CN112789173B - 拒液性膜 - Google Patents
拒液性膜 Download PDFInfo
- Publication number
- CN112789173B CN112789173B CN201980063968.XA CN201980063968A CN112789173B CN 112789173 B CN112789173 B CN 112789173B CN 201980063968 A CN201980063968 A CN 201980063968A CN 112789173 B CN112789173 B CN 112789173B
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- Prior art keywords
- liquid
- repellent
- repellent film
- hydrophilic
- fine
- Prior art date
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Abstract
本发明为耐久性优异的拒液性膜、及在表面具有该拒液性膜的包装材料，拒液性膜具备底涂层部(90)和面涂层部(60)，所述底涂层部(90)位于基材表面且由微粒(70)及热塑性树脂(80)形成了凹凸；所述面涂层部(60)具有：(i)包含粒径小于微粒(70)的亲水性微粒(20)的微细的凹凸结构部；(ii)与微细的凹凸结构部的表面结合的拒液性部位(40)；(iii)粘结剂树脂(50)，其夹设在底涂层部(90)的表面与微细的凹凸结构部之间，且以覆盖微细的凹凸结构部与拒液性部位(20)的结合部分的方式分布。
Description
关联申请
本申请要求于2018年9月27日申请的日本专利申请2018-182148号的优先权，将其援引于此。
技术领域
本发明涉及改善了耐久性的拒液性膜。
背景技术
对食品、药品、化妆品、日用品等生活品包装材料用薄膜、片材要求各种功能，强烈要求不易附着具有高粘性的液体、半固体、凝胶状物质等内容物、在接触部分不易残留内容物。若使用防附着功能差的包装材料用薄膜、片材，例如在内容物为蛋糕等的奶油、酸乳酪、布丁、果冻、果子露、米粉团的佐料汁之类的食品时，以在包装材料用薄膜、片材上有附着/残留的状态被废弃，产生食品浪费的问题、妨碍塑料再循环的促进的问题。另外还存在如下问题：在取出内容物时，附着于包装用薄膜、片材的内容物污染手、衣服或周边的问题。另外，若对残留有内容物的包装材料用薄膜、片材置之不理，会带来各种不良影响，如产生腐败、异臭或者招来虫子等。即使少、但能够减少包装材料用薄膜、片材上附着的内容物量的技术是非常重要的。
例如，专利文献1记载了一种拒油性涂覆层的发明，所述拒油性涂覆层具备：位于物品表面上的由粒径100nm以上的微粒形成的一次凹凸；由粒径7～90nm的微粒形成的二次凹凸；和涂覆于二次凹凸的拒油剂。
现有技术文献
专利文献
专利文献1：日本特开2011-140625号公报
发明内容
发明要解决的问题
但是，在专利文献1那样的由微粒及拒油剂形成的膜时，需要在实用化的基础上改善所必需的耐久性。本发明的目的在于，提供耐久性优异的拒液性(指拒水性及拒油性)膜及在表面使用该拒液性膜的包装材料、包装容器、物品。
用于解决问题的方案
本发明的一方式的拒液性膜为形成于基材表面的拒液性膜，其具备：
(i)包含亲水性微粒的微细的凹凸结构部；
(ii)与上述微细的凹凸结构部的表面结合的拒液性部位；
(iii)粘结剂树脂，其夹设于上述基材表面与上述微细的凹凸结构部之间，并且以覆盖上述微细的凹凸结构部和上述拒液性部位的结合部分的方式分布。
另外，本发明的一方式的拒液性膜为形成于基材表面的拒液性膜，其具备：
(A)所述(A)底涂层部位于上述基材表面且由微粒及热塑性树脂形成为凹凸；和
(B)面涂层部，其具有：(i)包含亲水性微粒的微细的凹凸结构部，所述亲水性微粒的粒径小于上述微粒；(ii)与上述微细的凹凸结构部的表面结合的拒液性部位；(iii)粘结剂树脂，其夹设在上述底涂层部的表面与上述微细的凹凸结构部之间，且以覆盖上述微细的凹凸结构部与上述拒液性部位的结合部分的方式分布。
根据以上构成的拒液性膜，在基材表面或形成有凹凸的底涂层部的表面，形成包含基于亲水性微粒的微细的凹凸结构部、与其表面结合的拒液性部位、和不具有拒液性部位的粘结剂树脂的拒液性涂覆层，膜表面的基于拒液性部位的拒液性得以维持。特别地，膜表面上，由数量众多的亲水性微粒形成有细小的凹凸结构，在该凹凸结构的表面，数量众多的拒液性部位形成向外侧取向的状态，因此可以使拒液性部位发挥优异的拒液性。而且，粘结剂树脂将基于亲水性微粒的微细的凹凸结构部牢固地固定于基材表面或底涂层部的表面，并且将拒液性部位牢固地固定于微细的凹凸结构部的表面。因此，能够提供改善了耐久性的拒液性膜。
在将拒液性膜设为底涂层部及面涂层部的两层结构时，底涂层部包含粒径大于面涂层部的亲水性微粒的微粒。由此，在底涂层部的由较大粒径的微粒形成的凹凸结构的表面形成基于面涂层部的亲水性微粒的微细的凹凸结构，整体上得到较大的凹凸结构。优选将底涂层部的微粒的最小粒径设为比面涂层部的亲水性微粒的最大粒径更大。两种微粒所形成的凹凸结构成为整体上起伏明显的凹凸结构，有进一步提高拒液性的效果。
拒液性膜中，可以是在基于亲水性微粒的微细的凹凸结构部的表面分布有拒液性部位的聚集部分和亲水性微粒的亲水性表面的露出部分(亲水性部位)的状态。或者，在粘结剂树脂包含亲水性部位时，可以是在基于亲水性微粒的微细的凹凸结构部的表面分布有拒液性部位的聚集部分和粘结剂树脂所含的亲水性部位的聚集部分的状态。在这些构成的情况下，可以提供特备适于防止O/W型乳液的附着的拒液性膜。若为在微细的凹凸结构部的表面例如交替分布有拒液性部位和亲水性部位的状态，则其亲水性部位吸引乳液的连续相的水，容易防止乳液中的胶束接触拒液性膜而遭破坏。另外，将拒液性膜从O/W型乳液剥离时、从拒液性膜去除O/W型乳液时，分布于表面的拒液性部位可防止O/W型乳液的附着，因此O/W型乳液不易残留于拒液性膜。特别地，即使在拒液性膜长时间持续接触O/W型乳液后也能够发挥防止O/W型乳液附着的功能。
需要说明的是，在使用一实施例的拒液性膜实施蛋糕奶油的附着试验时，确认与蛋糕奶油接触的表面发生了结露。
拒液性膜中，可以将亲水性微粒设为亲水性二氧化硅微粒、将粘结剂树脂设为乙烯基系树脂。特别地，可以将粘结剂树脂设为氯乙烯树脂与醋酸乙烯酯树脂的共聚物。通过使用亲水性二氧化硅微粒，与其它亲水性氧化物微粒相比，可以提供拒液性优异的拒液性膜。另外，若考虑到由粘结剂树脂带来的耐久性效果和涂布性这两者，优选亲水性二氧化硅微粒与乙烯基系树脂的组合。
本发明的另一方式的包装材料可通过在其表面使用上述拒液性膜而得到。另外，本发明的另一方式的包装容器使用上述拒液性膜作为盖材表面。上述拒液性膜可用于形成例如袋子用薄膜或片材、蛋糕包装用薄膜或片材等各种物品的表面。
发明的效果
根据本发明，可以提供耐久性优异的拒液性膜及在表面使用了该拒液性膜的包装材料、包装容器、物品。
附图说明
图1为一实施方式的拒液性薄膜的概略剖视图。
图2为上述拒液性薄膜的面涂层部的概略剖视图。
图3为示出实施例6的奶油附着试验的结果的照片，(A)为示出未处理的PET的照片、(B)为示出拒液性PET的照片、(C)为将这些一并示出的照片。
图4的(A)为实施例7的拒液性薄膜表面的电子显微镜图像，(B)～(D)为示出F元素、Si元素及C元素的分布的图像。
图5为实施例10的拒液性薄膜表面的3500倍、10000倍、50000倍及100000倍的电子显微镜图像。
图6为实施例11的拒液性薄膜表面的3500倍、10000倍、50000倍及100000倍的电子显微镜图像。
图7为示出涂液的成分彼此的悬浮性及分散性试验的结果的照片。
具体实施方式
以下参照附图详细说明本发明的优选的实施方式。
图1为一实施方式的拒液性薄膜的概略剖视图。如图1所示，拒液性薄膜具备基材和形成于该基材的至少一个面的拒液性膜10。
基材只要是成为支撑体的物品就没有特别限制，例如，具有至少1层以上的由包含树脂的薄膜、纸、或金属箔形成的层。作为包含树脂的薄膜，可使用选自苯乙烯系树脂、烯烃系树脂、聚酯系树脂、尼龙系树脂、乙烯/乙烯醇共聚物及丙烯酸系树脂中的至少1种的树脂薄膜。在基材为多层时，其层叠方法没有特别限定，可以使用干式层压法、湿式层压法、热层压法等。另外，可以对基材实施无机/金属蒸镀处理等。可以对基材实施印刷，其印刷方式也没有特别限定，可以使用凹版印刷、胶版印刷、丝网印刷等公知的印刷方式。
基材的厚度没有特别限定，制成薄膜时通常使用1～200μm的厚度，制成片材时通常使用200～10000μm左右的厚度。
拒液性膜10为形成较大的凹凸结构的底涂层90与形成微细的凹凸结构的面涂层60的两层构成。
底涂层90包含作为微粒的二氧化硅微珠70和包含热塑性树脂的树脂组合物80。二氧化硅微珠70包括结晶性二氧化硅、非晶性二氧化硅(干式二氧化硅、湿式二氧化硅、硅胶等)，没有特别限定，可以适宜地使用公知的亲水性二氧化硅颗粒。二氧化硅微珠70的形状没有特别限定，可以选择多面体、凹凸形等各种形状。另外，可以使用多孔性的二氧化硅微珠。
作为热塑性树脂，没有特别限定，可使用聚酯、聚烯烃、聚苯乙烯、尼龙、聚氯乙烯、聚偏氯乙烯、聚乙烯醇、丙烯腈/丁二烯/苯乙烯共聚物、乙烯醋酸乙烯酯共聚物、聚缩醛、聚甲基丙烯酸甲酯、甲基丙烯酸类/苯乙烯共聚物、醋酸纤维素、聚氨酯、聚碳酸酯等。
树脂组合物80的厚度没有特别限定，与二氧化硅微珠70的粒径相比稍小。二氧化硅微珠70不是完全埋入树脂组合物80中，而是形成二氧化硅微珠70的一部分从树脂组合物80露出的状态。
底涂层90可如下形成：在基材上涂布使二氧化硅微珠70及树脂组合物80溶解或分散于溶剂而成的底涂层涂液并进行干燥，从而形成。作为溶剂，只要可溶解或分散所使用的热塑性树脂即可，没有特别限定，包括正己烷、环己烷、甲苯、苯、二甲苯等烃类、丙酮、甲乙酮(MEK)等酮类、醇类等。
面涂层60为具有微细的凹凸结构30、拒液性部位40和粘结剂树脂50的层，以覆盖底涂层90的较大的凹凸结构的表面的方式形成。微细的凹凸结构30由以串珠状连接的数量众多的亲水性微粒20形成，成为多孔结构。该凹凸结构30由于粘结剂树脂50被牢固固定于底涂层90的表面。另外，拒液性部位40与微细的凹凸结构30的表面结合，其结合部分被粘结剂树脂50覆盖，拒液性部位40的前段向外侧取向。
面涂层60通过将面涂层涂液涂布于底涂层90的表面并进行干燥而形成，所述面涂层涂液在有机溶剂中溶解或分散有亲水性二氧化硅微粒、作为金属醇盐的锆醇盐、钛醇盐、硅醇盐等、作为拒液性部位40的具有氟基的全氟烷基硅烷(FAS)、作为粘结剂树脂50的氯乙烯/醋酸乙烯酯共聚物、水、作为水解催化剂的盐酸。
形成微细的凹凸结构30的亲水性微粒20为亲水性二氧化硅微粒彼此通过金属醇盐进行连接而成的聚集体。例如，硅醇盐变成二氧化硅(Si02)而残存在微细的凹凸结构中。这里，使用市售品的亲水性二氧化硅微粒进行说明，此外也可以使用钛氧化物、锌氧化物、铝氧化物(氧化铝)等来形成凹凸结构。
全氟烷基硅烷(FAS)在涂布过程中为其反应基部分(Si)与亲水性二氧化硅微粒的表面、金属醇盐发生结合、作为拒液性部位40的氟基向外侧取向的状态，与亲水性微粒20的微细凹凸结构30的表面共价键合。
全氟烷基硅烷(FAS)为烷基硅烷的一些烷基被氟代碳基(全氟基)取代的产物，可列举例如CF3(CH2)2Si(OCH3)3、CF3(CF2)5(CH2)2Si(OCH3)3、CF3(CF2)7(CH2)2Si(OCH3)3、CF3(CF2)7(CH2)2SiCH3(OCH3)2、CF3(CF2)3(CH2)2Si(OCH3)3、CF3(CF2)7(CH2)2SiCl3，其中优选C8的十七氟癸基三甲氧基硅烷、C6的十三氟辛基三甲氧基硅烷、或C4的九氟己基三甲氧基硅烷，从安全方面和拒油特性出发，更优选C6的十三氟辛基三甲氧基硅烷。
作为粘结剂树脂50，这里使用乙烯基系树脂进行了说明，但是也可以使用其它树脂。
在制备面涂层涂液时，将固体成分设为100％时粘结剂树脂的比例优选为约1～50％。粘结剂树脂50多时，微细的凹凸结构30会被粘结剂树脂50埋没，对拒液性产生影响。另一方面，粘结剂树脂50少时，对微细的凹凸结构30、拒液性部位40的固定产生影响，得不到充分的耐久性。本实施方式中，优选粘结剂树脂50覆盖微细的凹凸结构30的表面的一部分的程度，优选亲水性微粒20的亲水性的表面的一部分露出。
关于亲水性微粒20的粒径，平均一次粒径优选为5～100nm。平均一次粒径若在上述范围内，亲水性二氧化硅微粒形成适度的聚集状态，容易形成多孔状的微细的凹凸结构。
面涂层60的厚度没有特别限定，可以为0.1～3.0μm。
作为制备面涂层涂液时的溶剂，为溶解或分散固体成分的溶剂即可，没有特别限定。
根据本实施方式的拒液性薄膜，在形成有凹凸的底涂层90的表面形成面涂层60，所述面涂层60包含基于亲水性微粒20的微细的凹凸结构30、与其表面结合的拒液性部位40和粘结剂树脂50，拒液性部位40的拒液性得以维持。特别地，形成了如下状态：在面涂层60的表面由数量众多的亲水性微粒20形成了细小的凹凸结构30，在该凹凸结构30的表面上数量众多的拒液性部位40向外侧取向，因此拒液性部位40能够发挥优异的拒液性。而且，粘结剂树脂50将基于亲水性微粒20的微细的凹凸结构30牢固地固定于底涂层90的表面，并且将拒液性部位40牢固地固定在微细的凹凸结构30的表面。因此，能够提供改善了耐久性的拒液性薄膜。
底涂层90包含粒径大于面涂层60的亲水性微粒20的二氧化硅微珠70。由此，在底涂层90的由二氧化硅微珠70形成的凹凸结构的表面上，形成基于面涂层60的亲水性微粒20的微细的凹凸结构30，整体上得到较大的凹凸结构。使二氧化硅微珠70的最小粒径大于亲水性微粒20的最大粒径的方式较佳。两种微粒所形成的凹凸结构成为整体上起伏明显的凹凸结构，有进一步提高拒液性的效果。
根据以上，本实施方式可得到耐久性优异的拒液性薄膜，可以提供在表面使用该拒液性薄膜的包装材料、包装容器、物品。
需要说明的是，本实施方式的拒液性薄膜适于生活品包装材料用薄膜或片材。例如，可以利用本实施方式的拒液性薄膜作为装有食品、化妆品、洗剂、洗发水、护发素等的袋子用的包装材料、或作为例如酸乳酪、布丁、果冻等的食品容器的盖材用的包装材料。另外，还可以利用本实施方式的拒液性薄膜作为使用奶油的蛋糕用的包装材料、米粉团等需要有粘性的佐料汁的食品用的包装材料。
图2示出本实施方式的拒液性薄膜的面涂层60的概略剖视图。使用图2说明对鲜奶油等O/W型乳液的防附着性。在面涂层60的截面结构中，粘结剂树脂50夹设在基材或二氧化硅微珠70的表面与亲水性微粒20之间，并且以覆盖亲水性微粒20与拒液性部位40的结合部分的方式分布。需要说明的是，亲水性微粒20彼此通过源自硅醇盐的二氧化硅22而连接成串珠状。
在空气气氛下，由于其表面自由能的关系，拒液性部位40向外侧取向。拒液性部位40彼此容易聚集，如图2所示，拒液性部位40的聚集体分布在包含亲水性微粒20的微细的凹凸结构30的表面的各个位置。另一方面，形成亲水性微粒20的亲水性的表面在微细的凹凸结构30的表面的各个位置露出的状态。
例如，在鲜奶油(O/W型乳液)与拒液性薄膜接触的状态下，鲜奶油21中的胶束(油滴)能够保持稳定的状态。在拒液性薄膜的面涂层60与鲜奶油的界面处，亲水性微粒20的亲水性的表面(亲水性部位)吸引作为鲜奶油的连续相的水(或水蒸气)，因此，容易防止鲜奶油中的胶束接触面涂层60而被破坏。另外，将拒液性薄膜从鲜奶油剥离时、从拒液性薄膜去除鲜奶油时，分布在表面上的拒液性部位40可防止鲜奶油的附着，因此鲜奶油不易残留在拒液性薄膜上。特别地，即使拒液性薄膜长时间持续与鲜奶油接触的状态下，也能够发挥防止鲜奶油附着的功能。
如果本实施方式的拒液性薄膜的面涂层60的表面仅被拒液性部位40覆盖，比水更有亲和性的胶束与拒液层接触的可能性高。认为这样会破坏胶束、使鲜奶油的防附着性下降。与此相对地，如图2所示，为在面涂层60的表面上交替分布有拒液性部位和亲水性部位的状态时，其亲水性部位吸引作为鲜奶油的连续相的水，产生降低胶束与拒液层接触的可能性的效果，结果是得到鲜奶油防附着性优异的拒液性薄膜。
或者，在粘结剂树脂50包含亲水性部位时，形成在面涂层60的表面交替分布有拒液性部位40的聚集部分和粘结剂树脂50所含的亲水性部位的聚集部分的状态，也可得到同样的效果。
实施例
通过以下的实施例进一步详细地说明本发明，但是本发明不受这些例子限定。表1为实施例中使用的底涂层涂液的配方表。
[表1]
表2为实施例中使用的面涂层涂液的配方表。作为粘结剂树脂，使用氯乙烯与醋酸乙烯酯的共聚树脂(氯乙烯-醋酸乙烯酯共聚树脂)，作为亲水性微粒，使用平均一次粒径为40nm的市售品的亲水性气相二氧化硅微粒，作为金属醇盐，使用原硅酸四乙酯(TEOS)，作为含有拒油性部位的硅烷化合物，使用全氟烷基硅烷(FAS)。另外，使用必要的水解催化剂及溶剂，如表2那样进行配合。
[表2]
表3示出各样品中使用的基材、底涂层、面涂层、涂布量。
[表3]
＜评价方法＞
按照下述方法对表3的实施例1～11及比较例1的样品进行试验、评价。
(1)水的接触角：在拒液性薄膜上放纯水10μL，用接触角计CA-DT(协和界面科学公司制)进行测定。
(2)水的滚落角：在拒液性薄膜上放纯水10μL，测定使基材倾斜时纯水滚落时的基材的倾斜角度。
(3)油的接触角：在拒液性薄膜上放油酸10μL，用接触角计CA-DT(协和界面科学公司制)进行测定。
(4)密合性：在拒液性薄膜上贴合JIS Z 1522:2009规定的胶带12mm(注册商标、NICHIBAN公司：CT-12)后，测定将胶带剥离时有无涂膜剥离。
[表4]
如表4所示，实施例1为在基材上仅形成面涂层的例子，
水的接触角为150度、
水的滚落角为15度、
油的接触角为128度，
可知得到了一定以上的拒液性。
另外，实施例2～7为使用了与实施例1相同的面涂层且进行了涂装的例子，由于有底涂层，因此，
水的接触角为150度以上、
水的滚落角为12度以内、
油的接触角为133度以上，可知与实施例1相比拒液性提高。
另外，实施例8～11中，面涂层的拒液性部位的添加量不同但未观察到明显的拒液性下降，因此与未处理的薄膜比较了奶油的附着。
实施例1～实施例11中，未观察到胶带导致的剥离，但是不含粘结剂树脂的比较例1观察到了由胶带导致的整面剥离。有添加粘结剂的效果。
＜奶油附着试验＞
然后，通过下述方法对表3的样品进行了试验、评价。
(A)奶油附着试验：在亚克力板上放3g奶油，用实施例1～4的各样品(大小60mm×60mm)盖上，测定10分钟后的附着量。将测定结果示于表5。
(B)奶油附着试验：与未处理的薄膜，比较了对于市售品的4号尺寸的整个蛋糕使用实施例6的样品作为蛋糕带时的奶油附着量。(图3示出试验结果照片。)
(C)奶油附着试验：将市售品的冷冻酥饼在室温下解冻，将实施例8及9的各样品(大小55mm×70mm)贴到酥饼圆周部，冷藏保管72小时，测定附着量。将测定结果示于表6。
(D)奶油附着试验：在亚克力板上放奶油3g，用实施例10～11的各样品(大小60mm×60mm)盖上，测定10分钟后的附着量。将测定结果示于表7。
对于未涂布底涂层及面涂层中的任意者的未处理的基材，也同样地进行试验。获知：在任意奶油附着试验中，与未处理者相比，都能够大幅降低奶油对样品的附着。
[表5]
[表6]
[表7]
＜表面的观察＞
然后，图4的(A)示出实施例7的拒液性薄膜的电子显微镜图像(SEM图像)。将表示其白框内的F元素、Si元素及C元素的分布的图像(基于能量色散型X射线分析(EDX)的元素分析)示于图4的(B)～(D)。图4的(A)的SEM图像的明亮部分为二氧化硅，图4的(B)～(D)的各元素的分布中，明亮的部分也分布有较多的对象元素。
特别地，根据图4的(B)可知，不论二氧化硅微珠的配置如何，拒液性部位(氟元素)均几乎均匀地分布在整个表面。可认为，这样的拒液性部位的分布为拒液性优异的原因。
图5、6示出实施例10、11的拒液性薄膜的SEM图像(3500倍～10万倍)。根据3500倍的图像可知，二氧化硅微珠几乎均被面涂层覆盖。另外，覆盖整个图像的是亲水性微粒，根据5万倍的图像可知，每个亲水性微粒为100nm左右的粒径，整体上形成多孔状的凹凸结构。
＜涂液的悬浮性及分散性试验＞
然后，对于面涂层涂液的成分，按照表8的组合制备涂液，评价悬浮性及分散性。
如表8及图7所示，无论为何种成分组合涂液都没有发生分离。由此可知，面涂层涂液容易制备、涂布性优异。
关于悬浮性，包含亲水性二氧化硅微粒的涂液均观察到由亲水性二氧化硅微粒导致的白浊。另一方面，关于不含亲水性二氧化硅微粒的成分的组合，FAS/TEOS及FAS/氯乙烯-醋酸乙烯酯共聚树脂是透明的，TEOS/氯乙烯-醋酸乙烯酯共聚树脂则是悬浮的。因此，对于FAS/氯乙烯-醋酸乙烯酯共聚树脂而言，由于不发生分离而是透明的，因此判断面涂层中两者有某种程度的亲和性，认为FAS与亲水性微粒的表面的结合部分被氯乙烯-醋酸乙烯酯共聚树脂覆盖、由于氯乙烯-醋酸乙烯酯共聚树脂而牢固地保持FAS。
根据以上，能够形成氟元素在整个表面几乎均匀分布、并且通过氯乙烯-醋酸乙烯酯共聚树脂而被牢固地保持的拒液性部位。
[表8]
附图标记说明
10···拒液性膜
20···亲水性微粒
30···微细的凹凸结构
40···拒液性部位
50···粘结剂树脂
60···面涂层
70···二氧化硅微珠
80···含有热塑性树脂的树脂组合物
90···底涂层
Claims (9)
1.一种拒液性膜，其为形成于基材表面的拒液性膜，其具备：
(A)在所述基材表面上由微粒及热塑性树脂形成为凹凸的底涂层部；和
(B)面涂层部，其具有：(i)包含亲水性微粒的微细的凹凸结构部，所述亲水性微粒的粒径小于所述微粒；(ii)与所述微细的凹凸结构部的表面结合的拒液性部位；(iii)粘结剂树脂，其夹设在所述底涂层部的表面与所述微细的凹凸结构部之间，且以覆盖所述微细的凹凸结构部与所述拒液性部位的结合部分的方式分布。
2.根据权利要求1所述的拒液性膜，其中，在所述微细的凹凸结构部的表面分布有所述拒液性部位的聚集部分和所述亲水性微粒的亲水性表面的露出部分。
3.根据权利要求1所述的拒液性膜，其中，在所述微细的凹凸结构部的表面分布有所述拒液性部位的聚集部分和所述粘结剂树脂所含的亲水性部位的聚集部分。
4.根据权利要求2或3所述的拒液性膜，其适于防止O/W型乳液的附着。
5.根据权利要求1所述的拒液性膜，其中，所述亲水性微粒为亲水性二氧化硅微粒，所述粘结剂树脂为乙烯基系树脂。
6.根据权利要求5所述的拒液性膜，其中，所述粘结剂树脂为氯乙烯树脂与醋酸乙烯酯树脂的共聚物。
7.一种包装材料，其在表面具有权利要求1～6中任一项所述的拒液性膜。
8.一种包装容器，其在盖材表面具有权利要求1～6中任一项所述的拒液性膜。
9.一种物品，其在表面具有权利要求1～6中任一项所述的拒液性膜。
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| JP2018-182148 | 2018-09-27 | ||
| JP2018182148A JP6683983B2 (ja) | 2018-09-27 | 2018-09-27 | 撥液性の膜 |
| PCT/JP2019/034290 WO2020066464A1 (ja) | 2018-09-27 | 2019-08-30 | 撥液性の膜 |
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| JP (1) | JP6683983B2 (zh) |
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| JP2023031909A (ja) * | 2021-08-26 | 2023-03-09 | 大和製罐株式会社 | 撥液膜の製造方法、撥液膜および包装材 |
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| EP3858609A4 (en) | 2022-08-03 |
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| US20220033157A1 (en) | 2022-02-03 |
| CN112789173A (zh) | 2021-05-11 |
| WO2020066464A1 (ja) | 2020-04-02 |
| EP3858609A1 (en) | 2021-08-04 |
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