CN102119107A - 具有泡沫层的包覆成型容器 - Google Patents
具有泡沫层的包覆成型容器 Download PDFInfo
- Publication number
- CN102119107A CN102119107A CN2009801241318A CN200980124131A CN102119107A CN 102119107 A CN102119107 A CN 102119107A CN 2009801241318 A CN2009801241318 A CN 2009801241318A CN 200980124131 A CN200980124131 A CN 200980124131A CN 102119107 A CN102119107 A CN 102119107A
- Authority
- CN
- China
- Prior art keywords
- container
- preform
- blow
- mer
- poly
- 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.)
- Pending
Links
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- 239000004033 plastic Substances 0.000 claims description 50
- 229920003023 plastic Polymers 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 48
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 31
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 21
- 238000001746 injection moulding Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 206010000269 abscess Diseases 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 238000000071 blow moulding Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 241001597008 Nomeidae Species 0.000 claims description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 description 30
- 238000005516 engineering process Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 239000012530 fluid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 235000014171 carbonated beverage Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Images
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Abstract
公开了一种包覆成型的预成型品和由所述预成型品吹塑成型的容器,其中包覆成型的预成型品和包覆成型的容器包括外泡沫层。
Description
相关申请的交叉引用
本申请是2004年12月17日提交的美国专利申请11/015,360的部分继续申请,由此全文并入本申请,该申请要求享有2004年2月17日提交的美国临时专利申请60/545,049的利益,由此通过参考的方式全文并入本申请,本申请也是2003年10月14日提交的美国专利申请10/684,611的部分继续申请,由此通过参考方式全文并入本申请,该申请要求享有2002年10月30日提交的美国临时专利申请60/422,223的利益,由此通过参考的方式全文并入本申请。
技术领域
本发明总体涉及一种具有泡沫层的塑料容器。更特别地,本发明涉及一种包覆成型的多层塑料容器,其包括至少一层泡沫层,其中泡孔包含二氧化碳或氮气。
背景技术
双轴取向的多层瓶可以由塑料材料制成,例如,象使用加热预成型工艺的聚对苯二甲酸乙二醇酯(PET),其中多层预成型品被加热到所需的取向温度,然后拉伸并吹制成与围绕的模腔一致。多层预成型品可以由任何传统工艺制备,例如通过共注塑包括多层塑料的预成型品,或通过在先前注塑成型的预成型品上注塑后续的塑料层。通常多层是用于食品或碳酸饮料容器,以提高整个包装中氧气或二氧化碳的扩散阻隔性质。
现有技术中多层容器的各个塑料层一般是相互紧密接触,从而有利于通过容器的壁传导热量。这就使得容器内冷却的内容物能很快加温到环境温度。因此,这种容器通常例如覆套在泡沫聚苯乙烯壳内以给予容器热绝缘性能。
这就希望制备一种具有提高的热绝缘性能的多层容器。
附图说明
本发明的上述优点以及其它优点将通过以下根据附图考虑的优选实施方式的详细说明,对于本领域技术人员将变得显而易见,其中:
图1是依据本发明实施方式的包覆成型热塑性聚合物预成型品的横截面图;
图2是适于被包覆成型的非泡沫预成型品的实施方式的横截面图;
图3是依据本发明实施方式的图1的多包覆成型的预成型品形成的包覆成型容器的横截面图;以及
图4是依据本发明另一个实施方式制备图1的包覆成型的预成型品和图3的包覆成型容器的方法的示意图。
发明内容
与本发明相协调一致,令人惊奇地公开了一种具有上述特征的包覆成型容器。该包覆成型容器包括:第一塑料层,和与第一塑料层接触的第二塑料层,第二塑料层形成为泡沫。
具体实施方式
下面的详细说明和附图对本申请的多个示例性实施例进行描述和图示。这些说明和附图是为了使本领域技术人员能够制造和使用本发明,并不是以任何形式对本发明的范围进行限制。至于所公开的方法,列出的步骤本质上也是示例性的,因此这些步骤的顺序并不是必然或关键的。
本发明的一个实施例涉及容器,包括第一塑料层和与所述第一塑料层接触的第二塑料层,所述第二塑料层形成为泡沫,其中泡孔含有二氧化碳或氮气。
第一塑料层和第二塑料层在成分、厚度、取向等方面可以是相同或不同的。另外,本发明还预期一种具有任意数量(大于一)塑料层的容器,只要至少一层塑料层包含泡沫。此外,本发明预期使用多孔泡沫塑料层,其中泡孔不仅包含二氧化碳,还包含一种或多种其它气体。
可以制备第一塑料层和/或第二塑料层的适当的塑料包括,但不必局限于,聚酯、丙稀腈酸酯、氯乙烯、聚烯烃、聚酰胺及其类似物,和它们的衍生物、混合物和共聚物。用于一层或两层塑料层的优选塑料是PET。
除二氧化碳外,泡孔可以包含通常用于多孔泡沫结构的制造方法中的其它气体,包括氮气、氩气和类似气体。优选地,泡孔中存在的二氧化碳的总量按重量计算可以为约百分之四到百分之八,并且可能达到按重量计算的百分之十。泡沫层作为有效的热绝缘体,用于阻止热量从空气到容器内冷却的饮料的传导。
多层容器可以通过传统吹塑技术由多层预成型品制成。多孔泡沫塑料层可以与其它塑料层同延制备,例如共挤塑工艺,或者在多步注塑成型工艺中将第一塑料层施加到泡沫塑料层上或由泡沫塑料层接收。
为了制备预成型品,聚合物薄片在传统的塑化螺杆挤出机中被熔化,以在挤出机的排出口处形成热聚合物熔体的均质流。特别地,从挤出机排出的聚合物熔体流的温度的范围为约225摄氏度至约325摄氏度。本领域普通技术人员可以理解聚合物熔体流的温度由几个因素决定,包括使用的聚合物薄片的种类,输入挤出机螺杆的能量等。例如,PET通常在约260摄氏度到约290摄氏度的温度下挤出。非活性气体在压力下注入挤出机的混合区域内,以最终导致气体滞留作为聚合物材料的微孔间隙。本文使用的术语“非活性气体”表示与聚合物基本上不反应的气体。优选的非活性气体包括二氧化碳、氮气和氩气,以及这些气体相互或与其它气体的混合物。
众所周知,无定形PET的密度是1.335g/cm3。还知道熔化状态的PET的密度是大约1.200g/cm3。这样,如果预成型注射腔完全装满熔化的PET并使其冷却,那么形成的预成型品无法具有适当的重量并且会有许多严重的缺陷,例如凹痕。为了抵消无定形PET和熔化的PET之间密度的差异,现有技术注塑成型工艺教导的是,在腔体已被填满并且当材料在冷却时必须向部件加入少量的聚合物材料。这就是所谓的保压压力。这样,注塑成型周期的保压压力阶段期间需要加入大约百分之十的额外的材料,以保证由注塑成型制成的预成型品充分充满并充分成型。注塑成型操作中的保压压力阶段同样用于除PET之外的聚合物材料。
然而依照本发明,聚合物预成型品被注塑成型并同时利用非活性气体发泡。气体在注塑阶段被带入材料中。与在保压压力阶段期间注射额外聚合物材料的现有注塑成型过程不同,本发明利用最小的保压压力。由于聚合物材料仍然处于熔化状态,因此活性气体的部分压力足够促使溶解的气体从聚合物中释放为气态,在那里其形成微孔泡沫结构。这样,通过本发明工艺制成的预成型品比通过使用保压压力方法的传统注塑成型操作制成的聚合物预成型品轻,但具有相同的形式和几何结构。
完成注塑成型步骤后,预成型品冷却到低于聚合物软化温度以下的温度。例如,PET的软化温度大约为70摄氏度。由此,滞留的非活性气体保持在聚合物预成型品的壁内。该冷却步骤对本发明工艺至关重要,因为其使聚合物保持良好状态并且保证它成功制备吹塑成型容器所需要的特性。该冷却步骤在采用不能直接从挤压的型坯进行吹塑成型的聚合物时也是必要的,例如聚酯。冷却步骤可由聚合物成型工艺中使用的任何常规步骤实现,例如,在预成型品的表面之上通过一股冷空气流,或者通过冷却成型模具在模内冷却预成型品。
此后预成型品重新加热到聚合物软化温度之上的温度。该加热步骤可以通过已知的方式实现,例如,通过将预成品暴露在热气流中、用火焰冲击、暴露在红外能中、将预成型品通过传统的炉子或者类似的方式。PET通常要重新加热到高于其软化温度二十至二十五度的温度用于后续的吹塑成型操作。如果PET重新加热到远高于其玻璃化转变温度,或者保持在高于其软化温度过长时段,那么PET将不希望地开始结晶并变白。同样,如果预成型品加热高于这样的温度:在该温度通过增加微孔中非活性气体的压力使得材料的机械性能超出限度,那么微孔将不希望地开始膨胀以至于扭曲了预成型品。
最后,预成型品被吹塑成型以制备成容器,其基本上包括在微孔泡孔中含有非活性气体的微孔泡沫聚合物。由聚合物预成型品吹塑成型容器的方法和设备是众所周知的。
本领域技术人员很容易意识到,使用的塑料层的数量和类型、制造泡沫层的各种方法(化学的和物理的)是可以在宽范围内变化的以便于制造多种预期的根据本发明多层容器,容器包括第一塑料层和与所述第一层接触的第二塑料层,所述第二塑料层形成为泡沫,其中泡孔包含二氧化碳。
图2是依据本发明的实施例的包覆成型预成型品18。为了形成包覆成型预成型品18,如图1所示提供了适宜被包覆成型的预成型品14。使用本领域已知的工艺和机器,预成型品14通过塑料材料注塑成型制成,例如聚对苯二甲酸乙二醇酯(PET)。
接着预成型品14采用泡沫材料16被包覆成型形成包覆成型预成型品18。包覆成型预成型品18包括由预成型品14形成的内层和由泡沫材料16形成的外泡沫层。可以制备泡沫材料16的适宜的塑料包括,但不必限制于:聚酯、丙烯腈酸酯、氯乙烯、聚烯烃、聚酰胺及其类似物,和它们的衍生物、混合物和共聚物。泡沫材料16的优选塑料是PET。泡沫材料16可以通过共挤出工艺与形成预成型品14的材料同延形成,或者通过同时注塑成型泡沫材料16和形成预成型品14的材料从而可以将泡沫材料16施加到或者接收到预成型品14上。可选地,泡沫材料16可以在多步工艺中与预成型品14一起成型,例如多步骤注塑成型工艺。包覆成型预成型品18可以在与利用多步骤注塑成型工艺制造预成型品14相同的模具中成形,或者通过使用嵌件成型工艺将预成型品14转移到第二模具中进行包覆成型步骤。在预成型品14上多包覆成型的泡沫材料16的厚度和表面面积会基于设计考虑而变化,例如基于成本和包覆成型的容器20的所需外观。
接着,包覆成型预成型品18被吹塑成型以形成包覆成型的容器20,如图3所示容器具有外泡沫层和内非泡沫层。包覆成型容器20可以由传统吹塑成型技术形成,例如重热拉伸吹塑成型。
依照本发明的另一个实施例,制备包覆成型预成型品18和包覆成型容器20的过程示意地图示在图4中。首先,制备包覆成型预成型品18的泡沫材料16的聚合物熔体并将其包覆成型在预成型品14上。聚合物熔体通过在传统塑化螺杆挤出机中熔化的聚合物薄片而形成,以便在挤出机排出口处制备聚合物熔体的均质流。通常从挤出机排出的聚合物熔体流的温度范围为约225摄氏度到约325摄氏度。本领域普通技术人员可以理解聚合物熔体流的温度由几个因素决定,包括使用的聚合物薄片的种类、输入挤出机螺杆的能量等。例如,PET通常在约260摄氏度到约290摄氏度的温度下挤出。非活性气体在压力下注入挤出机的混合区域中,最终导致滞留气体作为聚合物材料内的微孔间隙。此处使用术语“非活性气体”表示与聚合物基本上不反应的气体。优选的非活性气体包括二氧化碳、氮气和氩气,以及这些气体相互或与其它气体的混合物。
挤出物注塑成型在预成型品14上形成包覆成型预成型品18,其具有在其壁内捕获有非活性气体的外泡沫层。注塑包覆成型聚合物预成型品的方法和设备是本领域已知的。
众所周知,无定形PET的密度是1.335g/cm3。还知道熔化状态的PET的密度是1.200g/cm3。这样,如果预成型注射腔完全装满熔化的PET并使其冷却,那么形成的预成型品无法具有适当的重量并且会有许多严重的缺陷,例如凹痕。为了抵消无定形PET和熔化的PET之间密度的差异,现有技术的注塑成型工艺中教导,在腔体被填满并且当材料冷却时必须加入少量的聚合物材料。这就是所谓的保压压力。这样,在注塑成型周期的保压压力阶段期间需要加入大约百分之十的额外的材料,以保证由注塑成型制成的预成型品充分充满并充分成型。注塑成型操作中的保压压力阶段同样也用于除PET之外的聚合物材料。
然而依照本发明,预成型品14利用聚合物熔体包覆成型件同时利用非活性气体发泡。气体在注射阶段被带入材料中。与在保压压力阶段期间注射额外聚合物材料的现有技术的注塑成型工艺不同,本发明利用最小的保压压力。由于聚合物材料仍然处于熔化状态,所以非活性气体的部分压力足够促使溶解的气体从聚合物中释放形成气态,在那里其形成微孔泡沫结构。这样,通过本发明工艺制成的包覆成型预成型品18比通过使用保压过程的传统注塑成型工艺制成的聚合物预成型品轻,但具有相同的形式和几何结构。
完成注塑成型步骤后,包覆成型预成型品18冷却到低于聚合物软化温度以下的温度。例如,PET的软化温度大约为70摄氏度。由此,滞留的非活性气体保持在包覆成型预成型品18的壁内。冷却步骤对本发明工艺至关重要,因为其使聚合物保持良好状态并且保证它成功制备包覆成型容器20所需要的性能。该冷却步骤在采用不能直接从挤压的型坯进行吹塑成型的聚合物时也是必要的,例如聚酯。冷却步骤可以由在聚合物成型技术中使用的任何常规步骤来实现,例如,在包覆成型预成型品18的表面之上通过冷气流,或者通过冷却成型模具在模塑过程中冷却包覆成型预成型品18。
此后包覆成型预成型品18重新加热到聚合物软化温度之上的温度。该加热步骤可以通过已知的方式实现,例如,将包覆成型预成型品18暴露在热气流中、火焰冲击、暴露在红外能中、将包覆成型预成型品18通过传统的炉子或者类似的方式。PET通常要为后续的吹塑成型操作重新加热到高于其软化温度二十至二十五度的温度。如果PET重新加热到远高于其玻璃化转变温度,或者保持在高于其软化温度过长时段,那么PET将不希望地开始结晶并变白。同样,如果包覆成型预成型品18加热到这样的温度,在该温度以上通过增加微孔中非活性气体的压力使得材料的机械性能超出限度,那么微孔将不希望地开始膨胀以至于扭曲了包覆成型预成型品18。
最后,包覆成型预成型品18被吹塑成型以制备成包覆成型制容器20,其包括非泡沫内层和包括在微孔泡孔内含有非活性气体的微孔泡沫聚合物外层。由聚合物预成型品吹塑成型成容器的方法和设备是众所周知的。
除优选的气体外,微孔可以含有通常用在制造微孔泡沫结构工艺中的其它气体。另外,微孔泡沫作为有效的热绝缘体,用于阻止热量从环境到容器内冷冻碳酸饮料的传导。
通过上面的描述,本领域技术人员可以很容易地领会本发明的本质特征,在不背离其精神和范围的基础上,可以进行多种改变和改进来以使本发明适用于各种使用和情况。
Claims (20)
1.一种吹塑成型容器,包括:适于吹塑成型的塑料内层;和与所述内层接触的适于吹塑成型的塑料外层,所述塑料外层形成为泡沫,其中泡孔包含二氧化碳和氮气中的一种。
2.如权利要求1所述的吹塑成型容器,其中所述塑料内层包含选自下列组的塑料,所述组包括聚酯、丙烯腈酸酯、氯乙烯、聚烯烃、聚酰胺,及其衍生物、混合物和共聚物。
3.如权利要求1所述的吹塑成型容器,其中所述塑料内层包含聚对苯二甲酸乙二醇酯。
4.如权利要求1所述的吹塑成型容器,其中所述塑料外层包含选自下列组的塑料:聚酯、丙烯腈酸酯、氯乙烯、聚烯烃、聚酰胺,及其衍生物、混合物和共聚物。
5.如权利要求1所述的吹塑成型容器,其中所述塑料外层包含聚酯。
6.如权利要求1所述的吹塑成型容器,其中所述塑料外层包括聚对苯二甲酸乙二醇酯。
7.如权利要求1所述的吹塑成型容器,其中所述塑料外层和所述塑料内层是相同的。
8.如权利要求1所述的吹塑成型容器,其中所述塑料外层和所述塑料内层是不同的。
9.如权利要求1所述的吹塑成型容器,其中泡孔包含选择下列组的气体,所述组包括:二氧化碳、氮气、氩气、空气、及其混合物和衍生物。
10.如权利要求1所述的吹塑成型容器,进一步包括形成在容器端部的螺纹部分,适于接收协作的盖。
11.一种多层预成型品,包括:塑料内层;和与所述内层接触的塑料外层,所述塑料外层形成为泡沫,其中泡孔内包含气体。
12.一种制备具有泡沫壁的容器的方法,包括步骤:注塑成型聚合物预成型品;用聚合物包覆成型所述聚合物预成型品,以使非活性气体被捕获在其壁内;将预成型品的温度冷却到聚合物软化温度之下的温度;将预成型品重新加热到高于聚合物软化温度的温度;和吹塑成型预成型品以制成主要包含微孔泡沫聚合物的容器,容器具有在微孔泡孔中含有非活性气体的外泡沫层。
13.如权利要求12所述的制备容器的方法,其中聚合物包括选自聚酯、聚丙烯、丙烯腈酸酯、氯乙烯、聚烯烃、聚酰胺,及其衍生物、混合物和共聚物的聚合物。
14.如权利要求12所述的制备容器的方法,其中聚合物包括聚对苯二甲酸乙二醇酯。
15.如权利要求12所述的制备容器的方法,其中非活性气体包括二氧化碳、氮气、氩气或者它们的混合物。
16.如权利要求12所述的制备容器的方法,其中非活性气体包括二氧化碳。
17.如权利要求12所述的制备容器的方法,其中非活性气体包括按重量计算达到浓度10%的二氧化碳。
18.如权利要求12所述的制备容器的方法,其中在多步注塑成型过程中用聚合物包覆成型聚合物预成型品,以使非活性气体被捕获在其壁内。
19.如权利要求12所述的制备容器的方法,其中在共挤过程中用聚合物包覆成型聚合物预成型品,以使非活性气体被捕获在其壁内。
20.如权利要求12所述的制备容器的方法,其中在共注塑过程中用聚合物包覆成型聚合物预成型品,以使非活性气体被捕获在其壁内。
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US5618486A (en) * | 1995-05-16 | 1997-04-08 | Sekisui Plastics Co., Ltd. | Process for manufacturing a heat-resistant molded foam product |
CN1440353A (zh) * | 2000-05-03 | 2003-09-03 | 伊斯曼化学公司 | 降低了吸热的容器底部杯型物 |
CN1925969A (zh) * | 2004-02-17 | 2007-03-07 | 塑料技术公司 | 具有发泡器壁的容器 |
Cited By (1)
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CN104943928A (zh) * | 2015-06-26 | 2015-09-30 | 广州一道注塑机械有限公司 | 一种气辅成型高阻隔瓶坯 |
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JP2011525880A (ja) | 2011-09-29 |
MX2010013990A (es) | 2011-02-25 |
EP2318282A1 (en) | 2011-05-11 |
KR20110033843A (ko) | 2011-03-31 |
CA2728359A1 (en) | 2009-12-30 |
AU2009262245A1 (en) | 2009-12-30 |
ZA201100509B (en) | 2011-10-26 |
BRPI0924570A2 (pt) | 2016-05-24 |
US20080251487A1 (en) | 2008-10-16 |
WO2009158397A1 (en) | 2009-12-30 |
RU2010150987A (ru) | 2012-07-27 |
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