CN111315576A - 具有阻隔性质的包装材料 - Google Patents

具有阻隔性质的包装材料 Download PDF

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Publication number
CN111315576A
CN111315576A CN201880072685.7A CN201880072685A CN111315576A CN 111315576 A CN111315576 A CN 111315576A CN 201880072685 A CN201880072685 A CN 201880072685A CN 111315576 A CN111315576 A CN 111315576A
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layer
barrier
barrier material
polyethylene
zinc ionomer
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V.里布
P.希尔西莱
K.巴克福克
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Stora Enso Oyj
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Stora Enso Oyj
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Abstract

本发明涉及包装材料，更具体地涉及具有气体和/或水分阻隔性质的包装材料，其中该材料包含阻隔材料，所述阻隔材料包含含有至少50％的锌离聚物的层、聚乙烯层和形成气体阻隔物的层。本发明还涉及使用所述阻隔材料的包装产品。这样的产品特别是适合用于化妆品和个人护理产品的包装。

Description

具有阻隔性质的包装材料
技术领域
本发明涉及包装材料，更具体地涉及具有气体和/或水分阻隔性质的包装材料，其中该材料包含阻隔材料，其具有含有至少50％的锌离聚物的层、聚乙烯层和形成气体阻隔物的层。本发明还涉及使用所述阻隔材料的包装产品。这样的产品特别是适合用于化妆品和个人护理产品的包装。
背景技术
当包装材料用于可能是敏感的、含有油性物质并且含有大量的水或水分的产品(比如化妆品)时，典型地使用铝来提供充足的阻隔性质。
为了制造出一种更可持续的并且是无铝的适用于这类应用的阻隔材料，需要解决几个技术问题。首先，包装的气体和水分透过性必须足够低。其次，阻隔层需要足够薄和柔软、可热密封且可胶合。理想地，该材料还应具有足够的耐热性，并适合于印刷，比如当使用含有矿物油的油墨进行印刷时，或用涉及使用矿物油的方法进行印刷时。
US3,775,239涉及可热密封的包装片材，其被描述为耐受油和油脂的透过。
US3,904,806涉及一种膜，其通过将具有2至20重量％的α,β-烯属不饱和一元羧酸的乙烯共聚物熔融挤出至玻璃纸的一侧上而制备。
仍然需要在高水分含量下也具有改进性能的改进的阻隔物，并且该阻隔物具有化学品耐受性并提供足够的气体阻隔性质。当阻隔物可能暴露于高湿度条件下时，比如该阻隔物在热带气候中使用时，性能足够的阻隔物是特别需要的。能承受侵蚀性化学品(比如化妆品、咖啡等以及油腻食物、具有高醇或溶剂含量的非食品液体等中所发现的化学品)的阻隔物也是特别需要的。此外，该阻隔物需要能够充当针对挥发性油墨成分比如矿物油的潜在迁移的阻隔物。
发明内容
已经令人惊奇地发现通过提供一种材料实现了特别有利的性质，该材料包含含有至少50％的锌离聚物的层、聚乙烯层和形成气体阻隔物的层。根据本发明的材料是可热密封的并且在不存在铝层的情况下提供阻隔性质。本发明提供这样的阻隔材料，其具有高耐久性和强度并且还适合用于使用含有例如矿物油的印刷油墨进行印刷。
因此，本发明涉及一种阻隔材料，其包含含有至少50％的锌离聚物的层、聚乙烯层和形成气体阻隔物的层。
含有至少50％的锌离聚物的层包含至少50重量％的锌离聚物，基于所述层的重量计。优选地，所述层中的锌离聚物的量为至少60％，至少70％，至少80％，至少90％或至少95％。除了锌离聚物之外，该层还可例如包含非锌离聚物的其他离聚物。该层还可包含填料、粘土、颜料等。
形成气体阻隔物的层可被定义为当气体阻隔物以5-50g/m2的克重存在时，在标准条件下(50％RH，23℃)测量的氧气透过率(OTR)小于100cm3/m2*天的层，优选小于10cm3/m2*天。形成气体阻隔物的层优选选自EVOH(乙烯-乙烯醇)和聚酰胺以及纤维素衍生物或聚合物，比如微原纤化纤维素(MFC)、羧甲基纤维素(CMC)、羟丙基纤维素(HPS)、乙基羟基乙基纤维素(EHEC)、聚偏二氯乙烯(PVDC)、聚乙醇酸(PGA)、聚乙烯醇(PVOH)、阳离子或阴离子PVOH、乙基化的PVOH、硅烷醇化的PVOH或羟基乙基纤维素(HEC)或其组合。该层典型地作为膜被涂覆或层压。该层的克重可为0.5-50g/m2，比如0.5-20g/m2或5-20g/m2。气体阻隔物可为单层或多层。当在作为膜的气体阻隔物中使用微原纤化纤维素时，其克重优选为5-50g/m2，并且OTR值小于10000，优选小于5000，更优选小于1000cm3/m2*天，在标准条件下测量。已发现当根据本发明将MFC与例如聚乙烯组合时，可获得有利的阻隔性质。
当阻隔材料以30-200g/m2的克重存在时，根据本发明的阻隔材料的OTR值小于20cm3/m2*天。
根据本发明的阻隔材料可被层压或挤出至基材的一侧或两侧上。基材可例如为纸或板基材。
在根据本发明的阻隔材料被层压或挤出至基材上之前，还可通过电晕处理和/或火焰处理来处理纸或板基材。
当将根据本发明的阻隔材料层压或挤出至基材上时，基材可提供有分开的水分阻隔物，其可为提供在板基材和根据本发明的阻隔材料之间的聚乙烯层。
根据本发明的阻隔材料还可任选地含有气味阻隔物，其可除了形成气体阻隔物的层之外而被提供。
为了进一步改进阻隔材料的性质，可在锌离聚物层和气体阻隔物之间和/或聚乙烯层和锌离聚物之间提供连接层(tie layer，粘结层)。
根据本发明的阻隔材料还可包含添加剂。添加剂的实例包括：填料，比如纳米纤维素纤维，纳米晶体纤维素，颜料，比如TiO2，CaCO3，纳米粘土，滑石等。可使用的其他添加剂包括调节例如光学、电学、流变学、化学或机械性质的添加剂。这样的添加剂在本领域中是已知的，并且可被引入到根据本发明的阻隔材料中。
附图说明
图1示出了阻隔材料，其包含锌离聚物层(1)、聚乙烯层(3)和形成气体阻隔物的层(5)。任选的连接层(2)可提供在锌离聚物层和气体阻隔物之间。任选的连接层(4)可提供在聚乙烯层(3)和形成气体阻隔物的层(5)之间。任选地，阻隔材料可被层压或挤出至纸或板基材(7)上。任选地，聚乙烯层(6)和/或连接层可提供在阻隔物和纸或板基材之间并且连接层可任选地提供在形成气体阻隔物的层(5)和任选的聚乙烯层(6)之间。聚乙烯层(6)还可包括两个或更多个层。
具体实施方式
本发明涉及包含锌离聚物层、聚乙烯层和形成气体阻隔物的层的阻隔材料。
锌离聚物可例如为以Surlyn为名市售的锌离聚物，比如Surlyn 1702-1或Surlyn1652。优选地，根据本发明的阻隔材料可具有一个包含锌离聚物的单层。
形成气体阻隔物的层优选选自EVOH、聚酰胺和纤维素衍生物或聚合物，比如微原纤化纤维素(MFC)、羧甲基纤维素(CMC)、羟丙基纤维素(HPS)、乙基羟基乙基纤维素(EHEC)或羟基乙基纤维素(HEC)或其组合。当阻隔材料是独立式的(free standing)时，即没有挤出至或层压至基材上时，形成气体阻隔物的层可提供有保护层。该保护层可例如为聚乙烯层。
除了任意连接层之外，阻隔材料的各层的重量为5-50g/m2，优选8-40g/m2，更优选10-35g/m2，所述连接层的重量为2-20g/m2，优选4-10g/m2。阻隔材料的总重量优选为30-200g/m2，更优选30-140g/m2，最优选40-120g/m2。
本发明的一个优选的实施方式为阻隔材料，其具有：
·一个含有至少50％的锌离聚物的单层；
·至少一个聚乙烯层；和
·一个形成气体阻隔物的单层。
本发明的一个更优选的实施方式为阻隔材料，其具有：
·一个重量为5-50g/m2的含有至少50％的锌离聚物的单层；
·至少一个聚乙烯层；和
·一个形成气体阻隔物的单层。
阻隔材料优选被挤出至或层压至基材上。
基材优选为纸或板基材。
结构的实例如下：
·锌离聚物/聚乙烯/连接层/气体阻隔物，比如锌离聚物/聚乙烯/连接层/EVOH或锌离聚物/聚乙烯/MFC
·锌离聚物/连接层/聚乙烯/气体阻隔物，比如锌离聚物/连接层/聚乙烯/EVOH或锌离聚物/连接层/聚乙烯/MFC
·锌离聚物/聚乙烯/连接层/气体阻隔物，比如锌离聚物/聚乙烯/连接层/EVOH或锌离聚物/聚乙烯/连接层/MFC
·锌离聚物/连接层/气体阻隔物，其中连接层为基于聚乙烯的树脂。
以及以下：
·聚乙烯/锌离聚物/气体阻隔物，比如聚乙烯/锌离聚物/EVOH或聚乙烯/锌离聚物/MFC
·聚乙烯/锌离聚物/连接层/气体阻隔物，比如聚乙烯/锌离聚物/连接层/EVOH或聚乙烯/锌离聚物/连接层/MFC
根据本发明的其他结构包括以下：
·锌离聚物/连接层/聚乙烯/连接层/EVOH/连接层/聚乙烯
·锌离聚物/连接层/EVOH
·聚乙烯/锌离聚物/连接层/EVOH
因此，当阻隔层已经被挤出至或层压至基材(比如板基材)上时，结构可为以下：
·锌离聚物/连接层/聚乙烯/连接层/EVOH/连接层/聚乙烯/板
·锌离聚物/连接层/EVOH/板
·聚乙烯/锌离聚物/连接层/EVOH/板
阻隔层可被提供在纸或板基材上，其任选地具有提供在阻隔层和纸或板基材之间的聚乙烯或聚丙烯层。所使用的聚乙烯可为低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)或其混合(物)。
根据本发明的阻隔层可通过将阻隔材料的各层层压或挤出在一起而制造。阻隔材料可被挤出在基材(比如板)上，或作为膜被挤出并且层压至基材(比如板)上。
根据本发明的阻隔层还可在锌离聚物上(即图1中的(1)的顶部上)提供有热密封层。热密封层赋予热密封性质。如果提供热密封层，则其可以LLDPE及其掺混物的形式提供。另外，可热密封层可以EPE(乙烯α-烯烃树脂/乙烯共聚物)或ULDPE、ULDPE共聚物(比如ULDPE/己烯共聚物)、EMA、EVA、弹性体、塑性体或这些的掺混物和/或与LDPE的掺混物的形式提供。
在本专利申请的上下文中，微原纤化纤维素(MFC)应意指至少一个维度小于100nm的纳米尺度的纤维素颗粒纤维或原纤维。MFC包括部分或完全原纤化的纤维素或木质纤维素纤维。释放的原纤维的直径小于100nm，而实际的原纤维直径或粒度分布和/或纵横比(长度/宽度)取决于来源和制造方法。最小的原纤维被称为基础原纤维(初级原纤维)并且直径约为2-4nm(参见例如Chinga-Carrasco,G.,Cellulose fibres,nanofibrils andmicrofibrils,:The morphological sequence of MFC components from a plantphysiology and fibre technology point of view,Nanoscale research letters2011,6:417)，而常见的是聚集形式的基础原纤维(其也被定义为微原纤维)(Fengel,D.,Ultrastructural behavior of cell wall polysaccharides,Tappi J.,March 1970,Vol53,No.3.)是在制造MFC时获得的主要产品，例如通过使用延长的精磨过程或压降分解过程制造。取决于来源和制造方法，原纤维的长度可在约1至大于10微米内变化。粗MFC级可含有相当大部分的原纤化纤维，即来自管胞(纤维素纤维)的突出原纤维，以及一定量的从管胞(纤维素纤维)释放的原纤维。
MFC有不同的首字母缩略词，例如纤维素微原纤维、原纤化纤维素、纳米原纤化纤维素、原纤维聚集体、纳米级纤维素原纤维、纤维素纳米纤维、纤维素纳米原纤维、纤维素微纤维、纤维素原纤维、微原纤状纤维素、微原纤维聚集体和纤维素微原纤维聚集体。MFC的特征还可在于各种物理或物理化学性质，例如大的表面积或其在分散在水中时在低固体(1-5重量％)下形成凝胶状材料的能力。纤维素纤维优选原纤化至这样的程度，即，使得所形成的MFC的最终比表面积为约1至约300m2/g，例如1至200m2/g或更优选50-200m2/g，用BET方法对冷冻干燥的材料进行测定。
存在制造MFC的各种方法，例如单次或多次精磨，预水解然后是精磨或高剪切分解或原纤维的释放。通常需要一个或若干个预处理步骤，以使MFC制造既节能又可持续。因此，待供应的纸浆的纤维素纤维可进行酶法或化学预处理，例如以降低半纤维素或木质素的量。纤维素纤维可在原纤化之前进行化学改性，其中纤维素分子含有除了在原始纤维素中所发现的之外(或更多)的官能团。这些基团尤其包括羧甲基(CM)、醛和/或羧基(通过N-氧基介导的氧化获得的纤维素，例如“TEMPO”)或季铵(阳离子纤维素)。在以上述方法之一中进行改性或氧化后，更容易将纤维分解成MFC或纳米原纤状尺寸原纤维。
纳米原纤状纤维素可含有一些半纤维素；量取决于植物来源。经预处理的纤维例如水解的、预溶胀的或氧化的纤维素原料的机械分解用合适的设备进行，例如精磨机，研磨机，均化器，胶体排出装置(colloider)，摩擦研磨机，超声波超声仪，流化器如微流化器、宏观流化器或流化剂型均化器。取决于MFC制造方法，产品还可含有细粒或纳米结晶纤维素或例如在木质纤维或造纸过程中存在的其他化学品。该产品还可含有各种量的未被有效地原纤化的微米尺寸的纤维颗粒。
MFC由木质纤维素纤维制备，包括硬木或软木纤维两者。其还可由微生物来源、农业纤维如麦草浆、竹子、甘蔗渣或其他非木质纤维来源制成。其优选由纸浆制成，包括来自原始纤维的纸浆，例如，机械、化学和/或热机械纸浆。其还可由损纸或再生纸制成。
上述MFC的定义包括但不限于在纤维素纳米原纤维(CMF)上新提出的TAPPI标准W13021，其定义了含有多个基础原纤维的纤维素纳米纤维材料，其具有结晶和无定形区域两者。
实施例
如下描述的材料作为在袋子内含有测试溶液(化妆用品，make up)的袋子被密封。将该袋子保存在45℃/85％RH的条件下以进行加速保质期测试。对袋子称重以测量来自袋子的重量损失。重量损失表明了经由蒸发从袋子损失的液体量，即重量损失越低则材料的气体渗透性越低。
材料：
样品1:10g/m2 Surlyn 1702和15g/m2聚乙烯
样品2:10g/m2 Surlyn 1802(钠离聚物)和15g/m2聚乙烯
样品3:75g/m2聚乙烯
样品4:56g/m2基于EVOH的阻隔物
在11天后对于样品1、3和4测定以％计的重量损失。对于样品2，在10天后测定以％计的重量损失。获得了以下结果：
重量损失，％
样品1 6.0
样品2 11.9
样品3 16.6
样品4 8.1
鉴于以上对本发明的详细描述，其他修改和变型对于本领域技术人员将变得显而易见。然而，显而易见的是，在不脱离本发明的精神和范围的情况下，可以进行这样的其他修改和变型。

Claims (11)

1.阻隔材料，其包含含有至少50％的锌离聚物的层、聚乙烯层和形成气体阻隔物的层。
2.根据权利要求1所述的阻隔材料，其中形成气体阻隔物的层选自聚酰胺和EVOH。
3.根据权利要求1或2中任意项所述的阻隔材料，其还包含在聚乙烯层和形成气体阻隔物的层之间和/或在含有至少50％的锌离聚物的层和形成气体阻隔物的层之间的连接层。
4.根据权利要求1-3中任一项所述的阻隔材料，其中阻隔材料的各层的重量为5-50g/m2并且连接层，如果存在的话，其重量为2-20g/m2。
5.根据权利要求4所述的阻隔材料，其中阻隔材料的各层的重量为8-40g/m2并且连接层，如果存在的话，其重量为4-10g/m2。
6.根据权利要求5所述的阻隔材料，其中阻隔材料的各层的重量为10-35g/m2并且连接层，如果存在的话，其重量为4-10g/m2。
7.根据权利要求1-6中任一项所述的阻隔材料，其具有一个含有至少50％的锌离聚物的单层、至少一个聚乙烯层和一个形成气体阻隔物的单层。
8.根据权利要求7所述的阻隔材料，其中阻隔材料的总重量为30-200g/m2。
9.根据权利要求1-8中任一项所述的阻隔材料，其中阻隔材料的氧气透过率低于20cm3/m2*天。
10.包含根据权利要求1-9中任一项所述的阻隔材料的包装材料。
11.根据权利要求10所述的包装材料，其中阻隔材料已被层压或挤出至纸或板基材上。
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US20210171259A1 (en) 2021-06-10
CA3081156A1 (en) 2019-05-16
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SE1751391A1 (en) 2019-05-11
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