CN1263654C - 具有碳处理内表面的塑料容器 - Google Patents

具有碳处理内表面的塑料容器 Download PDF

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Publication number
CN1263654C
CN1263654C CNB008016259A CN00801625A CN1263654C CN 1263654 C CN1263654 C CN 1263654C CN B008016259 A CNB008016259 A CN B008016259A CN 00801625 A CN00801625 A CN 00801625A CN 1263654 C CN1263654 C CN 1263654C
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CN
China
Prior art keywords
container
resin
blowing
internal layer
thickness
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.)
Expired - Fee Related
Application number
CNB008016259A
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English (en)
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CN1321132A (zh
Inventor
威廉·A·斯莱特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Plastipak Packaging Inc
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Plastipak Packaging Inc
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Filing date
Publication date
Priority claimed from US09/370,642 external-priority patent/US6475579B1/en
Application filed by Plastipak Packaging Inc filed Critical Plastipak Packaging Inc
Publication of CN1321132A publication Critical patent/CN1321132A/zh
Application granted granted Critical
Publication of CN1263654C publication Critical patent/CN1263654C/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/071—Preforms or parisons characterised by their configuration, e.g. geometry, dimensions or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
    • B29C59/103—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment of profiled articles, e.g. hollow or tubular articles
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    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
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    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0855—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
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    • B29C2791/00—Shaping characteristics in general
    • B29C2791/001—Shaping in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

一种吹塑容器(10)，具有抗渗性并包括具有开口(13)的上壁部；位于上壁部(12)下方的中间侧壁部(14)，以及位于中间侧壁部下方支持容器的底部(16)。该容器包括至少由40%回收塑料形成的具有内表面(22)和外表面的一模塑外层(24)，以及一碳涂层形成在外层(26)内表面并粘附其上且大体上与外层作同等扩张，其中所述碳涂层的厚度小于约10微米。所述碳涂层具有沿所述容器的垂直长度上在0.05到10微米范围内变化的厚度。

Description

具有碳处理内表面的塑料容器
技术领域
本发明涉及基于回收塑料的塑料容器。更特别是，本发明涉及基于回收塑料的吹塑塑料容器，其具有抗渗性和具有碳涂布的内表面。
背景技术
非常希望提供一种具有抗渗性的塑料容器，同时也非常希望提供一种利用回收塑料的塑料容器。然而，回收的塑料通常不具有抗渗性而且不能用于容器与容器内容物直接接触。因此，尽管利用回收塑料在经济上是可取的，但是这种材料的利用是困难的。
按照惯例，回收塑料用于容器，特别是那些容纳人消费的内容物的容器已限于多层塑料容器，在此回收塑料是不直接接触到容器内容物的外层。
多层塑料容器通常在很大的范围内被用于包装产品，包括食物和饮料，药物，既卫生又美观，以及家用产品。众所周知，塑料容器易于模塑，成本具有竞争性，重量轻，以及通常适合于许多应用。多层容器具有的好处是能够在每一层使用不同的材料，其中，每种材料具有适应执行所要求功能的特殊性能。
因为塑料容器可以允许低分子气体，如氧气和二氧化碳，缓慢地渗透入它们的物理结构，所以当与由其它渗透性较小的材料如金属或玻璃形成的容器比较时，使用塑料容器有时显示是不太理想的。在大多数的应用中，产品内容物的保存期限与能有效地对付这种分子渗透的包装能力直接相关。在碳酸饮料的情况中，如啤酒，容器周围大气中的氧能够逐渐向里渗透入容器的塑料壁到达容器的内部并使内容物变坏。而且，内容物产生的二氧化碳气体可以向外渗透入容器的塑料壁直到终于释放在外面，造成碳酸饮料损失一些味道并且可能变得“平淡”。
为了解决上述涉及的一些问题，塑料容器生产者已经利用各种技术去减少或消除诸如此类气体的吸收和/或渗透。一些更普通的技术包括：增加全部或部分容器壁的厚度；在壁结构中加入一个或多个阻隔层；包括在容器壁内的氧清除或反应材料；以及在容器的内和/或外表面上施加各种涂料。然而，许多传统的阻隔和/或清除剂材料将不会有效地减少氧或二氧化碳二者在延长期时间渗透。而且，通常还有与大多数传统技术有关的其它实际问题，最普通地，增加材料费用和/或生产无效率。
近来，塑料的使用已经成为一个重大的社会问题。回收已成为一种日益重要的环境事务，以及许多政府和管理专家继续研究解决该问题。在许多管区中，有关回收塑料最小含量和塑料容器的收集、返回和再使用的法规要么己经考虑或者已经颁布。例如，在塑料容器用于容纳消耗品的情况中，如食品或饮料，规定常常要求某种内容物和接触到该内容物的最里层的最小厚度。传统的方法，如共注塑或多注塑，常常受到能够有效地加入到容器结构中的回收塑料量的限制。通常能够有效地加入到适于食品内容物的传统共注塑容器的回收量小于容器总重量的40％。
因此，工业上存在一种需求及本发明的目的是提供一种具有高回收量的塑料容器，其适于盛装碳酸类产品如碳酸饮料，并且当与由其它材料制成的商品容器比较时，能够提供令人满意的性能水平。还存在着一种需要，即利用传统设备生产大批量商品量的这类容器的方法。
本发明还有一个目的并需要提供一种具有抗渗性的基于回收塑料的容器，以及将传统多层塑料容器的高成本麻烦减至最小或避免。还有更进一步的目的是在合理的成本以商业上适宜的工艺及有效的产品来做这些。
发明概述
已经发现根据本发明易于达到上述目的和优点。
认识这些有关传统多层塑料容器的问题和关系，特别是那些用于容纳碳酸类饮料的多层容器，提供一种具有增强的阻气性和高回收塑料含量的塑料容器是有益的。根据本发明原理构造的容器在那些上述可得优点之上提供几个优点。这些优点一般是通过使用合乎需要的回收塑料和在容器内表面上的碳涂层来实现的。一个重大的优点是本发明的容器可以有所希望的大回收量。而且，利用传统的加工技术和制造设备能够生产出改进的容器。
本发明的一个重要方面是具有功能和商业利益的现有容器的有效抗渗性在含有大量回收塑料的容器也具有。而且，根据本发明的原理生产的容器易于后来的回收使得本发明的实施非常有利。此外，本发明的另外的优点是允许制造者在沿着容器的内和/或外层的垂直长度上的任何给定位置，可控制地改变材料的配置和壁厚。
根据本发明的原理，提供的吹塑多层容器具有上壁部，位于上壁部下方的中间侧壁部，以及位于中间侧壁部下方的底部，底部适于非独立或独立地支持容器。该容器包括一层由回收塑料形成的模塑外层和一碳涂层邻接并合乎需要地在模塑外层的内表面上，模塑外层大体上是与内层作同等扩张的。回收的外层含有至少40％重量的回收塑料，但是，根据应用的需要可以含有大于75％重量的和希望超过90％重量的回收塑料。在优选的实施例中，外层的厚度沿其垂直长度可控制地调节。如果需要，外层也可以包括另外的抗渗性材料和/或氧清除/反应材料加入其中。
根据本发明的原理，吹塑多层容器也提供具有上壁部分，位于上壁部下方的中间侧壁部分以及位于中间侧壁部下方的底部，底部采取非独立地或独立地支持容器。容器包括(i)由塑料材料形成的模塑内层，该内层具有垂直长度和碳处理的内表面；和(ii)由回收塑料形成的模塑外层，它大体上是与内层作同等扩张的。回收的外层含有容器总重量的至少40％重量，但是，根据应用的需要，能够包含大于90％重量。在优选的实施例中，内和/或外层的厚度沿着它们各自的垂直长度可控制地调节。如果功能上需要，内层和/或外层也可以包括另外的抗渗性材料和/或氧清除/反应材料。
本发明的其它和更进一步的优点及新的特征，从下面实施本发明的最佳方式的详细说明，同时结合相关的附图是显而易见的，其中，以插图和例子的方式，公开本发明的实施方案。
附图简介
本发明根据附图预成型品将更容易地理解，其中：
图1是根据本发明原理的容器的正视图。
图1A，1B和1C是容器各部分的横截面和放大视图，其中表明了形成容器各层的相对厚度。
图2是多层预成型品的一个例子的局部剖面图。
图3是多层预成型品的另一例子的局部剖面图。
图4是根据本发明原理的容器的剖面图。
图5，6和7是容器各部分的横截面和放大视图，其中表明了形成容器各层的相对厚度。
图8是预成型品的一个例子的局部剖面图。
图9是预成型品的另一例子的局部剖面图。
优选实施例的详细说明
现在就附图作详细说明，其中相同的参考数字和字母指明相同部分。图1表示根据本发明的原理构造的容器10的正视图。容器10一般包括上壁部12，包括开口13；中间侧壁部14位于上壁部12的下面；以及底部16位于中间侧壁部14之下。底部16或者采用非独立地支持容器10，即在此使用另一个物体如基杯(未示出)，或者是独立的，即不需要另外的物体支持容器直立在普通平面上。在优选的实施例子中，由多个形成整体的脚18形成独立式底部支持容器10，如图1所示那样。
参见图1A-1C，它们分别表示图1的1A，1B和1C部分的放大详图，该容器10包括(a)模塑内层20，具有垂直长度和内表面22；(b)模塑外层24；和(c)中心垂直轴线A。模塑内层20的内表面22至少部分地涂布碳的薄层或薄膜26。当不需要用外层24完全包封内层20时，优选模塑外层26大体上是与内层20同等扩张的并对容器10的壁提供结构支持。
模塑内层20是由热塑性材料构成。下列树脂可用作内层20的塑料材料：聚乙烯树脂，聚丙烯树脂，聚苯乙烯树脂，环烯烃共聚物树脂，聚对苯二甲酸乙二醇酯树脂，聚萘二甲酸乙二醇酯树脂，乙烯-(乙烯醇)共聚物树脂，聚-4-甲基戊烯-1树脂，聚(甲基丙烯酸甲酯)树脂，丙烯腈树脂，聚氯乙烯树脂，聚偏二氯乙烯树脂，苯乙烯-丙烯腈树脂，丙烯腈-丁二烯-苯乙烯树脂，聚酰胺树脂，聚酰胺酰亚胺树脂，聚缩醛树脂，聚碳酸酯树脂，聚对苯二甲酸丁二醇酯树脂，离聚物树脂，聚砜树脂，聚四氟乙烯树脂等等。当涉及食品内容物时，内层20优选由纯聚对苯二甲酸乙二醇酯(PET)，聚萘二甲酸乙二醇酯(PEN)，和/或聚对苯二甲酸乙二醇酯和聚萘二甲酸乙二醇酯的共混物形成。然而，也可使用其它热塑性树脂，特别是被批准用于与食品接触的那些。
模塑外层24是由回收塑料材料构成的，包括前段文字中陈述的塑料，但是通常是由回收的聚对苯二甲酸乙二醇酯(PET)形成。但是，本发明不限于一种具体类型的回收塑料而且也可使用其它的回收塑料材料。
在一个优选实施例中，内层20的壁厚，沿其垂直长度取在0.5密耳-5密耳(0.0127mm-0.127mm)的范围内，更优选在1-2密耳(0.0254mm-0.0508mm)之间。在某些情况中，如涉及食品内容物的地方，可以指定内层20要求的最小厚度并且必须满足。如图1和图1A，1B及1C所示，内层的厚度可以沿垂直长度变化。在这种方式中，容器10的不同部分沿垂直长度能够有可变的控制厚度，提供改善的材料使用情况和增加设计适应性。例如，位于上部12的内层20(如图1A所示)的厚度可以比中间侧壁部14(如图1B所示)薄。而且，在壁底部16(如图1C所示)的内层20的厚度可以比在中间侧壁部14(如图1B所示)的同样的层厚度要厚。
与本发明的一个观点一致，内层含有少于容器10总重量的0.60重量，优选少于容器10总重量的0.30，更优选少于容器10总重量的约0.15。本发明利用异常薄的内层20的能力-具体地当与其它传统多层容器比较时-能够提供重大的经济利益和刺激，特别是在原材料比回收材料更贵和/或缺乏的情况。
如先前所述，内层20的内表面22涂布一薄碳层26，其为增强容器10提供增强的抗渗性。在优选的实施例中，碳涂层26是由掺杂氮气的高度氢化无定形碳构成。碳涂层26的厚度小于约10μm及涂层26的重量小于容器总重量的约1/10,000th。本发明的一个重要特征是处理500cc的塑料容器需要的碳涂层26仅为3mg。而且，尽管碳涂层26显著的薄，提供的抗渗防护量却是很大的，并且当与金属罐头和玻璃瓶中达到的防护比较时，氧和二氧化碳的渗透防护是满意的，初步的测试显示有关本发明提供的防止氧渗透的抗渗性可以比用未处理的PET制成的容器好30倍以上。提供的防止二氧化碳渗透的抗渗性比用未经处理的PET制成的容器好7倍以上；和提供的防止全部乙醛迁移的抗渗性能够比未经处理的PET好6倍以上。
模塑外层24含有容器10总重量的至少约0.40重量，但是对于某些应用可以含有超过容器10总重量的0.90重量。在优选的实施例中，外层24的壁厚，沿其垂直长度在6-23密耳(0.1524mm-0.5842mm)范围内。如图1和图1A，1B及1C所示，外层厚度也可沿其垂直长度分别地或独立地变化。在这种方式中，容器10的不同部分(垂直于中心纵轴A)可以有不同的内层厚度，不同的外层厚度和/或不同的总厚度尺寸，全部由设计而定。例如，位于上部12的模塑外层24的厚度(如图1A所示)可以比中间的侧壁部分14厚得多(如图1B所示)。同样地，在壁底部16的外层24的厚度(如图1C所示)可以比中间侧壁部14(如图1B所示)同层的厚度厚。因为模塑外层24通常是由不太贵的塑料材料构成，其不直接接触容器10的内容物，不太贵的材料可以用于成型许多容器结构的有机组成部分，如图1和图1A所示的颈部凸缘30和外螺纹30。
然而，常常是不必要的-并能够使回收过程复杂化-在特殊应用中，内层20和/或外层24可以进一步包括另外的抗渗性材料和/或氧清除/反应材料(未示出)，这在本领域里通常是已知的。使用阻隔层材料的更普通的一些例子包括，偏氯纶，乙烯乙烯醇共聚物(EVOH)和丙烯腈共聚物，如Barex。术语偏氯纶是使用其普通的商业意义规划例如由1，1-二氯乙烯和氯乙烯或丙烯酸甲酯聚合形成的聚合物。另外的单体可以包括众所周知的。最通常使用的经常是1，1-二氯乙烯聚合物，而且其它的防氧渗透材料是众所周知的。氧清除材料可以包括由几家大石油公司和树脂制造商为此目的而销售的材料。这种材料的一个具体例子是在商品名AMOSORB下销售的，并可从市场上买到来自阿莫科公司的。
本发明的又一显著优点是其提供有效抗渗性的能力，掺入高含量的回收塑料，以及有利于当今的回收。内层20和外层24两者都是由塑料材料构成且能够易于回收。不同于经常使用在多层容器方面的许多其它防渗材料，其难于分离，本发明的碳涂层26对于构成容器10的塑料材料的回收没有影响。
本发明包括另外的优点，即能提供抗渗性增强的容器10，其可用于容纳食品。内表面经无定形碳膜处理过的塑料容器经Technische NationalOnderzoek批准用于与食品接触，该标准组织为欧洲经济共同体所认可，美国食品和药物管理机构(USFDA)一般是在方法上批准。
本发明的容器10可以通过几种已知的加工技术的任一种形成，该技术允许多层吹塑容器10的制造具有塑料模塑内层20和相对厚的回收塑料模塑外层24。在优选的实施例中，多层容器10经过吹塑工序形成，包括一多层预成型品34，通常如图2中所描绘的。虽然没有要求的特点，但是，预成型品34可以包括颈部凸缘30(用于再加工目的)和外螺纹32(以保证封闭)，这与图1所示的同样特征相一致。在容器10吹塑后，如图1所示，但是在填充操作之前的一些时候，容器10的内层20的内表面22作碳处理，如下面进一步的讨论。
在第一优选实施例中，如图2所示，预成型品34是通过挤塑成型具有内表面22′的内层20′和注塑成型外层24′而生产的。预成型品34的内层20′和外层24′与容器10的内层20和外层24相一致。预成型品内层20′的挤塑允许制造厂家生产出比通常可能利用传统注塑或共注塑方法的更薄的层。例如，挤塑多层预成型品34的内层可以制成如15-20密耳(0.381mm-0.508mm)一样薄或更薄。相反，如果不是不可能，也是难于可靠地注塑一内层具有同等厚度外形。而且，挤塑或共挤塑方法允许制造厂家易于沿着挤出物长度改变所挤出材料的厚度，变化内层厚度是所希望的，由于包括美学的，有效的材料利用和成本降低，以及不同的强度要求的几个原因。
预成型品34的外层24′是由回收塑料材料成型，并且根据本发明，大体上比内层20′要厚，外层24′可以在内层20′之上注塑或压塑，尽管注塑通常是优选的。这样的重叠模塑法还允许成型颈部凸缘30和外螺纹32。
在第二个优选实施例中，多层预成型品34的生产是通过热成型一种塑料薄片材和成型该片材成为预成型品34的具有内表面22′的内层20′。热成型方法允许成型具有非常薄的内层20′的预成型品34。事实上，最小壁厚为3密耳(0.0762mm)或更小是可能的。如在挤塑内层20′的情况下，一旦预成型品34的内层20′形成，回收塑料外层24′就能在内层20′之上注塑或压塑从而提供多层预成型品34。图3是一个具有热成型内层20′和注塑外层24′的成型预成型品34的代表性例子。根据这种第二优选实施例的原理成型的预成型品34通常较好地适合于要求较大开口13或配嘴的应用。
然后多层容器可以利用传统的吹塑工序吹塑。由于在随后的吹塑加工中，预成型品34将被拉伸和“变薄”，预成型品34的厚度-在与吹塑容器相同部分相应的部分-将固有稍厚几分，事实上，预成型品34各部分的厚度通常是考虑形成成品容器10要求的外形厚度所必须的拉伸和环向膨胀量设计。为清晰性起见，在下文，具有未经碳处理的内层和外层20，24的容器，应与内表面22经碳处理过的容器10区别开。
在具有内层20和外层24的容器生产出来后，一碳涂层形成在内层20的内表面22的至少一部分。碳涂层26不必立刻施加到容器，然而，通常更有效的是在容器吹成之后并在适当的温度曲线内迅速地施加涂层26。
在优选的实施例中，将吹塑多层容器从传统的高速旋转吹塑机中取出，并随后直接或间接地(即，经过中间再加工步骤)传送到用于给容器施加碳涂层26的装置。在高速生产应用中，碳涂层装置通常也将是旋转型的，能够用于将碳涂层施加到容器10的内表面22的这种装置的一个例子从Sidelof Le Havre，France可得并且是在商品名“ACTIS”下在市场上销售。
用于碳涂布多层容器10的方法将在下面更进一步地细述。根据用于碳涂布容器10的内表面22的一种优选方法，提供一种具有旋转运动和中心立轴的传统的碳涂布或碳处理装置。碳涂布装置通常绕其中心立轴以第一旋转方向，即反时针方向以相当高的旋转速度旋转。吹塑机或其它旋转容器传递机构，通常位于很靠近碳涂层装置的地方，功能是为随后的涂碳处理的提供容器来源。为便于传递，旋转容器传递机构的旋转方向与碳涂布装置的旋转方向相反-即顺时针-并且多层容器10机械地从容器传递机构移动到碳涂布装置。尽管本发明的实践没有要求，容器10优选包括颈部凸缘30或其它物理手段用于机械传递过程中至少部分地支持容器10。
当容器10从传递机构传递到碳涂布装置时，容器10优选被上部12固定在垂直的方向，开口13一般朝上。如果需要，也可产生真空，并用以支持或部分地支持容器10。在传递过程中，单个容器10是通过接纳机构接纳，接纳机构是碳涂布装置的部件。接纳机构绕碳涂布装置的中心轴旋转，抓住或固定该容器，以及封闭该容器上部12的开口13，很像一个盖子。当适当地定位于超过并邻接开口13时，接纳机构产生密封从而“不透气”地在容器上密封。
该接纳机构包括至少有两个孔位于容器的开口13之上，用于从容器内引入或排除气体。在接纳机构中的第一个孔与真空源相通，如真空泵，在接纳机构已经可靠地密封住开口13后，容器内的空气用真空装置通过第一孔排出。真空度落在约10-2-10-5乇范围内是理想的，以便缩短达到真空的排出时间和节约为此必需的能量。在10-2乇以上的较低真空度下，容器中的杂质增加较大，另一方面，在10-5乇以下的较高真空度下，需要增加时间和大量能量以排出容器中的空气。
一旦容器中的空气被排空，随后用新气体填充或“进料”，其将用于碳涂层26的形成。新气体的流速优选在约1-100ml/min的范围内。优选容器内新气体的扩散通过提供扩张而增强，如一根具有多个吹孔的管子。根据一个实施例，在开口13被密封一会儿后扩张通过第二孔进入容器10内，并且扩张延伸到约25.4mm-50.8mm(1.0in-2.0in)范围内的容器最低部分。
新气体可以由脂族烃类、芳香族烃类、含氧烃类、含氮烃类等等组成，在室温为气态或液态。优选各具有6个或多于6个碳原子的苯、甲苯、邻二甲苯、间二甲苯、对二甲苯和环己烷。新气体可以单独使用，但也可使用两种或多于两种新气体的混合物。而且新气体也可在用惰性气体如氩和氦稀释的状态下使用。
容器被碳涂布装置的接纳机构接纳后的某一点，将容器插入提供来容纳容器的圆筒或其它中空空间。在优选的实施例中，碳涂布装置包括许多中空的圆筒，其与接纳机构同向并同步旋转。更优选固定和密封容器的开口13的接纳机构也起作用覆盖圆筒。
在新气体供入容器后，能量从高频电能源传递到容器，如微波产生装置，电能的效果产生等离子体和引起极度的分子激发离子化及碳涂层26在容器的内表面22上形成。
虽然上述方法说明了一种在容器内表面22上形成碳涂层26的过程，但是其它传统的方法也能成功地使用。例如，塑料容器可代之以被插入和接纳在外电极内，及具有位于容器内的内电极。容器排空并通过内电极提供进新气体后，电能由高频电源供应到外电极。供应的电能在外电极和内电极之间产生等离子体。因为内电极是接地的和外电极是通过绝缘件绝缘的，在外电极上产生负的自给偏压，结果碳膜均匀地沿着外电极形成在容器内表面上。
当等离子体在外电极和内电极之间产生时，电子堆积在绝缘外电极的内表面上对外电极负充电，在外电极上产生负的自给偏压。在外电极，由于电子的堆积产生电压降。此时，作为碳源的二氧化碳存在于等离子体中，并且正离子化碳源气体被选择地与容器的内表面22碰撞，其沿着外电极排列，然后，互相靠拢的碳结合在一起，由此在容器的内表面22上形成含有异常稠密的涂层的硬碳膜。
碳涂层26的厚度和均匀性的改变可以通过调节高频输出；容器中新气体的压力；为容器充气的气体流速；产生等离子体经过的时间周期；自给偏压和使用的原材料种类；以及其它诸如此类的变量。但是，碳涂层26的厚度优选在0.05-10μm范围内，从而得到对渗透有效的抑制和/或低分子有机化合物的吸收以及改善的气体抗渗性，除了对塑料极好的粘附性外，还有好的耐久性和好的透明性。
图4所示是根据本发明的原理构造的容器100的又一个实施例的正视图。容器100通常包括上壁部112，含有开口113；位于上壁部112下方的中间侧壁部114；以及位于中间侧壁部114下方的底部116。底部116适于或者是非独立地支持容器100，即此处采用另外的物件如基杯(未示出)，或是独立地，即此处不需要其它物件支持容器竖直立在一普通平面上。在一个优选实施例中，容器100是由多个整体形成的脚118形成的独立式基底支持，如图4所示的那些。
参见图5-7，它们分别表示图4的100A，100B和100C部分的放大详图，容器100包括一模塑外层120，具有垂直长度，一内表面122，一外表面123和一中心立轴B。模塑外层120的内表面122用碳薄层或膜124至少部分涂布，如在图1-3的实施例中。虽然，优选用碳层124完全包围内层120，但对具体的应用可以不需要的，优选模塑外层120大体上与碳层124作同等扩张并为容器100提供结构支持。
模塑外层120至少含有50％回收塑料，理想的是至少75％回收塑料，并可以含有多如90％回收塑料。如果需要，模塑外层可以是100％的回收塑料。优选地，模塑外层是由回收的聚对苯二甲酸乙二醇酯(PET)形成，但是本发明不限于此，并且事实上任何回收塑料可以方便地使用。
理想的是模塑外层120由一种热塑性塑料材料构成并可利用图1所列出的用于模塑内层20的材料。
特别理想的是，用小量的抗渗性材料和/或氧清除或反应材料与回收塑料混合，如关于图1所讨论的。例如，小于5％重量的赛纶，乙烯乙烯醇共聚物(EVOH)和丙烯腈共聚物，如Barex。此外，本发明能够易于利用特性粘度(IV)极低的材料，例如具有IV低于0.60或0.55的材料。这些材料时常是白色或带白色的颜色。本发明的显著优点是能够简单有效地处理加工过程中的碎片，甚至如前述材料。
外层120的内表面122涂布一薄碳层124，其对容器100提供增强的抗渗性。碳涂层124的特征、特性和制备已经在上面根据图1描述并且这也应用在图4-7的实施例中。
模塑外层120沿其垂直长度的壁厚在6-23密耳(0.1524mm-0.5842mm)的范围内。如图5-7所示，外层的厚度沿其垂直长度也可以分别地和单独地变化。如图1的外层24一样。在与图1的外层24同样的方式中，因为模塑外层120通常是由不太贵的塑料材料构成，该材料不与容器100的内容物直接接触，不太贵的材料可以用于形成容器的大部分，包括容器的许多结构整体部件，如图4所示的颈部凸缘126和外螺纹128。
同样地，内碳涂层可以很容易地改变，使其厚度沿着容器的垂直长度变化。然而，为方便理想的是提供大体上均匀的碳涂层。
图4-7的实施例显示有关图1-3描述的本发明的显著优点。
图4-7的容器可以由已知的几种加工技术的任何一种成型，其允许制造如图1所述的单层或多层吹塑容器。在优选实施例中，容器100经过吹塑工序成型包括预成型品130，如通常在图8中描述的。虽然没有一个要求的特征，但是预成型品130可以包括颈部凸缘132(用于再加工目的)和外螺纹134(为保证密封)，其相应于图4所示的相同特征。容器吹塑成型为成品容器100后，图4表示了一个实施例子，但是有时在填充工序前，容器内表面122作碳处理，如前面进一步讨论的。
在图9所示的一个实施例中，将成为容器的预成型品140是通过挤塑成型具有预成型品主体146和预成型品基底148，颈部凸缘142和外螺纹144的预成型品140生产的。挤塑加工允许制造者易于沿着挤出物长度改变挤出材料的厚度。由于几个原因预成型品厚度的改变所希望的，其包括美学的，有效的材料利用和成本降低，以及不同的强度要求。
预成型品140含有回收塑料，如上文指出的是本发明的一个特别优点。
在图8的实施例中，预成型品130的生产是通过热成型塑料薄片材和将该片材成型为将要成为预成型品130的，或注塑或压塑成型预成型品130。因此，图8的预成型品130可以包括颈部凸缘132和外螺纹134，将成为容器主体部分的主体部分136和将成为容器基底部分的底部138。
然后，可以用上述传统吹塑工序吹制容器。
在预成型品通过吹塑成型为半成品容器后，至少在容器120的内表面122的一部分上形成碳涂层，并优选在整个内表面上，如上对图1的描述。碳涂层124不必立即施加到容器，然而，通常更有效的是在半成品容器吹制成后以及在合适的温度曲线内迅速地施加碳涂层。
图4的容器显示出除图1那些外的显著优点。基础容器是单层材料，其能够通过传统方法很容易地加工。而且，回收的基础材料能够易于与其它材料混合，并且由于内部的碳涂层而不接触容器内容物。而且，抗渗性能够迅速和容易地得到以及容器内容物不受有害的香气或味道影响。此外，本发明消除了对单独的抗渗性衬里或原衬里的需要。少量的内部碳涂层对于回收没有不利的影响，并且易于使用有色材料提供所希望颜色的容器，例如，外层能够易于着色成所希望的商用颜色。
图4的容器显示出具有理想的技术性能的单层容器的显著优点，如抗渗性和低成本。因此，加工比多层容器容易得多，因为，人们对单层材料加工没有必要使用衬里的和复杂的共注塑加工。而且，人们可以把回收塑料与其它材料混合从而很容易地获得一些特殊性质同时仍然保留使用理想的低成本回收塑料。例如，人们可以定制产品以获得所希望的特性同时仍然利用回收塑料和一种单层材料。
内碳涂层是简单和方便地施加，并且很薄，还阻止有害气味和味道进入容器内容物。尤其理想的是将各种颜色用于回收塑料，例如琥珀色用于啤酒。非常理想的是使用如本发明中这种容器具有专用颜色和用于啤酒或软饮料或浆汁产品。作为更进一步的替换，人们可以将耐热塑料与回收塑料混合，从而得到非常想要的特性。
虽然已经描述了本发明的某些优选实施方案，但是本发明不限于描述和显示于此的举例说明，其被认为仅仅是实施本发明的最好方式的举例。人们或本领域的普通技术人员将了解某些替换，变型和变化都将在本发明的教导内，并且这类替换，变型和变化都在所附的权利要求的精神和广泛范围内。

Claims (20)

1.一种吹塑多层容器(10)，包括具有开口(13)的上壁部(12)；位于上壁部(12)下方的中间侧壁部(14)和位于中间侧壁部(14)下方并适合于支持容器(10)的底部(16)，该容器(10)包括：
由塑料形成的模塑内层(20)，具有垂直长度和内表面(22)；
模塑外层(24)，其大体上与内层(20)作同等扩张；
形成在内层(20)的内表面(22)上的碳涂层(26)，
其中外层(24)包括容器(10)总重量的至少0.40重量；
所述碳涂层(26)具有沿所述容器(10)的垂直长度上在0.05到10微米范围内变化的厚度，以及
其中所述容器能够被回收。
2.根据权利要求1的吹塑多层容器(10)，其中内层(20)是由一种树脂构成的一种塑料材料成型的，该树脂选自下列组中：聚乙烯树脂，聚丙烯树脂，聚苯乙烯树脂，环烯烃共聚物树脂，聚对苯二甲酸乙二醇酯树脂，聚萘二甲酸乙二醇酯树脂，乙烯-(乙烯醇)共聚物树脂，聚-4-甲基戊烯-1树脂，聚(甲基丙烯酸甲酯)树脂，丙烯腈树脂，聚氯乙烯树脂，聚偏二氯乙烯树脂，苯乙烯-丙烯腈树脂，丙烯腈-丁二烯-苯乙烯树脂，聚酰胺树脂，聚酰胺酰亚胺树脂，聚缩醛树脂，聚碳酸酯树脂，聚对苯二甲酸丁二酯树脂，离聚物树脂，聚砜树脂，聚四氟乙烯树脂，以及两种或更多的此类树脂的组合。
3.根据权利要求1的吹塑多层容器(10)，其中内层(20)是由选自一组包括挤塑和热成型的一种加工方法成型的，及外层(24)是选自一组包括注塑和压塑的一种加工方法成型的。
4.根据权利要求1的吹塑多层容器(10)，其中内层(20)包括选自下列组中的一种材料：原塑料材料，抗渗性材料，氧清除材料，以及抗渗性和氧清除的一种组合材料。
5.根据权利要求1的吹塑多层容器(10)，其中至少内层(20)和外层(24)之一具有沿其垂直长度变化的厚度。
6.根据权利要求1的吹塑多层容器(10)，其中内层(20)和外层(24)的厚度可控制地相互变化。
7.根据权利要求1的吹塑多层容器(10)，其中沿着容器(10)中间部分的内层(20)厚度小于外层(24)厚度的0.15。
8.根据权利要求1的吹塑多层容器(10)，其中碳涂层(26)的厚度小于10μm和碳涂层(26)的重量小于容器(10)总重量的约1/10000th。
9.根据权利要求1的吹塑多层容器(10)，其中碳涂层(26)是非晶体。
10.根据权利要求1的吹塑多层容器(10)，其中所述模塑外层(24)含有回收塑料。
11.根据权利要求1的吹塑多层容器(10)，包括含有支持凸缘(30)的容器(10)上部(12)和含有多个脚(18)的底部(16)中的至少一种。
12.一种吹塑多层容器(100)，包括具有开口(113)的上壁部(112)，位于上壁部(112)下方的中间侧壁部(114)，以及位于中间侧壁部(114)下方和适于支持容器(100)的底部(116)，所述容器(100)还包括：一模塑外层(120)，具有内表面(122)和外表面(123)并包括回收塑料；一碳涂层(124)邻近外层(120)的内表面(122)形成并粘附其上且大体上与外层(120)作同等扩张，其中所述碳涂层(124)具有沿所述容器(100)的垂直长度上在0.05到10微米的范围内变化的厚度，其中所述容器(100)能被回收。
13.根据权利要求12的容器，其中所述外层(120)的厚度为6-23密耳。
14.根据权利要求12的容器，其中所述外层(120)的厚度改变以使中间侧壁部(114)比上壁部(112)和底部(116)薄。
15.根据权利要求12的容器，含有抗渗性材料添加到外层(120)。
16.根据权利要求12的容器，其中来自至少一种气态烃的碳涂布在吹塑容器(100)的内表面(122)上。
17.根据权利要求12的容器，其中碳涂层(124)是非晶体。
18.根据权利要求12的容器，包括含有支持凸缘(126)的容器(100)上部(112)和含有多个脚(118)的底部(116)中的至少一种。
19.根据权利要求12的容器，其中外层(120)是有颜色的。
20.根据权利要求12的容器，其中外层(120)含有至少75％的回收塑料。
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EP1124729A4 (en) 2004-12-01
BR0006955A (pt) 2001-07-31
PL212687B1 (pl) 2012-11-30
US20030207058A1 (en) 2003-11-06
PL347136A1 (en) 2002-03-25
CA2341861C (en) 2006-09-19
AU6494500A (en) 2001-03-05
HK1040970A1 (en) 2002-06-28
NO331862B1 (no) 2012-04-23
EP1124729A1 (en) 2001-08-22
AU742923B2 (en) 2002-01-17
CZ2001729A3 (cs) 2001-07-11
WO2001010725A1 (en) 2001-02-15
US6592956B2 (en) 2003-07-15
NO20011053L (no) 2001-04-05
HK1040970B (zh) 2006-09-22

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