CN108724871A - 一种含有偏振膜的包装复合材料及含有该材料的包装 - Google Patents

一种含有偏振膜的包装复合材料及含有该材料的包装 Download PDF

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Publication number
CN108724871A
CN108724871A CN201710257517.2A CN201710257517A CN108724871A CN 108724871 A CN108724871 A CN 108724871A CN 201710257517 A CN201710257517 A CN 201710257517A CN 108724871 A CN108724871 A CN 108724871A
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CN
China
Prior art keywords
composite material
packaging
polarizing coating
layer
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710257517.2A
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English (en)
Inventor
马珣
赵志恒
程志军
曾文
熊桓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coca Cola Co
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Coca Cola Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coca Cola Co filed Critical Coca Cola Co
Priority to CN201710257517.2A priority Critical patent/CN108724871A/zh
Priority to PCT/US2018/028276 priority patent/WO2018195258A1/en
Priority to US16/605,716 priority patent/US11685587B2/en
Priority to EP18787083.7A priority patent/EP3612387A4/en
Priority to JP2019556580A priority patent/JP7277377B2/ja
Publication of CN108724871A publication Critical patent/CN108724871A/zh
Pending legal-status Critical Current

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Abstract

本发明公开了一种含有偏振膜的包装复合材料，它包含：偏振层，包含两层以上偏振膜；其中，至少有两层偏振膜的偏振方向的夹角不为0°。本发明的包装复合材料结构简单，对光具有强的阻隔性，阻光率高，具有广谱的阻光效果。本发明还公开了该包装复合材料在包装中的应用以及该包装复合材料在标签中的应用，其作为包装或标签使用可延长需避光保存的产品的货架期。

Description

一种含有偏振膜的包装复合材料及含有该材料的包装
技术领域
本发明涉及包装复合材料。更具体地，涉及一种能够阻光的包装复合材料及含有该材料的包装。
背景技术
包装为在流通过程中保护产品、方便贮运、促进销售，按一定技术方案而采用的容器、材料及辅助物的总体名称，在日常生活中应用广泛。如食品包装、建材包装、药物包装等。随着包装安全要求以及消费者的消费水平的提高，包装材料的种类也日趋多样化。进一步地，包装材料的特性如光阻隔性、氧气阻隔性、二氧化碳阻隔性、水汽阻隔性、耐高温性、力学性能、以及化学稳定性等均制约着其在实际生产生活中的应用。
食品包装材料的一大特征就是追求食品的美味与安全性，同时还需要延长包装食品的货架期。基于这样的需求，各种阻隔性包装材料和包装技术的开发得以推动。对于一些需要避光保存的材料或食品饮品类产品，实现其有效的存储对于包装材料的阻光性具有较高的要求。比如，对于光敏食品(包含饮品)，紫外光和可见光的照射能诱导其中的维他命、脂肪、蛋白质等物质发生光氧化降解，而使产品变质，产生异味。对于饮料，尤其是牛奶和果汁等，需要足够的阻光保护从而来延长其货架期。
现有技术中，一般通过向包装材料中添加无机添加剂(如，TiO2等)或有机阻光添加剂等，从而赋予包装材料一定程度的阻光性能。例如，公开号为CN102604184A(发明名称：一种用于食品包装的阻光PE膜)的中国发明专利的申请中，通过向PE母料中添加光敏剂核黄素，增加PE膜对特定波段(400～500nm)光线的阻隔得到阻光薄膜，将该阻光薄膜用作食品包装用于减缓所包食品的光照氧化。但该发明所提供的阻光薄膜仅能阻隔波长为400～500nm波段范围内的光照，阻光范围狭窄，应用范围和效果受到限制。题目为“用于超市微加工蔬菜可选择吸光包装材料的研究”的天津科技大学2011年的硕士学位论文中，作者贾金匣通过在LDPE薄膜中添加紫外线吸收剂和受阻胺类光稳定剂，获得降低透光率的薄膜材料。将这种可降低透光率的薄膜材料用作包装材料，在一定程度上延长了超市蔬菜的货架寿命。公开号为CN105813836A(发明名称：用于包装食品和化妆品、医疗器械和药品的具有阻湿、阻氧和阻光性的可热成型泡罩材料)的发明专利的申请中，公开了一种用于包装含有益生性微生物的制剂的多层材料。该专利申请中，通过将聚合物PP、PVC、PET等材料表面金属化，再经过胶粘结合可得到用于包装含有益生性微生物的制剂的多层材料。
但上述公开的技术方案均无法实现广谱的阻光效果。
发明内容
本发明的一个目的在于提供一种结构简单、具有广谱的阻光效果的包装复合材料。
本发明的第二个目的在于提供具有广谱的阻光效果的包装复合材料在包装中的应用,以期延长光敏感的产品的货架期。
本发明的第三个目的在于提供上述具有广谱的阻光效果的包装复合材料在标签中的应用。
为达到上述第一个目的，本发明提供一种含有偏振膜的包装复合材料，它包含：
偏振层，包含两层以上偏振膜；
其中，至少有两层偏振膜的偏振方向的夹角不为0°。
优选地，所述包装复合材料还包含位于偏振层一侧的第一面层。
更优选地，所述包装复合材料还包含位于偏振层另一侧的第二面层。
优选地，所述面层的材料选自PE、PETG、PVC、PVA、PC、PP、PS、PET、PBT、EVA、EVOH、PLA、PEF、PEN、PCTG、PBAT、PBST、PVDC和PA中的一种。
优选地，所述偏振层进一步包含位于各偏振膜之间的偏振膜粘结层。
更优选地，所述偏振膜粘结层的材料选自聚乙烯醇系粘合剂、丙烯酸酯类粘合剂、乙烯-醋酸乙烯共聚物粘合剂、环氧树脂粘合剂、不饱和聚酯胶粘剂和醋酸乙烯树脂型粘合剂中的一种。
优选地，所述包装复合材料进一步包含位于所述偏振层与所述第一面层之间的面层粘结层。
优选地，所述包装复合材料进一步包含位于所述偏振层分别与所述第一面层和第二面层之间的面层粘结层。
更优选地，所述面层粘结层的材料选自聚乙烯醇系粘合剂、丙烯酸脂类粘合剂、乙烯-醋酸乙烯共聚物粘合剂、环氧树脂粘合剂、不饱和聚酯胶粘剂和醋酸乙烯树脂型粘合剂中的一种。
优选地，至少有两层偏振膜的偏振方向的夹角为45°～135°。
更优选地，至少有两层偏振膜的偏振方向的夹角为80°～100°。
最优选地，至少有两层偏振膜的偏振方向的夹角为90°。
优选地，各偏振膜间至少有两个偏振膜的偏振方向的夹角不为0°。
优选地，所述偏振层包含2～10层偏振膜。
更优选地，所述偏振层包含2～6层偏振膜。
本发明的第二个目的在于提供上述含有偏振膜的包装复合材料在包装中的应用。
本发明中的包装复合材料可根据实际避光需求而作为包装应用在包装领域，例如，可作为食品包装、药物包装、建筑包装等。
优选地，所述含有偏振膜的包装复合材料直接接触内容物。
优选地，所述含有偏振膜的包装复合材料中，偏振层的厚度为20纳米～10毫米，各偏振膜的厚度为10纳米～1毫米。
本发明的第三个目的在于提供上述含有偏振膜的包装复合材料在标签中的应用。
本发明的含有偏振膜的包装复合材料作为具有隔光效果的标签使用时，标签具有阻光性能。其中，该包装复合材料中偏振层的厚度本领域技术人员可根据标签的厚度等实际情况选择。
优选地，所述包装复合材料中，偏振层的厚度为20纳米～10毫米。各偏振膜的厚度为10纳米～100微米。
更优选地，所述包装复合材料中，偏振层的厚度为20纳米～1毫米。
最优选地，所述包装复合材料中，偏振层的厚度为20纳米～200微米。
本发明的有益效果如下：
本发明的包装复合材料结构简单，通过在包装复合材料中设置包含两层以上偏振膜的偏振层，且通过对各偏振膜间偏振方向的夹角的控制，使得到的包装复合材料具有广谱的阻光效果。同时，该包装复合材料作为包装使用可极大的延长需避光保存的产品的货架期。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出偏振膜的偏振方向的夹角示意图。
图2示出本发明实施例1的含有偏振膜的包装复合材料的示意图。
具体实施方式
为了更清楚地说明本发明，下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
图1示出偏振膜的偏振方向的夹角示意图如所示。图中，两偏振膜a和b各自的偏振方向间的夹角θ即为偏振膜的偏振方向的夹角。
图2示出本发明实施例1含有偏振膜的包装复合材料的示意图。包装复合材料100依次包含第一面层101，包括第一偏振膜201和第二偏振膜202的偏振层，第二面层102，其中第一偏振膜201偏振方向和第二偏振膜202偏振方向的夹角大致为90°。自然光110透过第一面层101后，再通过第一偏振膜201时，经第一偏振膜201起偏得到偏振光111。偏振光111在经过第二偏振膜202时，只有少量或极少量的光线透过第二偏振膜202，几乎没有光线通过包装材料100的第二面层102，从而实现了对光的阻隔。附着在第一偏振膜201和第二偏振膜202外侧的第一面层101和第二面层102一方面起到对偏振膜的保护作用，避免偏振膜因为在使用中的磨损而导致偏振特性的损失；另一方面可根据包装复合材料的使用环境，提供满足使用要求的安全和强度性能。当偏振膜自身能够提供所需的性能和足够的强度时，可省略一个或两个面层，将包含第一偏振膜201和第二偏振膜202的偏振层直接用作包装复合材料。可以理解，根据包装材料的使用环境，可仅在偏振层一侧形成面层，也可以如上所述在偏振层两侧均形成面层。光线入射包装复合材料的方向，可以与偏振层的方向无关而与面层材料的选择有关。
其中，上述偏振膜的主体材料包括但不限于选自PVA、EVA、PETG和PE等。通过赋予主体材料偏振特性，从而得到偏振膜。可用于本发明的获得偏振膜的方法包括但不限于，例如，通过吸收碘和/或二向色性的染料于聚乙烯醇薄膜，或者是一种乙烯-醋酸乙烯共聚物皂化膜或类似物，并对其进行拉伸处理后制备得到偏振膜。用于包装复合材料中的各偏振膜的厚度优选地控制在10纳米～100微米之间，偏振层的厚度则可根据实际应用中所用包装材料的厚度等进行适应性选择。
各偏振膜间通过层叠的方式结合形成偏振层。层叠的方式有多种，本领域技术人员可根据实际偏振膜的结构及性能来选择具体的层叠方法。例如，可通过直接施加力于各偏振膜表面，实现偏振膜间的结合，具体的实施方法包括但不限于压合，例如热压。
此外，也可通过在各偏振膜之间设置偏振膜粘结层来实现偏振膜间的结合。其中，偏振膜粘结层用于将相邻的偏振膜牢固结合，同时又不影响偏振膜的偏光特性，偏振膜粘结层材料具体可依据偏振膜材料的特性来选择。具体的实施方式中，偏振膜粘结层材料可选择粘合剂。例如，粘合剂包括但不限于选自聚乙烯醇系粘合剂、丙烯酸脂类粘合剂、乙烯-醋酸乙烯共聚物粘合剂、环氧树脂粘合剂、不饱和聚酯胶粘剂和醋酸乙烯树脂型粘合剂等中的一种。
附着在偏振层外侧的第一面层和第二面层的材料可以相同或不同。本领域技术人员可依据偏振膜材料的特性，在保证偏振层的偏光效果以及考虑到材料与偏振膜材料的相容性等前提下，选择相应的面层材料。例如，第一面层和/或第二面层的材料可分别独立的选自PE、PETG、PVC、PVA、PC、PP、PS、PET、PBT、EVA、EVOH、PLA、PEF、PEN、PCTG、PBAT、PBST、PVDC和PA中的一种。进一步地，在具体的实施方式中，可根据具体选择的面层材料来选择该材料较为合适的用于成型面层的方法。例如，面层的成型方法包括但不限于流延法、压延法、溶剂法等。
面层附着在偏振层外侧的方法有多种，能使所述面层能与偏振层牢固结合且不影响偏振层的偏光效果以及能使所得复合材料作为包装材料使用的方法均可。较为优选地结合方法为直接施加力于面层与结合的偏振层表面，实现两者的结合，例如，热压；又一种较为优选地结合方法可将面层在成型的过程中与偏振层结合，例如，采用溶剂法将面层材料溶解，再浇注在偏振层表面，干燥后，实现结合；另一种较为优选地结合方法可通过在偏振层与第一面层或偏振层与第二面层或偏振层分别与第一面层和第二面层之间设置面层粘结层，用于将第一面层和/或第二面层和偏振层牢固的结合，而又不影响偏振层的偏光特性。面层粘结层的材料可选择粘合剂，例如，聚乙烯醇系粘合剂、丙烯酸脂类粘合剂、乙烯-醋酸乙烯共聚物粘合剂、环氧树脂粘合剂、不饱和聚酯胶粘剂和醋酸乙烯树脂型粘合剂等中的一种。其中，面层的厚度可根据实际应用中所用包装材料强度以及安全性等的要求来进行适应性选择。
本领域技术人员可以根据偏振膜的光学特性、材料特性、使用要求及透光效果，确定上述包装复合材料中偏振膜的个数和各偏振膜偏振方向间的夹角。根据本发明的另一个优选实施例，偏振层可以包含多个偏振膜，优选2～10层偏振膜，更优选2～6层偏振膜。各偏振膜间至少两个偏振膜的偏振方向的夹角不为0°，这样能保证达到好的阻光效果。优选地，各偏振膜之间的偏振方向的夹角分别不为0°。进一步地，各偏振膜间优选至少有两个偏振膜的偏振方向的夹角为45°～135°，更优选为80°～100°，最优选为90°。
采用了以上的技术方案后，可获得具有广谱阻光效果的包装复合材料。
本发明中含有偏振膜的包装复合材料具有广谱的阻光效果，从而可应用在需阻光处理的领域中，如包装领域。在本发明的又一个优选实施例中，根据实际避光需求，将包装复合材料作为包装应用在包装领域。例如，上述包装复合材料可作为食品包装、药物包装、建筑包装等。在本发明的又一个优选实施例中，含有偏振膜的包装复合材料直接接触内容物，其中，内容物可为需避光保存的食品、药物、建材等。在本发明的又一个优选实施例中，用于包装的包装复合材料中，偏振层的厚度优选为20纳米～10毫米，各偏振膜的厚度为10纳米～1毫米。
本发明能够阻光的包装复合材料可作为具有隔光效果的标签使用，从而赋予标签阻光性能。在本发明的又一个优选实施例中，包装复合材料中偏振层的厚度为20纳米～10毫米，各偏振膜的厚度为10纳米～100微米。在本发明的另一个优选实施例中，包装复合材料中偏振层的厚度为20纳米～1毫米。在本发明的又一个最优选的实施例中，包装复合材料中偏振层的厚度为20纳米～200微米。
如无特殊说明，本发明中所用试剂和原料均可通过市售购买获得或本领域常规手段获得。
另外需注意的是，如无特殊说明，本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。
除上述说明外，本发明的制备方法中未具体提及的工序以及所用设备均可采用所属领域中的常规设备或参照所属领域的现有技术进行。
以下结合一些具体的实施例来进行说明：
实施例1
一种含有偏振膜的包装复合材料，制备方法为：
将两层厚度为60微米的聚乙烯醇膜(聚合度2400，皂化度99.9mol％以上)分别置于30℃的纯水中，使膜不松弛而保持紧张状态，浸渍约130秒，使膜充分地膨润；接着，将膜浸渍在碘/碘化钾/水的重量比为0.02/1.5/100的水溶液中进行染色处理，一边进行单轴拉伸。然后，一边将膜浸渍在碘化钾/硼酸/水的重量比为10/5/100的60℃的水溶液中进行硼酸处理，一边进行单轴拉伸，直到从原反开始的累积拉伸倍数为5.9倍，再迅速将两层单轴拉伸后的膜层合，其中，两层膜层合后的拉伸方向夹角为90°(即，两偏振膜的拉伸方向垂直，偏振方向夹角为90°)。并施加垂直于膜表面的力使膜层结合紧密。最后，在10℃的纯水中水洗约10秒后，在60℃下干燥5分钟，制得厚度为21.6微米的偏振层；
再取两层未经过上述处理的厚度为14微米的聚乙烯醇薄膜，分别作为第一面层和第二面层，将两个面层分别结合在偏振层的两侧，热压，使得面层与偏振层紧密结合，得到含有偏振膜的包装复合材料。该包装复合材料具有广谱的阻光效果，作为包装使用时可延长光敏感的产品的货架期。
实施例2
一种含有偏振膜的包装复合材料，制备方法为：
将厚度为75微米的聚乙烯醇膜(聚合度2400，皂化度99.9mol％以上)置于30℃的纯水中，使膜不松弛而保持紧张状态，浸渍约130秒，使膜充分地膨润；接着，将膜浸渍在碘/碘化钾/水的重量比为0.02/1.5/100的水溶液中进行染色处理，一边进行单轴拉伸。然后，一边将膜浸渍在碘化钾/硼酸/水的重量比为10/5/100的60℃的水溶液中进行硼酸处理，一边进行单轴拉伸，直到从原反开始的累积拉伸倍数为5.9倍；接着，一边将膜在40℃下在碘化钾/硼酸/水的重量比为10/3/100的水溶液中浸渍约30秒，进行第2次硼酸处理，一边使膜的拉伸沿拉伸方向松弛约3％(最后拉伸倍数为5.72倍)。最后，在10℃的纯水中水洗约10秒后，在60℃下干燥5分钟，制得厚度为13.1微米的偏振膜；
取三层该制备得到的偏振膜，通过在偏振膜上涂布聚乙烯醇系粘合剂的方式，实现偏振膜间的结合，层合过程中保证第一、二层偏振膜层间的偏振方向夹角为45°，第一、三层偏振膜间的偏振方向夹角为80°(偏振方向为偏振膜的拉伸方向)，在60℃温度下干燥2分钟，得偏振层；
再取一层未经过上述处理的厚度为18微米的聚乳酸膜，作为第一面层，再在其一个面上涂布聚乙烯醇系粘合剂，粘合在偏振层的一个外表面，在62℃温度下干燥5分钟，得到含有偏振膜的包装复合材料。该包装复合材料具有广谱的阻光效果，作为包装使用时可延长光敏感的产品的货架期。
实施例3
一种含有偏振膜的包装复合材料，制备方法为：
按申请号为“200780031784.2”发明名称为“多层偏振纤维以及使用该多层偏振纤维的偏振片”的发明专利中公开的“实例-单纤维”，以及“实例-裸纤维阵列”部分的制备方法制备偏振层：其中，X聚合物为LMPEN(由90％PEN/10％PET制成的共聚物)，Y聚合物为PETG。
制备得到的偏振层可直接作为包装复合材料使用。本领域技术人员也可根据实际需要，在所得偏振层的外表面结合面层作为包装复合材料使用。该包装复合材料具有广谱的阻光效果，作为包装使用时可延长光敏感的产品的货架期。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。

Claims (16)

1.一种含有偏振膜的包装复合材料，其特征在于，它包含：
偏振层，包含两层以上偏振膜；
其中，至少有两层偏振膜的偏振方向的夹角不为0°。
2.根据权利要求1所述的包装复合材料，其特征在于，所述包装复合材料还包含位于偏振层一侧的第一面层。
3.根据权利要求2所述的包装复合材料，其特征在于，所述包装复合材料还包含位于偏振层另一侧的第二面层。
4.根据权利要求2或3所述的包装复合材料，其特征在于，所述面层的材料选自PE、PETG、PVC、PVA、PC、PP、PS、PET、PBT、EVA、EVOH、PLA、PEF、PEN、PCTG、PBAT、PBST、PVDC和PA中的一种。
5.根据权利要求1所述的包装复合材料，其特征在于，所述偏振层进一步包含位于各偏振膜之间的偏振膜粘结层。
6.根据权利要求5所述的包装复合材料，其特征在于，所述偏振膜粘结层的材料选自聚乙烯醇系粘合剂、丙烯酸酯类粘合剂、乙烯-醋酸乙烯共聚物粘合剂、环氧树脂粘合剂、不饱和聚酯胶粘剂和醋酸乙烯树脂型粘合剂中的一种。
7.根据权利要求2所述的包装复合材料，其特征在于，所述包装复合材料进一步包含位于所述偏振层与所述第一面层之间的面层粘结层。
8.根据权利要求3所述的包装复合材料，其特征在于，所述包装复合材料进一步包含位于所述偏振层分别与所述第一面层和第二面层之间的面层粘结层。
9.根据权利要求7或8所述的包装复合材料，其特征在于，所述面层粘结层的材料选自聚乙烯醇系粘合剂、丙烯酸脂类粘合剂、乙烯-醋酸乙烯共聚物粘合剂、环氧树脂粘合剂、不饱和聚酯胶粘剂和醋酸乙烯树脂型粘合剂中的一种。
10.根据权利要求1所述的包装复合材料，其特征在于，至少有两层偏振膜的偏振方向的夹角为45°～135°，优选为80°～100°，更优选为90°。
11.根据权利要求10所述的包装复合材料，其特征在于，各偏振膜间至少有两个偏振膜的偏振方向的夹角不为0°。
12.根据权利要求1所述的包装复合材料，其特征在于，所述偏振层包含2～10层偏振膜，优选包含2～6层偏振膜。
13.如权利要求1所述的含有偏振膜的包装复合材料在包装中的应用。
14.根据权利要求13所述的应用，其特征在于，所述含有偏振膜的包装复合材料直接接触内容物。
15.如权利要求1所述的含有偏振膜的包装复合材料在标签中的应用。
16.根据权利要求13或15所述的应用，其特征在于，所述含有偏振膜的包装复合材料中，偏振层的厚度为20纳米～10毫米，各偏振膜的厚度为10纳米～1毫米；优选地，偏振层的厚度为20纳米～1毫米，各偏振膜的厚度为10纳米～100微米。
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