CN100410071C - 用于饮料包装的阻隔叠层结构 - Google Patents

用于饮料包装的阻隔叠层结构 Download PDF

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CN100410071C
CN100410071C CNB038098393A CN03809839A CN100410071C CN 100410071 C CN100410071 C CN 100410071C CN B038098393 A CNB038098393 A CN B038098393A CN 03809839 A CN03809839 A CN 03809839A CN 100410071 C CN100410071 C CN 100410071C
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CN1649729A (zh
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克里斯托弗·S·克利夫兰
理查德·A·特德福特
特里西娅·S·赖格哈德
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1303—Paper containing [e.g., paperboard, cardboard, fiberboard, etc.]
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    • Y10T428/1303—Paper containing [e.g., paperboard, cardboard, fiberboard, etc.]
    • Y10T428/1307—Bag or tubular film [e.g., pouch, flexible food casing, envelope, etc.]
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    • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
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Abstract

一种阻隔叠层包装材料，依照其制备从其最外表面至接触容器内容物的最内表面包括：第一个低密度聚乙烯聚合物外层，纸板基材，与一个连接树脂层一起并涂布尼龙的第一个内层叠层，一个包含第一个低密度聚乙烯聚合物层、一个连接层、第一个EVOh内层、第二个连接层、第二个EVOH内层、第三个连接层和第二个低密度聚乙烯聚合物内层的吹塑薄膜层，和一个最内侧接触产品的低密度聚乙烯层。

Description

用于饮料包装的阻隔叠层结构
相关申请
本申请要求2002年5月2日公开的临时专利申请系列No.60/376875的优先权。
发明背景
本申请涉及纸板叠层，尤其是一种无箔纸板叠层，用于制备诸如酒精饮料包括葡萄酒、清酒和类似物以及其它饮料之类的产品的容器，其中叠层具有优秀的隔氧特性和防止其中的产品受潮的性能。
在亚洲，酒精饮料如葡萄酒、清酒和类似物包装在基于各种材料的容器中，包括基于纸板的容器。为了保护产品隔绝氧气以及防止可能出现的腐化，通常由多层结构组成容器的构造，该多层结构包括位于其中的铝箔，聚对苯二甲酸乙二醇酯，金属化的聚对苯二甲酸乙二醇酯，或其至少两种的结合。已经证明箔是最好的隔氧层，但是它相对较贵，并且难以在不破裂或不产生针孔的情况下制成成纸盒。
本发明的目的是要制备一种用于葡萄酒、清酒或其它酒精饮料纸盒的改进的酒精饮料包装热封材料，其不会透过氧气和湿气或水汽，并且在六个月或更长的产品上架期内表现出良好的热封结构。
发明概述
通过本发明可实现上述目标，其给出一种无箔复合结构，它能很好的阻隔氧气，水汽和湿气，并且是容易密封的。优选的实施方式从容器的外表面至接触内容物的内表面包括：施加在纸板基材外表面上的第一个聚烯烃层，施加在纸板基材内表面上的聚酰胺层，通过适宜的连接树脂叠置在聚酰胺层上的薄膜，和将会与容器内容物接触的施加在薄膜上的第二个并且是最内侧的聚烯烃层。优选的薄膜由第一个聚烯烃层，一个连接层，第一个乙烯乙烯基醇共聚物内层，第二个连接层，第二个乙烯乙烯基共聚物内层，第三个连接层，和第二个聚烯烃层构成。
发明详述
各种材料的相对用量和其各自的结构按照涂布重量范围以磅/每3000平方英尺(lb/3msf)为单位列出。基材由基重为100～300磅/每3000平方英尺的漂白板构成。
结构A：叠层薄膜结构
  层   涂布重量(lb/3msf)   材料
  1   8-20   聚烯烃
  2   基材
  3   2-10   聚酰胺
  4   5-20   连接树脂
  5   50-70   薄膜(结构B)
  6   5-15   聚烯烃
结构A包含纸板基材2(100～300磅)，在其一面上施加一个挤出涂布的聚烯烃层1如低密度聚乙烯作为叠层的外表面，涂布密度为8～20磅并优选约12磅。层1是外“光泽”层。优选地，聚烯烃是聚乙烯，并更优选是低密度聚乙烯。典型的可用于层1的优选低密度聚乙烯为可从Voridian，Kingsport，TN获得的Tenite 1924P和可从Chevron Phillips Chemical Co.，Houston，TX获得的Chevron 4517。
在基材2的内侧，施加聚酰胺层3(2～10磅)。聚酰胺聚合物层可非限制地为尼龙6，尼龙66，尼龙10，尼龙6-10，尼龙12，无定型尼龙，MXD-6，尼龙纳米复合物，和其它适宜的聚酰胺。一种合适的尼龙6材料为Honeywell B73QP(Morristown，NJ)。在层3的内表面上施加一个连接层4(5～20磅)，非限制地优选基于用马来酸酐官能团改性的基于乙烯的共聚物如MSI Technologies制备的
Figure C0380983900061
Figure C0380983900071
5125。聚酰胺层3和连接层4用于将薄膜5叠置在基材2上。薄膜5的涂布重量为约50～70磅。然后在薄膜层5下面施加一个聚烯烃层6，其优选为聚乙烯如低密度聚乙烯或茂金属。
结构B优选吹塑薄膜，其包含多层乙烯乙烯基醇共聚物，用于阻隔氧气。该薄膜叠层优选用共挤出涂布，以便允许以单向操作制备完整的结构，并用于改善薄膜的物理特性如改善的磨损性能、更大的刚性、和耐破裂性。一个优选的薄膜供应商为FlexTech(Cincinnati，OH)。
结构B：薄膜结构
  层   涂布重量(lb/3msf)   材料
  10   5-20   聚烯烃
  20   3-5   连接树脂
  30   2-5   EVOH
  40   3-20   连接树脂
  50   2-5   EVOH
  60   3-5   连接树脂
  70   5-20   聚烯烃
层30和50中的乙烯乙烯基醇共聚物用作叠层结构中主要的隔氧材料。可使用包含25～48摩尔％乙烯的EVOH材料。在可比较的涂布重量方面，EVOH是优于聚对苯二甲酸乙二醇酯(PET)的隔氧层。优选的EVOH供应商为Soarus LLP(Arlington Height，IL)。
聚烯烃层10和70为EVOH层30和50提供耐湿性，并为薄膜提供机械强度。连接层20，40和60非限制地优选基于用马来酸酐官能团改性的基于乙烯的共聚物。优选地每个所述连接层包含
Figure C0380983900072
本发明优选的实施方式在层40中使用基于高密度聚乙烯的连接树脂，以增加耐湿性。
在整个的叠层结构A中，起始的和最终的聚烯烃层用作防水层，以容纳液态产品并防止内部的聚合物和基材不受潮。该聚烯烃层还顾及到叠层和纸盒的热封以及填塞可能由多层折叠造成的任何孔或沟槽。附加的聚烯烃层为多层结构的内部提供额外的耐湿性和机械强度。在漂白板上挤出聚酰胺层，主要用于改善耐热性，机械强度，和耐久性。连接树脂用于促进两种聚合物之间的粘合，该聚合物之间通常是不相互粘合的。通过减慢氧气进入包装容器的速率，可进一步延长产品的新鲜度。乙烯乙烯基醇共聚物用作隔氧材料。本发明使用的乙烯乙烯基机醇共聚物材料(EVOH)包含29摩尔百分比的乙烯。在涂布重量相仿的情况下，EVOH是优于PET(聚对苯二甲酸乙二醇酯)的隔氧层。
在本发明第二个实施方式中，用任意的聚对苯二甲酸乙二醇酯或无定型或半结晶聚酰胺取代一个EVOH层。在本发明其它的实施方式中，可用除氧EVOH材料，EVOH纳米复合物，或EVOH与聚烯烃如低密度聚乙烯、聚酰胺、或聚对苯二甲酸乙二醇酯的混合物取代EVOH层。在这些实施方式的任意一个中，可使用包含25～48摩尔％乙烯的EVOH基树脂。
起始的和最终的聚烯烃层优选低密度聚乙烯，但也可以用线型低密度聚乙烯(LLDPE)，金属化低密度聚乙烯，或其与其它材料的混合物取代，以改善密封性。
本发明制备出适宜的具有优秀阻隔性能的容器，其采用可安全热封的叠层。该叠层不仅显示出显著的阻隔性能，延长饮料(葡萄酒，清酒或类似物)的上架期，而且该叠层能够使用常规装置制备。
本发明优选的实施方式构成如下：
在基材2上挤出涂布聚烯烃层1。然后沉积作为共挤出涂布层的聚酰胺层3和连接层4，以便将薄膜5叠置在基材2上。然后在薄膜5上施加聚烯烃层6，制成结构A。这只是形成结构A的一种方法，采用其它的方法也能够得到相同的最终结构。
现在，可在常规温度(250°F至500°F)下从前至后(聚烯烃至聚烯烃)热封完成的叠层。可采用新形成的叠层制备用于酒精饮料或其它液态产品的容器如纸盒，三角形或矩形容器或箱，袋，杯，甚至是圆柱形管。
可通过下列实施例理解由本发明的叠层提供的独特的阻隔效果和物理性能。
实施例
实施例1：
评估四种结构(C1～C4)的阻隔和物理性能，与结构A进行比较。用于测试的结构及其特定的涂布重量(lb/3msf)列于表1中。
表1：评估的结构
  A   C1   C2   C3   C4
  12LDPE   12LDPE   12LDPE   12LDPE   12LDPE
  205基材   265基材   205基材   265基材   265基材
  5尼龙   16LDPE   80LDPE   5尼龙   5尼龙
  7连接树脂   箔   14连接树脂   14连接树脂
  57吹塑薄膜(B)*   4连接树脂   4连接树脂   4连接树脂
  11LDPE   30LDPE   4EVOH   4EVOH
  18LLDPE   4连接树脂   4连接树脂
  8LDPE   8LDPE
  41LLDPE/LDPE混合物**
*见表2的结构B
**该混合物为80重量％LLDPE和20重量％LDPE。
表2：结构B
  15LDPE
  3连接树脂
  3EVOH
  15连接树脂
  3EVOH
  3连接树脂
  15连接树脂
如上所述，结构A为本发明的实施例。结构C1～C4为对照结构。C1为采用厚涂布重量的LDPE和LLDPE的箔基材料，以增加磨损和密封强度。C2由很重涂布重量的LDPE构成。C4与商业上可获得的用于液体包装的结构相似。最后，C3为C4的改进，采用了厚LDPE和LLDPE层，以确定其是否改善密封强度。
这五种结构的水蒸气(WVTR)和氧气(OTR)穿透速率列于表3。WVTR测试在38℃和90％相对湿度(RH)下进行。OTR值在23℃/50％RH和23℃/75％RH下测得。
表3：评估的结构的阻隔值
  结构A   C1   C2   C3   C4
  WVTR(38℃，90RH)(g/100in<sup>2</sup>/天)   0.031   0.005   0.059   0.057   0.059
  OTR(23℃，50RH)(cc/100in<sup>2</sup>/天)   0.015   0.009   15.915   0.018   0.013
  OTR(23℃，75RH)(cc/100in<sup>2</sup>/天)   0.049   0.015   22.268   0.028   0.036
从WVTR看，C1明显表现比其它结构好。在四种无箔结构中，A显示出最低的水蒸气穿透速率。C2，C3和C4的表现相对来说相同。当考虑到C2和C3具有比C4高得多的LDPE涂布重量，这是有点令人惊讶的。LDPE通常被认为是优秀的水蒸气阻隔材料，并且涂布重量越大应导致穿透速率越低。
在减慢氧气穿透方面，C1在两种环境条件下都表现得最好。在50％RH下，结构A，C3和C4具有的穿透速率只稍微高于C1。C2不含隔氧材料，因此它在这些测试中表现得非常差。
在75％RH下，五种结构的OTR值都增加了。与预期的一样，箔结构，即C1表现出的增加最小。三种多层结构表现大致相同。结构C2作为隔氧材料依然表现非常差。
实施例2：
结构A和C2物理性能的测量列于表4。比较的结果是恰当的，因为各个结构中的纸板基重和聚合物涂布重量是相同的。在可使用处的轴向(MD)和横向(CD)进行测量。
表4：评估的结构的物理性能的测量
  结构A   C2
  测量的参数
  耐破度(lb/in<sup>2</sup>)   211   204
  湿耐破度(lb/in<sup>2</sup>)   130   120
  硬度(挺度)-MD(g-cm)   316.8   283.2
  硬度(挺度)-CD(g-cm)   150.4   115.8
  湿硬度(挺度)-MD(g-cm)   108   97
  湿硬度(挺度)-CD(g-cm)   52   --
  磨损-MD(g)   649.9   597.7
  磨损-CD(g)   802.3   643.2
  湿磨损-MD(g)   983.0   757.9
  湿磨损-CD(g)   1339.9   910.0
  抗张强度-MD(lb/in)   82.0   73.6
  抗张强度-CD(lb/in)   37.5   32.9
  湿抗张强度-MD(lb/in)   18.5   15.7
  湿抗张强度-CD(lb/in)   10.9   9.5
当用吹塑薄膜叠层取代LDPE时，观察到在干和湿的破裂度(耐破度)，硬度(挺度)，和抗张强度方面得到适度的改善。
观察到磨损强度有很明显的改善，分别增加了52.2g(MD)和159.1g(CD)。这可归因于A和C2中聚合物硬度的不同，以及吹塑薄膜的双轴取向。
在试样打湿之后，板变弱，而此时聚合物的磨损性能开始起主导作用。在C2中，MD和CD磨损强度分别增加160.2g和266.8g。而对于结构A，MD和CD磨损强度分别增加333.1g和537.6g。这归因于聚合材料，它能防止湿润和潮湿条件下液体包装容器的磨损。
还发现在湿润条件下A和C2之间有显著的不同。MD的差额从52.2g增加至225.1g。CD磨损强度的差额从159.1g增加至429.9g。对于包括许多尖锐角度折叠的包装容器设计而言，结构A将提供额外的耐磨损性和防止包装损坏。而且在销售和消费者搬运过程中，还能增加对坠落时损坏的抗性。
五种结构的密封强度列于表5。
表5：密封强度测量
  结构A   C1   C2   C3   C4
  密封强度(lb/in)   10.7   10.0   3.5   16.6   7.3
相比于C4，通过同时增加C1和C3中密封层的涂布重量和LLDPE的含量可增加密封强度。但发现其不适用于C2。通过增加整个结构的热容量也可以改善密封强度，如结构A，C1，C3和C4将比C2吸收更多的热量并维持更长时间。

Claims (11)

1. 一种叠层包装材料，包括：
纸板基材，其具有内表面和外表面；
涂布在所述纸板基材的所述外表面上的一个热封聚烯烃聚合物外层；
涂布在所述纸板基材的所述内表面上的一个聚酰胺层；
涂布在所述聚酰胺层的内表面上的一个连接层；
一个薄膜层，其包含一个聚烯烃聚合物外层，一个连接层，第一个乙烯聚乙烯醇共聚物层，第二个连接层，第二个乙烯聚乙烯醇共聚物层，第三个连接层和第二个并且是最后的聚烯烃层，在涂布于所述聚酰胺层的内表面上的所述连接层的内表面上涂布所述薄膜层；
和涂布在所述薄膜层的所述最后聚烯烃层上的最内侧的聚烯烃层。
2. 根据权利要求1的叠层包装材料，其中每个所述连接层包含用马来酸酐官能团改性的基于乙烯的共聚物。
3. 根据权利要求1的叠层包装材料，其中每个所述连接层包含Plexar
Figure C038098390002C1
。
4. 根据权利要求1的叠层包装材料，其中一个所述乙烯聚乙烯醇共聚物EVOH层用选自聚对苯二甲酸乙二醇酯、聚酰胺、除氧EVOH、EVOH纳米复合物、EVOH与聚烯烃的混合物、EVOH与聚酰胺的混合物、或EVOH与聚对苯二甲酸乙二醇酯的混合物的物质取代。
5. 根据权利要求1的叠层包装材料，其中所述乙烯聚乙烯醇共聚物包含25～48摩尔％乙烯。
6. 根据权利要求1的叠层包装材料，从外表面至接触容器内容物的内表面包括：
a)基重为100～300磅/3000平方英尺的纸板基材，具有内表面和外表面；
b)涂布在所述纸板基材的所述外表面上的涂布重量为8～20磅/3000平方英尺的聚烯烃外层；
c)涂布在所述纸板基材的所述内表面上的涂布重量为2～10磅/3000平方英尺的一个聚酰胺层；
d)涂布在所述聚酰胺层内表面上的涂布重量为5～20磅/3000平方英尺的一个连接层；
e)一个薄膜层，其包含5～20磅/3000平方英尺的第一个聚烯烃层，3～5磅/3000平方英尺的第一个连接层，2～5磅/3000平方英尺的第一个乙烯聚乙烯醇共聚物层，3～20磅/3000平方英尺的第二个连接层，用量为2～5磅/3000平方英尺的第二个乙烯聚乙烯醇共聚物层，用量为3～5磅/3000平方英尺的第三个连接层和用量为5～20磅/3000平方英尺的第二个聚烯烃层；
f)涂布在薄膜层所述内表面上的用量为5～15磅/3000平方英尺的最内侧的聚烯烃层。
7. 一种酒精饮料容器，所述容器由根据权利要求1的叠层包装材料构成。
8. 一种酒精饮料容器，所述容器由根据权利要求4的叠层包装材料构成。
9. 一种酒精饮料容器，所述容器由根据权利要求6的叠层包装材料构成。
10. 一种阻隔氧气和湿气的叠层结构毛坯，用于制备不透氧气和湿气的容器，其由根据权利要求1的叠层包装材料构成。
11. 一种改善叠层阻隔氧气和湿气性能的方法，其包括以下步骤：
a)在纸板基材的外表面上涂布一个聚烯烃外层；
b)在纸板基材的内表面上涂布一个聚酰胺层；
c)在所述聚酰胺层的内表面上涂布一个连接层；
d)施加一个薄膜层，其包含第一个聚烯烃聚合物层，一个连接层，第一个EVOH内层，第二个连接层，第二个EVOH内层，第三个连接层和第二个聚烯烃聚合物内层；和
e)在所述薄膜层的所述最后提及的聚烯烃层上涂布一个聚烯烃层，该聚烯烃层包含最内侧的饮料接触层。
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