CN107405904A - 用于冷封应用的单网阻挡膜 - Google Patents

用于冷封应用的单网阻挡膜 Download PDF

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CN107405904A
CN107405904A CN201680011816.1A CN201680011816A CN107405904A CN 107405904 A CN107405904 A CN 107405904A CN 201680011816 A CN201680011816 A CN 201680011816A CN 107405904 A CN107405904 A CN 107405904A
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barrier film
single net
net barrier
top layer
cold seal
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CN201680011816.1A
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B·安布鲁斯
F·盖斯汀诺
L·尚特兰
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Jinda America Co Ltd
Jindal Films Americas LLC
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Jinda America Co Ltd
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Abstract

公开了用于冷封应用的单网阻挡膜的组合物、结构及方法。所述单网阻挡膜可以包括具有第一面及第二面的芯层。另外，所述单网阻挡膜还可以包括紧邻所述第一面的第一表层，其中所述第一表层包含基于乙烯‑乙烯醇或基于聚乙烯醇的涂层，所述涂层用于接受一种或多种冷封粘着剂。又另外，所述单网阻挡膜可以包括紧邻所述第二面的第二表层，其中所述第二表层包含经处理表面，其中所述第一表层在卷筒中防止粘连至所述第二表层。

Description

用于冷封应用的单网阻挡膜
相关申请的引用
本申请是专利合作条约(PCT)申请，其要求2015年2月24日提交的美国临时专利申请系列号62/120,158的优先权，所述专利申请以全文引用的方式并入本文中。
技术领域
本公开涉及用于冷封应用的单网阻挡膜(monoweb barrier film)的组合物、结构及方法。
背景技术
层压至离型膜以形成冷封的材料是已知的。已知的层压物例如包括在层压至作为离型膜的Jindal18CSR-M上的经过处理的Jindal35MU842三元共聚物(即，乙烯乙烯醇(“EVOH”)上金属)上使用冷封。另一实例是在层压至作为离型膜的20μm定向聚丙烯(“OPP”)上的Jindal45MW647(即，丙烯酸类)上使用冷封。金属化的EVOH或丙烯酸类涂层赋予香气阻挡保护。
加工者(converter)将冷封施加于阻挡膜上以便允许密封热敏性产品，例如巧克力棒，并且将层压物施加至离型膜上以便避免在卷筒(reel)中发生粘连。这些组合物和应用完整或部分地描述于例如三个参考文献中，即美国专利号8,596,867、美国专利号8,815,377及美国公开申请号2008/0223007，所有这些都以此引用的方式并入本文中。尽管已知层压物及应用，但简化及成本效益激发了替代解决方案，这些方案使用单网，赋予香气阻挡保护，并且维持经包装产品的适当脱模特性。
发明内容
公开了用于冷封应用的单网阻挡膜的组合物、结构及方法。在一个实施例中，存在一种单网阻挡膜，所述阻挡膜可以包括具有第一面及第二面的芯层。另外，所述单网阻挡膜还可以包括紧邻所述第一面的第一表层，其中所述第一表层包含基于乙烯-乙烯醇或基于聚乙烯醇的涂层，所述涂层用于接受一种或多种冷封粘着剂。又另外，所述单网阻挡膜可以包括紧邻所述第二面的第二表层，其中所述第二表层包含经处理表面，其中所述第一表层在卷筒中防止粘连至所述第二表层。
在另一示例实施例中，一种方法可以包括接收至少一个如前一段中所描述的单网阻挡膜，而在其它实施例中，所接受的单网膜可以包括一个或多个层、涂层、组分、离型衬垫或其组合。所述方法接下来是由所述单网阻挡膜形成包装、标记或标签。
附图说明
为了实现并且可以详细地了解本公开的上述特征、优势及目的，上文的简要概述可以参照其实施例较具体地说明，所述实施例在附图中图解说明。
然而，应注意，附图仅说明本公开的典型实施例且因此不应被视为限制本公开的范围，因为本公开可以承认其它同等有效的实施例。
图1是根据本公开的膜结构及组合物的示例性实施例的表格形式。
图2是根据本公开的膜结构及组合物的示例性实施例的图画形式。
图3提供可以用于根据本公开的膜结构及组合物中的粘结层的示例实施例。
图4提供根据本公开的膜结构及组合物的示例实施例。
图5显示针对图4中描绘的膜结构及组合物的示例实施例所取得的测量值。
图6显示针对含有防粘清漆(release lacquer，“RL”)以及根据本公开的膜结构及组合物的示例实施例(如图4中的那些)的各种样品膜结构及组合物所取得的冷封强度测量值。
具体实施方式
本公开大体上涉及与单网膜包装解决方案有关的组合物、结构、方法、包装、标签、标记等等，所述单网膜包装解决方案可以例如用作如包括巧克力棒在内的食物等产品的层压物的替代，其中本发明的包装膜及应用是用可再封闭的冷封密封。在一个示例实施例中，大体上公开一种结构，所述结构可以是60μm的空化膜(cavitated film)，而在其它示例实施例中，所述空化膜可能较薄或较厚，或者仅仅不是空化的。在各种实施例中，所述膜可以涵盖从透明到白色及从半透明到不透明的整个范围。转向在一个示例实施例中的空化膜的各层，第一表层的一侧可以包括用于香气阻挡保护的EVOH-表层，所述EVOH-表层可以涂布有冷封粘着剂。空化膜的相对侧可以具有第二表层和/或经历处理、印刷、金属化或其组合。意外的是，当两个表面在卷筒中接触时，金属不会粘连至EVOH-表层。中间部分可以含有空化芯层，所述空化芯层可以邻接第一粘结层，所述第一粘结层邻接EVOH-表层，并且任选地，所述芯层可以任选地紧靠第二粘结层、经处理表层或其组合，其中所述处理可以任选地经由电晕放电处理、火焰处理和/或其它方式进行。
空化膜的经处理和/或金属化表面可以印刷和/或涂布有防粘清漆以避免粘连于冷封涂层。所述经处理层可以是聚乙烯(“PE”)、聚丙烯(“PP”)的均聚物或共聚物，或其共混物。意外的是，EVOH-表层除提供香气阻挡保护及针对经表面处理的层或金属化层的粘连抗性以外，还是冷封粘着剂的良好接收表面。
另外及替代地，公开了可以被接受和用于例如制造众多包装、标记、标签及其它实施方案的膜；并且此类膜可以经历涂布、金属化、印刷或其组合。金属化可以例如由铝、AlOx、SiOx及其它来源发生。涂料例如可以是丙烯酸、聚偏二氯乙烯(“PVDC”)或可印刷涂料，如常规或数字印刷中使用的那些。
转向示例实施例的更详细说明，图1以表格形式提供了可以共挤出并且符合本文中的论述的膜结构。图2以更类似图画的形式描绘类似的示例实施例。
在又另外的示例实施例中，EVOH层的厚度可能比图1及2中所显示的厚度要高得多或低得多，例如0.1-5μm。在又另外的示例实施例中，共挤出的EVOH层可以被一个或多个EVOH涂层替代，如美国专利号7,473,439中所描述并且所述专利以此引用的方式并入本文中。也就是说，本公开的膜涂层并入至少一种包含乙烯醇单元及衍生自乙烯的单元的交联EVOH共聚物。出于本公开的目的，术语“EVOH共聚物”和“乙烯乙烯基共聚物”是指并入包括乙烯醇单元及衍生自乙烯的单元在内的两种或超过两种单体的聚合物。举例来说，如本文所使用，这些术语包括含衍生自乙烯的单元及乙烯醇单元，以及以至多10mol％含量存在的一种或多种额外单体的共聚物。示例性额外单体包括α-烯烃，如丙烯、1-丁烯、异丁烯及1-己烯；乙烯基醚，如甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、异丙基乙烯基醚及正丁基乙烯基醚；含羟基的乙烯基醚，如乙二醇乙烯基醚、1,3-丙二醇乙烯基醚及1,4-丁二醇乙烯基醚；烯丙基醚，如乙酸烯丙基酯、丙基烯丙基醚、丁基烯丙基醚及己基烯丙基醚；含有氧基亚烷基的单体；乙烯基硅烷，如乙烯基三甲氧基硅烷；含羟基的α-烯烃，如乙酸异丙烯基酯、3-丁烯-1-醇、4-戊烯-1-醇、5-己烯-1-醇、7-辛烯-1-醇、9-癸烯-1-醇及3-甲基-3-丁烯-1-醇；含磺酸基的单体，如乙烯磺酸、烯丙基磺酸、甲基烯丙基磺酸及2-丙烯酰胺-2-甲基丙烷磺酸；以及含阳离子基团的单体，如乙烯基氧基乙基三甲基氯化铵、乙烯基氧基丁基三甲基氯化铵、乙烯基氧基乙基二甲基胺、乙烯基氧基甲基二乙胺、N-丙烯酰胺甲基三甲基氯化铵、3-(N-甲基丙烯酰胺)丙基三甲基氯化铵、N-丙烯酰胺乙基三甲基氯化铵、N-丙烯酰胺二甲基胺、烯丙基三甲基氯化铵、甲基烯丙基三甲基氯化铵、二甲基烯丙基胺及烯丙基乙胺。
另外及替代地，共挤出的EVOH层可以被一个或多个EVOH涂层替代，如一个或多个聚乙烯醇(“PVOH”)涂层，如美国专利号6,444,750中所描述的涂层，并且所述专利以此引用的方式并入本文中。举例来说，PVOH可以包括呈水溶液形式的促进交联的酸催化剂(如磷酸、硝酸、盐酸或顺丁烯二酸)及交联剂(如三聚氰胺甲醛)。PVOH可以具有低粘度并且是超强水解的(superhydrolyzed)。不过，其它可商购的PVOH，例如制造的7130也是可接受的。此外，共挤出的EVOH层可以被交替的EVOH和PVOH涂层，或一个或多个由EVOH/PVOH涂层构成的涂层替代，其中所述涂层是呈溶液或分散液形式。在各种替代性示例实施例中，涂层可以在一条直线上、不在一条直线上或其组合方式施加。
图1及2显示了空化的PP芯层，而在其它示例实施例中，所述芯层可以另外或替代地包括PE，如呈HDPE及LLDPE，任选地经茂金属催化的聚对苯二甲酸亚乙酯(“PET”)，及前述任一种的组合的示例形式。此外，在其它示例实施例中，所述芯层可以是未空化的(即，不含有如图1及2中的聚对苯二甲酸亚丁酯(“PBT”))或包括如本公开其它部分处论述的替代性空化剂。
在所述膜层中的任一个中可以包括各种添加剂，如颜料、加工助剂、挤出助剂、防粘连剂、润滑添加剂、抗静电添加剂或其它添加剂。在一个实例中，将TiO2颜料添加至处于电晕处理的表层之下的粘结层中将改善电晕处理的表层的白度，如先前所公开，所述电晕处理的表层可以例如被加工者用作印刷表面。在另一示例实施例中，将一种或多种氟聚合物添加至EVOH层中。
空化或空隙形成添加剂可以包括与芯层聚合材料不相容的任何适合的有机或无机材料。除图1及2中使用的PBT以外或另外的适合空化剂的实例有耐纶、实心或中空预成型玻璃球、金属珠粒或金属球、陶瓷球、CaCO3、滑石、白垩等，或其组合。空隙形成粒子的平均直径典型地可以是0.1至10μm。以芯层的总重量计，芯层中可以存在小于30wt％，优选小于25wt％，最优选在2至20wt％范围内的这些空隙形成粒子。可以使用高于或低于5％的GE195PBT作为空化剂或使用其它类型的适合空化剂，以便视需要调整膜的空化/密度，这种变化可以制造出具有不同刚度及EVOH-表层粘着性的膜。
转向在图2描绘的示例实施例中邻接EVOH-表层的粘结层，在各种示例实施例中可能存在占所述粘结层在25到100wt％范围内的顺丁烯二酸酐接枝的PP(“PPgMAH”)。PPgMAH可以改善EVOH-表层的粘着性。当冷封打开时，为了减少(如果无法完全避免)表层剥离，还可以使用在约0至75％范围内的PP类弹性体，如
图3描绘应用所公开的组合物的一个或多个粘结层的替代性示例实施例。使用图3，可以看出各种粘结层组合物可以基于两种主要组分，即PPgMAH和55％(或其它PP类弹性体)的组合而形成。借助于实例进一步解释，如果使用25％PPgMAH及55％则此粘结层组合物其余部分中PP的最大补充量是20％，其中最大补充量是在所述粘结层中不存在其它添加剂，如本文所公开或本领域中已知类型的那些添加剂的情况下使用的术语。如果将此类添加剂添加至本实例中，则PP的补充量小于以重量计所述粘结层的20％的最大补充量。
在其它示例实施例中，在EVOH层之下的可能的粘结层可以是如美国专利号5,153,074中所描述的那些层，并且所述专利以在此引用的方式并入本文中。另外及替代地，在经处理表层之下的粘结层可以不是PP均聚物，如PP共聚物、PE，或PP均聚物、共聚物和/或PE的组合。
图4描绘符合在图1及2显示和关于其描述的那些的膜结构。图5概述了针对图4中略述的实验性单网阻挡膜(即，膜)所取得的测量值。实验膜的密度是通过用实验膜的厚度除以实验膜的重量来计算，其中厚度，即光学测量值，是用微米度量。光透射率测量值是根据ASTM D1003取得。
本公开中膜的三元共聚物处理的表面通过印刷和涂布防粘清漆(“RL”)，如购自的10-609596-1.1650而转化。基于EVOH的表层用以3.8g/m2施加的图案化冷封，例如Sun ChemicalTM的CS8113涂布，而其它图案和沉积量在其它实施例中可能不同。
最后，参看图6，描绘了使用Otto Brugger密封机(在23℃温度下，压力＝60N/cm2或600kPa，且停留时间在1s)测量的商购膜以及实验膜(即，现借助于本公开呈现的膜，如图1-5中公开的那些)的室温冷封强度的表格概述。冷封强度是根据ASTM F2029测量。
实验膜展示与具有标准表面，如经过处理的双轴取向的PP(“BOPP”)及丙烯酸涂布的BOPP的商购膜类似的冷封性能。在其它示例实施例中，所述膜只是单轴取向的。
尽管前述是针对所公开的发明的示例实施例，但在不脱离其基本范围的情况下，可以预想其它以及另外的实施例，其中所公开的应用、组合物、结构、标记、方法等等的范围是由权利要求书决定。
权利要求书(按照条约第19条的修改)
1.一种单网阻挡膜，包括：
具有第一面和第二面的芯层；
紧邻所述第一面的第一表层，其中所述第一表层包含基于乙烯-乙烯醇或基于聚乙烯醇的涂层，所述涂层用于接受一种或多种冷封粘着剂；以及
紧邻所述第二面的第二表层，其中所述第二表层包含经处理表面，
其中所述第一表层在卷筒中防止粘连到所述第二表层。
2.如权利要求1所述的单网阻挡膜，另外在所述芯层与至少由所述第一表层、所述第二表层及两者组成的组的成员之间包括一个或多个粘结层。
3.如权利要求2所述的单网阻挡膜，其中所述一个或多个粘结层包含聚丙烯聚合物、聚乙烯聚合物、用顺丁烯二酸酐接枝的聚合物或其组合。
4.如权利要求1所述的单网阻挡膜，其中所述芯层包含聚丙烯、聚乙烯、聚对苯二甲酸亚乙酯或其组合。
5.如权利要求1所述的单网阻挡膜，其中所述芯层包含空化剂。
6.如权利要求1所述的单网阻挡膜，其中所述第二表层包含一种或多种乙烯-丙烯-丁烯三元共聚物。
7.(删除)。
8.如权利要求1所述的单网阻挡膜，其中所述经处理表面包含通过电晕放电或火焰处理。
9.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜是透明或带白色的。
10.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜是半透明或不透明的。
11.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的可印刷涂层。
12.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的金属化层。
13.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的涂层，其中所述涂层包含防粘清漆。
14.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的一种或多种冷封粘着剂。
15.如权利要求14所述的单网阻挡膜，其中所述一种或多种冷封粘着剂是可再封闭的。
16.如权利要求14所述的单网阻挡膜，其中所述一种或多种冷封粘着剂在23℃温度及60N/cm2压力下持续1秒压接时间具有至少170g/25.4mm的冷封强度。
17.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜具有至少22％的光透射率。
18.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜的密度在0.6g/cm3与0.8g/cm3之间。
19.如权利要求1所述的单网阻挡膜，另外在所述单网阻挡膜的一个或多个层中包含一种或多种添加剂。
20.一种方法，包括接受至少如权利要求1所述的单网阻挡膜，其中所述至少所述单网阻挡膜任选地包括一个或多个层、涂层、组分、离型衬垫或其组合；以及由所述单网阻挡膜形成包装、标记或标签。
21.(新)如权利要求1所述的单网阻挡膜，其中所述第一表层另外包含一种或多种促进交联的酸催化剂、交联剂或这两种。

Claims (20)

1.一种单网阻挡膜，包括：
具有第一面和第二面的芯层；
紧邻所述第一面的第一表层，其中所述第一表层包含基于乙烯-乙烯醇或基于聚乙烯醇的涂层，所述涂层用于接受一种或多种冷封粘着剂；以及
紧邻所述第二面的第二表层，其中所述第二表层包含经处理表面，
其中所述第一表层在卷筒中防止粘连到所述第二表层。
2.如权利要求1所述的单网阻挡膜，另外在所述芯层与至少由所述第一表层、所述第二表层及两者组成的组的成员之间包括一个或多个粘结层。
3.如权利要求2所述的单网阻挡膜，其中所述一个或多个粘结层包含聚丙烯聚合物、聚乙烯聚合物、用顺丁烯二酸酐接枝的聚合物或其组合。
4.如权利要求1所述的单网阻挡膜，其中所述芯层包含聚丙烯、聚乙烯、聚对苯二甲酸亚乙酯或其组合。
5.如权利要求1所述的单网阻挡膜，其中所述芯层包含空化剂。
6.如权利要求1所述的单网阻挡膜，其中所述第二表层包含一种或多种乙烯-丙烯-丁烯三元共聚物。
7.如权利要求1所述的单网阻挡膜，其中所述经处理表面包含经电晕处理的表面。
8.如权利要求1所述的单网阻挡膜，其中所述经处理表面包含通过电晕放电或火焰处理。
9.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜是透明或带白色的。
10.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜是半透明或不透明的。
11.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的可印刷涂层。
12.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的金属化层。
13.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的涂层，其中所述涂层包含防粘清漆。
14.如权利要求1所述的单网阻挡膜，另外包括在所述第一表层上与所述芯层相对的一侧上的一种或多种冷封粘着剂。
15.如权利要求14所述的单网阻挡膜，其中所述一种或多种冷封粘着剂是可再封闭的。
16.如权利要求14所述的单网阻挡膜，其中所述一种或多种冷封粘着剂在23℃温度及60N/cm2压力下持续1秒压接时间具有至少170g/25.4mm的冷封强度。
17.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜具有至少22％的光透射率。
18.如权利要求1所述的单网阻挡膜，其中所述单网阻挡膜的密度在0.6g/cm3与0.8g/cm3之间。
19.如权利要求1所述的单网阻挡膜，另外在所述单网阻挡膜的一个或多个层中包含一种或多种添加剂。
20.一种方法，包括接受至少如权利要求1所述的单网阻挡膜，其中所述至少所述单网阻挡膜任选地包括一个或多个层、涂层、组分、离型衬垫或其组合；以及由所述单网阻挡膜形成包装、标记或标签。
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