗糙度通常以微米或微英寸的形式提供。
用在本文中的术语“可剥离密封”是指剥离力在每英寸样品宽度为0.5lbs至撕裂密封的力之间的密封。通常，上限值小于或等于每英寸样品宽度5lbs。在其他变体中，上限值小于或等于每英寸样品宽度4lbs，或小于膜基底上的撕裂强度。
用在本文中的术语“剥离力”是指如在ASTM F-88(通过引用合并至本文)中定义的分离两个层的力。例如，它是指通过拉动而将一英寸宽度的两个层分离所需的力。
用在本文中的术语“密封初始温度”是指以0.5lbs每英寸的剥离力形成密封时的最低温度。具体地，密封初始温度是接触要被密封的层从而促进这种密封的表面(通常是金属)的温度。在一些变体中，表面接触层的停留时间为约0.5至1秒，压力为5psi至1200psi。
术语“可剥离密封温度范围”是指这样的温度范围，在该范围两种材料之间形成的密封使得剥离力如上所述在每英寸样品宽度为0.5lbs至撕裂密封的力之间。
参考图1A-1G，提供了展示各种密封失效机制的示意图。在这些图中的每个变体中，密封100由第一密封层102的一部分与第二密封层104的一部分接触以形成密封而形成。图1A展示本发明的一个或多个实施方式中的可剥离密封的行为。当层102和104之间的密封经受将这两层拉开的力时，层102和104在分离表面106、108处相对干净地分开。这种密封失效被称作粘合剂A型失效。图1B展示一个密封，其中当密封被施加应力时，层102的结构完整性被破坏，形成撕裂口109。这种密封失效被称作粘合剂B型失效。图1C展示包括额外层以形成多层层压结构的密封。层110附着至层102，而层104附着至层112。图1C所示的失效模式是在位置114处分层。这种密封失效被称作分层C型失效。图1D展示材料失效，其中层104在靠近层102、104仍彼此粘合的区域的位置120处破裂。这种密封失效被称作破裂D型失效。图1E展示材料失效，其中层104在远离层102、104仍彼此粘合的区域的位置122处破裂。这种密封失效被称作破裂E型失效。图1F展示材料失效，其中层102和104在未包含在密封100的部分130、132处被拉伸。这种密封失效被称作伸长F型失效。最后，图1G展示材料失效，其中层102和104通过剥离机制以及同时发生的在部分136、138处的拉伸而在密封100处分离。这种密封失效被称作剥离+伸长G型失效。本发明的实施方式有利地形成经由粘合剂A型失效机制失效的可剥离密封。
在本发明的一个实施方式中，提供一种可剥离密封结构。该实施方式的可剥离密封结构包括热塑性聚合物和被分散在至少一部分热塑性聚合物中的添加剂。可剥离密封结构界定出可在可剥离密封温度范围内的所有温度下形成可剥离密封的密封表面。在该实施方式的变体中，可剥离密封温度范围是从密封初始温度到高于密封初始温度至少50°F的温度。在本发明的另一个实施方式中，可剥离密封温度范围是从密封初始温度到高于密封初始温度至少75°F的温度。在本发明的又一个实施方式中，可剥离密封温度范围是从密封初始温度到高于密封初始温度至少100°F的温度。通常，对于包装应用，密封初始温度为约170°F至约350°F。在另一种变体中，对于包装应用，密封初始温度为约170°F至约250°F。
参考图2A、2B和2C，提供了用在本发明的包装系统中的可剥离密封结构的图示。在该实施方式中，可剥离密封结构附着至基底以形成可剥离密封或密封部分。图2A是单层密封结构的示意性截面图。在该变体中，可剥离密封结构150包括密封层152。图2B是双层密封结构的示意性截面图。可剥离密封结构150包括密封层152和额外层154。图2C是三层密封层的示意性截面图。在该变体中，可剥离密封结构150包括密封层152和额外层154、156。
应当意识到的是，在图2A、2B和2C的各变体中，密封层152包含热塑性聚合物和分散在热塑性聚合物中的添加剂。在本实施方式的变体中，有用的添加剂的表面积大于100m2/g且长宽比大于10。另外，有用的添加剂是晶状的或多晶的。有用的添加剂的例子包括但不限于有机粘土。密封层152适于接触容器的基底部分以形成可剥离密封。这种容器可以是可用于包装物体的几乎任何形状。这种形状的例子包括但不限于，泡罩、托盘、包、袋和它们的组合。
已惊人地发现，由此组合物形成的密封层具有如以下更完全地描述的改善的和均匀的剥离性能。利用可剥离密封结构150的密封界面以稳定的模式剥离，即使当在各种包/袋包装体类型中膜样品包括细纹、褶皱和衬料结构时，密封的气密完整性也不受损害。可剥离密封结构150以下述组合的形式表现出稳定的可剥离行为：1)密封层152接触具有类似或相同组合物的另一密封层；2)密封层152接触由纯密封剂形成的结构(例如，有机粘土/聚乙烯层紧靠着纯聚丙烯层，有机粘土/聚乙烯层紧靠着纯聚酯层，有机粘土/聚乙烯层紧靠着纯聚乙烯层)。加工助剂，例如防结块剂、抗氧化剂、润滑添加剂(slip additive)等，被任选地包括在密封层中且不影响密封结构150的剥离模式。
额外层154、156被用来为本实施方式提供许多有用的特性。例如，额外层154、156可为包含可剥离密封部分的包装系统提供结构支持、耐热性、隔离性和改善的外观。应当意识到的是，除单层可剥离密封结构外，本实施方式还包括具有任何数目的额外层的多层结构。在本实施方式的每个变体中，多层密封结构包括具有本文所述的组合物的可剥离密封。
密封层152的进一步特征是具有各种物理和结构变化以及改进之处，某种程度上取决于期望的特定包装。在本实施方式的一个变体中，密封层152的厚度为约6微米至约120微米。在本实施方式的另一个变体中，密封层152的厚度为约6微米至约30微米。在本实施方式的又一个变体中，密封层152的厚度为约40微米至约120微米。密封层152与不含有机粘土或含不足量的有机粘土形成的类似层的进一步区别在于具有更高程度的表面粗糙度。在一个改进中，密封层152的表面粗糙度的特征是平均粗糙度为约1500至约5000埃。在另一个改进中，密封层152的表面粗糙度的特征是平均粗糙度为约2000至约4000埃。应当容易意识到，在本发明的变体中，表面粗糙度的程度和性质取决于用来形成密封层152的方法和工艺参数。各种实施方式的密封层还表现出比没有有机粘土的类似层稍微高些的拉伸模量。在一种改进中，密封层152的拉伸模量为约500至约2000MPa。
参考图3A和3B，描述了包含上述可剥离密封结构的包装系统。图3A是包含本发明的可剥离密封结构的实施方式的袋状包装系统的截面图。图3B是包含本发明的可剥离密封结构的实施方式的袋状包装系统的侧视图。包装系统160包括容器部分162和可剥离密封部分164。可剥离密封部分164附着至容器部分162。图3A图示了可剥离密封部分164和容器部分162是连续的的实施例，每个部分由相同的多层结构(即，片)形成。容器部分162可具有用于将物品包装在袋中的几乎任何形状。密封部分164包括可剥离密封结构150。在如图3A所示的变体中，可剥离密封结构150包括设置在额外层154上的密封层152。如以上关于图2A、2B和2C的描述，密封层152包含热塑性聚合物和分散在热塑性聚合物内的添加剂(例如有机粘土)。
仍参考图3A和3B，包装系统160进一步包括第二密封结构150’，该第二密封结构与可剥离密封结构150接触以形成可剥离密封170。密封170密封在包装系统160的顶侧172的开口。相似的可剥离密封任选地位于底侧174、左侧176和右侧178。可剥离密封结构150’还包括设置于额外层154上的密封层152。具体地，设置在额外层154上的密封层152的组合的第一部分形成密封结构150，而设置在额外层154上的密封层152的组合的第二部分形成密封结构150’。密封结构150、150’与容器部分162是连续的。在本实施方式的变体中，设置在额外层154上的密封层152的组合的第三部分至少部分地形成容器部分162。有利地，包装系统160适于包含物品180(即，可为一个或多个物品)。可被包装的物品180的例子包括，但不限于，食物产品和灭菌物品(例如，医疗器械)。
参考图4A和4B，图示了如用在袋状包装系统中的可剥离密封部分164的变体。图4A是下述改进的示意性截面图，在该改进中密封层152基本上被限制在可剥离密封部分164的附近。这种变体是通过限制有机粘土的加入或沉积不同的层于密封结构164附近来实现的。这种变体还包括内层182和一个或多个额外层154。图4B是一种改进的示意性截面图，在该改进中包装系统160包括第二密封层186，可剥离密封170被形成在第一密封层152和第二密封层186之间。在后一种改进中，密封层152最低限度地(如果有的话)延伸进容器部分162。而且，在该改进中，容器部分162任选地包括不同于第一密封层152的衬垫层182。在此变体的进一步改进中，密封部分164进一步包括设置在第一密封层152和/或第二密封层186之上的一个或多个额外的聚合物层154。在该改进的特别有用的实施例中，一个或多个额外的聚合物层154至少部分地形成容器部分162。
参考图5A和5B，图示了利用本发明的可剥离密封结构和刚性容器部分的包装系统的变体。图5A提供利用本发明的可剥离密封结构的杯状包装系统的示意性截面图。包装系统190包括可剥离密封结构150和容器部分194的密封开口192。可剥离密封结构150的外围部分设置在容器部分194的基底部分196上并与其接触。图5B提供包括多个杯状容器的泡罩包装系统的示意性截面图。泡罩包装系统200包括可剥离密封结构152和容器部分206、208的密封开口202、204。可剥离密封结构152的一部分设置在容器部分206、208的基底部分210、212之上并与其接触。
如上所述，本发明的各种实施方式的可剥离密封结构包括例如有机粘土的添加剂。有用的有机粘土的例子包括，但不限于，高岭土、蒙脱土-绿土粘土、膨润土粘土、伊利石粘土和它们的组合。U.S.专利第5,780,376号、第5,739,087号、第6,034,163号和第5,747,560号提供了可用于实践本发明的纳米粘土(nanoclay)的特定实施例。通过引用将这些专利的每一个的全部公开内容合并至本文。在本发明的一个改进中，有机粘土的存在量为热塑性聚合物和有机粘土的组合重量的1wt％至20wt％。在本实施方式的另一个改进中，有机粘土的存在量为热塑性聚合物和有机粘土的组合重量的2wt％至10wt％。
用在可剥离密封层152中的有机粘土通常包含多个颗粒。在一个变体中，有机粘土包含的多个颗粒具有至少一个小于200nm的空间尺寸。在另一个变体中，有机粘土包含的多个颗粒具有至少一个小于100nm的空间尺寸。在另一个变体中，有机粘土包含的多个颗粒具有至少一个小于50nm的空间尺寸。在又一个变体中，有机粘土包含的多个颗粒具有大于或等于1nm的空间尺寸。在又一个变体中，有机粘土包含的多个颗粒具有大于或等于5nm的空间尺寸。在另一个变体中，有机粘土包含小片(platelet)，小片具有至少20埃的平均间隔(separation)。在另一个变体中，有机粘土包含的小片具有至少30埃的平均间隔。在又一个变体中，有机粘土包含的小片具有至少40埃的平均间隔。通常，在与热塑性聚合物混合之前，有机粘土包含的小片具有20至45埃的平均间隔。有利地，一旦与热塑性混合物混合，有机粘土保持此片状状态，使得平均间隔被保持或增加。
如上所述，可剥离密封层152还包括热塑性聚合物。合适的热塑性聚合物包括，但不限于，尼龙、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯和它们的混合物。在一个变体中，热塑性聚合物包含选自乙烯丙烯酸、乙烯丙烯酸乙酯、乙烯离子交联聚合物(例如，可从E.I.du Pont deNemours and Company获得的
Figure BPA00001248575200111
系列树脂)和它们的组合的成分。在本发明的实践中，聚烯烃是特别有用的热塑性聚合物。在一个变体中，聚烯烃选自乙烯、丙烯、乙酸乙烯酯和它们的组合的均聚物和共聚物。特别是当添加剂是有机粘土时，聚烯烃与乙烯乙酸乙烯酯(“EVA”)的混合物被发现在形成可剥离密封中特别有用。
本发明的各种实施方式的容器部分由几乎任何用于包装的材料形成。这种材料包括，但不限于，纸、金属箔、聚合物片材、金属化的聚合物片材和它们的组合。更具体的例子包括取向的或非取向的聚酯、取向的或非取向的聚丙烯、取向的或非取向的尼龙和它们的组合。这些材料的每一个可被涂布或未涂布。有用的涂料的例子包括，但不限于，清漆、硝基漆(lacquer)、粘合剂、油墨和隔离材料(即，PVDC)。用于包装医疗器械的有用材料包括高密度聚烯烃。可购自Dupont，Inc.的
Figure BPA00001248575200121
(由高密度聚乙烯纤维制成的合成材料)是这种用于包装医疗器械的材料的一个例子。
在本发明的又一个实施方式中，提供一种形成上述包装系统的方法。参考图6，提供了图示本实施方式的方法的图表。在步骤a)中，将热塑性聚合物(“TP”)与有机粘土(“OC”)混合以形成有机粘土-聚合物混合物(“OCB”)。在一个变体中，这种混合发生在压出机220中。密封层152随后在步骤b)中由有机粘土-聚合物混合物通过从模具222压出而形成。在一个变体中，额外层通过向模具222提供来自额外的压出机(例如压出机230)的材料来形成。在本发明的一个改进中，热塑性聚合物和有机粘土在混合器224中被预混合，随后被引入到压出机220中。通常，密封层152与一个或多个额外层154、156一起形成或形成在一个或多个额外层154、156之上(如图2所示)。随后在步骤c)中形成开放的包装系统160。该过程可包括侧边被密封以形成图3-4的袋状结构的步骤。在一个变体中，开放的包装系统160的形成出现在步骤b)中。
在本发明的一个变体中，通过将母料与纯聚合物混合而将热塑性聚合物与有机粘土混合。在该变体中，母料包含有机粘土和至少一部分热塑性聚合物。在该改进中，母料通常包括10至80wt％的有机粘土。
形成密封层152的步骤通过任何能够由热塑性组合物形成层或膜的方法来完成。这些方法的例子包括，但不限于，压出、共挤压、吹塑、流延、挤压吹塑和薄膜吹塑(film blowing)。
仍参考图6，本实施方式的方法任选地进一步包括将物品180放置到开放的包装系统160内(步骤d)。通常，物品180位于容器部分162内。在物品180被放置在容器部分162内后，密封层152在步骤e)中与密封基底(即，密封结构150’)接触以形成密封。密封可通过本领域已知的许多密封方法来完成。例子包括，但不限于，热传导密封、超声密封和感应密封。
以下实施例说明本发明的各种实施方式。本领域技术人员将认识到属于本发明的实质和权利要求的范围内的许多变体。
图7A提供由密封层形成的密封的剥离力与温度的曲线图，其中密封层是由共挤压的HDPE和LLDPE/EVA以及有机粘土混合物(即，双层)制成。在这些试验中，撕开密封包的密封。图中提供了有机粘土装载量为5wt％和6wt％的曲线图。图7A证实本发明的密封可在50°F的密封形成温度范围内通过稳定的打开力打开。而且，观察到密封强度在200°F至250°F的温度范围内是可剥离的且是相对平坦的。图7B提供剥离力与密封形成温度的曲线图。图中提供了不含有机粘土的参照物以及具有5wt％有机粘土的测试样品的曲线图。参照样品是由2.4密耳的膜构成的，所述膜是由高密度聚乙烯(“HDPE”)、乙烯乙烯醇、线型低密度聚乙烯(“EVOH”)和乙烯乙酸乙烯酯混合物与LLDPE的混合物的三层共挤压而形成的。测试样品是由2.4密耳的膜构成的，所述膜是由HDPE、EVOH以及LLDPE、EVA和5wt％有机粘土的混合物的三层共挤压而形成的。参照样品和测试样品在Sentinal密封机中被密封。根据ASTM F-88测定剥离力。图7B中的点的密封时间为0.50秒，密封钳压力为30PSI。观察到，对于具有有机粘土的样品，剥离力在175°F至265°F的温度范围内的变化差异较小。而且，用有机粘土形成的密封在密封形成的整个温度范围内是可剥离的。图7C提供了由层压至密封膜的箔制成的密封的剥离力与密封形成温度的曲线图。在该试验中，48ga PET/50ga箔被粘性地层压至3.2密耳的测试膜上。测试膜是由LDPE/LLDPE/有机粘土混合物制成的。密封被制成相同结构的膜。参照样品和测试样品在Sentinal密封机中被密封，并根据ASTM F-88测定剥离力。图7C清楚地显示，在300°F至425°F的温度范围形成了稳定的可剥离密封。
在单螺杆压出机中将NanoblendTM MB 2001或NanoblendTM MB2101(“母料”)与商业上的聚乙烯(“PE”)混合物袋密封剂混合，其中本发明的密封剂层在第二薄膜吹塑操作中形成。根据ASTM D638(表1)、利用50mm/min的测试速度评价所产生的膜的拉伸性质。在测试之前，所有样品在30℃退火21天。发现包含有机粘土的膜比没有有机粘土的膜具有更高的模量，而不损害强度或最大伸长率。对于3wt％有机粘土，模量增加了75％，对于6wt％有机粘土模量增加了150％，对于9wt％有机粘土模量增加了240％。
表1.由未添加有机粘土和添加了各种量的有机粘土形成的膜的拉伸性质
Figure BPA00001248575200141
*未填充-TS：双螺杆挤出的纯净PE
表2总结VICAT热挠曲测试的结果。已观察到，Vicat软化温度随着有机粘土含量的增加而增加，具有9wt％纳米粘土的样品，其软化温度增加了23℃。表2的数据表明，向聚乙烯密封剂成分中添加有机粘土基本上不影响结晶度。
表2.Vicat软化温度随有机粘土含量变化
Figure BPA00001248575200151
也评估了结晶温度和熔化温度。这些测量是通过根据ASTM D3417测量熔化与结晶的焓来进行的。图8提供了测定含有变化的量的NanoblendTM MB 2001的层的熔化温度(“Tm”)的曲线图，而图9提供了测定含有变化的量的NanoblendTM MB 2001的层的结晶温度(“Tc”)的曲线图。已观察到，与纯聚乙烯样品相比，添加纳米粘土基本上不影响Tm和Tc。图10A提供了一组x射线衍射图，其显示来自Nanoblend 2001的有机粘土在包含聚乙烯的密封层中的分散。图10B提供了一组x射线衍射图，其显示来自Nanoblend 2101的有机粘土在包含聚乙烯的密封层中的分散。x射线衍射数据证实，有机粘土小片的平均间隔被保留(即，最低程度的附聚)。这种间隔的保留使得本发明实施方式实现了有关可剥离性、拉伸强度、HDT和断裂伸长的性质。
表3和表4提供由本发明形成的密封层的表面粗糙度测量。在这些实施例中，形成了共挤压的双层。较光滑的面是来自不具有有机粘土的HDPE层。较粗糙的面是具有有机粘土的LLDPE/EVA层。本发明的含有有机粘土的层被发现比不含有机粘土的类似样品具有更高的粗糙度。而且，具有6wt％有机粘土的样品比具有5wt％有机粘土的样品具有更大量的表面粗糙度，表明表面粗糙度的量往往增加约10％或更少。
表3.在密封剂层中具有5wt％有机粘土的双层样品的较光滑的面
Figure BPA00001248575200161
表4.在密封剂层中具有5wt％有机粘土的双层样品的较粗糙的面
Figure BPA00001248575200162
表5.在密封剂层中具有6wt％有机粘土的双层样品的较光滑的面
表6.在密封剂层中具有6wt％有机粘土的双层样品的较粗糙的面
Figure BPA00001248575200171
图11提供了密封强度与密封形成温度的曲线图。在这些实验中，利用高频熔接机来形成密封。在这种熔接机中，温度是由拨盘(dial)位置来设定的。图11提供了密封强度与拨盘位置的关系。估计温度被提供在图11的顶部。图11再次证实了聚乙烯、EVA和有机粘土的组合的协同作用，由此组合形成的密封在宽的密封形成温度范围内是可剥离的。
以约1000psi的压力和约8秒的密封时间形成一系列25.4mm的密封。在这些实验中，使用了液压机。虽然这些条件比用在通常的商业密封操作中的条件苛刻，但在这些条件下的可剥离密封的形成进一步说明本发明的制剂形成可剥离密封的能力。图12A和12B提供了密封层的各种组合的密封强度与密封形成温度的曲线图。在这些实验中，在第一密封层和第二密封层之间形成密封。在图12A中，每个密封层包括聚乙烯或聚乙烯与EVA的混合物。通常，对于这些组合，在110℃至140℃的温度范围内，密封强度随着温度的增加而增加。在图12B中，至少一个密封层包括聚乙烯、EVA和有机粘土的混合物。对于以这种方式形成的密封，图12B图示了在110℃至140℃的温度范围内的可剥离密封的形成。图13A和13B提供表6，其总结了图12A和12B的密封强度数据，同时表征了失效模式的类型(参见图1A-1G)。表6清楚地显示了在宽的温度范围内的可剥离密封的形成。
在本发明的又一个实施方式中，提供了适于提供防漏密封的可剥离密封，其中所述防漏密封中具有一个或多个褶皱。参考图14A和14B，提供了具有一个或多个折叠的可剥离密封的示意性截面图。可剥离密封250包括第一密封层252和第二密封层254。第一密封层252包括弯曲258、260和折叠262。相似地，第二密封层254包括弯曲264、266。第一密封层252包括第一密封表面270，而第二密封层254包括第二密封表面272。外密封表面274、276附着至额外层，如以上关于图1-5的描述中所述。第一密封表面270与第二密封表面272接触以形成密封280。图14B提供了第二密封层254包括最少的弯曲或折叠的图示。
密封层252和254的成分的细节与以上所述相同。特别地，第一密封层252和第二密封层254的至少一个包括热塑性聚合物和分散在热塑性聚合物中的添加剂。在一个变体中，添加剂的存在量足以在可剥离密封温度范围内的所有温度下在第一密封层252和第二密封层254之间形成可剥离密封280。如上所述，在一个改进中，可剥离密封温度范围为从密封初始温度到至少比密封初始温度高100°F的温度。在特别有用的变体中，添加剂是分散在至少一部分热塑性聚合物中的有机粘土。在此变体中，第一密封层252和第二密封层254中的一个或两者具有约170°F至约350°F的密封初始温度。关于添加剂、有机粘土和热塑性聚合物的额外的详细信息已在上文叙述。
参考图15，提供了往往在密封中具有折叠或弯曲的包装系统的俯视图。包装体290包括可剥离密封292、294、296。应当意识到，只有一面或两面具有可剥离密封的包装也是可能的。包装体290被图示为含有食品298。在包装过程中，食品298存在于容器部分300内导致容器壁302起皱。如以上关于图14A和14B的描述中所述的，容器壁302的这种起皱诱导在可剥离密封292、294、296中形成弯曲和折叠。如图15中所示的包装体被发现具有减少的泄露发生率。例如，在利用如上所述的有机粘土成分的包装体中的氧水平被发现平均比商业上可获得的密封组合物低。而且，利用含有染料的液体测试也发现具有低泄露发生率。
虽然本发明的实施方式已被图示和描述，但并不意味着这些实施方式图示和描述了本发明的所有可能的形式。相反，说明书的叙述仅是描述性的叙述而不是限制性的，且要理解可作出各种改变而不背离本发明的实质和范围。

Claims (21)

1.一种可剥离密封，其包括：
具有第一密封表面的第一密封层；
具有第二密封表面的第二密封层，所述第一密封表面接触所述第二密封表面以界定出密封，使得所述第一密封层和所述第二密封层的一个或两个中具有一个或多个细纹或褶皱，其中所述第一密封层和第二密封层的至少一个包括：
热塑性聚合物；和
分散在至少一部分所述热塑性聚合物内的有机粘土，其中所述第一密封层和所述第二密封层的至少一个具有170°F至350°F的密封初始温度，所述第一密封层和所述第二密封层的至少一个具有500至2000MPa的拉伸模量，所述有机粘土包含小片，所述小片的平均间隔为至少20埃，密封表面的平均粗糙度为1500至5000埃。
2.权利要求1的可剥离密封，其中所述有机粘土包含多个颗粒，所述颗粒具有至少一个小于200nm的空间尺寸。
3.权利要求1的可剥离密封，其中所述有机粘土包含小片，所述小片的平均间隔为至少30埃。
4.权利要求1的可剥离密封，其中所述有机粘土包括选自以下的粘土：高岭土、蒙脱土-绿土粘土、膨润土粘土、伊利石粘土和它们的组合。
5.权利要求1的可剥离密封，其中所述有机粘土的存在量为所述热塑性聚合物与所述有机粘土的组合重量的1wt％至20wt％。
6.权利要求1的可剥离密封，其中所述有机粘土的存在量为所述热塑性聚合物与所述有机粘土的组合重量的2wt％至10wt％。
7.权利要求1的可剥离密封，其中所述热塑性聚合物包含选自以下的成分：尼龙、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯、乙烯的共聚物、丙烯的共聚物、乙烯乙酸乙烯酯和它们的混合物。
8.权利要求1的可剥离密封，其中所述热塑性聚合物包含选自以下的成分：乙烯丙烯酸、乙烯丙烯酸乙酯、乙烯离子交联聚合物和它们的组合。
9.权利要求1的可剥离密封，其中所述热塑性聚合物包含乙烯乙酸乙烯酯。
10.一种可剥离密封，其包含：
具有第一密封表面的第一密封层；
具有第二密封表面的第二密封层，所述第一密封表面接触所述第二密封表面以界定出密封，使得所述第一密封层和所述第二密封层的一个或两个中具有一个或多个细纹或褶皱，其中所述第一密封层和所述第二密封层的至少一个包括：
热塑性聚合物；和
分散在所述热塑性聚合物内的有机粘土，所述有机粘土的存在量足以在可剥离密封温度范围内的所有温度下在所述第一密封层和所述第二密封层之间形成可剥离的密封，所述可剥离密封温度范围为从密封初始温度至比所述密封初始温度高至少100°F的温度，其中所述第一密封层和所述第二密封层的至少一个具有170°F至350°F的密封初始温度，所述第一密封层和所述第二密封层的至少一个具有500至2000MPa的拉伸模量，所述有机粘土包含小片，所述小片的平均间隔为至少20埃，密封表面的平均粗糙度为1500至5000埃。
11.一种包装系统，其包括：
容器部分；和
附着至所述容器部分的可剥离密封部分，所述可剥离密封部分包括：
具有第一密封表面的第一密封层；
具有第二密封表面的第二密封层，所述第一密封表面接触所述第二密封表面以界定出密封，使得所述第一密封层和所述第二密封层的一个或多个中具有一个或多个细纹或褶皱，其中所述第一密封层和第二密封层的至少一个包括：
热塑性聚合物；和
分散在所述热塑性聚合物内的有机粘土，所述有机粘土的存在量足以在可剥离密封温度范围内的所有温度下在所述第一密封层和所述第二密封层之间形成可剥离的密封，所述可剥离密封温度范围为从密封初始温度至比所述密封初始温度高至少100°F的温度，其中所述第一密封层和所述第二密封层的至少一个具有170°F至350°F的密封初始温度，所述第一密封层和所述第二密封层的至少一个具有500至2000MPa的拉伸模量，所述有机粘土包含小片，所述小片的平均间隔为至少20埃，密封表面的平均粗糙度为1500至5000埃。
12.权利要求11的包装系统，其中有机粘土被分散在至少一部分所述热塑性聚合物中，所述有机粘土的表面积大于100m2/g且长宽比大于10，其中所述可剥离密封结构界定出密封表面。
13.权利要求11的包装系统，其中所述有机粘土包含选自以下的粘土：高岭土、蒙脱土-绿土粘土、膨润土粘土、伊利石粘土和它们的组合。
14.权利要求11的包装系统，其中所述有机粘土的存在量为所述热塑性聚合物与所述有机粘土的组合重量的1wt％至20wt％。
15.权利要求11的包装系统，其中所述有机粘土包含多个颗粒，所述颗粒具有至少一个小于200nm的空间尺寸。
16.权利要求11的包装系统，其中所述热塑性聚合物包括选自以下的聚合物：尼龙、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯、乙烯的共聚物、丙烯的共聚物和它们的混合物。
17.权利要求16的包装系统，其中所述热塑性聚合物包含乙烯乙酸乙烯酯。
18.权利要求11的包装系统，其中所述密封部分进一步包括设置在所述第一密封层上的一个或多个额外的聚合物层。
19.权利要求11的包装系统，所述包装系统进一步包含容纳在其内的食品。
20.权利要求11的包装系统，其中所述密封部分包括沿两个或多个独立的侧边的可剥离密封。
21.权利要求11的包装系统，其中所述容器部分具有选自泡罩、托盘、包、袋和它们的组合的形状。
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