CN104908300A - 包覆模制容器的制造方法、包覆模制容器和预制坯、以及回收包覆模制容器的方法 - Google Patents

包覆模制容器的制造方法、包覆模制容器和预制坯、以及回收包覆模制容器的方法 Download PDF

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Publication number
CN104908300A
CN104908300A CN201510280230.2A CN201510280230A CN104908300A CN 104908300 A CN104908300 A CN 104908300A CN 201510280230 A CN201510280230 A CN 201510280230A CN 104908300 A CN104908300 A CN 104908300A
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CN
China
Prior art keywords
overmolded
container
elastomer
bottle
preform
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510280230.2A
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English (en)
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CN104908300B (zh
Inventor
石昱
D·J·德拉姆
R·L·雷迪
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Coca Cola Co
Colgate Palmolive Co
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Coca Cola Co
Colgate Palmolive Co
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Publication of CN104908300A publication Critical patent/CN104908300A/zh
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/08—Injection moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14598—Coating tubular articles
    • B29C45/14622—Lining the inner or outer surface of tubular articles
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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    • B29C45/1603—Multi-way nozzles specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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    • B29C45/1676—Making multilayered or multicoloured articles using a soft material and a rigid material, e.g. making articles with a sealing part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
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    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

本发明公开了一种包覆模制容器(20)及其制造方法，其可以提供增强的视觉和触觉特性，从而允许新颖的包装设计、改进的握持性能和热绝缘性。该容器能够以成本节省的方式进行制造，并对聚合物回收物流影响最小化。该制造容器的方法包括以下步骤：提供容器预制坯(12)，该预制坯包括譬如PET共聚物的热塑性聚合物；将弹性体材料(14)包覆模制在预制坯的至少一部分之上，由此形成包覆模制预制坯；以及对所述包覆模制预制坯进行吹塑模制，以形成包覆模制容器。在一个实施例中，所述包覆模制容器是饮料容器。此外，还公开了包覆模制的预制坯。

Description

包覆模制容器的制造方法、包覆模制容器和预制坯、以及回收包覆模制容器的方法
本分案申请是基于中国发明专利申请号200680008246.7(国际申请号PCT/US2006/005656)、发明名称为“包覆模制容器的制造方法、包覆模制容器和预制坯、以及回收包覆模制容器的方法”申请日为2006年2月17日的专利申请的分案申请。
技术领域
本发明总的涉及模制的聚合物容器，更具体地，涉及用于制造包覆模制(overmolded)容器的方法，该方法可提高容器的某些性能，譬如表面纹理和手感、色彩和其他视觉设计变量、绝热性以及其他功能。
背景技术
基于聚对苯二甲酸乙二醇酯(PET)的聚酯由于其良好的机械性能和隔离性能，已经广泛用作容器的材料。然而，由PET制成的容器通常具有坚硬且光滑的表面。这些表面难于握持，容器可能从使用者的手中滑出，并导致容器内含物发生溢出。如果将在低温条件(譬如冰箱)储藏过的装满东西的容器产品(譬如，包含饮料的瓶子)在室温下取出使用以致水分凝结在容器外侧，通常会更容易失手。因此，非常期望对PET容器和其他热塑性聚合物容器的握持性能(grippability)进行改善，尤其是对于那些在冷凝物形成于容器外侧的状态下频繁使用的容器产品。在此使用的术语“可握持性”和“握持性能”表示容器表面能够牢固握持而不会滑出的性能。
由于PET已经在饮料和生活消费品领域获得日益增长的运用，商标拥有者被迫找出方法(尤其是通过包装创新)来区别他们的产品。创新设计特征的例子包括在容器上使用不同的纹理和着色的容器。虽然许多这种营销创新在概念上引人入胜，但它们的执行从生产、成本或环境考虑来说并不实际，或者容器可能拥有某些使设计在其他方面不适当的特性。例如，着色的容器会严重破坏PET回收物流，因为它们不能容易地与其余PET物流分离。此外，制作带纹理的容器需要纹饰模具。这种模具通常非常昂贵，并一旦产生模具之后难于改变纹理。因此，在本领域期望能够使PET包装产品变得独特、而不会对PET回收物流产生有害影响或是过度增加成本。
包覆模制或多组份模制已经在注射模制领域获得广泛使用。包覆模制主要被定义为这样一种过程：通过注射模制法使用两种或多种热塑性树脂来制造成品元件。包覆模制已经在电缆领域使用了多年，并日益影响到工业和生活用品领域。在这些领域中，许多运用将柔软触感材料与刚性部件相接合。柔软触感材料可提供改进的美观、更好的触感性能以及改进的握持性能。接合软质和刚性材料最为广泛使用的方法是使用包覆模制。传统上，将软质材料直接包覆模制到刚性材料上以产生成品部件。期望提供一种方法来将柔软触感材料运用于譬如饮料容器的刚性容器。
因此在包装领域存在以下需求：产生一种易于着色且具备可控制的握持功能、绝缘功能和/或其他功能的容器；以及获得上述设计特征而不会对PET或其他热塑性回收物流产生负面影响。此外，在包装领域还存在以节省成本的方式来生产上述容器的需求。
发明内容
现提供一种用于制造包覆模制容器的方法以及包覆模制容器。该包覆模制容器可有利地提供增强的视觉和触觉特性，并允许新颖的包装设计、改进的握持性能和热绝缘性。这种制造方法以成本节省的方式实现上述容器优点，而不会影响材料回收物流或是使得影响最小化。
按照一个方面，上述制造容器的方法包括下列步骤：提供用于容器的预制坯，该预制坯包括热塑性聚合物；将弹性体的包覆模制材料至少包覆模制在预制坯的一部分上，由此形成包覆模制预制坯；以及对包覆模制预制坯进行吹塑模制，由此形成包覆模制容器。在一个优选实施例中，所述包覆模制容器是饮料容器。
上述预制坯可以由多种热塑性聚合物制成。在一个实施例中，热塑性聚合物包括一种或多种聚酯。在一个优选实施例中，热塑性聚合物是或包括聚对苯二甲酸乙二醇酯共聚物。
上述包覆模制材料被选择为可以在适当温度和压力下通过吹塑模制工艺进行加工，这样包覆模制材料能够与预制坯相符地延展，并呈现为最终所得的吹塑模制容器的形状。在一个实施例中，包覆模制材料包括热塑性弹性体。合适的包覆模制材料的例子包括聚烯烃弹性体、聚烯烃塑性体、改性的聚烯烃弹性体、改性的聚烯烃塑性体、热塑性聚氨酯弹性体及其组合。
在一个实施例中，包覆模制材料具备小于1.00g/cc的密度，这样可以譬如通过水浮沉工艺(其依赖于热塑性聚合物与包覆模制材料之间的密度差)方便对热塑性聚合物进行最终的回收。
作为选择，包覆模制材料可以包括一种或多种添加剂。可能的添加剂的例子包括着色剂、UV阻断剂、润滑剂、增滑剂、加工助剂、氧化稳定剂、热稳定剂及其组合。
在一个实施例中，包覆模制材料覆盖包覆模制容器外表面的大部分。
按照另一方面，提供了一种吹塑模制容器。在一个实施例中，该容器包括：具有外表面和内部空间的容器主体，其中容器主体通过对热塑性聚合物的预制坯进行吹塑而形成；以及与容器主体外表面的至少一部分相符地固定的包覆模制层。
在一个实施例中，所述容器是瓶子。在一个实施例中，该瓶子是圆柱形的并包括具备外螺纹的瓶颈，所述外螺纹布置在开口端瓶口与压盖凸缘之间。在一个实施例中，包覆模制层包括包覆模制材料，其覆盖底端和侧壁且其边沿终止在压盖凸缘处。在另一实施例中，包覆模制层覆盖底端、侧壁和压盖凸缘。
按照另一方面，提供了一种封装饮料。在一个实施例中，该封装饮料包括具有外表面和内部空间的容器主体，其中容器主体通过对热塑性聚合物的预制坯进行吹塑而形成；与容器主体外表面的至少一部分相符地固定的包覆模制层；以及装在容器内部空间中的饮料。
在一个具体实施例中，提供了一种饮料容器，其包括至少由PET共聚物形成的吹塑模制瓶；包括乙烯α-烯烃树脂或其他聚烯烃弹性体或塑性体的包覆模制层，其中该包覆模制层相符地固定到所述瓶的外表面的至少一部分上；以及装在瓶中的饮料。
按照又一方面，提供了一种用于回收包覆模制容器的方法。在一个实施例中，该方法包括下列步骤：将上述容器分割成多个碎块；以及使用物理分离工艺将所述包覆模制层的碎块从容器主体的碎块分离。在一个示例中，所述物理分离工艺包括空气分离工艺或浮沉工艺。
附图说明
图1概略性显示了用于制造包覆模制容器的一个实施例的工艺流程；
图2是用于容器的热塑性聚合物预制坯的一个实施例的横截面视图；
图3是用于容器的热塑性聚合物包覆模制预制坯的一个实施例的横截面视图；
图4是包覆模制容器的一个实施例的平面图(图4A)和横截面视图(图4B)，其中包覆模制材料仅仅覆盖了容器主体的一部分；
图5是包覆模制容器的一个实施例的平面图(图5A)和横截面视图(图5B)，其中包覆模制材料覆盖了容器主体并终止于压盖凸缘之下；
图6是包覆模制容器的一个实施例的横截面视图，其中包覆模制材料覆盖了容器的主体并延伸到压盖凸缘处；
图7是处于包覆模制容器中的封装饮料的一个实施例的平面图，该包覆模制容器的一部分表面上具有刻点；
图8是工艺流程图，显示了用于回收热塑性包覆模制容器的流程的一个实施例；
图9是(温度与时间的)曲线图，显示了两个示例的热塑性包覆模制容器与非PET容器绝热性能之间的比较。
具体实施方式
热塑性包覆模制容器及其制造方法已经获得发展。在优选实施例中，制造该容器的方法包括下列步骤：提供用于容器的预制坯，该预制坯由热塑性聚合物制成；将弹性体的包覆模制材料包覆模制到预制坯的至少一部分上，由此形成包覆模制预制坯；然后对包覆模制预制坯进行吹塑模制，由此形成包覆模制容器，该容器可以是饮料容器。这种新的方法使得可以节省成本地生产广泛多种具有柔软触感材料涂层的容器，这可以提供增强的视觉和触觉特性(譬如鲜明的色彩、柔软的触觉)、新颖的包装设计、改进的握持性能和/或热绝缘性，除了这些技术优点之外，这种容器还可以有利地进行回收而不会影响聚合物材料回收物流或是使得影响最小化。
按照一个具体优点，相对柔软的弹性体包覆材料允许了包覆模制容器的外表面能够模制成在表面上具有精美细节、微小而锐利的高度变化。这样使得容器的外表面能够譬如模制有复杂的纹饰表面、以及文字和图案。与此相反，像传统PET共聚物这类的较硬材料通常不能吹塑模制有上述锐利细节。
在此使用的术语“包括”、“包含”期望是开放而非限制的术语，除非特意给予了说明。
制造包覆模制容器的方法
图1中显示了该流程的一个实施例。图1显示了用于制造热塑性包覆模制容器20的工序10的步骤。首先，提供能够进行包覆模制的合适预制坯12。接着，譬如通过利用注射模制法将预制坯12与包覆模制材料14进行包覆模制，由此形成包覆模制预制坯16。然后，包覆模制预制坯16譬如利用延展吹塑模制工艺进行吹塑模制。
在优选实施例中，预制坯通过利用本领域公知的技术和设备由热塑性聚合物组份注射模制形成。在一个典型实施例中，通过将聚酯组份注射模制为可吹塑的几何形状来形成容器预制坯。作为替换，预制坯也可以通过其他的公知技术(譬如压缩模制法)进行制造。
在优选实施例中，包覆模制材料通过利用本领域公知的技术和设备由包覆模制材料注射模制形成。例如，包覆模制可以在形成预制坯的相同模具中完成(譬如，利用两次模制工艺或双组份注射模制工艺)，或者预制坯被传送到用于包覆模制步骤的第二模具中(例如利用夹物模制法)。在包覆模制工艺步骤的一个实施例中，合适的弹性体被熔融然后注射模制到预制坯上，由此形成其原始坯体上具有弹性体层的包覆模制预制坯。取决于最终的包覆模制容器的具体设计考虑，包覆模制材料的厚度及其所覆盖的表面区域可以发生改变。
在一个替换实施例中，可以在单个步骤中形成包覆模制预制坯。例如，可以采用本领域公知的共注射工艺，此时热塑性聚合物和弹性体包覆模制材料被同时注射到用于预制坯和包覆模制结构的模具中。
在优选实施例中，包覆模制预制坯利用本领域的技术和设备通过延展吹塑工艺而转变成包覆模制容器。例如，该过程步骤包括利用与非包覆模制的预制坯相类似的加热廓线对包覆模制的预制坯进行加热(譬如在红外线炉中)，然后利用压缩空气和拉伸杆将包覆模制的预制坯延展吹塑模制为最终的容器形式。作为替换，也可以通过本领域技术人员公知的单步吹塑模制法制得上述容器。一些吹塑模制参数可能需要进行调整以适应包覆模制材料层的存在；然而，这些调整都落在常规热塑性塑料(譬如PET)工艺条件的范围内。
在一个具体实施例中，上述方法适用于制造充碳酸气和无碳酸气软饮料领域和食品领域中的包装应用容器。形成这些容器的常规制造方法包括注射模制容器预制坯，然后在单级或双级吹塑模制制造系统中由预制坯制得容器。这类方法对于本领域的技术人员是公知的。可能的预制坯和容器结构的例子在美国专利5,888,598中得到公开，该公开在此结合作为参考。这类方法易于适应包覆模制弹性体层在容器预制坯上的存在。在一个实施例中，如制造薄壁一次性PET饮料容器所用的市售设备可以用于制造在此描述的包覆模制容器。在另一实施例中，也可以使用像制造常规厚壁可再装PET容器所用的商业设备。
热塑性聚合物和预制坯
预制坯可以由多种热塑性聚合物制成。在一个实施例中，热塑性聚合物包括一种或多种聚酯。在一个实施例中，热塑性聚合物包括聚丙烯。在一个优选实施例中，热塑性聚合物是或包括聚对苯二甲酸乙二醇酯共聚物。在一个实施例中，上述聚合物适用于封装带碳酸气或不带碳酸气的的饮料以及氧敏感型的饮料或食品。合适的聚合物包括PET共聚物、聚萘二甲酸乙二酯(PEN)、聚间苯二甲酸乙二酯、乙二醇改性的无定形PET共聚物(通常称之为PETG)、二价酸改性的无定形PET等。PET共聚物由于在多种容器运用中得到使用而尤其有用。在此使用的“PET共聚物”表示那些包含二元醇组份和二价酸组份的化合物，所述二元醇组份具有由乙二醇构成的重复单元而所述二价酸组份具有由对苯二酸构成的重复单元。合乎期望的是，在一些实施例中，基于100摩尔％的二价酸组份和100摩尔％的二元醇组份来说，PET共聚物具备小于20％的二价酸组份变体和/或小于10％的二元醇组份变体。这类PET共聚物是公知的。
作为选择，也可以使用多层的预制坯。例如，预制坯可以如本领域所公知地包括3层或5层的结构。在3层预制坯结构的一个实施例中，中间层是阻挡层，产品接触层和外层是聚酯层。在5层预制坯结构的一个实施例中，内层和外层是纯净的聚酯层，第二和第四层是可回收的PET层，而第三层是阻挡层。
在一个优选实施例中，预制坯包括圆柱形的注射模制预制坯，其具有开口顶端和瓶颈。在一个实施例中，预制坯还包括锥形的肩部形成部分、厚度基本相同的中间圆柱形部分，以及基部形成部分。在各种实施例中，预制坯是无定形和基本透明的。
图2中显示了预制坯30的一个实施例。该预制坯30通过对PET基树脂注射模制形成，并包括其下端终止在压盖凸缘34处的带螺纹瓶颈32。在压盖凸缘34下面，存在大致圆柱形的部位35，该部位终止在外径逐渐增大的部位36处，由此提供递增的壁厚。在部位36之下，是拉长的主体部位38。
包覆模制材料和包覆模制过程
在优选实施例中，包覆模制步骤包括将弹性体包覆模制材料与容器预制坯一起注射模制或注射模制到其上。弹性体包覆模制材料的选择取决于具体运用所期望的特定功能。例如，可以将包覆模制材料组份选择为获得所需的纹理或柔软手感、一定的握持性能或其他功能。工艺上的考虑和其他因素对此选择也有影响。例如，不同包覆模制材料的密度、延伸比、颜色、成本和可回收性可以不同，这取决于包覆模制容器的最终用途或设计约束。
譬如取决于所制造容器的具体设计，预制坯的表面被包覆模制材料所覆盖的量可以发生改变。在一个实施例中，包覆模制材料覆盖住包覆模制容器外表面的大部分。例如，包覆模制材料可以覆盖预制坯外部表面积的50％到95％。在其他实施例中，可以覆盖小于50％的外表面。
在此使用的术语“弹性体包覆模制材料”表示那些包含热塑性弹性体的组合物，所述热塑性弹性体能够在与预制坯和吹塑模制工艺相一致的适当条件下被包覆模制。在优选实施例中，将包覆模制材料选择为可以在与吹塑模制工艺相一致的适当温度和压力下进行加工，这样包覆模制材料能够与预制坯相符地延展，并呈现为最终所得的吹塑模制容器的形状。弹性体包覆模制材料层可以通过借助于粗糙表面的机械式联锁或借助于弹性体官能团的机械结合，与下层的热塑性聚合物结构可分离地固定。
弹性体包覆模制材料被选择为足够柔软以致在处理过程中以及在处理之后呈现模具的形状。下层的热塑性聚合物在吹塑模制处理之后一旦被冷却，则足够的硬以便将弹性体包覆模制材料维持为它的延展、模制后形状。
在此使用的术语“热塑性弹性体”包括弹性体、塑性体、改性的弹性体和改型的塑性体，它们在本领域是公知的。合适热塑性弹性体的代表性例子(它们可以通过常规的注射模制设备来使用)包括聚烯烃弹性体(譬如乙烯-丙烯橡胶)、聚烯烃塑性体、改性的聚烯烃弹性体(譬如乙烯、丙烯和苯乙烯的三元共聚物)、改性的聚烯烃塑性体、热塑性聚氨酯弹性体、丙烯酸-烯烃共聚物弹性体、聚酯弹性体及其组合。具体但非限制地，市售包覆模制材料的例子包括Dow ChemicalCompany的VERSIFYTM塑性体和AffinityTM弹性体；DSM的SarlinkTM和VersalloyTM；GLS Corporation的DynaflexTM、KratonTM和VersaflexTM；Exxon Mobil的SantopreneTM；Uniprene；Tekbond；Elexar；Monprene；Teknor Apex的Tekron等。这些材料中的一些还在Batistini,Macromol.Symp.100:137-42(1995)中得以描述。
在一个实施例中，期望的是热塑性弹性体具备小于1.00g/cc的密度。这样可便于对热塑性聚合物和/或包覆模制材料进行分离和回收。
在一个实施例中，包覆模制容器上的包覆模制材料层具备0.1mm到5mm的厚度，优选从0.1mm到3mm。
期望的是，热塑性弹性体具备Shore(肖氏)D 45以下、优选Shore D 30以下的柔软度/硬度。
在可选实施例中，包覆模制材料可以包括一种或多种添加剂。可能的添加剂的例子包括颜料和其他着色剂、UV阻断剂、润滑剂或增滑剂、加工助剂、抗氧化剂、抗菌剂、热稳定剂及其组合，它们在本领域是公知的。在一个实施例中，添加增滑剂以改善瓶与瓶之间在生产线上(譬如，气流式输送器)所发生的摩擦。在其他实施例中，包覆模制材料可以包括具备下列官能团的化合物，该官能团在需要时能够改善包覆模制层与下层的热塑层之间的粘附。
此外显而易见的是，如果需要，通过采用两种或多种包覆模制组份，包覆模制可以包括一次以上的包覆模制操作来形成包覆模制预制坯。例如，两种或多种不同类型或色彩的弹性体树脂可以覆盖预制坯的不同区域，这样由此得到的吹塑模制容器具有不同外观或触感的部位。
图3中显示了包覆模制预制坯40的一个实施例。图示的包覆模制预制坯40包括图2中所示的基体预制坯30，还包括处于部位36的一部分和部位38上的弹性体包覆模制材料42。在其他实施例中(未显示)，取决于容器产品设计上的考虑，包覆模制材料42可以形成为(包覆模制为)或多或少地覆盖住基部预制坯(譬如，仅仅覆盖部位38的一部分，或所有的部位38、36和35等)。
吹塑模制
一般来说，本发明的实施例可以通过吹塑模制来制造。吹塑模制的各种方式是众所周知的。在一个优选实施例中，吹塑模制过程包括对预制坯进行再加热延展吹塑模制的过程，这些在本领域是公知的。
在一个实施例中，包覆模制预制坯被放置在吹塑模制设备中，该设备包括与瓶颈相接合的上部模件、具有内腔用于形成容器侧壁形状的中间模件、以及具有上表面用于形成容器基部的向外凹拱部位的下部模件。在一个具体实施例中，基础材料是PET共聚物。按照常规的再加热延展吹塑模制工艺，注射模制的预制坯首先被再加热至适于进行延展和定位的温度(譬如80至130℃)并被放置到吹塑模具中，然后将轴向拉伸杆插入开口上端并向下移动以便轴向延展预制坯。在其之后或与此同时，膨胀气体被导入到预制坯内部，由此将肩部、侧壁和基部形成部向外轴向膨胀至与模具部件的内表面相接触。由此所得的吹塑容器具有与预制坯相同的带外螺纹瓶颈和最下的颈部凸缘。容器的其他部分也发生膨胀，尽管程度不同。典型地，包覆模制材料以相称方式与基体预制坯一起膨胀和延展。
包覆模制容器
可以制造出广泛多种包覆模制的吹塑模制容器。该包覆模制容器主要可用于食品、饮料、个人护理或药物产品。合适类型的包覆模制容器的代表性例子包括瓶、罐、桶、玻璃水瓶、冷却器等。
在一个实施例中，所述容器包括具有外表面和内部空间的容器主体，其中该容器主体通过对热塑性聚合物的预制坯进行吹塑模制而形成；以及与容器主体外表面的至少一部分相符固定的包覆模制层。在一个实施例中，所述容器主体包括底端、开口端瓶口以及从底端延伸到开口端瓶口的侧壁。
在一个优选实施例中，所述容器是瓶子。在一个实施例中，所述瓶是圆柱形的并包括具有外螺纹的瓶颈，所述外螺纹布置在开口端瓶口与压盖凸缘之间。在一个实施例中，包覆模制材料覆盖住底端和侧壁，且其边沿终止于压盖凸缘处。在另外一个实施例中，包覆模制材料覆盖底端、侧壁和压盖凸缘。
图4A-4B中显示了包覆模制容器的一个实施例。该容器50包括：热塑性聚合物的主体52，其包括限定瓶口56的带螺纹瓶颈54；位于带螺纹瓶颈下面的压盖凸缘58；从压盖凸缘延伸的锥形部位60；在锥形部位之下延伸的主体部位62；以及处于容器底部的基部64。容器50包括覆盖部位62但未覆盖部位60的包覆模制层66。在给容器充满产品(譬如饮料)之后，封闭件68对容器50的瓶口56进行密封。
图5A-5B中显示了包覆模制容器的另外一个实施例。该容器70包括：热塑性聚合物的主体52，其包括限定瓶口56的带螺纹瓶颈54；位于带螺纹瓶颈下面的压盖凸缘58；从压盖凸缘延伸的锥形部位60；在锥形部位之下延伸的主体部位62；以及处于容器底部的基部64。容器70包括包覆模制层72，其覆盖部位62和部位60并终止于压盖凸缘58之下。在给容器充满产品(譬如饮料)之后，封闭件68对容器70的瓶口56进行密封。
图6中显示了包覆模制容器的另外一个实施例。该容器80包括：热塑性聚合物的主体52，其包括限定瓶口56的带螺纹瓶颈54；位于带螺纹瓶颈下面的压盖凸缘58；从压盖凸缘延伸的锥形部位60；在锥形部位之下延伸的主体部位62；以及处于容器底部的基部64。容器80包括包覆模制层82，其覆盖部位62和部位60并延伸到压盖凸缘58上。
封装饮料
在一个具体实施例中，提供了一种封装饮料，该饮料包括上述包覆模制容器。这种饮料产品是加压的(譬如带碳酸气的软饮料、啤酒)或不加压的(譬如水、果汁、运动饮料)。上述包覆模制容器可以与冷装填产品或热装填产品一起使用。
在一个实施例中，封装饮料包括：具有外表面和内部空间的容器主体，其中该容器主体通过对热塑性聚合物的预制坯进行吹塑模制而形成；与容器主体外表面的至少一部分相符固定的包覆模制层；以及装在容器内部空间中的饮料。所述容器主体通常包括开口及其可拆除固定的封闭件。
在一个具体实施例中，提供了一种饮料容器，其包括至少由PET共聚物形成的吹塑模制瓶；包括烯烃基TPE树脂的包覆模制层，其中该包覆模制层与瓶的外表面的至少一部分相符地固定；以及装在瓶中的饮料。
图7中显示了封装饮料的一个实施例。封装饮料90包括具有热塑性聚合物主体52的包覆模制瓶94，所述主体具有包覆模制材料92，点刻区域94模制在包覆模制材料92的一部分表面上。
图7中的刻点是细节精细程度的示范，其可以凭借相对于下层较硬热塑性聚合物的柔软性和可塑性而模制到包覆模制材料的表面上。刻点或其他模制纹理可以提供用于美观设计目的，或是提高瓶或其他容器的握持性能。在其他示例中，这类模制细节可以形成在包覆模制材料的其他区域。此外，该模制细节可以呈现文字或图案的形式。典型地，这些精细模制细节仅仅形成在包覆模制材料上而不延伸到下层的热塑性聚合物。
回收方法
有利的是，包覆模制容器可以进行回收。在优选实施例中，该回收方法包括下列步骤：其中包覆模制材料和优选是PET共聚物的热塑性聚合物譬如通过利用PET回收工艺所公知的一种或多种常规技术而物理分离。在一个实施例中，该方法包括下列步骤：将容器分割(譬如研磨、撕碎、切割等)成多个碎块(有时称之为薄片)；然后利用物理分离方法将包覆模制材料层的碎块与容器主体和热塑性容器材料的碎块分离。在一个示例中，该物理分离方法包括空气分离工艺或浮沉工艺。在浮沉工艺的一个实施例中，弹性体包覆模制材料的碎块浮在水槽面上，而热塑性基体聚合物(譬如PET共聚物)则沉在水槽底部。
图8中显示了包覆模制容器的回收过程的一个示例。包覆模制容器100被输送至分割工序，此时容器被切割、分割、撕碎或研磨成多个微小碎块或颗粒。接着，这些碎块/颗粒被输送至分离工序，此时包覆模制材料102(譬如，弹性体)的碎块/颗粒与热塑性聚合物104(譬如PET共聚物)的碎块/颗粒相分离。
上述方法及制造产品可以通过下列非限制性示例而得以进一步理解。
示例1：AffinityTM PF 1140G包覆模制所得的500ml PET瓶
以下将制造一种500ml的包覆模制瓶。所有的注射模制过程将在实验室规模的Arburg单腔注射模制设备中执行。首先，预制坯由市售的CSD PET(Invista,Spartanburg,SC)形成，其在140℃的真空炉烘干整夜至少于500ppm的水分含量。然后在270℃的熔融温度下通过注射模制制得16-g的PET预制坯。
包覆模制材料是AffinityTM PF 1140G树脂(一种乙烯基热塑性塑料，Dow Chemical公司)。在包覆模制步骤中，PET预制坯被传送及放置在一个腔中，在该腔中包覆模制材料随之将以212℃的料筒温度注射模制于PET预制坯上。在一些瓶的包覆模制之前，通过将红色和银色着色剂添加于Affinity PF 1140G，可以形成红色和银色的包覆模制瓶。
接着，包覆模制预制坯被传送至实验室规模的SBO1吹塑模制机。包覆模制预制坯被加热至90至100℃的温度，并在500ml的瓶模具中吹塑模制为500ml的瓶子。
这种热塑性包覆模制瓶展现出良好的握持性能，并在彩色样品中展现可识别的红色和银色。
示例2：TekbondTM 6000-45包覆模制所得的500ml PET瓶
该过程与示例1中所述的相同，但使用了TekbondTM 6000-45树脂(一种热塑性弹性体，Teknor Apex)作为包覆模制材料在158至165℃的料筒温度进行包覆模制。接着，包覆模制预制坯在500ml的瓶模具中吹塑模制为500ml的瓶子。在包覆模制之前，通过将红色或银色着色剂添加于Tekbond 6000-45树脂，可以形成彩色的包覆模制瓶。该包覆模制瓶呈现良好的可握持性、色彩以及柔软的手感。
示例3：包覆模制容器的绝热性能
如示例2所述制得的容器被进行测试，由此确定可以减小热量传递到容器中的速度的程度。将包覆模制和非包覆模制的PET容器都充满冷水并允许加热至室温。对水温进行测量，由此产生温度与时间之间的曲线。如图9中所示，包覆模制PET容器与非包覆模制PET容器相比展现出能够将低温维持更长时间的特性，由此展现出更好的绝热性能。
示例4：由Affinity PF 1140G包覆模制所得的PET瓶的回收性
示例1所制得的包覆模制瓶在模拟回收过程中被分割成小块并浸泡在水中。Affinity PF 1140G树脂的红色或银色小块浮在水面上，而清澈的PET小块立即沉到水底。包覆模制树脂与PET的碎块毫无困难地与水相分离。该过程模拟了常规PET回收分离过程中的沉浮工艺。
示例5：由TekbondTM 6000-45包覆模制所得的PET瓶的回收性
示例2所制得的包覆模制瓶在回收过程中被分割成小块并浸泡在水中。TekbondTM 6000-45树脂的红色或银色小块浮在水面上，而清澈的PET小块立即沉到水底。包覆模制树脂与PET的碎块毫无困难地与水相分离。该过程模拟了常规PET回收分离过程中的沉浮工艺。
示例6：各种包覆模制瓶结构及聚合物
示例1和2中所描述的常规过程可以采用不同的着色剂(包括黑色、黄色和蓝色)和不同形状的瓶子并改变包覆模制到瓶上的覆盖量来重复执行。此外可以使用不同的弹性体，包括某些丙烯酸-烯烃共聚物弹性体。
在一些情况下，包覆模制基本覆盖瓶颈线之下的整个瓶，而在另外一些情况下，包覆模制仅仅覆盖瓶的下半部。
在此引用的公开文献结合作为参考。通过上述的具体说明，在此所描述的方法及装置的修改和改变对于本领域的技术人员显而易见。这些修改和改变期望落在附属权利要求的范围之内。

Claims (32)

1.一种用于制造包覆模制容器的方法，包括：
提供用于容器的预制坯，所述预制坯包括热塑性聚合物；
将弹性体的包覆模制材料包覆模制到所述预制坯的至少一部分之上，以形成一包覆模制预制坯，所述包覆模制材料包括热塑性弹性体；以及
对所述包覆模制预制坯进行延展吹塑模制以形成包覆模制容器，其中所述延展吹塑模制工艺使所述弹性体的包覆模制材料与所述容器的外表面的至少一部分相符地延展并通过借助于粗糙表面的机械式联锁或借助于弹性体官能团的机械结合而可分离地固定。
2.如权利要求1的方法，其中所述包覆模制容器是饮料容器。
3.如权利要求1的方法，其中所述热塑性聚合物包括一种或多种聚酯。
4.如权利要求3的方法，其中所述热塑性聚合物包括聚对苯二甲酸乙二醇酯共聚物。
5.如权利要求1的方法，其中所述包覆模制材料选自于包括以下材料的组：聚烯烃弹性体、聚烯烃塑性体、改性的聚烯烃弹性体、改性的聚烯烃塑性体及其组合。
6.如权利要求1的方法，其中所述包覆模制材料选自于包括以下材料的组：丙烯酸-烯烃共聚物弹性体、聚酯弹性体及其组合。
7.如权利要求1的方法，其中所述包覆模制材料具有小于1.00g/cc的密度。
8.如权利要求1的方法，其中所述包覆模制材料还包括一种或多种添加剂。
9.如权利要求8的方法，其中所述一种或多种添加剂选自于包括以下添加剂的群组：着色剂、UV阻断剂、润滑剂、增滑剂、加工助剂、抗氧化剂、抗菌剂、热稳定剂及其组合。
10.如权利要求1的方法，其中所述延展吹塑模制工艺包括对所述包覆模制预制坯进行预热，然后对预热的所述包覆模制预制坯进行延展吹塑模制。
11.如权利要求1的方法，其中所述包覆模制材料覆盖所述包覆模制容器的外表面的大部分。
12.一种吹塑模制容器，包括：
具有外表面和内部空间的容器主体；以及
包括热塑性弹性体的包覆模制层，所述包覆模制层通过对热塑性聚合物的预制坯进行延展吹塑模制而与所述容器主体的外表面的至少一部分相符地延展并通过借助于粗糙表面的机械式联锁或借助于弹性体官能团的机械结合而可分离地固定。
13.如权利要求12的容器，所述容器主体具有包括一个或更多侧壁、闭合底端和开口端的瓶子的形状。
14.如权利要求12的容器，其中所述热塑性聚合物包括一种或多种聚酯。
15.如权利要求12的容器，其中所述热塑性聚合物包括聚对苯二甲酸乙二醇酯共聚物。
16.如权利要求12的容器，其中所述包覆模制层包括包覆模制材料，该材料选自包括以下材料的组：聚烯烃弹性体、聚烯烃塑性体、改性的聚烯烃弹性体，改性的聚烯烃塑性体及其组合。
17.如权利要求12的容器，其中所述包覆模制层包括包覆模制材料，该材料选自包括以下材料的组：丙烯酸-烯烃共聚物弹性体、聚酯弹性体及其组合。
18.如权利要求12的容器，其中所述包覆模制层包括密度小于1.00g/cc的包覆模制材料。
19.如权利要求12的容器，其中所述包覆模制层还包括一种或多种添加剂。
20.如权利要求19的容器，其中所述一种或多种添加剂选自于包括以下添加剂的组：着色剂、UV阻断剂、润滑剂、增滑剂、加工助剂、抗氧化剂、抗菌剂、热稳定剂及其组合。
21.如权利要求12的容器，其中所述包覆模制层覆盖所述包覆模制容器的外表面的大部分。
22.如权利要求12的容器，其中所述包覆模制层具有0.1mm到5mm的厚度。
23.如权利要求13的容器，其中所述瓶子是圆柱形的并包括瓶颈和压盖凸缘，所述瓶颈具有外螺纹，所述外螺纹布置在开口端瓶口与压盖凸缘之间。
24.如权利要求23的容器，其中所述包覆模制层覆盖底端和侧壁，且所述包覆模制层的边沿终止在所述压盖凸缘处。
25.如权利要求23的容器，其中所述包覆模制层覆盖底端、侧壁和压盖凸缘。
26.如权利要求12的容器，其中所述包覆模制层具有小于肖氏D30的硬度。
27.如权利要求13的容器，其中所述容器的内部空间中装有饮料。
28.一种封装饮料，包括：
至少由PET共聚物形成的延展吹塑模制瓶；
包括热塑性弹性体的包覆模制层，其中所述包覆模制层在所述瓶的外表面的至少一部分之上相符地延展并通过借助于粗糙表面的机械式联锁或借助于弹性体官能团的机械结合而可分离地固定；以及
装在所述瓶中的饮料。
29.如权利要求28的封装饮料，其中所述延展吹塑模制瓶包括底端、侧壁和瓶颈，所述瓶颈具有布置在开口端瓶口与压盖凸缘之间的外螺纹，并且其中所述包覆模制材料的上边沿终止于所述压盖凸缘处或所述压盖凸缘之下。
30.如权利要求28的封装饮料，其中所述热塑性弹性体包括聚烯烃塑性体。
31.如权利要求28的封装饮料，其中所述包覆模制层能够通过机械工艺与所述PET共聚物分离。
32.一种包覆模制的预制坯，包括：
适合于吹塑模制成瓶子的热塑性聚合物预制坯，所述瓶子具有底端、侧壁和瓶颈，所述瓶颈具有布置在开口端瓶口与压盖凸缘之间的外螺纹；以及
包括热塑性弹性体的包覆模制材料，所述包覆模制材料至少包覆模制在所述热塑性聚合物预制坯的底端和一部分侧壁之上，
其中所述包覆模制材料具有一上边沿，所述上边沿终止于所述压盖凸缘处或所述压盖凸缘之下。
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