CN101815749A - 包装部件及其制备方法 - Google Patents

包装部件及其制备方法 Download PDF

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CN101815749A
CN101815749A CN200880105293A CN200880105293A CN101815749A CN 101815749 A CN101815749 A CN 101815749A CN 200880105293 A CN200880105293 A CN 200880105293A CN 200880105293 A CN200880105293 A CN 200880105293A CN 101815749 A CN101815749 A CN 101815749A
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M·迪佩尔
W·洛瓦泽
M·霍夫曼
A·威萨德
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Amcor Flexibles Kreuzlingen AG
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Alusuisse Technology and Management Ltd
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    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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    • B65D1/02Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • B65D1/0215Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
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    • C08J7/04Coating
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    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/046Forming abrasion-resistant coatings; Forming surface-hardening coatings
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    • C08J7/048Forming gas barrier coatings
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    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
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Abstract

本发明涉及由塑料成形的包装部件,其具有对水蒸气和气体有好的阻透作用的无机阻挡层,该包装部件含有在真空下用具有所需阻透作用的材料产生的涂层。该真空涂层被涂以罩面漆层,来防磨损和防腐蚀和用于改进机械稳定性。

Description

包装部件及其制备方法
本发明涉及由成形的塑料制成的包装部件,其具有对水蒸气和气体有好的阻透作用的无机阻挡层(Barriereschicht),该包装部件含有在真空下用具有所需阻透作用的材料产生的涂层。本发明还涉及适于制备该包装部件的方法。
长期以来,食品是包装在玻璃或铝中。该两种材料可百分之百地防止气体和水蒸气渗透。这意味着没有气体能从外向里穿过包装壁,使得防止食品腐烂。同时还可实现无气体从里向外逸出,以防产品失去香味和发生干燥。
从生态角度看,这两种包装不是最佳的,并在包装形状结构上自由度很小。铝的缺点是不可制成透明包装,玻璃包装除有自重大外还具有总是必需顾及破裂或玻璃碎片的缺点。塑料包装有明显的优点。因为塑料本身通常仅具有不足够的阻气作用,所以必须对相应的包装提供附加的阻挡层。为此已知各种可能方法:
一个实例是其内侧含例如由EVOH制成的阻氧层的多层平膜的热成形。用此技术可实现透明的阻挡层包装。但这种包装的缺点是,由于热成形过程大大限制了其结构自由度。此外还已知,在可能的(已充填的包装)灭菌过程中该借助于EVOH的气体阻挡层会在此期间破裂,以致经过一定的时间,氧可通过包装壁进入食品。完全类似的局限性也适用于通过注塑和吹塑组合(注射吹塑)或挤出和吹塑组合(挤出吹塑)可产生的具有EVOH-阻挡层的“扁平类”容器。
另一实现可能性是具有整合的“模内标签(inmoldlabel)”,在其制备中,将具有所需阻挡层的箔引入注塑模具中并接着用塑料背喷(hinterspritzt)。但所得容器的成形自由度也大大受限于制备过程。
此外,在EP-B-1048746中描述了用真空涂覆制备具有阻挡作用的容器。其中阻挡层包装的制备是通过容器成形(注塑、热成形、吹塑)和接着真空涂覆由对此合适的材料组成的阻挡层实现。该包装用柔性阻挡薄膜作为盖箔包封。
如此制备的塑料-阻挡层包装基于下列观点仍不是最佳的:
-仅通过真空涂层常常仍达不到由顾客规定的食品的可保存性所需的阻挡作用。
-该特别薄的真空层易于机械磨损以及易于腐蚀,如在自动化装填(Abfüllen)所需操作中会导致阻挡作用的损失。
-鉴于该包装的灭菌应用,大部分纯真空涂层均未显示所需的稳定性。
-通过用柔性阻挡薄膜作为盖-密封薄膜,该包装在首次打开后不可再密封或仅不充分地再密封。
因此本发明的目的是提供一种改进的前述类型的包装部件,该包装部件如容器和密封盖不具有现有技术所附随的缺点。
该真空涂层被涂以罩面漆层(überlackiert)来防磨损和防腐蚀和用于改进机械稳定性,从而实现了本发明的目的。
该包装部件的成形可通过平膜材料(Flachfolienmaterial)的热成形、通过注塑或通过注塑和吹塑的组合(注射吹塑)或者挤出和吹塑的组合(挤出吹塑)实现。
该真空涂层可用下列方法之一实现:
-借助于等离子体-CVD涂覆以陶瓷层,优选通过PECVD(等离子体增强化学气相沉积)法涂覆以HMDSO(六甲基二硅氧烷)或TEOS(四乙氧基硅烷),特别优选以等离子体预处理涂覆以HMDSO和氧、HMDSO和氮、TEOS和氧或TEOS和氮。
-借助于DC-溅射法、AC-溅射法或RF-溅射法涂覆以氧化物层或氮化物层或硫化物层,优选借助于DC-溅射法,如下:
o在非反应性模式中,由氧化物靶、硫化物靶或氮化物靶出发。优选是导电的陶瓷靶如掺杂的氧化锌的DC-溅射。备选地,也可用非导电的陶瓷靶的RF-溅射涂覆。
o在反应性模式(如氧化锡、氧化钛)中,由金属靶出发在添加氧和或氮的情况下,借助于AC-溅射法或DC-溅射法进行。
-借助于溅射法涂覆以铝、钢、铜、锡、锌、银或它们的混合物的金属层,对非灭菌应用,优选为铝金属层,对灭菌应用,优选银、钢、锡或锌的金属层。
对经真空涂覆过的包装部件涂以罩面漆层
Figure GPA00001038765100021
例如可通过浸涂、流涂、浇涂、喷涂、胶头套印(Tampondruck)或借助于喷射进行。为降低包装部件上所施加的漆层厚度或为改进漆的分布,在涂罩面漆层过程后可后接离心过程。
通常基于天然粘合剂、缩聚树脂、加聚树脂、聚合树脂或其它粘合剂如溶胶凝胶漆、硅酸盐和硅酮的漆体系均适合用作罩面漆。该粘合剂也可与各种交联树脂如异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐(Metallalkoxide)交联。
为改进阻氧特性(Sauerstoffbarriereeigenschaft),特别优选基于EVOH、PVDC的漆、阳离子或自由基UV-硬化漆或基于烷氧基硅烷和/或金属醇盐和/或无机颗粒的溶胶凝胶漆。这类漆还可与各种交联树脂如异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐交联。
除具有阻氧性(Sauerstoffbarriere)之外还具有耐灭菌特性的漆也特别是基于EVOH、PVDC的漆、阳离子或自由基UV-硬化的漆或基于烷氧基硅烷和/或金属醇盐和/或无机颗粒的溶胶凝胶漆。这类漆也可与各种交联树脂如异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐交联。
特别优选的是基于丙烯酸酯或阳离子交联的环氧化物的溶胶凝胶漆体系和UV-硬化漆。该硬化可经热硬化或辐照硬化实现。特别优选的是通过UV-光或电子束硬化。
包装部件例如可以以用于容纳充填物的容器和/或针对容器的盖子的形式存在。
该容器以及容器和视需要的盖子的涂罩面漆层可在内侧或外侧进行。该外侧涂层使得可以例如在已充填和包封的包装上施加阻挡层和罩面漆层
Figure GPA00001038765100031
本发明制备的含用于容纳充填物的容器的阻挡层包装例如可如下包封:
-借助于包封在该容器上的有阻挡作用的柔性箔,或
-用推进式盖(Stülpdeckel)、锁扣盖(Schnappdeckel)或活盖(Klappdeckel)或用可由金属或塑料制成的螺旋封闭。在用塑料制成的螺旋封闭和由此不具完全阻挡作用的情况下,如前所述,可通过真空涂层和涂罩面漆层提供相应的气体阻隔。
本发明的包装部件也可以是由玻璃、硬纸板或其它材料制成的包装的盖子,如用于玻璃瓶的盖、适用于饮料纸盒的螺旋盖。
本发明的方法使得可由多种原料制备包装部件。具有可成型特性的透明塑料是特别适用的,如聚乙烯(PE)、聚丙烯(PP)、环烯烃共聚物(COC)、环烯烃聚合物(COP)、聚氯乙烯(PVC)、聚对苯二甲酸乙二酯(PET)、聚酰胺(PA)以及由所述材料制备的层压体。
可成堆肥(kompostierbar)和可生物降解的聚合物和/或基于可重复使用的原材料的聚合物也可用作制备包装部件的原料。
合适的成堆肥的聚合物特别是按EN 13432证实的和基于可重复使用和或不可重复使用的原材料的聚合物,如基于淀粉的聚合物(淀粉共混物)、PLA(聚交酯)、PHA(聚羟基烷酸酯)型聚酯如PHB(聚羟基丁酸酯)、PHV(聚羟基戊酸酯(Polyhydroxyvaleat))、由化学改性纤维素制成的纤维素材料、其它的由化学改性的纤维素制成的材料,以及特殊的由原油或天然气制备的合成聚酯。
基于可重复使用的原材料的聚合物例如由糖、淀粉、植物油或由纤维素制备。谷物、土豆、杂粮(Cerealien)、甘蔗和木材均为最常用的原材料。
合适的基于可重复使用的原材料的聚合物特别是特殊的聚酯,如基于PDO(生物丙二醇)的;特殊的聚酰胺,如由篦麻油制备的;以及PE(聚乙烯)、聚丙烯(PP)和PVC(聚氯乙烯)、基于如由甘蔗制备的生物乙醇。
本发明的具有罩面漆层的真空涂层使由具有高阻挡作用和按标准EN 13432证实可成堆肥的可重复使用的原材料制备包装部件成为可能。
如果需要抗灭菌条件的耐受性,则优选使用生物聚合物如PHA或基于可重复使用的原材料的聚丙烯。
在本发明方法的一个特别优选方案中,包装部件的制备、涂覆和涂覆罩面漆连续(in einer Linie)进行。
由下面的表可看出阻挡层和各种罩面漆体系对包装部件在灭菌处理前和后的阻氧性的影响。
表1示出均无罩面漆层的由未经涂覆的和涂有银(Ag)、钢(V2A)和锡(Sn)的聚丙烯(PP)制备的包装部件的阻挡作用。
表2示出具有各种漆体系的罩面漆层的由涂有银(Ag)和钢(V2A)的聚丙烯(PP)制备的包装部件的阻挡作用。
表3示出无罩面漆层的由涂有银(Ag)和钢(V2A)的聚交酯(PLA)制备的包装部件的阻挡作用。
表1:25℃和50%相对湿度下的阻氧性(cm3/(m224h bar)),无机阻挡层的影响
  包装材料   灭菌前   在121℃下灭菌30min
  PP500未涂覆   500   500
  PP/Ag   15   75
  PP/V2A   30   370
  PP/Sn   36   350
表2:25℃和50%相对湿度下的阻氧性(cm3/(m224h bar)),另外涂以罩面漆层的影响
  包装材料   灭菌前   在121℃下灭菌30min
  PP/Ag/漆1   0.5   0.98
  PP/Ag/漆2   9.4   28
  PP/Ag/漆3   1.1   2.3
  PP/V2A/漆1   0.4   6.2
  PP/V2A/漆2   31   210
  PP/V2A/漆3   3.1   6.4
漆1=100%UV-体系(无溶剂),阳离子硬化
漆2=100%UV-体系(无溶剂),自由基硬化
漆3=热硬化(含溶剂的)溶胶凝胶体系
表3:25℃和50%相对湿度下的阻氧性(cm3/(m224h bar)),无机阻挡层的影响
  包装材料
  PLA(1mm)未涂覆   14.5
  PLA(1mm)/Ag   1.9

Claims (24)

1.由成形的塑料制成的包装部件,其具有对水蒸气和气体好的阻透作用的无机阻挡层,该包装部件含有在真空下用具有所需阻透作用的材料产生的涂层,其特征在于,该真空涂层被涂以罩面漆层来防磨损和防腐蚀和用于改进机械稳定性。
2.权利要求1的包装部件,其特征在于,该罩面漆层的厚度为1-30μm,优选1-5μm。
3.权利要求1或2的包装部件,其特征在于,该包装部件由聚乙烯(PE)、聚丙烯(PP)、环烯烃共聚物(COC)、环烯烃聚合物(COP)、聚氯乙烯(PVC)、聚对苯二甲酸乙二酯(PET)、聚酰胺(PA)以及由所述材料制备的层压体成形。
4.权利要求1或2的包装部件,其特征在于,该包装部件由下列物质成形:可成堆肥的聚合物,特别是基于可重复使用的原材料的聚合物,如基于淀粉的聚合物(淀粉共混物)、PLA(聚交酯)、PHA(聚羟基烷酸酯)型聚酯如PHB(聚羟基丁酸酯)、PHV(聚羟基戊酸酯)、由化学改性纤维素制成的纤维素材料、其它的由化学改性纤维素制成的材料;基于可重复使用的原材料的聚合物特别是特殊的聚酯,如基于PDO(生物丙二醇)的;特殊的聚酰胺,如由篦麻油制备的;以及PE(聚乙烯)、聚丙烯(PP)和PVC(聚氯乙烯)、基于由例如甘蔗制备的生物乙醇,以及特殊的由原油或天然气制备的合成聚酯或由所述材料制备的层压体。
5.权利要求1-4之一的包装部件,其特征在于,该包装部件通过平膜材料的热成形、通过注塑或通过注塑和吹塑的组合(注射吹塑)或挤出和吹塑的组合(挤出吹塑)成形。
6.权利要求1-5之一的包装部件,其特征在于,该阻挡层由借助于等离子体-CVD,优选通过PECVD(等离子体增强化学气相沉积)法使用HMDSO(六甲基二硅氧烷)或TEOS(四乙氧基硅烷),特别是借助等离子体预处理使用HMDSO和氧、HMDSO和氮、TEOS和氧或者TEOS和氮产生的陶瓷层组成。
7.权利要求1-6之一的包装部件,其特征在于,该阻挡层由借助于溅射法产生的氧化物层或氮化物层或硫化物层组成。
8.权利要求1-7之一的包装部件,其特征在于,该阻挡层由借助于溅射法产生的铝、钢、铜、锡、锌、银或它们的混合物的金属层组成,对非灭菌应用,优选为铝的金属层,对灭菌应用,优选为银、钢、锡或锌的金属层。
9.权利要求1-8之一的包装部件,其特征在于,该罩面漆由基于天然粘合剂的漆体系组成,视需要与交联树脂特别是异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐、缩聚树脂、加聚树脂、聚合树脂,特别是溶胶凝胶漆、硅酸盐和硅酮交联。
10..权利要求1-8之一的包装部件,其特征在于,用于改进阻氧特性和/或耐灭菌特性的罩面漆由基于EVOH、PVDC的漆、阳离子或自由基UV-硬化漆或基于烷氧基硅烷和/或金属醇盐和/或无机颗粒的溶胶凝胶漆组成,视需要与交联树脂特别是异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐交联。
11.权利要求1-8之一的包装部件,其特征在于,该罩面漆由热硬化的或通过辐照硬化特别是通过UV-光硬化或电子束硬化的溶胶凝胶漆体系或丙烯酸酯漆组成。
12.权利要求1-11之一的包装部件,其为容纳充填物的容器和/或针对容器的盖子的形式。
13.用于制备具有对水蒸气和气体有好的阻透作用的包装部件的方法,其中该包装部件由塑料成形,且该包装部件成形后对水蒸气和气体的阻透作用以使用具有所需阻透作用的材料在真空下形成的涂层的形式产生,其特征在于,该真空涂层被涂以罩面漆层来防磨损和防腐蚀和用于改进机械稳定性。
14.权利要求13的方法,其特征在于,该容器和视需要的盖子由聚乙烯(PE)、聚丙烯(PP)、环烯烃共聚物(COC)、环烯烃聚合物(COP)、聚氯乙烯(PVC)、聚对苯二甲酸乙二酯(PET)、聚酰胺(PA)以及由所述材料制备的层压体成形。
15.权利要求13的方法,其特征在于,该容器和视需要的盖子由下列物质成形:可成堆肥的聚合物,特别是基于可重复使用的原材料的聚合物,如基于淀粉的聚合物(淀粉共混物)、PLA(聚交酯)、PHA(聚羟基烷酸酯)型聚酯如PHB(聚羟基丁酸酯)、PHV(聚羟基戊酸酯)、由化学改性纤维素制成的纤维素材料、其它的由化学改性纤维素制成的材料;基于可重复使用的原材料的聚合物特别是特殊的聚酯,如基于PDO(生物丙二醇)的;特殊聚酰胺,如由篦麻油制备的;以及PE(聚乙烯)、聚丙烯(PP)和PVC(聚氯乙烯)、基于如由甘蔗制备的生物乙醇,以及特殊的由原油或天然气制备的合成聚酯或由所述材料制备的层压体。
16.权利要求14或15的方法,其特征在于,该容器和视需要的包装的盖子通过平膜材料的热成形、通过注塑或通过注塑和吹塑的组合(注射吹塑)或者挤出和吹塑的组合(挤出吹塑)进行成形。
17.权利要求14-16之一的方法,其特征在于,借助于等离子体-CVD涂以陶瓷层,优选通过PECVD(等离子体增强化学气相沉积)涂以HMDSO(六甲基二硅氧烷)或TEOS(四乙氧基硅烷),特别优选以等离子体预处理涂以HMDSO和氧、HMDSO和氮、TEOS和氧或者TEOS和氮。
18.权利要求14-16之一的方法,其特征在于,借助于溅射法涂以氧化物层或氮化物层或硫化物层。
19.权利要求14-16之一的方法,其特征在于,借助于溅射法涂以铝、钢、铜、锡、锌、银或它们的混合物的金属层,对非灭菌应用,优选为铝的金属层,对灭菌应用,优选为银、钢、锡或锌的金属层。
20.权利要求14-19之一的方法,其特征在于,为了涂以罩面漆层,使用基于天然粘合剂的漆体系,视需要与交联树脂特别是异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐、缩聚树脂、加聚树脂、聚合树脂,特别是溶胶凝胶漆、硅酸盐和硅酮交联。
21.权利要求14-19之一的方法,其特征在于,用于改进阻氧特性和/或耐灭菌特性,为了涂以罩面漆层,使用基于EVOH、PVDC的漆、阳离子或自由基UV-硬化漆或基于烷氧基硅烷和/或金属醇盐和/或无机颗粒的溶胶凝胶漆,视需要与交联树脂特别是异氰酸酯、蜜胺树脂或脲树脂、硅烷或金属醇盐交联。
22.权利要求14-19之一的方法,其特征在于,为了涂以罩面漆层,使用溶胶凝胶漆体系和丙烯酸酯漆,和通过加热或通过辐照硬化特别是通过UV-光或电子束进行硬化。
23.权利要求14-22之一的方法,其特征在于,该包装部件是容纳充填物的容器和/或针对容器的盖子。
24.权利要求14-23之一的方法,其特征在于,该包装部件的制备、涂覆和涂覆罩面漆层连续地进行。
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