CN104768755A - 含有具有对矿物油的屏障特性的膜的食品包装 - Google Patents
含有具有对矿物油的屏障特性的膜的食品包装 Download PDFInfo
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- CN104768755A CN104768755A CN201380058697.1A CN201380058697A CN104768755A CN 104768755 A CN104768755 A CN 104768755A CN 201380058697 A CN201380058697 A CN 201380058697A CN 104768755 A CN104768755 A CN 104768755A
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Classifications
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Abstract
本发明涉及含有基于聚烯烃的膜的食品包装,其具有对矿物油的屏障特性。
Description
本发明涉及含有基于聚烯烃的膜的食品包装,所述膜具有对矿物油的屏障特性。
现今,基于聚烯烃的膜、尤其是双轴取向的丙烯膜(boPP)被用作宽范围应用中的包装膜。聚丙烯膜表现出许多有利的使用特性,比如高透明性、光泽、对水蒸气的屏障、良好的可打印性、刚性、穿透强度等。聚丙烯膜能够作为透明的膜和作为不透明的膜使用。
上述膜常常也与其它包装材料组合使用,尤其是在食品领域中。
卡纸板包装常常用于食品包装,由于其可获得性常常以回收卡纸板形式存在。这产生问题,原因在于回收卡纸板一般含有300-1000mg/kg的具有相对低摩尔质量(主要为n-C18至n-C22)的矿物油和15-20%的芳族组分含量(联邦风险评估局"BfR"意见编号008/2010,2009年09月12日)。
回收卡纸板中检测到的矿物油混合物是石蜡类(开链、通常支化)和环烷烃类(环状)的烃,其称为"矿物油饱和烃"(MOSH);并且是芳烃或"矿物油芳烃"(MOAH),其主要由高度烷基化的系统组成(参见Biedermann M,Fiselier K,Grob K,2009,"Aromatic hydrocarbons ofmineral oil origin in foods:Method for determining the totalconcentration and first results.Journal of Agricultural and FoodChemistry 57:8711-8721)。
在不采取适宜防止措施、例如卡纸板的金属化的情况下,从而存在上述指定的矿物油混合物会污染待包装或已包装的食品的风险。
用基于聚烯烃膜、尤其是双轴取向的聚丙烯膜(boPP)的膜作为上述指定的矿物油混合物的屏障的第一途径显示的是,聚烯烃膜单独无法有效地防止迁移。从而,膜需要额外的修饰,以便充当上述指定的矿物油混合物的屏障。
举例来说,适宜的是具有足够光密度的金属化的膜。该金属层形成对矿物油的有效屏障。然而,对于某些应用所述金属层是出于美学原因或成本原因所不希望的。尤其是,在膜包装需要透明时不能使用这些金属层。另外,屏障的效力也取决于涂层的品质,因此仅高品质的高成本金属化满足上述意图。
本发明的任务是,为从回收卡纸板形成的食品包装提供基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜,该膜具有对矿物油混合物的充足屏障并且同时保留良好的应用特性,从而回收卡纸板中的矿物油混合物对待包装的或已包装的食品的污染得以避免。
从而,本发明涉及食品包装,其包含:
a)食品,
b)基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜,所述膜包围食品,
c)基于回收卡纸板的卡纸板,其包围含有食品的基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜,
其特征在于所述基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜具有包含(i)丙烯酸聚合物和/或(ii)含卤素的乙烯基聚合物和/或亚乙烯基聚合物和/或(iii)基于乙烯基醇(VOH)的聚合物的至少一个涂层,并且所述涂层至少存在于膜朝向所述基于回收卡纸板的卡纸板的一侧上。
根据本发明的食品包装不需要任何通过表面金属化制成的屏障层,从而能够比例如金属化的卡纸板或金属化的膜更成本有利地制备。此外,在采用透明的实施方式的情况下,本发明使得之前由于金属化而不可能的新类型包装成为可能。
本发明能够通过不同构造设计的食品包装来实现。在一种实施方式中,袋包装或包裹包装采用本身已知的技术制备并且含有食品。然后,填充的袋包装或包裹包装在进一步包围的卡纸板包装中进行包装。在袋包装或包裹包装外侧的涂层防止矿物油从卡纸板迁移入食品。在又一实施方式中,卡纸板能够用涂覆膜层压或衬底。然后,从涂覆的卡纸板制备含有食品的包装。这种变型对包装是有利的,否则在所述包装中食品会直接与卡纸板接触。
膜:
在本发明范围内使用的基于聚烯烃的膜尤其是基于双轴取向的聚丙烯膜(boPP)的膜。这些膜能够单层或多层地构建和具有包含(i)丙烯酸聚合物和/或(ii)含卤素的乙烯基聚合物和/或亚乙烯基聚合物和/或(iii)基于乙烯基醇(VOH)的聚合物的涂层。
单层膜或多层构造膜的基底层含有各自有效量的聚烯烃、优选丙烯聚合物和任选其它的常规添加剂。基底层一般含有至少70至<100%重量,优选75至98%重量,尤其是85至95%重量的聚烯烃,各自基于层重量。
丙烯聚合物是优选的基底层聚烯烃或是用于单层膜的材料。这些丙烯聚合物含有90至100%重量、优选95至100%重量、尤其是98至100%重量的丙烯单元和具有120℃或更高、优选150至170℃的熔点,和一般在230℃和21.6N的力(DIN 53735)具有1至10g/10分钟、优选2至8g/10分钟的熔体流动指数。代表用于基底层的优选丙烯聚合物的是,无规比例为15%重量和更少的全同立构丙烯均聚物,乙烯含量为5%重量或更少的乙烯和丙烯共聚物,烯烃含量为5%重量或更少的丙烯和C4-C8烯烃的共聚物,和乙烯含量为10%重量或更少且丁烯含量为15%重量或更少的丙烯、乙烯和丁烯三元共聚物,其中全同立构丙烯均聚物是特别优选的。指定的百分比重量是指各自的聚合物。
另外,指定的丙烯均聚物和/或共聚物和/或三元共聚物和其它聚烯烃的混合物、尤其是2至6个C原子的单体是适宜的,其中混合物含有至少50%重量、尤其是至少75%重量的丙烯聚合物。聚合物混合物中适宜的其它聚烯烃是聚乙烯,尤其是HDPE,MDPE,LDPE,VLDPE和LLDPE,其中这些聚烯烃各自相对聚合物混合物的比例不超过15%重量。
在不透明的实施方式中,膜的基底层或单层膜含有空泡引发的填料,其量为至多30%重量、优选5至25%重量,相对不透明基底层的重量。
空泡引发的填料是固体颗粒,其与聚合物基质不相容的,并且随膜伸展导致空泡状空洞的形成。空泡引发的填料一般具有1μm的最小尺寸以导致有效的、也即致不透明的空泡量。颗粒的平均颗粒直径一般是1至6μm、优选1.5至5μm。颗粒的化学性质发挥次要作用。
常规的空泡引发填料是与聚丙烯不相容的无机和/或有机物质,比如氧化铝、硫酸铝、硫酸钡、碳酸钙、碳酸镁、硅酸盐比如硅酸铝(白陶土粘土)和硅酸镁(滑石)和二氧化硅,其中优选使用碳酸钙和二氧化硅。常规使用的与基底层聚合物不相容的聚合物能够是有机填料,尤其是描述于EP-A-O 623463环状烯烃的共聚物(COC),聚酯,聚苯乙烯,聚酰胺,卤化的有机聚合物,其中优选聚酯比如聚对苯二甲酸丁二酯和环烯烃共聚物。不相容的物质或不相容的聚合物在本发明意义中意指物质或聚合物在膜中以分离颗粒的形式或以分离的相的形式存在。
在又一不透明的实施方式中,基底层或单层膜除空泡引发的填料外额外地或另选地含有色素,例如其量为0.5至10%重量、优选1至8%重量、尤其是1至5%重量。指定的量涉及层重量。
色素在本发明意义中是不相容的颗粒,其基本上不随膜伸展而导致空泡形成。色素的例如着色效果是由颗粒本身引起的。色素是所谓的"白色色素"和"彩色色素",前者将膜染成白色,后者为膜提供彩色或黑色。一般来说,色素的平均颗粒直径的范围是0.01至1μm,优选0.01至0.7μm,尤其是0.01至0.4μm。
常规的色素是物质比如氧化铝,硫酸铝,硫酸钡,碳酸钙,碳酸镁,硅酸盐比如硅酸铝(白陶土粘土)和硅酸镁(滑石),二氧化硅和二氧化钛,其中优选使用白色色素比如碳酸钙,二氧化硅,二氧化钛和硫酸钡。二氧化钛是特别优选的。TiO2的各种修饰和涂层在现有技术中是本身已知的。
膜的密度基本上取决于基底层的密度。基底层的密度一般的范围是0.45-0.95g/cm3。与聚丙烯(~0.9g/cm3)密度相比,空泡降低基底层密度,而色素增加基底层密度。
膜厚度一般的范围是20至100μm,优选25至60μm,尤其是30至50μm。如果膜具有多层结构,则基底层厚度是10至60μm,优选10至40μm。上述厚度应理解为不含包含(i)丙烯酸聚合物和/或(ii)含卤素的乙烯基和/或亚乙烯基聚合物和/或(iii)基于乙烯基醇(VOH)的聚合物的涂层。
如果膜为多层构造,则膜除指定的基底层之外还包含施用至少至基底层的一侧或相对的两侧的层。从而在两个覆盖层的情况下引起膜的三层结构。
覆盖层的厚度一般是0.5-3μm。在本发明的又一实施方式中,中间层也位于覆盖层与基底层之间的一侧或两侧上,所述中间层的厚度的范围是1至8μm。在中间层和覆盖层组合的情况下,它们一起优选具有2至8μm的总厚度。
覆盖层能够构造为可密封的层,其理解为热可密封的和冷可密封的层。冷密封涂层能够直接施用至单层膜的表面。然而,一般优选首先将基底层用共挤出的聚合物层覆盖并将冷密封涂层施用至该聚合物覆盖层。用于热可密封的覆盖层的适宜物质是下文指定的均聚物、共聚物和三元共聚物。
为了改善附着,在涂层之前以本身已知的方式通过电晕、火焰或等离子体对膜表面应用增加表面张力的方法。然后,如此处理的层的表面张力一般的范围是35至45mN/m。该表面处理能够在膜的一个表面或两个表面上进行。
上文描述的覆盖从和中间层一般含有至少80%重量,优选90至<100%重量的烯烃聚合物或其混合物,和任选也含各自有效量的常规添加剂。适宜的聚烯烃是例如聚乙烯,丙烯共聚物和/或丙烯三元共聚物,以及已描述与基底层结合的丙烯均聚物。
适宜的丙烯共聚物或三元共聚物一般由作为共聚单体的至少50%重量的丙烯单元和乙烯单元和/或丁烯单元构成。优选的混合聚合物是乙烯含量为2至10%重量、优选5至8%重量的无规乙烯-丙烯共聚物,或丁烯含量为4至25%重量、优选10至20%重量的无规丙烯-丁烯-1共聚物,各自以共聚物总重量计;或乙烯含量为1至10%重量、优选2至6%重量且丁烯-1含量为3至20%重量、优选8至10%重量的无规乙烯-丙烯-丁烯-1三元共聚物,各自以三元共聚物总重量计。这些共聚物和三元共聚物一般具有3至15g/10分钟、优选3至9g/10分钟(230℃,21.6N DIN 53735)的熔体流动指数和70至145℃、优选90至140℃(DSC)的熔点。
适宜的聚乙烯是例如HDPE,MDPE,LDPE,LLDPE和VLDPE,其中HDPE和MDPE类型是特别优选的。HDPE一般具有按照DIN 53735测量大于0.1至50g/10分钟、优选0.6至20g/10分钟的MFI(50N/190℃),和按照DIN 53728第4部分或ISO 1191测量的100至450cm3/g、优选120至280cm3/g的粘度数。结晶度是35至80%,优选50至80%。在23℃按照DIN 53479方法A或ISO 1183测量的密度的范围是>0.94至0.96g/cm3。用DSC(熔化曲线最大值,加热速率20℃/min)测量的熔点是120至140℃。适宜的MDPE一般具有按照DIN 53735测量的大于0.1至50g/10分钟、优选0.6至20g/10分钟的MFI(50N/190℃)。在23℃按照DIN 53479方法A或ISO 1183测量的密度的范围是>0.925至0.94g/cm3。用DSC(熔化曲线最大值,加热速率20℃/min)测量的熔点是115至130℃。
膜一般在各层中含有常规量的常规稳定剂和中和剂,和任选地在一个或多个覆盖层中含有防粘连剂。仅向层加入不损伤涂层的添加剂或添加剂量作为润滑剂和抗静电剂。
作为稳定剂能够使用具有对乙烯、丙烯和其它烯烃聚合物的稳定化效果的常规化合物。所述化合物的加入量是0.05至2%重量。酚类稳定剂,碱/碱土金属硬脂酸盐和/或碱/碱土金属碳酸盐是特别适宜的。酚稳定剂优选的量是0.1至0.6%重量、尤其是0.15至0.3%重量,和具有大于500g/mol的摩尔质量。四-3-(3,5-二-叔丁基-4-羟基苯基)丙酸季戊四基酯或1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯是特别有利的。
中和剂优选是碳酸钙和/或水滑石(dihydrotalcite)(DHT),其平均颗粒尺寸为至多0.7μm,绝对颗粒尺寸为小于10μm,和比表面积为至少40m2/g。一般使用相对层50至1000ppm的量的中和剂。
适宜的防粘连剂是无机添加剂比如二氧化硅、碳酸钙、硅酸镁、硅酸铝、磷酸钙等和/或不相容的聚合物比如聚甲基丙烯酸甲酯(PMMA)聚酰胺、聚酯、聚碳酸酯等,优选聚甲基丙烯酸甲酯(PMMA)、二氧化硅和碳酸钙。防粘连剂的有效量是0.1至2%重量,优选0.1至0.5%重量,基于各覆盖层计。平均颗粒尺寸是1至6μm,尤其是2和5μm,其中如描述于EP-A-0236945和DE-A-3801535的球形颗粒是特别适宜的。
根据本发明包装中提供的膜通过本身已知的过程和方法来制备。
就随后的涂层而言,膜应一般在任何层中都不具有迁移添加剂,例如应不含润滑剂或抗静电剂,原因在于它们可以导致与涂层附着有关的问题。
涂层:
在本发明范围内使用的基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜具有包含(i)丙烯酸聚合物和/或(ii)含卤素的乙烯基和/或亚乙烯基聚合物和/或(iii)基于乙烯基醇(VOH)的聚合物的涂层。该涂层可以存在于膜的一侧或两侧。
膜每侧涂层的总厚度一般是0.1-5μm,优选0.5-3μm。涂层可以多层地施用,其中也使用不同的物质/聚合物例如丙烯酸聚合物和聚偏二氯乙烯(PVDC)的组合。在此情况中多层意指,每层中选自丙烯酸聚合物、聚偏二氯乙烯(PVDC)或基于乙烯基醇(VOH)的聚合物的指定物质之一作为主要组分存在。
膜一般最初在待涂覆侧上进行处理以便增加表面张力。一旦表面张力已被增加,通常将增附剂施用至待涂覆的表面。所述增附剂是本身已知的并且基于例如聚氨酯、丙烯酸聚合物或聚乙烯亚胺。增附剂还能够多层地施用(第二增附剂层),其中不同增附剂的组合也是可能的。在此情况下多层意指,每层中上述增附剂之一作为主要组分存在。如果聚乙烯亚胺水溶液作为增附剂施用,则其通常含有1%重量的聚乙烯亚胺。聚乙烯亚胺溶液有助于随后的涂层,如EP-A-0255870的描述。
根据本发明的涂层材料是(i)丙烯酸聚合物和/或(ii)含卤素的乙烯基聚合物和/或亚乙烯基聚合物和/或(iii)基于乙烯基醇(VOH)的聚合物。这些各自安排为实体层。实体层是由所定义的涂层材料构成的均质层。此处,对各自的涂层材料来说,上述指定的物质/聚合物的混合物是不希望的,但不排除共聚物形式。
除上述指定物质之外,涂层可能也含有进一步组分,例如作为润滑剂、优选非迁移润滑剂比如蜡和/或防粘连剂。
根据本发明的涂层材料作为分散体、尤其是含水分散体施用,其固含量为10至70%重量、优选20-60%重量。
按照本发明所用的丙烯酸聚合物优选是丙烯酸酯均聚物和/或丙烯酸酯共聚物,其基于例如烷基丙烯酸类比如甲基丙烯酸甲酯和/或丙烯酸乙酯,或其它共聚单体比如不饱和的羧酸或取代的乙烯基化合物。丙烯酸酯共聚物能够由2种或更多种不同单体构建。另外可能的是,各丙烯酸酯均聚物和/或丙烯酸酯共聚物的混合物。该类型的物质可在市场上获得,例如名为NeoCryl BT-36和NeoCryl FL-711(DSM NeoResins公司(荷兰))或其它名称(BASF公司)。优选的基于丙烯酸聚合物的含水涂层分散体包含至少80%重量的丙烯酸酯分散体,至少10%重量的蜡分散体,至少12%重量的胶体二氧化硅分散体,和至少7%重量的防粘连剂分散体。与100%重量的差异由水组成。膜每侧的丙烯酸酯涂层的量在干燥之后一般是0.1至1.5g/m2。该丙烯酸酯层的厚度是<2.0μm,包括增附剂层。
按照本发明使用的含卤素的乙烯基聚合物和/或亚乙烯基聚合物优选是基于氯乙烯均聚物和/或偏二氯乙烯均聚物和/或共聚物的聚合物,其中共聚单体源自乙酸乙烯酯、卤化乙烯或丙烯酸类。单独单体能够以不同权重存在于共聚物中。所述物质可在市场上获得,例如名为A 297,A 114和B 200(SolVin.S.A.公司(比利时))。优选的基于含卤素的乙烯基聚合物和/或亚乙烯基聚合物、尤其是聚偏二氯乙烯(PVDC)的含水涂层分散体包含至少95%重量的PVDC丙烯酸酯共聚物分散体,至少10%重量的蜡分散体,至少7%重量的防粘连分散体。与100%重量的差异由水组成。膜每侧涂层的量在干燥之后一般是2.5至4g/m2。该层的厚度是<4.5μm,包括增附剂层。
按照本发明所用的基于乙烯基醇(VOH)的聚合物是本身已知的乙烯基聚合物。优选的基于乙烯醇(VOH)的含水涂层材料是乙烯/乙烯醇共聚物(EVOH)和包含5-15%重量的乙烯/乙烯醇共聚物和聚乙烯醇的混合物,优选比率为0.8-1.2比1.2-0.8,尤其是1:1重量比。对于基于乙烯醇(VOH)的涂层材料,膜每侧涂层的量在干燥之后一般是0.5至1.0g/m2。该层的厚度是<2.0μm,包括增附剂层。
根据本发明的涂层材料优选在例如通过电晕处理增加表面张力从而改善附着之后施用。如已经提及的,增附剂通常在表面处理后施用至待涂覆侧和干燥。如果第二增附剂(第二增附剂层)是有利的,则也将其施用。增附剂和涂层材料按照本身已知的方法比如辊涂(轧辊施用系统例如刻槽轧辊)、帘式涂层、喷雾涂层来施用。然后,用常规的干燥方法(例如热空气)干燥施用的涂层。
按照本发明来使用涂覆的膜,使得膜涂覆侧面朝加载的卡纸板。令人惊讶地,与加载的卡纸板直接接触的涂层构造有效的迁移屏障。从而,能够省略备择的膜或卡纸板金属化。因此,根据本发明的包装优选不含额外的金属层。然而,这并不排除金属印刷或相似金属装饰。从而,由加载的卡纸板包装制得的成本有效的包装能够得以制备,其中并无可察觉量或甚至并无任何量的矿物油迁移进入食品。
回收卡纸板的定义:
本发明范围内使用的基于回收卡纸板的卡纸板是卡纸板包装,其包含可察觉量的矿物油从而涉及2004年10月27日的VERORDNUNG(EG)Nr.1935/2004 DER KOMMISSION的规定(下文也提为加载的卡纸板包装)。
该类型的基于回收卡纸板的卡纸板包装一般含有至少300-1000mg/kg矿物油。这些矿物油称为"矿物油饱和烃"(MOSH)或"矿物油芳烃"(MOAH)。MOSH和MOAH矿物油常常也在其碳链方面进行指定,例如MOSH 14-24,MOSH 24-35,MOAH 14-24和MOAH 24-35,其中数值反映碳原子数。MOSH和MOAH矿物油的具体组成取决于回收卡纸板类型,也即MOSH 14-24,MOSH 24-35,MOAH 14-24和MOAH24-35的级分是不同的。
根据本发明的食品包装中提供的膜具有对MOSH和MOAH矿物油、尤其是MOSH 14-24,MOSH 24-35,MOAH 14-24和MOAH 24-35的良好的屏障特性。
根据本发明的食品包装中提供的膜优选具有对MOSH和MOAH矿物油的良好屏障,从而按照2004年10月27日的VERORDNUNG(EG)Nr.1935/2004DER KOMMISSION可以与食品接触。模拟干燥食品的食品模拟物也即测试介质依照2011年1月14日的VERORDNUNG(EU)Nr.10/2011DER KOMMISSION理解为食品。该食品模拟物通过其行为模拟自接触食品的物质的迁移。
优选地,在根据本发明将涂覆膜用于根据本发明的食品包装的情况下,在回收卡纸板包含至少300-1000mg/kg矿物油(MOSH 14-24,MOSH24-35,MOAH 14-24和MOAH 24-35的总和)和矿物油中级分MOSH14-24的比例为至少30%重量的情况下,仅至多1%、尤其是至多0.5%的存在于回收卡纸板中的MOSH 14-24级分迁移进入依照2011年1月14日的VERORDNUNG(EU)Nr.10/2011DER KOMMISSION的食品模拟物(可从Buchem B.V公司获得,聚(2,6-二苯基-对-亚苯基氧化物),颗粒尺寸60-80目,孔径尺寸200nm)。上述迁移测量在40℃进行10天的持续时间。
优选,在根据本发明将涂覆膜用于根据本发明的食品包装的情况下,在回收卡纸板包含至少300-1000mg/kg矿物油(MOSH 14-24,MOSH24-35,MOAH 14-24和MOAH 24-35的总和)和级分MOSH 24-35在矿物油中的比例为至少10%重量的情况下,仅至多1.6%、尤其是至多1.4%的存在于回收卡纸板中的MOSH 24-35级分迁移入依照2011年1月14日的VERORDNUNG(EU)Nr.10/2011DER KOMMISSION的食品模拟物(可从Buchem B.V公司获得,聚(2,6-二苯基-对-亚苯基氧化物),颗粒尺寸60-80目,孔径尺寸200nm)。上述迁移测量在40℃进行10天的持续时间。
优选地,在根据本发明将涂覆膜用于根据本发明的食品包装的情况下,在回收卡纸板包含至少300-1000mg/kg矿物油(MOSH 14-24,MOSH24-35,MOAH 14-24和MOAH 24-35的总量)和级分MOAH 14-24在矿物油中的比例至少为10%重量的情况下,仅至多0.5%,尤其是至多0.3%的存在于回收卡纸板中的MOAH 14-24级分迁移依照2011年1月14日的VERORDNUNG(EU)Nr.10/2011DER KOMMISSION的食品模拟物,(可从Buchem B.V公司获得,聚(2,6-二苯基-对-亚苯基氧化物),颗粒尺寸60-80目,孔径尺寸200nm)。上述迁移测量在40℃进行10天的持续时间。
优选地,在根据本发明将涂覆膜用于根据本发明的食品包装的情况下,在回收卡纸板包含至少300-1000mg/kg矿物油(MOSH 14-24,MOSH24-35,MOAH 14-24和MOAH 24-35的总和)和级分MOAH 24-35在矿物油中的比例为至少1%重量的情况下,仅至多3.5%、尤其是至多2.0%、特别优选至多1.0%的存在于回收卡纸板中的MOAH 24-35级分迁移入依照2011年1月14日的VERORDNUNG(EU)Nr.10/2011DERKOMMISSION的食品模拟物,(可从B.V公司获得,聚(2,6-二苯基-对-亚苯基氧化物),颗粒尺寸60-80目,孔径尺寸200nm)。上述迁移测量在40℃进行10天的持续时间。
本发明也涉及前文描述的膜用于制备包含回收卡纸板的食品包装的用途。
包含于根据本发明的食品包装中的膜通过本身已知的挤出或共挤出方法来制备,其中尤其优选的是拉幅机方法。
为此,将相应于膜单独层的熔体通过平膜模(Flachdüse)共挤出,移除这样获得的膜用于在一个或多个轧辊上固化,然后将膜伸展(取向),然后热固化伸展的膜和任选在期望进行处理的表面层上进行等离子体、电晕或火焰处理。
具体来说,如挤出方法中此处将单独层的聚合物或聚合物混合物在挤出机中挤压和液化,其中任选加入添加剂可以已经包含于聚合物或聚合物混合物中。另选地,这些添加剂还能够经由母料掺入。
然后,任选将熔体共同且同时地挤压通过平膜模(缝型模(Breitschlitzdüse)),并于5至100℃、优选10至50℃的温度在一个或多个引出轧辊上移除挤压的多层膜,其中所述膜冷却和固化。
然后,相对挤出方向纵向地和横向地伸展这样获得的膜,这导致分子链的取向。纵向伸展优选在80至150℃的温度、方便地借助以不同速度运行的两个轧辊、按照所需拉伸比进行,而横向伸展优选在120至170℃的温度、借助适当的夹伸框架(Kluppensrahmen)进行。纵向拉伸比的范围是4至8,优选4.5至6。横向拉伸比的范围是5至10,优选7至9。
在膜的伸展后进行所述膜的热定形(热处理),其中将膜在100至160℃的温度保持大约0.1至10s。然后,通常用缠绕装置将膜卷起。
在双轴伸展之后,优选按照已知方法之一进行膜的一个或两个表面等离子体、电晕或火焰处理。处理强度一般是35至45mN/m,优选37至45mN/m,尤其是38至41mN/m。
对于备择的电晕处理,将膜通过充当电极的两个导体元件,其中将足够高的电压、通常为交流电压(大约10,000V和10,000Hz)施加于电极之间,从而能够发生喷雾或电晕放电。由于喷雾或电晕放电,膜表面上的空气被离子化并与膜表面的分子反应,从而在基本上单极的聚合物基质中产生极性沉积。处理强度位于常规范围内,其中37至45mN/m是优选的。
然后,按照本身已知的方法在一侧或两侧在一个或两个外表面上为共挤出的多层膜提供上文描述的涂层。
为了表征原料和膜,采用下述测量方法:
熔体流动指数
熔体流动指数按照DIN 53 735测量,采用21.6N负载和230℃。
乙烯含量的确定
聚烯烃共聚物的乙烯含量通过13C-NMR谱确定。测量采用BrukerAvance 360公司的核磁共振光谱仪。将待表征的共聚物溶于四氯乙烷,从而产生10%混合物。加入八甲基四硅氧烷(OTMS)作为内标。在120℃测量核磁共振谱。谱图按J.C.Randall Polymer Sequence Distribution(Academic Press,New York,1977)的描述评价。
熔点和熔化焓
熔点和熔化焓通过DSC(差示扫描量热法)测量(DIN 51 007和DIN53 765)来确定。将数毫克(3至5mg)待表征原料在差示量热计中以20℃/分的加热速率加热。将热流速对温度作图,作为熔化曲线最大值确定熔点,而作为各熔化峰的面积确定熔化焓。
密度
密度按照DIN 53 479方法A确定。
表面张力
表面张力通过墨水方法按照DIN 53 364确定。
摩擦
摩擦按照DIN 533375测量。
迁移测量
MOSH和MOAH矿物油的迁移按照BfR(联邦风险评估局)与苏黎世Kantonalen Labor合作开发的方法来测量。其基于在人工柱色谱法预分离后进行矿物油的气相色谱法分析("Bestimmung vonKohlenwasserstoffen aus(MOSH und MOAH)oderKunststoffen(POAH,PAO)in Verpackungsmaterialien und trockenenLebensmitteln mittels Festphasenextraktion und GC-FID")。该方法在2011年9月22和23日于柏林举行的"inLebensmittelverpackungen-Entwicklungen und"会议上提出。可从Buchem B.V公司获得的试验物质(聚(2,6-二苯基-对-亚苯基氧化物),颗粒尺寸60-80目,孔径尺寸200nm)用作食品模拟物。
试验结构(图1):用待测样品覆盖含饱和的定义量的矿物油的卡纸板,在其上分布并将整个组装物储存在铝制成的封闭系统中(温度40℃,时间10天)。
在贮藏时间之后,用己烷萃取和加入适宜内标(固相萃取),然后通过液相色谱法(LC)进行分离:用掺杂0.3%硝酸银的硅胶作固定相和最初己烷、然后己烷、二氯甲烷和甲苯的混合物作流动相。在第三步中通过气相色谱法分离洗脱物,并基于上述引用的BfR方法通过GC-MS/FID进行检测。
本发明现通过下述实施例来解释。
制备未经涂覆的膜:
膜类型1至3按照已知的共挤出方法来制备。此处,通过共挤出并随后在纵向和横向分步取向制备两侧均有覆盖层的透明的三层膜,其总厚度25μm。覆盖层各具有0.9μm的厚度。
膜类型1:
基底层:
大约100%重量 全同立构的丙烯均聚物,熔点为163℃和熔体流动指数为3.2g/10分钟。
覆盖层:
大约100%重量 无规乙烯-丙烯-丁烯三元共聚物,其乙烯含量为3%重量和丁烯含量为6%重量(余量为丙烯)
0.1%重量 SiO2作为防粘连剂,平均颗粒尺寸d50为5μm
各方法步骤的制备条件是:
膜的全部层含有常规量的中和剂和稳定剂。两个表面均通过电晕预处理以便增加表面张力。
膜类型2
按照膜类型1制备膜。与膜类型1相比,两个覆盖层均含有无规乙烯-丙烯共聚物,其中乙烯含量为大约4.5%重量和软化点为大约130℃。
膜类型3(比较实施例)
按照膜类型1制备膜。与膜类型1相比,基底层额外含有作为润滑剂的量为0.05%重量的芥酸酰胺和量为0.09%重量的二乙氧基化的胺。
涂层:
首先,将聚乙烯亚胺增附剂施用至上文描述的未经涂覆的膜,然后干燥。然后通过刻槽轧辊施用由丙烯酸聚合物、PVDC或乙烯醇聚合物制成的不同涂层。
实施例1:
将1%重量的聚乙烯亚胺分散体施用至膜类型1的两侧,并干燥。然后,将来自NeoResins的商品名BT36的具有20%重量固含量的丙烯酸聚合物分散体类似地施用在两侧,并干燥。除丙烯酸聚合物分散体之外,还使用添加剂比如巴西棕榈蜡和防粘连剂。对用量进行选择以实现用于展开膜轧辊的充足防粘连效果以及大约0.3的摩擦系数。
丙烯酸聚合物层的厚度是0.8μm,其相应于0.8g/m2的涂层重量。
实施例2:
制备描述于实施例1的膜。然而与之实施例1相比,仅膜类型1的侧面1涂覆了丙烯酸聚合物分散体。侧面2在增附剂层上涂覆Solvin公司的商品名Diofan A114的具有50%重量固含量的聚氯乙烯分散体。与实施例1类似地,此处也向两侧加入添加剂(巴西棕榈蜡和防粘连剂)。聚氯乙烯层的厚度是2.0μm,其相应于3.5g/m2的涂层重量。
实施例3:
将1%重量的聚乙烯亚胺分散体施用至膜类型2的侧面1上,和干燥。对其施用Kurary公司的商品名Mowiol 3-98和Exceval AQ-4005(比率1:1)的具有10%重量总固含量的乙烯醇分散体,和干燥。
涂覆层的厚度是0.8μm,其相应于0.8g/m2的涂层重量。此外,使用添加剂比如巴西棕榈蜡和防粘连剂。对用量进行选择以实现用于展开膜轧辊的充足防粘连效果以及大约0.3的摩擦系数。
实施例4:
按照实施例3制备膜。与之实施例3相比,将1%重量的聚乙烯亚胺分散体额外地施用至侧面2,和干燥。将NeoResins公司商品名BT36的具有20%重量固含量的丙烯酸聚合物分散体施用至该增附剂层,和干燥。除丙烯酸聚合物分散体之外,还使用添加剂比如巴西棕榈蜡和防粘连剂。对用量进行选择以实现用于展开膜轧辊的充足防粘连效果以及大约0.3的摩擦系数。丙烯酸聚合物层的厚度是0.8μm,其相应于0.8g/m2的涂层重量。
比较实施例:
不加涂覆地使用膜类型3。
按照本发明变化上述涂层并总结于表1:
Claims (24)
1.食品包装,包含:
a)食品,
b)基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜,所述膜包围食品,
c)基于回收卡纸板的卡纸板,其包围含有食品的基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜,
其特征在于,所述基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜具有包含(i)丙烯酸聚合物和/或(ii)含卤素的乙烯基聚合物和/或亚乙烯基聚合物和/或(iii)基于乙烯基醇(VOH)的聚合物的至少一个涂层,并且所述涂层至少存在于膜朝向所述基于回收卡纸板的卡纸板的一侧上。
2.根据权利要求1的食品包装,其特征在于所述膜和/或所述卡纸板不具有防止矿物油迁移入包装的食品中的金属化。
3.根据权利要求1的食品包装,其特征在于所述膜是单层或多层构造的和优选基底层,各自基于层重量包含至少70%重量、优选75至98%重量、尤其是85至95%重量的聚烯烃。
4.根据权利要求3的食品包装,其特征在于所述膜是单层的和含有90至100%重量、优选95至100%重量、尤其是98至100%重量的丙烯聚合物,所述丙烯聚合物的熔点是120℃或更高、优选150至170℃,并且其在230℃和21.6N的力(DIN 53735)具有1至10g/10分钟、优选2至8g/10分钟的熔体流动指数。
5.根据权利要求1或4的食品包装,其特征在于所述丙烯聚合物是丙烯均聚物和/或共聚物和/或三元共聚物和其它聚烯烃的混合物,尤其是来自具有2至6个C原子的单体,其中所述混合物含有至少50%重量、尤其是至少75%重量的丙烯聚合物。
6.根据权利要求1至5的食品包装,其特征在于膜的聚烯烃、尤其是聚丙烯含有优选0.5至10%重量的量的色素。
7.根据权利要求1至6的食品包装,其特征在于所述基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜具有20至100μm、优选25至60μm、尤其是30至50μm的厚度。
8.根据权利要求1至7的食品包装,其特征在于所述基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜在一侧或两侧具有聚乙烯亚胺构成的增附剂,在所述增附剂上施用了一个或多个涂层。
9.根据权利要求1至8的食品包装,其特征在于所述涂层存在于所述膜的两个侧面上。
10.根据权利要求1至9的食品包装,其特征在于所述膜的涂层在各侧上的各自具有0.4-5μm、优选0.6-3μm的总厚度。
11.根据权利要求1至10的食品包装,其特征在于所述涂层是多层构造的和优选在涂层由含卤素的乙烯基聚合物和/或亚乙烯基聚合物构成的情况下,但尤其是在聚偏二氯乙烯(PVDC)的情况下,最初具有基于乙酸乙烯酯/丙烯酸酯的第二底漆层,并且第二底漆层的层厚占由含卤素的乙烯基聚合物和/或亚乙烯基聚合物、尤其是聚偏二氯乙烯(PVDC)构成的涂层层厚的50-100%。
12.根据权利要求1至11的食品包装,其特征在于丙烯酸酯是丙烯酸酯均聚物和/或丙烯酸酯共聚物,其基于丙烯酸烷基酯,尤其是基于甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯和/或丙烯酸甲酯。
13.根据权利要求1至12的食品包装,其特征在于含卤素的乙烯基聚合物和/或亚乙烯基聚合物是基于乙烯基氯化物和/或亚乙烯基氯化物的聚合物,其优选包含基于乙酸乙烯酯或丙烯酸酯的共聚物。
14.根据权利要求1至13的食品包装,其特征在于所述由基于乙烯基醇(VOH)的聚合物构成的涂层材料包含乙烯/乙烯醇共聚物(EVOH)和聚乙烯醇的混合物,优选包含5-15%重量的乙烯/乙烯醇共聚物和聚乙烯醇的混合物的混合物,优选比率为0.8-1.2比1.2-0.8、尤其是1:1(重量比)。
15.根据权利要求1至14的食品包装,其特征在于对于由基于乙烯基醇(VOH)的聚合物、尤其是乙烯/乙烯醇共聚物(EVOH)构成的涂层材料来说,膜每侧的涂层的量(在干燥之后)是0.5至1.0g/m2,并且层厚优选是1至1.5μm(±0.2μm)。
16.根据权利要求1至15的食品包装,其特征在于对于基于丙烯酸酯的涂层材料来说,膜每侧的涂层的量在干燥之后是0.5至1.5g/m2,并且层厚优选是1至1.5μm。
17.根据权利要求1至16的食品包装,其特征在于对于基于含卤素的乙烯基聚合物和/或亚乙烯基聚合物、尤其是聚偏二氯乙烯(PVDC)的涂层材料来说,膜每侧的涂层的量在干燥之后是2.5至4g/m2,其中上述量包括基于乙酸乙烯酯/丙烯酸酯的第二底漆层,并且层厚优选是1.5至2.0μm(±0.2μm)。
18.根据权利要求1至17的食品包装,其特征在于回收卡纸板含有至少300-1000mg/kg矿物油、优选MOSH和MOAH矿物油,尤其是类型MOSH 14-24、MOSH 24-35、MOAH 14-24和MOAH 24-35的矿物油。
19.根据权利要求1至18的食品包装,其特征在于所述膜具有针对存在于回收卡纸板中的矿物油的屏障,并且在级分MOSH 14-24在回收卡纸板的矿物油中的比例是至少30%重量的情况下,仅至多1%、尤其是至多0.5%的存在于回收卡纸板中的MOSH 14-24级分扩散进入食品模拟物。
20.根据权利要求1至19的食品包装,其特征在于所述膜具有针对存在于回收卡纸板中的矿物油的屏障,并且在级分MOSH 24-35在回收卡纸板的矿物油中的比例是至少10%重量的情况下,仅至多1.6%、尤其是至多1.4%的存在于回收卡纸板中的MOSH 24-35级分扩散入食品模拟物。
21.根据权利要求1至20的食品包装,其特征在于所述膜具有针对存在于回收卡纸板中的矿物油的屏障,并且在级分MOAH 14-24在回收卡纸板的矿物油中的比例是至少10%重量的情况下,仅至多0.5%、尤其是至多0.3%的存在于回收卡纸板中的MOAH 14-24级分扩散进入食品模拟物。
22.根据权利要求1至20的食品包装,其特征在于所述膜具有针对存在于回收卡纸板中的矿物油的屏障,并且在级分MOAH 24-35在回收卡纸板的矿物油中的比例是至少1%重量的情况下,仅至多3.5%、尤其是至多2.0%的存在于回收卡纸板中的MOAH 24-35级分扩散进入食品模拟物。
23.如权利要求1至22中所定义的基于聚烯烃的膜、尤其是基于双轴取向的聚丙烯膜(boPP)的膜的用途,其用于制备防矿物油的食品包装、尤其是含有回收卡纸板的包装,所述回收卡纸板具有可察觉量的矿物油并因此按照2004年10月27日的VERORDNUNG(EG)Nr.1935/2004DER KOMMISSION不适于与食品接触。
24.根据权利要求1至20中任一项的食品包装,其特征在于所述食品包装由卡纸板和膜组成和不包括其它金属层。
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CN2037727U (zh) * | 1988-09-28 | 1989-05-17 | 四川省造纸工业研究所 | 高脂肪食品保鲜用软包装材料 |
JPH101162A (ja) * | 1996-06-13 | 1998-01-06 | Toppan Printing Co Ltd | 食品包装用シート |
EP2476551A1 (de) * | 2011-01-17 | 2012-07-18 | VG Nicolaus GmbH & Co KG | Verpackung aus Karton |
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US4363841A (en) | 1981-12-28 | 1982-12-14 | Champion International Corporation | Laminated packaging material |
FI980086A (fi) | 1997-05-28 | 1998-11-29 | Enso Oyj | Päällystetty kartonki, sen valmistusmenetelmä sekä siitä muodostetut astiat ja pakkaukset |
US20050042443A1 (en) | 2003-08-22 | 2005-02-24 | Miller Gerald D. | PVOH barrier performance on substrates |
EP1770215A1 (de) | 2005-09-29 | 2007-04-04 | Mondi Packaging AG | Verpackungsmaterial mit Barriereschicht |
MX2013013615A (es) | 2011-05-30 | 2014-01-08 | Basf Se | Empaque de papel y carton con revestimiento de barrera. |
CA2857715A1 (en) | 2011-12-06 | 2013-06-13 | Basf Se | Paper and cardboard packaging with barrier coating |
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2013
- 2013-11-08 WO PCT/EP2013/003369 patent/WO2014072066A1/de active Application Filing
- 2013-11-08 DK DK13789487.9T patent/DK2917034T3/en active
- 2013-11-08 ES ES13789487T patent/ES2604588T5/es active Active
- 2013-11-08 HU HUE13789487A patent/HUE032511T2/en unknown
- 2013-11-08 LT LTEP13789487.9T patent/LT2917034T/lt unknown
- 2013-11-08 CA CA2891169A patent/CA2891169A1/en not_active Abandoned
- 2013-11-08 US US14/441,913 patent/US20150314939A1/en not_active Abandoned
- 2013-11-08 PL PL13789487.9T patent/PL2917034T5/pl unknown
- 2013-11-08 CN CN201380058697.1A patent/CN104768755B/zh not_active Expired - Fee Related
- 2013-11-08 SI SI201330405A patent/SI2917034T1/sl unknown
- 2013-11-08 PT PT137894879T patent/PT2917034T/pt unknown
- 2013-11-08 MX MX2015005921A patent/MX2015005921A/es active IP Right Grant
- 2013-11-08 EP EP13789487.9A patent/EP2917034B2/de active Active
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CN2037727U (zh) * | 1988-09-28 | 1989-05-17 | 四川省造纸工业研究所 | 高脂肪食品保鲜用软包装材料 |
JPH101162A (ja) * | 1996-06-13 | 1998-01-06 | Toppan Printing Co Ltd | 食品包装用シート |
EP2476551A1 (de) * | 2011-01-17 | 2012-07-18 | VG Nicolaus GmbH & Co KG | Verpackung aus Karton |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110139754A (zh) * | 2016-12-15 | 2019-08-16 | 特里奥凡德国有限公司及两合公司 | 含有具有对矿物油的屏障特性的膜的食品包装 |
WO2018137168A1 (en) * | 2017-01-25 | 2018-08-02 | The Procter & Gamble Company | Polypropylene film having unique aesthetics |
Also Published As
Publication number | Publication date |
---|---|
HUE032511T2 (en) | 2017-09-28 |
EP2917034B2 (de) | 2023-07-12 |
PL2917034T5 (pl) | 2023-11-20 |
WO2014072066A1 (de) | 2014-05-15 |
CN104768755B (zh) | 2017-09-05 |
PL2917034T3 (pl) | 2017-02-28 |
EP2917034A1 (de) | 2015-09-16 |
SI2917034T1 (sl) | 2017-01-31 |
CA2891169A1 (en) | 2014-05-15 |
ES2604588T5 (es) | 2023-10-26 |
LT2917034T (lt) | 2016-10-25 |
US20150314939A1 (en) | 2015-11-05 |
DK2917034T3 (en) | 2016-12-05 |
PT2917034T (pt) | 2016-11-04 |
MX2015005921A (es) | 2015-09-08 |
EP2917034B1 (de) | 2016-09-07 |
ES2604588T3 (es) | 2017-03-07 |
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