CN101186800B - 包装膜中可剥离的复合热塑性密封剂 - Google Patents

包装膜中可剥离的复合热塑性密封剂 Download PDF

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Publication number
CN101186800B
CN101186800B CN2007101532392A CN200710153239A CN101186800B CN 101186800 B CN101186800 B CN 101186800B CN 2007101532392 A CN2007101532392 A CN 2007101532392A CN 200710153239 A CN200710153239 A CN 200710153239A CN 101186800 B CN101186800 B CN 101186800B
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Prior art keywords
sealing
organic clay
thermoplastic polymer
strippable
sealed structure
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CN2007101532392A
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CN101186800A (zh
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P·基尼加基斯
K·波库萨
G·阿尔鲍姆
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Intercontinental Great Brands LLC
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Kraft Foods Global Brands LLC
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Priority to CN201310053242.2A priority Critical patent/CN103213756B/zh
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • 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
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/52—Details
    • B65D75/58—Opening or contents-removing devices added or incorporated during package manufacture
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
    • B29C65/481—Non-reactive adhesives, e.g. physically hardening adhesives
    • B29C65/4815—Hot melt adhesives, e.g. thermoplastic adhesives
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles
    • B29C66/431—Joining the articles to themselves
    • B29C66/4312—Joining the articles to themselves for making flat seams in tubular or hollow articles, e.g. transversal seams
    • B29C66/43121—Closing the ends of tubular or hollow single articles, e.g. closing the ends of bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/53—Joining single elements to tubular articles, hollow articles or bars
    • B29C66/534—Joining single elements to open ends of tubular or hollow articles or to the ends of bars
    • B29C66/5346—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat
    • B29C66/53461—Joining single elements to open ends of tubular or hollow articles or to the ends of bars said single elements being substantially flat joining substantially flat covers and/or substantially flat bottoms to open ends of container bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
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Abstract

一种包装膜中可剥离的复合热塑性密封剂，具体涉及可剥离的密封结构，包括密封层和一个或多个任选的其它层。该可剥离的密封结构包括在可剥离的密封温度范围内全部温度下与密封基底接触时可形成到可剥离密封中的密封表面。另外，该可剥离的密封结构包括热塑性聚合物和分散于至少一部分该热塑性聚合物之内的添加剂，具有限定密封表面的可剥离的密封结构。

Description

包装膜中可剥离的复合热塑性密封剂
技术领域
本发明涉及包装系统，其包括可剥离的密封，且特别地，本发明涉及用于形成该可剥离的密封的组合物和方法。
背景技术
包装是销售和推销大多数产品时重要的特征。食物，特别地，具有相当严格的包装要求以保存新鲜度和提高储存寿命。一些医疗设备也存在严格的包装要求以保存该设备的无菌性。这些应用中，包装典型地为真空包装或充气的且随后气密地密封。虽然产品的有效包装是强制性的，但是产品包装的各种美观性也是重要的。例如，产品的外观在引起消费者关注中是重要的。另外，许多应用中且，特别地，对于食物，包装的可再用性和容易打开也是重要的考虑。一些应用中，容易打开包装的能力将取决于该密封的机械性能。
一种特别重要的包装结构采用了可剥离的密封。在至少一种现有技术包装系统中，通过将可热密封的聚合物材料涂覆到金属箔上形成可剥离的密封。由于结合了这种密封的包装经常不可渗透空气和污染物，可剥离的密封也不许是不能渗透这些材料。将具有可剥离密封的包装打开时，可以将密封层从基底中剥开。期望采用低的和相对恒定的剥离力可以实现这种剥离。该可剥离密封的弹性使得该包装的弯曲和正常处理中不会发生密封的失效。一些现有技术包装中，可剥离的密封由多层片材构成。具有该密封的包装系统的实例包括盘型食物包装、瓶或气泡包装等。虽然一些现有技术可剥离的密封包装表现相当好，但是难以构成始终如一地形成防止渗漏的气密性密封同时最终使用者容易打开的包装系统。另外，这种现有技术可剥离的包装系统趋于在较窄的范围内、且特别是窄的温度范围内操作。窄的密封温度范围趋于产生包装缺陷。例如，在可使用的温度范围的底端，可能形成泄漏的密封(并非气密性密封)。在可使用的温度范围的高端，形成打开时撕裂的不可剥离的密封。
由此，存在对于改进的可剥离的包装系统的需求，其防止渗漏、提供气密性密封，和容易打开。
发明内容
本发明通过在至少一种实施方式中提供可剥离的密封结构，解决了一种或多种现有技术的问题。该实施方式的可剥离的密封结构有益地包括，在可剥离的密封温度范围内的全部温度下与密封基底接触时可形成到可剥离密封中的密封表面。另外，该实施方式的可剥离的密封结构包括热塑性聚合物，和分散于至少一部分该热塑性聚合物之内的添加剂。
本发明的另一实施方式中，可剥离的密封结构用于在容器开口处形成可剥离的密封。该实施方式的可剥离的密封结构包括密封层和一个或多个任选的附加的层。有益地，该密封层包括分散于热塑性聚合物之内的功能化有机粘土。发现，将功能化有机粘度结合到通常使用的可热密封的热塑性聚合物之内，提供了宽范围的热密封条件下一致的剥离强度。另外，可商购获得的有机粘土聚合物浓缩物与宽范围的聚烯烃密封剂树脂的共混有益地显示了与有机粘土的百分比加载量成反比的剥离强度。虽然采用该密封层的密封界面以一致的方式剥离，但是即使在各种袋/囊包装类型中密封试样包括皱纹、褶皱和结点板构型时也不会损害密封的气密性完整性。
本发明的另一实施方式中，提供了结合了本发明的可剥离的密封结构的包装系统。本发明的包装系统包括容器部分和连接于该容器部分的可剥离的密封部分。该密封部分包括前述的本发明的密封层。
附图说明
图1A为粘合剂A型失效的示意图；
图1B为粘合剂B型失效的示意图；
图1C为层压体C型失效的示意图；
图1D为断裂D型失效的示意图；
图1E为断裂E型失效的示意图；
图1F为拉伸F型失效的示意图；
图1G为剥离+拉伸G型失效的示意图；
图2A为单层密封结构的示意横截面；
图2B为双层密封部分的示意横截面；
图2C为三层密封层的示意横截面；
图3A为囊状包装系统的示意横截面，其结合了本发明的可剥离密封结构的实施方式；
图3B为图3A的囊状包装系统的侧视图；
图4A为其中密封基底包括第二密封层的改进的示意横截面；
图4B为其中密封基底160包括第二密封层170的改进的示意横截面，具有形成于第一密封层152和第二密封层186之间的可剥离的密封162；
图5A为采用了本发明的可剥离的密封结构的杯状包装系统的示意横截面；
图5B为采用了本发明的可剥离的密封结构的且结合了多个杯状容器的气泡包装系统的示意横截面；
图6为阐述形成本发明的包装系统的方法的图表；
图7A提供了剥离力相对于由具有5wt％和6wt％有机粘土的密封层形成的顶盖密封的温度的曲线；
图7B提供了剥离力相对于由HDPE、EVOH、和LLDPE与EVA的共混物的三层共挤出而制得的密封的温度的曲线，具有和不具有添加的有机粘土；
图7C提供了剥离力相对于由层压到密封膜上的箔制得的密封的密封形成温度的曲线；
图8为用于确定熔融温度(“Tm”)的一组曲线；
图9为用于确定结晶温度(“Tc”)的一组曲线；
图10A为显示包含聚乙烯的密封层之内Nanoblend 2001中有机粘土的分散的一组X-射线衍射图；
图10B为显示包含聚乙烯的密封层之内Nanoblend 2001中有机粘土的分散的一组X-射线衍射图；
图11提供了密封强度相对于由脉冲热封机制得的密封的密封形成温度的曲线；
图12A提供了密封强度相对于由聚乙烯或者聚乙烯与EVA的共混物通过传导密封方法制得的密封的密封形成温度的曲线；
图12B提供了密封强度相对于其中至少一个密封层包括聚乙烯、EVA、和有机粘土的共混物的密封的形成温度的曲线；
图13A提供了概括图12A和12B的密封强度数据的表6；
图13B为图13A的延续部分。
具体实施方式
现在将详细地参照本发明的目前优选的组合物、实施方式和方法，其构成了实施发明者目前已知的发明的最佳模式。附图并不必须依比例衡量。但是，将理解的是，所公开的实施方式仅是本发明的示例，本发明可以以不同的和替换的方式来实施。由此，本文中所公开的具体详细内容并非解释为限定，而仅是本发明各个方面的代表性基础，和/或用于教导本领域技术人员不同地应用本发明的代表性基础。
除了在实施例中，或者另外清楚指明时，该说明书中表明材料的量或者反应和/或使用的条件的所以数量，将被理解为由描述本发明的最宽范围中的词语“约”来修正。通常优选在所述数值限度之内实施。另外，除非清楚地相反陈述，百分比、“份数”、和比例值是按重量计算；术语“聚合物”包括“低聚物”、“共聚物”、“三元共聚物”等；描述一组或一类材料适合或优选用于与本发明有关的给定目的，含义是任意两种或多种该组或该类成员的混合物是相等适合的或优选的；化学术语中组成的描述表示在添加到本说明书中规定的任意组合中时的组成，且并非必须地排除一旦混合的混合物的组成之中的化学相互作用；首字母缩略词或其它缩写的第一定义适用于本文中相同所写的所有随后使用，且对最初定义的所写的正常语法变化加以必要的变更；且，除非清楚地相反地陈述，性能的测量是通过对于相同性能在先或在后引用的相同技术来确定的。
也将理解的是，本发明并非限定于下面所述的具体实施方式和方法，因为具体组分和/或条件可以，当然地，变化。另外，本文中所使用的术语学仅用于描述本发明的特定实施方式的目的，且并非在于以任意方式限定。
也必须指出的是，该说明书和所附权利要求中使用的单数形式“一个(a)”、“一个(an)”、和“这个(the)”包括复数指示物，除非上下文清楚地另外指出。例如，以单数形式提及一种组分旨在包括多种组分。
该申请之中，提及出版物时，这些出版物的公开内容由此全部引入本申请作为参考，以更全面地描述本发明所属于的技术的状态。
本文中所使用的术语“有机粘土”含义为有机改性的粘土。典型地，这种改性赋予粘土更大相容性且由此可与聚合物混合。
本文中所使用的术语“平均粗糙度”(“Ra”)含义为依据ANSI B46.1在整个测量长度或面积之内计算的表面的平均高度。经常以微米或微英寸为单位来提供。
本文中所使用的术语“可剥离的密封”含义为剥离力在0.5 lbs/1英寸样品宽度到撕裂密封的力之间的密封。典型地，上限为小于或等于5 lbs/1英寸样品宽度。其它变形中，上限为小于或等于4 lbs/1英寸样品宽度，或者小于膜基底上的撕裂强度。
本文中所使用的术语“剥离力”含义为将两个层分开的力，如ASTM F-88(引入作为参考)中所定义的那样。例如，通过牵引将1英寸的两个层分开所必需的力。
本文中所使用的术语“密封开始温度”含义为形成具有0.5 lbs/英寸的剥离力的密封时的最低温度。具体地，密封开始温度为接触待密封的一个层或多个层由此促进该密封的表面(典型地为金属)的温度。一些变形中。该表面接触层时的停留时间为约0.5～1秒且压力为5psi～1200psi。
术语“可剥离密封温度范围”含义为在两种材料之间形成密封时的温度范围，使得剥离力在0.5 lbs/1英寸样品宽度到撕裂密封的力之间，如前所述。
参照图1A-1G，提供了阐述各种密封失效原理的示意图。在这些附图的每种变形中，密封100是由一部分第一密封层102与一部分第二密封层104的接触而形成的，由此形成密封。图1A阐述了依据本发明的一种或多种实施方式的可剥离的密封的行为。当层102和104之间的密封经受作用于将这些层拉开的力时，层102、104在分离表面106、108上相对干净地分开。这种密封失效称为粘合剂A型失效。图1B阐述了一种密封，其中当形成应力109撕裂该密封时层102的结构完整性失效。这种密封失效称为粘合剂B型失效。图1C阐述了一种密封，其包括其它层以形成多层层压体结构。层110粘着于层102同时层104粘着于层112。图1C中所示的失效模式为位置114处的分层。这种密封失效称为分层C型失效。图1D阐述了一种材料失效，其中层104在靠近其中层102、104仍彼此粘着的区域的位置120处断裂。这种密封失效称为断裂D型失效。图1E阐述了一种材料失效，其中层104在远离其中层102、104仍彼此粘着的区域的位置122处断裂。这种密封失效称为断裂E型失效。图1F阐述了一种材料失效，其中层102和104在并未结合到密封100中的部分130、132处拉伸。这种密封失效称为拉伸F型失效。最后，图1G阐述了一种材料失效，其中层102、104通过在部分136、138具有同时发生的拉伸的剥离原理而在密封100处分开。这种密封失效称为剥离+拉伸G型失效。本发明的实施方式有益地形成借助于粘合剂A型失效原理而失效的可剥离的密封。
本发明的一种实施方式中，提供了可剥离的密封结构。这种实施方式的可剥离的密封结构包括热塑性聚合物和分散于至少一部分该热塑性聚合物之内的添加剂。该可剥离的密封结构限定了在可剥离的密封温度范围内的全部温度下可形成到可剥离密封中的密封表面。在这种实施方式的变形中，该可剥离的密封温度范围为从密封开始温度到高于该密封开始温度至少50
Figure 2007101532392_5
的温度。本发明的另一种实施方式中，该可剥离的密封温度范围为从密封开始温度到高于该密封开始温度至少75
Figure 2007101532392_6
的温度。本发明的仍另一种实施方式中，该可剥离的密封温度范围为从密封开始温度到高于(above)该密封开始温度至少100
Figure 2007101532392_7
的温度。典型地，对于包装应用来说，该密封开始温度为约170
Figure 2007101532392_8
～约350
Figure 2007101532392_9
。另一变形中，对于包装应用来说，该密封开始温度为约170
Figure 2007101532392_10
～约250
Figure 2007101532392_11
。
参照图2A、2B、和2C，提供了本发明的包装系统中所使用的可剥离的密封结构的示意图。这种实施方式中，该可剥离的密封结构粘贴到基底上以形成可剥离的密封或者密封部分。图2A为单层密封结构的示意横截面。这种变形中，可剥离的密封结构150包括密封层152。图2B为双层密封结构的示意横截面。可剥离的密封结构150包括密封层152和其它层154。图2C为三层密封结构的示意横截面。这种变形中，可剥离的密封结构150包括密封层152和其它层154、156。
应当理解的是，在图2A、2B和2C的每种变形中，密封层152包括热塑性聚合物、和分散于该热塑性聚合物之内的添加剂。这种实施方式的变形中，有用的添加剂的表面积大于100m2/g且长宽比大于10。另外，有用的添加为晶体或多晶体。有用的添加剂的实例包括，但并非限定于，有机粘土。使密封层152适合于接触容器的基底部分以形成可剥离的密封。这种容器可以是基本上适用于包装物体的任意形状的。这种形状的实例包括，但并非限定于，气泡、盘、袋、囊及其组合。
令人吃惊地发现，由这种组合物形成的密封层具有如下更彻底描述的改进的和均匀的剥离性能。利用可剥离密封结构150的密封的界面以一致的形状剥离，该密封的气密完整性不会被损害，即使各种袋/囊包装类型中膜样品包括皱纹、褶皱和结点板构型时。可剥离的密封结构150在下列组合方面显示一致的可剥离的行为：1)密封层152接触类似或相同组成的另一密封层；2)密封层152接触由纯密封剂形成的结构(例如，有机粘土/聚乙烯层相对于纯的聚丙烯层，有机粘土/聚乙烯层相对于纯的聚酯层，有机粘土/聚乙烯层相对于纯的聚乙烯层)。加工助剂如抗粘连剂、抗氧剂、滑爽剂等可以任选地包含于该密封层中，且不会影响密封结构150的剥离模式。
其它层154、156用于给这种实施方式提供各种有用的特征。例如，其它层154、156可以提供结构支持、耐热性、阻隔性、和改进的外观给结合了可剥离的密封部分的包装系统。也应当理解的是，除了单层可剥离的密封结构之外，这种实施方式包括具有任意数量的其它层的多层结构。在这种实施方式的每种变形中，该多层密封结构包括具有本文中所述的组合物的可剥离的密封。
密封层152的进一步特征在于各种物理和结构变化和改进，其一定程度上取决于期望的具体包装。在这种实施方式的一种变形中，密封层152的厚度为约6微米至约120微米。在这种实施方式的另一种变形中，密封层152的厚度为约6微米至约30微米。在这种实施方式的仍另一种变形中，密封层152的厚度为约40微米至约120微米。密封层152进一步区别于不采用或者采用不足量的有机粘土形成的类似层，具有更高程度的表面粗糙度。一种改进中，密封层152的表面粗糙度特征为约1500～约5000埃的平均粗糙度。另一改进中，密封层152的表面粗糙度特征为约2000～约4000埃的平均粗糙度。应当容易理解的是，本发明的各种变形中，表面粗糙度的程度和质量取决于用于形成密封层152的方法和工艺参数二者。各种实施方式的密封层也显示相对于无有机粘土的类似层稍微更高的拉伸模量。一种改进中，该密封层152的拉伸模量为约500～约2000MPa。
参照图3A和3B，描述了结合了前述可剥离的密封结构的包装系统。图3A为结合了本发明的可剥离的密封结构的一种实施方式的囊状包装系统的横截面。图3B为结合了本发明的可剥离的密封结构的一种实施方式的囊状包装系统的侧视图。包装系统160包括容器部分162和可剥离的密封部分164。可剥离的密封部分164粘着于容器部分162。图3A阐述了一种实例，其中可剥离的密封部分164和容器部分162是连续的，各自由相同的多层结构(即，片材)形成。容器部分162可以基本上具有适用于在囊中包装物体的任意形状。密封部分164包括可剥离的密封结构150。在图3A中所示的变形中，可剥离的密封结构150包括置于其它层154之上(over)的密封层152。如前与图2A、2B、和2C的描述相关地描述的那样，密封层152包括热塑性聚合物和分散于该热塑性聚合物之内的添加剂如有机粘土。
仍参照图3A和3B，包装系统160进一步包括接触可剥离的密封结构150以形成可剥离密封170的第二密封结构150’。密封170在包装系统160的顶侧172的开口处密封。将类似的可剥离密封置于底侧174、左侧176、和右侧178上。可剥离的密封结构150’也包括置于其它层154之上的密封层152。具体地，置于其它层154之上的密封层152的组合的第一部分形成密封结构150，同时置于其它层154之上的密封层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相连。这种实施方式的变形中，置于其它层154之上的密封层152的组合的第三部分至少部分地形成容器部分162。有益地，使包装系统160适合于容纳物体180(即，可以是一个或多个物体)。可以包装的物体的实例包括，但并非限定于，食品和消毒物体(例如，医疗器械)。
参照图4A和4B，阐述了囊状包装系统中所使用的可剥离的密封部分164的变形。图4A为一种改进的示意横截面，其中密封层152基本上受限于可剥离密封部分164的附近。通过限制有机粘土的引入或者通过在密封结构164的附近中沉积截然不同的层，实现了这种变形。这种变形进一步包括内层182和一个或多个其它层154。图4B为一种改进的示意横截面，其中包装系统160包括第二密封层186，且在第一密封层152和第二密封层186之间形成可剥离的密封170。在后一种改进中，密封层152最低限度地延伸，无论在任何程度上，到容器部分162。另外，在这种改进中，容器部分162任选地包括内层182，其不同于第一密封层152。在这种变形的进一步改进中，密封部分164进一步包括一个或多个其它聚合物层154，其位于第一密封层152和/或第二密封层186之上。在这种改进的特别有用的实例中，一个或多个其它聚合物层154至少部分地形成容器部分162。
参照图5A和5B，阐述了采用本发明的可剥离的密封结构、具有刚性容器部分的包装系统的变形。图5A提供了采用本发明的可剥离的密封结构的杯状包装系统的示意横截面。包装系统190包括可剥离的密封结构150和容器部分194的密封开口192。将外围部分的可剥离的密封结构190置于容器部分194的基底部分196之上且与其接触。图5B提供了气泡包装系统的示意横截面，其结合了多个杯状容器。气泡包装系统200包括可剥离的密封结构152和容器部分206、208的密封开口202、204。将一部分可剥离的密封结构190置于容器部分206、208的基底部分210、212之上且与其接触。
如前所述，本发明的各种实施方式的可剥离的密封结构包括添加剂如有机粘土。有用的有机粘土的实例包括，但并非限定于，高岭石、蒙脱土-蒙脱石粘土(montmorillonite-smectite clays)、膨润粘土(bentonite clays)、伊利粘土(illite clays)及其组合。US 5,780,376、5,739,087、6,034,163、和5,747,560提供了适用于实施本发明的纳米粘土的具体实例。这些专利的每一个的全部公开内容由此引入作为参考。在本发明的一种改进中，该有机粘土的存在量为热塑性聚合物和有机粘土的总重的1wt％～20wt％。在本发明的另一种改进中，该有机粘土的存在量为热塑性聚合物和有机粘土的总重的2wt％～10wt％。
用于可剥离的密封层152的有机粘土典型地包括多个颗粒。一种变形中，该有机粘土包括具有至少一种小于200nm的空间尺寸的多个颗粒。另一种变形中，该有机粘土包括具有至少一种小于100nm的空间尺寸的多个颗粒。另一种变形中，该有机粘土包括具有至少一种小于50nm的空间尺寸的多个颗粒。仍另一种变形中，该有机粘土包括具有大于或等于1nm的空间尺寸的多个颗粒。仍另一种变形中，该有机粘土包括具有大于或等于5nm的空间尺寸的多个颗粒。另一种变形中，该有机粘土包括平均间距为至少20埃的片晶(platelet)。仍另一种变形中，该有机粘土包括平均间距为至少30埃的片晶。仍另一种变形中，该有机粘土包括平均间距为至少40埃的片晶。典型地，在与热塑性聚合物混合之前，该有机粘土包括平均间距为20～45埃的片晶。有益地，在与热塑性聚合物混合时，该有机粘土保持在这种剥离状态下，使得平均间距得以保持或增加。
如前所述，可剥离的密封层152也包括热塑性聚合物。示意的热塑性聚合物包括，但并非限定于，尼龙、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯及其混合物。一种变形中，该热塑性聚合物包括选自乙烯丙烯酸(ethylene acrylic acid)、乙烯丙烯酸乙酯(ethylene ethyl acrylate)、乙烯离聚物(ethylene Ionomer)(例如，可从E.I.du Pont de Nemours and Company获得的Surlyn系列树脂)及其组合的组分。聚烯烃为实施本发明时特别有用的热塑性聚合物。一种变形中，该聚烯烃选自乙烯、丙烯、乙酸乙烯酯的均聚物和共聚物，及其组合。发现聚烯烃与乙烯乙酸乙烯酯(ethylene vinyl acetate)(“EVA”)的共混物特别适用于形成可剥离的密封，特别是在添加剂为有机粘土时。
本发明各种实施方式的容器部分基本上由用于包装的任意材料来形成。这种材料包括，但并非限定于，纸张、金属箔、聚合物片材、金属化聚合物片材，及其组合。更具体的实例包括，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，及其组合。这些材料的每一种可以是涂覆的或未涂覆的。示意涂层的实例包括，但并非限定于，清漆、漆、粘合剂、油墨、和阻隔材料(即，PVDC)。适用于包装医疗器械的材料包括高密度聚烯烃。可从Dupont，Inc.商购获得的Tyvek
Figure 2007101532392_13
(由高密度聚乙烯纤维制得的合成材料)为这种用于包装医疗器械的材料的实例。
本发明的仍另一实施方式中，提供了形成如前所述的包装系统的方法。参照图6，提供了阐述这种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-聚合物共混物(“OCB”)。一种变形中，这种混合在挤出机220中发生。随后在步骤b)中通过由该有机粘土-聚合物共混物从模具222中挤出形成密封层152。一种变形中，通过从其它挤出机(例如挤出机230)中提供材料到模具222而形成其它层。在本发明的一种改进中，将热塑性聚合物和有机粘土在混合器224中预混合且随后引入到挤出机220中。典型地，将密封层152与一个或多个其它层154、156(如图2中所示)一起形成，或者形成于其上。随后在步骤c)中形成打开的包装系统160。该方法可以包括其中将侧边密封以形成图3-4的囊结构的步骤。一种变形中，在步骤b)期间形成打开的包装系统160。
在本发明的一种变形中，通过将母料与纯聚合物混合，将热塑性聚合物与有机粘土来混合。这种变形中，该母料包括有机粘土和至少一部分热塑性聚合物。这种改进中，该母料典型地包括10～80wt％的有机粘土。
通过能够由热塑性聚合物制备层或膜的任意方法实现了形成密封层152的步骤。这种方法的实例包括，但并非限定于，挤出、共挤出、吹塑、浇铸、挤出吹塑、和薄膜吹塑。
仍参照图6，本实施方式的方法任选地进一步包括将物体180置于打开的包装系统160中(步骤d)。典型地，物体180驻留在容器部分162中。将物体180置于容器部分162中之后，将密封层152与密封基质(即，密封结构150’)在步骤e)期间接触以形成密封。可以通过本领域中已知的多种密封方法实现密封。实例包括，但并非限定于，传导加热密封、超声密封、和感应密封。
下列实施例阐述了本发明的各种实施方式。本领域技术人员将认识到在本发明的精神和权利要求的范围之内的各种变形。
图7A提供了对于由共挤出的HDPE和LLDPE/EVA与有机粘土共混物(即双层)制得的密封层形成的密封，剥离力相对于温度的曲线。这些试验中，将密封袋的密封拉开。提供了有机粘土载荷为5和6wt％的曲线。图7A证实了本发明的密封可以通过一致的开启力打开，在50
Figure 2007101532392_14
的密封形成温度范围内。另外，观察到密封强度是可剥离的且在200
Figure 2007101532392_15
～250
Figure 2007101532392_16
的温度范围内是相对平坦的。图7B提供了剥离力相对于密封形成温度的曲线。提供了无有机粘土的参照和具有5wt％有机粘土的试验样品的曲线。参照样品由高密度聚乙烯(“HDPE”)、乙烯乙烯醇(“EVOH”)、线性低密度聚乙烯、和乙烯乙酸乙烯酯与LLDPE的共混物的三层共挤出形成的2.4mil膜组成。试验样品由HDPE、EVOH、和LLDPE EVA与5wt％有机粘土的共混物的的三层共挤出形成的2.4mil膜组成。将参照和试验样品在Sentinal密封器中密封。依据ASTMF-88测量剥离力。图7B中各点的密封时间为0.50秒且密性封卡爪压力为30PSI。发现，对于具有有机粘土的样品来说，在175
Figure 2007101532392_17
～265
Figure 2007101532392_18
的温度范围内剥离力的变化改变较小。另外，采用有机粘土形成的密封在整个密封形成的范围内是可剥离的。图7C提供了对于由层压到密封膜上的箔制得的密封，剥离力相对于密封形成温度的曲线。这种试验中，将48g PET/50g箔粘合地层压到3.2mil试验膜上。该试验膜由LDPE/LLDPE/有机粘土共混物制得。将该密封制成相同构造的膜。将参照和试验样品在Sentinal密封器中密封，依据ASTM F-88测量剥离力。图7C清楚地显示了在300
Figure 2007101532392_19
～425
Figure 2007101532392_20
的温度范围下形成一致可剥离的密封。
将NanoblendTM MB 2001或NanoblendTM MB 2101(母料)与商购的聚乙烯(“PE”)共混物囊密封剂在单螺杆挤出机中混合物，在第二膜喷吹操作中形成本发明的密封剂层。采用50mm/min的试验速度，依据ASTM D638(表1)评价获得的膜的拉伸性能。试验之前，将所有样品在30℃下退火处理21天。发现包括有机粘土的膜相对于无有机粘土的膜具有更高模量，并不会牺牲强度或最大伸长率。模量增加对于3wt％有机粘土为75％，对于6wt％有机粘土为150％，且对于9wt％有机粘土为240％。
表1：采用无添加的有机粘土和各种量的有机粘土形成的膜的拉伸性能。
Figure 2007101532392A00800011
*未填充的-TS：双螺杆挤出的纯的PE
表2概括了VICAT热变形试验的结果。发现维卡软化温度随着有机粘土含量的增加而增加，具有9wt％有机粘土的样品显示23℃的软化温度增加。表2的数据表明，通过将有机粘土加到聚乙烯密封剂组合物中，基本上不会影响结晶度。
表2：维卡软化温度随有机粘土含量的变化
Figure 2007101532392A00800021
也评价了结晶温度和熔融温度。通过依据ASTM D 3417测量溶化和结晶的焓，进行这些测量。图8提供了测量熔融温度(“Tm”)的曲线，同时图9提供了测量结晶温度(“Tc”)的曲线，对于含有不同量的NanoblendTM MB 2001层。观察到Tm和Tc相对于纯的聚乙烯样品基本上不受纳米粘土的加入的影响。图10A提供了一组x-射线衍射图，显示了Nanoblend 2001中有机粘土在包含聚乙烯的密封层之内的分散。图10B提供了一组x-射线衍射图，显示了Nanoblend 2101中有机粘土在包含聚乙烯的密封层之内的分散。该x-射线衍射数据证实了有机粘土片晶的平均分离得以保持(即，最小的聚集)。这种分离的保持使得能实现关于本发明实施方式的可剥离性、拉伸强度、HDT、和断裂伸长率的性能。
表3和4提供了对于本发明形成的密封层的表面粗糙度测量。这些实例中，形成共挤出的双层。较平滑侧来自于不具有有机粘土的HDPE层。较粗糙侧为具有有机粘土的LLDPE/EVA层。发现本发明的含有机粘土的层相对于不具有有机粘土的类似样品具有更高程度的粗糙度。另外，具有6wt％有机粘土的样品现对于具有5wt％有机粘土的样品具有更大量的表面粗糙度，由此显示，表面粗糙度的量趋于增加约10％或更小。
表3：密封剂层中具有5wt％有机粘土的双层样品的较光滑侧
Figure 2007101532392A00800022
表4：密封剂层中具有5wt％有机粘土的双层样品的较粗糙侧
Figure 2007101532392A00800031
表5：密封剂层中具有6wt％有机粘土的双层样品的较光滑侧
表6：密封剂层中具有6wt％有机粘土的双层样品的较粗糙侧
Figure 2007101532392A00800033
图11提供了密封强度相对于密封形成温度的曲线。这些实例中，采用脉冲热封机来形成密封。在这种密封机中，通过刻度盘位置来设定温度。图11提供了密封强度随刻度盘位置的变化。在图11顶部提供了估算的温度。图11，再次，证实了组合聚乙烯、EVA、和有机粘土的协同效应，同时由这种组合形成的密封在宽的密封形成温度范围内是可剥离的。
在约1000psi的压力下制得一系列25.4mm密封，密封时间为约8秒。这些试验中，使用液压机。虽然这些条件相对于典型商业密封操作中采用的条件更苛刻，但是这些条件下可剥离密封的形成进一步证实了本发明的配方能形成可剥离密封的能力。图12A和12B提供了对于密封层的各种组合，密封强度相对于密封形成温度的曲线。这些试验中在第一密封层和第二密封层之间形成密封。图12A中，每个密封层包括聚乙烯或者聚乙烯与EVA的共混物。通常，对于这些组合在110℃～140℃温度范围内，密封强度随温度增加而增加。图12B中，至少一个密封层包括聚乙烯、EVA、和有机粘土的共混物。对于以这种方式形成的密封，图12B阐述了在110℃～140℃温度范围内可剥离密封的形成。图13A和13B提供了观看图12A和12B中密封强度数据的表6，同时表征了失效模式的类型(参见图1A-1G)。表6清楚地显示了在宽范围的温度内形成可剥离的密封。
虽然阐明和描述了本发明的实施方式，但是并非在于这些实施方式阐明和描述了本发明的全部可能的形式。相反地，该说明书中所使用的词语是描述性而非限定性的词语，且认为可以进行各种改变而不背离本发明的精神和范围。

Claims (29)

1.一种可剥离的密封结构，包括：
热塑性聚合物；
分散于至少一部分该热塑性聚合物之内的有机粘土，其中该有机粘土的存在量为热塑性聚合物和有机粘土的总重的1wt％～20wt％，并且其中该可剥离的密封结构包括限定密封表面的密封层，该密封表面在可剥离的密封温度范围内的全部温度下可形成到可剥离密封中，该可剥离的密封温度范围为从密封开始温度到高于该密封开始温度至少100°F的温度，其中该密封开始温度为170°F～350°F，该有机粘土包括平均间隔为至少20埃的片晶，该密封表面的平均粗糙度为1500～5000埃，该密封层的拉伸模量为500～2000MPa。
2.权利要求1的可剥离的密封结构，其中该有机粘土包括具有小于200nm的空间尺寸的多个颗粒。
3.权利要求1的可剥离的密封结构，其中该有机粘土包括平均间隔为至少30埃的片晶。
4.权利要求1的可剥离的密封结构，其中该有机粘土包括选自高岭石、蒙脱土-蒙脱石粘土、膨润粘土、伊利粘土及其组合的粘土。
5.权利要求1的可剥离的密封结构，其中该有机粘土的存在量为热塑性聚合物和有机粘土的总重的2wt％～10wt％。
6.权利要求1的可剥离的密封结构，其中该热塑性聚合物包括选自尼龙、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯及其混合物的组分。
7.权利要求1的可剥离的密封结构，其中该热塑性聚合物包括选自乙烯丙烯酸、乙烯丙烯酸乙酯、乙烯离聚物及其组合的组分。
8.权利要求1的可剥离的密封结构，其中该热塑性聚合物包括乙烯乙酸乙烯酯。
9.权利要求1的可剥离的密封结构，其中该热塑性聚合物包括选自乙烯共聚物、丙烯共聚物及其混合物的聚合物。
10.一种可剥离的密封结构，包括：
热塑性聚合物；
分散于至少一部分该热塑性聚合物之内的有机粘土，该有机粘土的表面积大于100m2/g且纵横比大于10，其中该有机粘土的存在量为热塑性聚合物和有机粘土的总重的1wt％～20wt％，并且其中该可剥离的密封结构限定密封表面， 该密封表面的平均粗糙度为1500～5000埃，该密封层的拉伸模量为500～2000MPa，该有机粘土包括平均间隔为至少20埃的片晶。
11.权利要求10的可剥离的密封结构，其中该有机粘土包括具有小于200nm的空间尺寸的多个颗粒。
12.权利要求10的可剥离的密封结构，其中该热塑性聚合物包括选自尼龙、聚烯烃、聚苯乙烯、聚酯、聚碳酸酯及其混合物的聚合物。
13.权利要求10的可剥离的密封结构，其中该热塑性聚合物包括选自乙烯丙烯酸、乙烯丙烯酸乙酯、乙烯离聚物及其组合的组分。
14.权利要求10的可剥离的密封结构，其中该热塑性聚合物包括乙烯乙酸乙烯酯。
15.权利要求10的密封结构，其中该热塑性聚合物包括选自乙烯共聚物、丙烯共聚物及其混合物的组分。
16.一种包装系统，包括：
容器部分；和
连接于容器部分的可剥离密封部分，该密封部分具有密封基底和第一密封层，该第一密封层至少部分地布置在密封基底之上且与其接触，该第一密封层包括：
热塑性聚合物；
分散于至少一部分该热塑性聚合物之内的有机粘土，其中该有机粘土的存在量为热塑性聚合物和有机粘土的总重的1wt％～20wt％，并且其中该可剥离的密封结构限定密封表面，该密封表面在可剥离的密封温度范围内的全部温度下可形成到可剥离密封中，该可剥离的密封温度范围为从密封开始温度到高于该密封开始温度至少100°F的温度，其中该密封开始温度为170°F～350°F，该有机粘土包括平均间隔为至少20埃的片晶，该密封表面的平均粗糙度为1500～5000埃，该密封层的拉伸模量为500～2000MPa。
17.权利要求16的包装系统，其中该有机粘土的表面积大于100m2/g且纵横比大于10，其中该可剥离的密封结构限定密封表面。
18.权利要求16的包装系统，其中该有机粘土包括选自高岭石、蒙脱土-蒙脱石粘土、膨润粘土、伊利粘土及其组合的粘土。
19.权利要求16的包装系统，其中该有机粘土包括具有小于200nm的空间尺寸的多个颗粒。
20.权利要求16的包装系统，其中该热塑性聚合物包括选自尼龙、聚烯烃、 聚苯乙烯、聚酯、聚碳酸酯及其混合物的聚合物。
21.权利要求16的包装系统，其中该热塑性聚合物包括选自乙烯共聚物、丙烯共聚物及其混合物的聚合物。
22.权利要求16的包装系统，其中该密封结构包括与第一密封层接触的第二密封层。
23.权利要求22的包装系统，其中该第二密封层包括：
热塑性聚合物；和
分散于该热塑性聚合物之内的有机粘土。
24.权利要求16的包装系统，其中该密封部分进一步包括布置在第一密封层之上的一个或多个其它层。
25.权利要求16的包装系统，其进一步包括其中所含的食物。
26.权利要求16的包装系统，其进一步包括其中所含的消毒对象。
27.权利要求26的包装系统，其中该消毒对象为医疗器械。
28.权利要求16的包装系统，其中该容器部分具有选自气泡、盘、袋、囊及其组合的形状。
29.权利要求16的包装系统，其中该热塑性聚合物包括乙烯乙酸乙烯酯。 
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BRPI0705698B1 (pt) 2018-09-25
NZ561812A (en) 2009-02-28
EP1927463B1 (en) 2018-06-20
CN101186800A (zh) 2008-05-28
AR062989A1 (es) 2008-12-17
US7871696B2 (en) 2011-01-18
IL216816A0 (en) 2012-01-31
US20080118688A1 (en) 2008-05-22
PL1927463T3 (pl) 2018-10-31
AR093866A2 (es) 2015-06-24
EP1927463A1 (en) 2008-06-04
IL185473A0 (en) 2008-01-20
JP2008127106A (ja) 2008-06-05
JP2016052917A (ja) 2016-04-14
IL185473A (en) 2012-04-30
ZA200707237B (en) 2008-11-26
RU2007136062A (ru) 2009-04-10
NO20074901L (no) 2008-05-22
AU2007209816A1 (en) 2008-06-05
JP2014028664A (ja) 2014-02-13
CA2598657A1 (en) 2008-05-21
KR20080046083A (ko) 2008-05-26
CN103213756A (zh) 2013-07-24

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