CN105980154B - 包装材料的制造方法 - Google Patents

包装材料的制造方法 Download PDF

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CN105980154B
CN105980154B CN201580008471.XA CN201580008471A CN105980154B CN 105980154 B CN105980154 B CN 105980154B CN 201580008471 A CN201580008471 A CN 201580008471A CN 105980154 B CN105980154 B CN 105980154B
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layer
weight
lldpe
blend
polymeric layer
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CN105980154A (zh
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K.内瓦莱宁
J.拉萨宁
V.里布
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Stora Enso Oyj
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Stora Enso Oyj
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    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods 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
    • B32B37/153Methods 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
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Abstract

本发明涉及覆盖有聚合物的包装材料、其制造方法、以及由所述材料制成的产品,例如一次性饮用杯。所述包装材料包括纸或板的纤维质基体(1)以及经挤出的聚合物层(2),所述经挤出的聚合物层(2)包含以下物质的共混物:(i)0~25重量%的具有较低熔体粘度的支化低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE)。本发明的包装材料包括多层覆盖物,例如,所述共混物的粘合性最内部的层和能够热封接的最外部的层(2、4)以及至多90重量%的高密度聚乙烯(HDPE)的蒸气阻挡性中间层(3)。通过共挤出,产生所述层(2、3、4)并使它们附着至所述纤维质基体(1)。为了使所述材料的可再生性最大化,用于结构体的HDPE和LLDPE是生物来源的。

Description

包装材料的制造方法
技术领域
本发明涉及包装材料的制造方法,其中,向纤维质基体(例如纸、纸板或卡纸)上挤出聚合物覆盖层。进一步地,本发明涉及通过该方法提供的覆盖有聚合物的包装材料、以及由所述材料制成的一次性饮用杯和其它产品。
背景技术
用于容器和产品包装的基于纤维的包装材料(例如包装用的纸或板)通常具有聚合物型覆盖层,所述聚合物型覆盖层使得材料不透过液体并允许通过热封接来形成容器或包装物。由覆盖有聚合物的纸或板制成的典型物品为液体包装物和一次性餐具,例如饮用杯。由于LDPE(低密度聚乙烯)的良好的热封接性能,其被广泛地用来作覆盖物。
近来,在市场上,对于这样的仅由或者至少主要地由来自可再生来源的原材料(即,生物来源的原材料)制成的纸或板产品存在着逐渐增多的需要。传统地,由化石原材料例如石油来生产聚乙烯。更近来地,已经开发了由甘蔗、糖用甜菜或小麦籽粒制成的聚乙烯,尤其是具有容易的可得性的生物LLDPE(线型低密度聚乙烯)和生物HDPE(高密度聚乙烯)。此外,生物LDPE(即,通常的具有支化结构的低密度聚乙烯)是已知的但具有受限的供应且因此具有高的价格。迄今为止,已经对所有这些聚合物产物进行设计以用于制造聚合物膜,而且,已经发现,它们对于挤出覆盖的适用性差。
EP1059162A2描述了这样的包装材料,其具有在纸板基体上的LDPE和LLDPE的共混物的层作为单层或者作为多层覆盖物的最内部的层或最外部的层。该教导主要针对液晶聚合物阻挡物,且没有提及共混物中的LDPE和LLDPE的比例。
WO00/776862A1公开了在纸板基体上的LDPE和LLDPE的共混物的单层,其没有教导所述共混物中的各聚合物的比例。在该参考文献中,主要的教导集中于作为氧气和水分阻挡物的聚合物/纳米粘土复合材料层。
发明内容
因此,需要这样的改善的工艺,其允许LLDPE(尤其是在现在的市场上易于得到的生物来源的薄膜级LLDPE)在用作位于纤维质基体(例如纸、纸板或卡纸)上的挤出覆盖物中的技术上有效且成本有效率的使用。主要的要求是实现所述覆盖物层与纤维质基体的良好粘附性。此外,所述覆盖物层应当有利地用作具有良好的蒸气阻挡性和热封接特性且具有尽可能低的覆盖物层重量的多层覆盖物的最内部的层。
根据本发明,已经令人惊讶地通过如下得到了优良的聚合物覆盖物:向纤维质的纸、纸板或卡纸基体上共挤出多层覆盖物,使得所述多层覆盖物与所述纤维质的纸、纸板或卡纸基体直接接触,所述多层覆盖物包括:最内部的聚合物层,其包含如下物质的共混物:(i)10~25重量%的具有较低熔体粘度的支化低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE);中间的蒸气阻挡性聚合物层;以及与所述最内部的层相同的共混物的最外部的热封接层,所述最内部的层使所述覆盖物附着至所述纤维质基体,而且,所述最外部的层形成热封接层,所述多层覆盖物不包括包含超过90重量%的高密度聚乙烯(HDPE)的共挤出层的材料。
因此,所要求保护的方法不包括这样的材料的制造方法,所述材料包括相比于所述最内部的层进一步设置的共挤出层,例如在最内部的层的外侧上或者在最内部的层和最外部的层之间。前面的放弃排除了与现有技术瑞典专利申请1300276-1(其在本申请的优先权日时仍未公开)的重叠部分。
相比于100%LDPE的常规覆盖物,本发明带来了改善的封接强度,而且,相比于100%LLDPE的覆盖物,本发明带来了改善的挤出流动性以及改善的与纤维质基体的粘附。结果是这样的可使用的解决方案,其在材料的易得性和可接受的成本下具有显著提高的生物基材料份额的优点。
本身地,不同类型的聚乙烯的共混是平常的,而且,在文献中可找到多种这样的制法(recipe)。但是,那些教导主要针对制造聚合物膜,而非位于纤维质基体上的覆盖物,且因此,没有叙述这样的共混物与纤维质基体的粘附性(其为本发明的重要方面)。此外,当与较大份额的通常的支化LDPE共混时,一般描述较少量的LLDPE,而非由本发明人所教导的相反情形。
作为本发明的优选实施方式,所述聚合物共混物可包含80~90重量%、优选80~85重量%、且最优选80重量%的LLDPE以及10~20重量%、优选15~20重量%、且最优选20重量%的LDPE。
优选地,用于本发明的LDPE具有至少25g/10分钟(190℃,2.16kg)的熔体指数,而且,用于本发明的LLDPE具有至多10g/10分钟(190℃,2.16kg)的熔体指数。
因此,本发明使得能够提高生物HDPE的使用,以便通过简单的手段来实现纸或板产品中的改善的水蒸汽阻挡性。
在提供优良的水蒸汽阻挡性方面(所述优良的水蒸汽阻挡性是在液体容器和包装物中非常期望的),HDPE相对于LDPE或LLDPE通常具有优点。另一方面,由于HDPE相比于LDPE的较高的熔融温度,HDPE具有差的热封接性能,且甚至,HDPE与纤维质基体直接接触的粘附性是欠缺的。此外,由于纯HDPE的窄的分子量分布(MWD),其不适合用于单层挤出覆盖。当生产覆盖物重量为15-25g/m2的薄覆盖物时,纯HDPE在挤出覆盖中具有高的颈缩和差的流动性。
在现有技术(参见例如US7,335,409)中,内部的HDPE层和外部的LDPE层的组合已经被描述为提供了水蒸汽阻挡性和热封接性能。但是,这样的组合与纤维质基体的粘附性是不足的,而且,从环境的角度来看,目前,生物级LDPE的差的可得性是另一阻碍。
借助于LDPE和LLDPE的共混物的最内部的覆盖物层,本发明克服了HDPE在挤出中的颈缩和流动性问题,而且,作为双层结构体,允许与纤维质基体的改善的粘附。将如前所述的聚合物共混物的层共挤出作为在纤维质基体和至多90重量%HDPE的外部层之间的内部层。
因此,至多90重量%HDPE的外部的蒸气阻挡性层具有至少10重量%的其它聚合物(例如LDPE或LLDPE)的份额,这将改善所述阻挡性层的热封接性能。
因此,本发明提供了LDPE和LLDPE的共混物的层,其用作与纤维质基体直接接触的粘合层。同时,当将包装材料形成为容器或封闭的产品包装物时,还设置了类似的聚合物共混物层作为最外部的热封接层。将至多90重量%HDPE的蒸气阻挡性层夹在所述两个聚合物共混物层之间。生物聚合物的较大份额使产品变成主要是基于可再生的,尽管较小份额的LDPE是石油来源的。
根据本发明的有利实施方式,将LDPE和生物LLDPE的共混物的最内部的粘合层、50-90重量%的HDPE和10-50重量%的LDPE或LLDPE的共混物的中间层、以及这样的共混物的最外部的能够热封接的层在单一步骤中共挤出到纤维质基体上。优选地,将相同的共混物用于最内部的聚合物层和最外部的聚合物层这两者。所述结构体可由在纤维质基体上的最内部的聚合物层、中间的聚合物层和最外部的聚合物层组成,或者,可存在例如夹在所述最内部的聚合物共混物层和最外部的聚合物共混物层之间的EVOH或聚酰胺的进一步的聚合物层,例如氧气阻挡性层。
只要用在根据本发明的结构体中,HDPE就优选为生物来源的,即,也在中间的全HDPE层中。
本发明的进一步的实施方式规定:所述共混物的最内部的粘合层的重量为至多15g/m2、优选至多10g/m2、且最优选约5g/m2,所述共混物的最外部的热封接层的重量为至多15g/m2、优选至多10g/m2、且最优选约5g/m2,而且,HDPE+LDPE或HDPE+LLDPE共混物的中间层的重量为至多15g/m2、优选至多10g/m2、且最优选约5g/m2。优选地,在三层覆盖物中,聚合物层的总重量是至多25g/m2、优选至多20g/m2、且最优选约15g/m2。因此,通过本发明可制得非常薄的多个聚合物层的结构体。
从经济以及环境的角度来看,覆盖物层重量的甚至进一步的降低是合乎期望的。如果通过现有的共挤出技术有可能制得的话,在本发明的范围内,可预期具有4+4+4g/m2或甚至4+2+4g/m2的相应覆盖物层重量的三个层。
本发明进一步涵盖了能够热封接的包装材料,其可通过所要求保护的本发明的方法获得。
优选地,根据本发明的能够热封接的包装材料包括:
-(a)纸、纸板或卡纸的纤维质基体,
-(b)以下物质的共混物的最内部的粘合层:(i)10~25重量%的具有较低熔体粘度的低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE),所述最内部的层与所述纤维质基体直接接触,
-(c)蒸气阻挡性聚合物或聚合物共混物的中间层,和
-(d)以下物质的共混物最外部的能够热封接的层:(i)10~25重量%的具有较低熔体粘度的低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE),
所述最内部的层、中间的层以及最外部的层已经通过共挤出产生于所述纤维质基体上。
优选地,根据本发明的包装材料在两侧上均覆盖有一个或多个聚合物层。
本发明范围内所包括的最终产品包括通过由如前所述的包装材料热封接而制得的饮用杯。本发明所涵盖的其它物品为一次性的盘子、托盘及其它餐具,以及其中可期望进一步的氧气和光的阻挡性层的封闭的液体包装物,例如乳制品和汁液的箱子。
关于本发明,高密度聚乙烯是指密度超过0.940g/cm3的聚乙烯。
本发明尤其适用于生产用于包装食品(尤其是冷冻食品)的材料,但是,本发明不限于该应用。
附图说明
图1示出了根据本发明的第一包装材料的多层结构体,
图2示出了根据本发明的第二包装材料的多层结构体,和
图3示出了根据本发明的第三包装材料的多层结构体。
具体实施方式
图1中所示的包装材料包括:纤维质基体1;与所述纤维质基体1直接接触的内部粘合层2,所述粘合层2包含(i)10~25重量%的较低熔体粘度的支化低密度聚乙烯(LDPE)和(ii)75~90重量%的较高熔体粘度的线型低密度聚乙烯(LLDPE)的共混物;50-90重量%的HDPE和10-50重量%的LDPE或LDPE的共混物的中间层3;以及与用于所述最内部的粘合层2的共混物类似、优选相同的聚合物共混物的最外部的层4。在形成内部粘合层2和最外部的层4的共混物中,低密度聚乙烯(LDPE)优选具有至少15g/10分钟(190℃,2.16kg)的熔体指数,而且,线型低密度聚乙烯(LLDPE)优选具有至多10g/10分钟(190℃,2.16kg)的熔体指数。所述结构体中所用的HDPE和LLDPE是可再生生物来源的。所述纤维质基体1可为重量40-500g/m2的纸、纸板或卡纸,优选重量170-350g/m2的板。举例来说,当将所述材料变成容器例如一次性饮用杯时,所述最外部的层4用作热封接层。通过共挤出,在纤维质基体1上产生所述2、3、4三个层。所述经共挤出的聚合物层2、3、4中的每一个的重量可为例如3-12g/m2、优选5-10g/m2
根据图2的包装材料与图1中所示的材料的区别在于其甚至包括位于纤维质基体1的相反侧上的热封接层4′。优选地,该热封接层4′具有这样的聚合物共混物,所述聚合物共混物与用于位于纤维质基体的相反侧上的最内部的层和最外部的层2,4的共混物相同,当将所述材料变成饮用杯时,所述最外部的层4形成内侧。
根据图3的包装材料包括位于纤维质基体1的两侧上的经共挤出的多层结构体2、3、4;2′,3′,4′。这些多层结构体均可对应于前面结合图1所述的多层结构体。图3的材料适用于这样的经热封接的产品包装物,其屏蔽了来自所述包装物的内侧(即,来自潮湿产品)以及来自所述包装物的外侧(即,来自湿润环境)这两者的水蒸汽渗透。
实施例
将20重量%的石油来源的挤出级LDPE与80重量%的甘蔗来源的薄膜级生物LLDPE干燥共混以形成聚合物共混物。向纸板表面上挤出该聚合物共混物的覆盖物重量为15g/m2的层,使得纸板表面与所述层直接接触。所述覆盖物层实现了良好的流动性、可接受的颈缩、以及与纸板的良好的粘附。
实施一系列试验以确定前述共混物作为在纸板和经共挤出的多层覆盖物中的一个或多个外部聚合物层之间的粘附层的性能。使用100重量%生物HDPE的层用于测试,但是,在粘附方面,这些与本发明范围内的50-90重量%的HDPE和10-50重量%的LDPE或LLDPE的共混物没有显著差异。作为比较,包括具有最内部的HDPE+LDPE共混物层的经共挤出的多层覆盖物以及经挤出的单层覆盖物。
使用基于油的挤出级LDPE、薄膜级生物HDPE和薄膜级生物LLDPE(由巴西的Braskem从甘蔗制得的生物HDPE和生物LLDPE)用于所述试验。测量挤出中的颈缩和最终材料的热封接温度,并且,按照等级1(无粘附)至5(完美的粘附)来评价与板基体的粘附。结果呈现于下表1中。
表1
*对比
尽管层厚度最大,但作为对比的HDPE单层覆盖物具有最差的颈缩和粘附。最薄的HDPE单层未能完全地挤出。增加LLDPE与20重量%的LDPE的共混物的内层改善了粘附并减少了颈缩,尽管降低了总的覆盖物重量和厚度,而且,在LLDPE+LDPE的情况中,通过增加该相同共混物的最外部的层显著地改善了热封接性能。

Claims (19)

1.能够热封接的包装材料的制造方法,包括:向纤维质的纸、纸板或卡纸基体上共挤出多层覆盖物,使得所述多层覆盖物与所述纤维质的纸、纸板或卡纸基体直接接触,所述多层覆盖物包括:最内部的聚合物层,其由如下物质的共混物组成:(i)10~25重量%的具有较低熔体粘度的低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE);中间的蒸气阻挡性聚合物层;以及由与所述最内部的聚合物层相同的共混物组成的最外部的热封接层,所述最内部的聚合物层使所述覆盖物附着至所述基体,而且,最外部的层形成热封接层,所述多层覆盖物不包括包含超过90重量%的高密度聚乙烯(HDPE)的共挤出层的材料。
2.权利要求1的方法,特征在于,所述共混物包含80~90重量%的所述LLDPE以及10~20重量%的所述LDPE。
3.权利要求2的方法,特征在于,所述共混物包含80~85重量%的所述LLDPE。
4.权利要求3的方法,特征在于,所述共混物包含80重量%的所述LLDPE。
5.权利要求1-4中任一项的方法,特征在于,所述LDPE具有在190℃,2.16kg下至少25g/10分钟的熔体指数且所述LLDPE具有在190℃,2.16kg下至多10g/10分钟的熔体指数。
6.权利要求1-4中任一项的方法,特征在于,最内部的聚合物层、中间的蒸气阻挡性聚合物层和最外部的热封接层中的每一个的重量为至多15g/m2
7.权利要求6的方法,特征在于,最内部的聚合物层、中间的蒸气阻挡性聚合物层和最外部的热封接层中的每一个的重量为至多10g/m2
8.权利要求7的方法,特征在于,最内部的聚合物层、中间的蒸气阻挡性聚合物层和最外部的热封接层中的每一个的重量为至多5g/m2
9.权利要求1-4中任一项的方法,特征在于,将包含最高达90重量%的生物来源的HDPE的共混物用于所述中间的蒸气阻挡性聚合物层。
10.权利要求1-4中任一项的方法,特征在于,将生物来源的LLDPE用于所述共混物。
11.通过权利要求1-10中任一项的方法制得的能够热封接的包装材料,特征在于,其包括
(a)纸、纸板或卡纸的纤维质基体,
(b)由以下物质的共混物组成的最内部的聚合物层:(i)10~25重量%的具有较低熔体粘度的低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE),最内部的聚合物层与所述基体直接接触,
(c)中间的蒸气阻挡性聚合物层,以及
(d)由以下物质的共混物组成的最外部的热封接层:(i)10~25重量%的具有较低熔体粘度的低密度聚乙烯(LDPE)和(ii)75~90重量%的具有较高熔体粘度的线型低密度聚乙烯(LLDPE),
所述最内部的聚合物层、中间的蒸气阻挡性聚合物层以及最外部的热封接层已经通过共挤出产生于所述基体上。
12.权利要求11的包装材料,特征在于,最内部的聚合物层、中间的蒸气阻挡性聚合物层以及最外部的热封接层中的每一个的重量为至多15g/m2,而且,多层覆盖物的总重量为至多25g/m2
13.权利要求12的包装材料,特征在于,最内部的聚合物层、中间的蒸气阻挡性聚合物层以及最外部的热封接层中的每一个的重量为至多10g/m2
14.权利要求13的包装材料,特征在于,最内部的聚合物层、中间的蒸气阻挡性聚合物层以及最外部的热封接层中的每一个的重量为至多5g/m2
15.权利要求12的包装材料,特征在于,多层覆盖物的总重量为至多20g/m2
16.权利要求15的包装材料,特征在于,多层覆盖物的总重量为至多15g/m2
17.权利要求11-16中任一项的包装材料,特征在于,已经将包含最高达90重量%的生物来源的HDPE的共混物用于所述中间的蒸气阻挡性聚合物层。
18.权利要求11-16中任一项的包装材料,特征在于,已经将生物来源的LLDPE用于具有LDPE的所述共混物。
19.饮用杯,其由通过权利要求1-10中任一项的方法制得的包装材料或者由权利要求11-18中任一项的包装材料通过热封接制得。
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