CN1250391C - 包括聚烯烃/聚酰胺共混物层的多层纸板包装结构 - Google Patents

包括聚烯烃/聚酰胺共混物层的多层纸板包装结构 Download PDF

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CN1250391C
CN1250391C CNB018145582A CN01814558A CN1250391C CN 1250391 C CN1250391 C CN 1250391C CN B018145582 A CNB018145582 A CN B018145582A CN 01814558 A CN01814558 A CN 01814558A CN 1250391 C CN1250391 C CN 1250391C
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G·J·卡斯特勒
D·R·约瀚逊
K·S·希赫
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Abstract

一种容器用包装层压材料，该层压材料使得共混物单层能够有效挤出涂敷到纸板基材上作为产品接触层而不需要结合层或多层共挤出设备。与直接聚乙烯单层相比，共混物单层具有优异的耐氧透过性和优异的耐针孔性。在优选的实施方案中，产品接触层由聚烯烃聚合物，聚酰胺，和增容剂的共混物组成。单层共混物是多层结构的低成本替代物。

Description

包括聚烯烃/聚酰胺共混物层的多层纸板包装结构
本申请要求2000年8月25日提交的U.S.临时专利申请S.N.60/227,589的优先权。
发明领域
本发明涉及从如下物质制备的包装纸板：包含纸板的多层层压材料和至少一个聚烯烃和聚酰胺的聚合物共混物层。
发明背景
牛奶用包装结构中的最近改进要求在纸板基材上的多层共挤出工艺，作为产品接触层，包括尼龙6/结合层/低密度聚乙烯。此多层可以在线共挤出和因此产生涂敷的基材。尽管它仅可以在非常特别的共挤出设备上共挤出，尼龙6/结合层/低密度聚乙烯的多层共挤出提供氧气阻隔性，密封，强度，和耐针孔性。
特别需要开发可以在纸板包装的产品接触侧上挤出作为单层的阻隔性材料，该单层具有多层的性能。此方案相对于多层共挤出生产线可以生产更低成本的结构。
发明概述
本发明涉及：
1.一种容器用纸板包装层压材料，包括：
a)纸板基材；和
b)涂敷到该纸板基材上的聚酰胺聚合物和聚烯烃聚合物的共混物层，其中当将层压材料成型为容器时共混物层相当于产品接触层。
2.根据上述1的容器用纸板包装层压材料，所述共混物层进一步包含增容剂。
3.根据上述1的容器用纸板包装层压材料，其中将所述共混物层挤出涂敷到纸板基材上。
4.根据上述2的容器用纸板包装层压材料，其中将所述共混物层挤出涂敷到纸板基材上。
5.根据上述2的容器用纸板包装层压材料，其中所述共混物层包含65wt％聚烯烃聚合物，30wt％聚酰胺聚合物和5wt％增容剂。
6.根据上述1的容器用纸板包装层压材料，其中聚酰胺聚合物是尼龙6、尼龙6-6、尼龙6-10、无定形尼龙、或MXD6尼龙。
7.根据上述2的容器用纸板包装层压材料，其中增容剂是马来酸酐改性的聚乙烯、金属中和的乙烯甲基丙烯酸类共聚物、乙烯丙烯酸共聚物、乙烯甲基丙烯酸共聚物、马来酸酐改性的聚丙烯、环氧官能化的聚乙烯或环氧官能化的聚丙烯。
8.根据上述1的容器用纸板包装层压材料，进一步包括涂敷到基材未涂敷侧上的低密度聚乙烯聚合物层，其中当将层压材料成型为容器时低密度聚乙烯聚合物相当于外印刷层。
9.根据上述2的容器用纸板包装层压材料，进一步包括涂敷到基材未涂敷侧上的低密度聚乙烯聚合物层，其中当将层压材料成型为容器时低密度聚乙烯聚合物相当于外印刷层。
10.根据上述8的容器用纸板包装层压材料，其中共混物层的重量为41-49克每平方米；基材的基础重量为228-489克每平方米；和外印刷层的重量为16-25克每平方米。
11.根据上述3的容器用纸板包装层压材料，其中在将共混物层加入到挤出涂敷机中之前将共混物层干燥共混。
12.根据上述1的容器用纸板包装层压材料，其中聚烯烃聚合物是低密度聚乙烯、高密度聚乙烯、金属茂聚乙烯、线性低密度聚乙烯、聚丙烯、或金属茂聚丙烯。
13.根据上述1的容器用纸板包装层压材料，所述共混物层进一步包含选自如下的填料：碳酸钙、滑石、云母、粘土及其结合物。
14.根据上述2的容器用纸板包装层压材料，所述共混物层进一步包含选自如下的填料：碳酸钙、滑石、云母、粘土及其结合物。
15.一种容器用纸板包装层压材料，包括：
a)重量为432克每平方米的纸板基材；和
b)挤出涂敷到基材侧上作为产品接触层的共混物层，该共混物层包含65wt％低密度聚乙烯，30wt％尼龙6和5wt％马来酸酐官能化的增容剂，和重量为41-49克每平方米。
16.根据上述15的容器用纸板包装层压材料，进一步包括挤出涂敷到纸板基材未涂敷侧上作为外印刷层和重量为16-25克每平方米的低密度聚乙烯层。
17.一种容器用纸板包装层压材料，包括：
a)纸板基材；和
b)涂敷到该纸板基材上的聚酰胺聚合物和聚烯烃聚合物的共混物层，其中当将层压材料成型为容器时共混物层相当于外层。
根据本发明，提供了聚酰胺和聚烯烃，如尼龙6和低密度聚乙烯，与其它要求的或非必要组分的聚合物共混物，该共混物作为单层被挤出到纸板包装结构的产品接触侧上。
该结构相对于商业单层结构，改进了耐针孔性以及氧气阻隔性能，和通过单层挤出涂敷工艺产生了具有更好的耐膨胀性的改进结构。
附图简述
图1是在已经进行红色染料耐针孔性测试之后，对照纸板箱底部的照片；和
图2是在已经进行红色染料耐针孔性测试之后，采用本发明优选结构的纸板箱底部的照片。
发明详述
本发明涉及用于纸板包装层压材料结构的单层聚烯烃/聚酰胺共混物层。适当的增容剂如马来酸酐改性的聚乙烯使得可以将尼龙6和低密度聚乙烯的共混物挤出到纸板基材上。使用马来酸酐官能化的增容剂，适于挤出的组合物包括至多大约40wt％聚酰胺。采用其它增容剂，聚酰胺的重量百分比范围可超过40wt％。特别适合的起始材料共混物包括尼龙6和低密度聚乙烯。
提供了一种结构，该结构包括作为外印刷层的12磅每3,000平方英尺(大约20克每平方米)的低密度聚乙烯层；265磅每3,000平方英尺(大约432克每平方米)的纸板基材；25-30磅每3,000平方英尺(大约41-49克每平方米)如下物质的共混物：尼龙6和低密度聚乙烯与增容剂。尽管它在本公开内容中不是限制性的，但这是优选的结构。以两种方式实施熔融共混工艺：
(1)在挤出涂敷生产线的挤出机内
在此情况下，首先将树脂和增容剂干燥共混和然后加入到挤出机的料斗中。或者，人们可以使用重量加料器在适当的比例下将每种成分加入到挤出机的料斗中。
(2)使用单独的挤出机(单螺杆或双螺杆)首先制备共混物(优选制成粒料形式)和然后将共混物粒料加入到用于挤出涂敷的挤出机料斗中。
可以采用低密度聚乙烯单层挤出的典型加工温度来将该新颖共混物挤出涂敷到纸板上。
用于本发明的聚酰胺是尼龙6、尼龙6-6、尼龙6-10、无定形尼龙、MXD6尼龙等。尼龙6是优选的组分。使用的聚烯烃包括低密度聚乙烯、高密度聚乙烯、金属茂聚乙烯、线性低密度聚乙烯、聚丙烯、或金属茂聚丙烯。
使用的增容剂是马来酸酐改性的聚乙烯。可以用作增容剂的其它类型聚合物包括：金属中和的乙烯甲基丙烯酸共聚物(Surlyn)、乙烯丙烯酸共聚物(Primacor)、乙烯甲基丙烯酸共聚物(Nucrel)、马来酸酐改性的聚丙烯(Oravac)、环氧官能化的聚乙烯或环氧官能化的聚丙烯(Lotader)。
使用的纸板基材的基础重量可以为140磅-300磅每3,000平方英尺(大约228-489克每平方米)。对于聚乙烯聚合物，熔体流动指数为1-15。对于聚丙烯聚合物，熔体流动指数为4-60。
非必要地，可以向共混物中加入填料以增加劲度或阻隔性能。这些填料可以是碳酸钙、滑石、云母、粘土等。可以在共混工艺期间在挤出机中加入填料。或者，可以采用包含预分散填料的聚合物和将它与另一种聚合物共混。例如，可以熔融共混碳酸钙填充的低密度聚乙烯与尼龙6。相似地，可以熔融共混滑石填充的尼龙6与低密度聚乙烯。由于为共混物带来阻隔和机械性能的粘土粒子的精细分散，一个特别优选的实施方案包括含有纳米粘土的尼龙6和低密度聚乙烯。此外，可以加入第四种聚合物组分到共混物中，代替填料来调整共混物的性能。
在本发明的另外实施方案中，提供了一种容器用纸板包装层压材料，该层压材料包括纸板基材，和涂敷到该纸板基材上的聚酰胺聚合物和聚烯烃聚合物的共混物层，其中当将层压材料成型为容器时共混物层相当于外层。
生产了具有优选结构实施方案的容器，并将它测试和与对照物比较，如以下实施例所示：
实施例1
将低密度聚乙烯或LDPE(65wt％)，聚酰胺(尼龙6)(30wt％)和增容剂(5wt％)的共混物，作为产品接触层挤出涂敷到基础重量为265磅每3,000平方英尺(大约432克每平方米)的纸板基材上。
也制备了对照结构，它由作为产品接触层的一层LDPE组成。在两个结构中，外印刷层由LDPE层组成。通过MOCON OX-TRAN型号2/20机在23℃和50％RH下测量这两种涂敷纸板的氧透过率(OTR)。为直接比较数据，两个样品的涂层重量相同。结果见表1。
表1.两个样品的OTR结果
  对照板   在粗糙侧上具有共混物的试验板
  OTR(cc/100in2-天)   106   66
在共混物中引入尼龙6，显着改进了涂敷纸板的氧透过率。这是该共混物优于直接的LDPE的一个优点。
实施例2
在中试装置中，将低密度聚乙烯或LDPE(65wt％)，聚酰胺(尼龙6)(30wt％)和增容剂(5wt％)的共混物，作为产品接触层直接挤出涂敷到基础重量为265磅每3,000平方英尺(大约432克每平方米)的纸板基材上。将三种组分在水泥浆搅拌机中干燥共混至少两分钟和然后加入到挤出机料斗中。也通过挤出涂敷LDPE到纸板基材上作为产品接触层而制备对照结构。在两种结构中，外印刷层由一层LDPE组成。然后将涂敷纸板转变成具有J型底部的毛坯和使用Evergreen填充机将这些毛坯成型为半加仑尺寸纸板箱。使用Scarlett Moo红色染料水溶液在这两种纸板箱上进行耐针孔性染料测试。首先将红色染料溶液倾入空纸板箱中一分钟，然后将染料溶液倾出纸板箱。然后采用流动自来水充分清洗纸板箱几分钟。最后将纸板箱放置在开放空气中干燥。
如果在涂层上有针孔，由于红色染料容易渗透入纤维，在染料干燥之后会留下红点形式的标记。通过从红点形成的程度判断，可以评价纸板箱的耐针孔性。在粗糙侧上具有LDPE的对照纸板箱显示非常严重数量的针孔，主要是由于在纸板箱成型期间的密集热量(图1)。在粗糙侧上具有LDPE/尼龙6共混物的试验结构显示较小程度的针孔形成(图2)。
实施例3
在牛奶场包装设备处进行牛奶填充试验以评价具有LDPE/尼龙6共混物作为产品接触层的纸板箱的性能。纸板箱的基础重量为265磅每3,000平方英尺(大约432克每平方米)。具有LDPE作为产品接触层的对照样品也包括在此试验中。在两种结构中，外印刷层由LDPE层组成。两种结构都具有J型底部和在两者中割出侧缝。使用EvergreenEH-1填充机在正常商业操作条件下将2％UHT(超高温)牛奶填充入纸板箱中。然后将这些纸板箱压入波纹箱中和堆叠在标准托板上和运输回位于Cincinnati，Ohio的实验室。性能评价测试包括膨胀和口味小组评价。在我们的实验室进行耐膨胀性测试。在外部独立实验室由受过训练的小组成员进行口味小组评价。周期性进行这些测试直到第12周或第13周。
将用于耐膨胀性测试的样品静置和在4℃下贮存在冷房中。相对于完全正方形或非膨胀纸板箱以1/32英寸测量纸板箱的平均膨胀(人字板(gable)到人字板距离和侧面到侧面距离)。结果见表2。
表2.膨胀性测试结果(以1/32英寸表示)
  时间，周   0   1   2   3   4   5   6   7   8   9   10   11   12
  对照物   4.6   9.5   12.8   14.4   15.2   16.1   17   18   18.8   19.1   19.6   19.8   20
  试验   4.8   9.1   12   13.3   14.6   15.2   15.9   17.1   17.8   18.2   18.6   18.5   18.5
实施例4
在外部实验室，将贮存在由实施例3所述的填充试验中生产的纸板箱中的2％UHT牛奶周期性评价它的口味。通过将纸板箱放入包含产生厌恶性气味的物质的冷冻室中进行该测试。这些物质包括洋葱、熟苹果、和熟香蕉。受过训练的小组成员根据0-100等级排列牛奶的口味，0是最差的。小组成员也对测试样品的味觉属性给出简要描述。结果见表3。
表3.外部受过训练的小组成员的味觉小组评价结果
  时间，周   周3   周5  周9   周13
  对照物   80(奶油，牛奶，轻微板味道)   60(板味道，臭味，洋葱/物质)  40(臭味，物质)   20(臭味，洋葱，不可接受的)
  试验   80(干净，奶油，牛奶)   100(奶油，牛奶)  80(干净，奶油，牛奶)   80(干净，奶油，牛奶，轻微板味道)
应当理解，可以对本发明进行改变和改进，而不背离本发明的范围。也理解本发明的范围并不解释为受限于在此公开的具体实施方案。

Claims (17)

1.一种容器用纸板包装层压材料，包括：
a)纸板基材；和
b)涂敷到该纸板基材上的聚酰胺聚合物和聚烯烃聚合物的共混物层，其中当将层压材料成型为容器时共混物层相当于产品接触层。
2.根据权利要求1的容器用纸板包装层压材料，所述共混物层进一步包含增容剂。
3.根据权利要求1的容器用纸板包装层压材料，其中将所述共混物层挤出涂敷到纸板基材上。
4.根据权利要求2的容器用纸板包装层压材料，其中将所述共混物层挤出涂敷到纸板基材上。
5.根据权利要求2的容器用纸板包装层压材料，其中所述共混物层包含65wt％聚烯烃聚合物，30wt％聚酰胺聚合物和5wt％增容剂。
6.根据权利要求1的容器用纸板包装层压材料，其中聚酰胺聚合物是尼龙6、尼龙6-6、尼龙6-10、无定形尼龙、或MXD6尼龙。
7.根据权利要求2的容器用纸板包装层压材料，其中增容剂是马来酸酐改性的聚乙烯、金属中和的乙烯甲基丙烯酸类共聚物、乙烯丙烯酸共聚物、乙烯甲基丙烯酸共聚物、马来酸酐改性的聚丙烯、环氧官能化的聚乙烯或环氧官能化的聚丙烯。
8.根据权利要求1的容器用纸板包装层压材料，进一步包括涂敷到基材未涂敷侧上的低密度聚乙烯聚合物层，其中当将层压材料成型为容器时低密度聚乙烯聚合物相当于外印刷层。
9.根据权利要求2的容器用纸板包装层压材料，进一步包括涂敷到基材未涂敷侧上的低密度聚乙烯聚合物层，其中当将层压材料成型为容器时低密度聚乙烯聚合物相当于外印刷层。
10.根据权利要求8的容器用纸板包装层压材料，其中共混物层的重量为41-49克每平方米；基材的基础重量为228-489克每平方米；和外印刷层的重量为16-25克每平方米。
11.根据权利要求3的容器用纸板包装层压材料，其中在将共混物层加入到挤出涂敷机中之前将共混物层干燥共混。
12.根据权利要求1的容器用纸板包装层压材料，其中聚烯烃聚合物是低密度聚乙烯、高密度聚乙烯、金属茂聚乙烯、线性低密度聚乙烯、聚丙烯、或金属茂聚丙烯。
13.根据权利要求1的容器用纸板包装层压材料，所述共混物层进一步包含选自如下的填料：碳酸钙、滑石、云母、粘土及其结合物。
14.根据权利要求2的容器用纸板包装层压材料，所述共混物层进一步包含选自如下的填料：碳酸钙、滑石、云母、粘土及其结合物。
15.一种容器用纸板包装层压材料，包括：
a)重量为432克每平方米的纸板基材；和
b)挤出涂敷到基材侧上作为产品接触层的共混物层，该共混物层包含65wt％低密度聚乙烯，30wt％尼龙6和5wt％马来酸酐官能化的增容剂，其重量为41-49克每平方米。
16.根据权利要求15的容器用纸板包装层压材料，进一步包括挤出涂敷到纸板基材未涂敷侧上作为外印刷层和重量为16-25克每平方米的低密度聚乙烯层。
17.一种容器用纸板包装层压材料，包括：
a)纸板基材；和
b)涂敷到该纸板基材上的聚酰胺聚合物和聚烯烃聚合物的共混物层，其中当将层压材料成型为容器时共混物层相当于外层。
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