CN106232347B - 阻气性膜及阻气性层叠体 - Google Patents

阻气性膜及阻气性层叠体 Download PDF

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Publication number
CN106232347B
CN106232347B CN201580021462.4A CN201580021462A CN106232347B CN 106232347 B CN106232347 B CN 106232347B CN 201580021462 A CN201580021462 A CN 201580021462A CN 106232347 B CN106232347 B CN 106232347B
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coating agent
gas barrier
epithelium
water
resin
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CN106232347A (zh
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尾村悠希
星沙耶佳
神永纯
神永纯一
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Toppan Inc
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Toppan Printing Co Ltd
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Abstract

本发明的阻气性膜具备树脂膜基材、以及依次层叠于所述树脂膜基材的至少一面上的第1皮膜和第2皮膜，所述第1皮膜由含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)形成，所述第2皮膜由含有氧化钛的涂覆剂(D)形成。

Description

阻气性膜及阻气性层叠体
技术领域
本发明涉及一种干燥食品·糕点·面包·美味食品等怕潮气及氧的食品、及一次性怀炉、片剂·粉末药物或敷剂·贴剂等医药品的包装领域所使用的阻气性膜及阻气性层叠体。
本申请基于2014年4月25日在日本所申请的日本特愿2014-091988号主张优先权，其内容以引用方式并入文本。
背景技术
为了抑制内容物的变质或腐败等并保持内容物的功能或性质，用于食品或医药品等包装的包装材料要求阻挡水蒸气、氧、及其它使内容物变质的气体的进入的性质(阻气性)。
因此，一直以来，在这些包装材料上设置有由具有阻气性的材料形成的阻气层。迄今为止，在膜或纸等基材上利用溅射法或沉积法、湿涂法、印刷法等设置阻气层。另外，作为阻气层，可使用由铝等金属形成的金属箔或金属沉积膜、聚乙烯醇、乙烯-乙烯醇共聚物、聚偏二氯乙烯等的树脂膜(例如参照专利文献1～5)。
但是，金属箔或金属沉积膜虽然阻气性优异，但是，存在如下各种问题：“由于为不透明，因此，不能确认内容物”、“由于伸缩性差，因此在伸长数％后产生裂缝，阻气性降低”、“在使用后的废弃时，需要作为不燃物进行处理”等。
另外，由聚偏二氯乙烯的树脂膜形成的阻气层虽然显示没有湿度依赖性的良好的阻气性，但是，由于含有氯，因此，在废弃处理等时，有可能成为二噁英等有害物质的产生源。因此，存在避讳使用由聚偏二氯乙烯的树脂膜所形成的阻气层作为包装材料的倾向。
另一方面，由非氯系的聚乙烯醇或乙烯-乙烯醇共聚物的树脂膜所形成的阻气层虽然在低湿度气氛下显示高的阻气性，但是，由于具有湿度依赖性，因此，具有伴有湿度的上升而阻气性大大降低的缺点。
另外，其它阻气性的树脂膜与聚偏二氯乙烯的树脂膜、或低湿度气氛下的聚乙烯醇的树脂膜进行比较时，阻气性差。
为了改善这些树脂膜的阻气性，提出了将聚乙烯醇或乙烯-乙烯醇共聚物等和无机层状矿物进行了复合化的树脂膜。对于该树脂膜，为了提高阻气性，需要在膜的内部将无机层状矿物整齐地分布、排列。但是，伴随将无机层状矿物有规则地分布、排列，树脂膜的凝聚力或对基材的密合力降低，因此，兼备高的阻气性和作为包装材料的充分的层压强度非常困难。
与此相对，提出一种在聚乙烯醇或乙烯-乙烯醇共聚物等和层状化合物的复合体中添加具有水溶性或水分散性的水性聚氨酯树脂来改善对基材的密合性的阻气性膜(例如参照专利文献6)。
该阻气性膜的高湿度气氛下的阻气性及对基材的密合性良好。但是，由于皮膜的凝聚强度差，因此，与其它膜贴合而用作包装材料时，层压强度不充分。
现有技术文献
专利文献
专利文献1：日本特开2001-287294号公报
专利文献2：日本特开平11-165369号公报
专利文献3：日本特开平6-93133号公报
专利文献4：日本特开平9-150484号公报
专利文献5：日本专利第3764109号公报
专利文献6：日本专利第3351208号公报
发明内容
发明所要解决的课题
本发明是鉴于上述情况而完成的发明，其目的在于，提供一种阻气性膜及阻气性层叠体，所述阻气性膜在高湿度气氛下的阻气性优异，且作为包装用材料长期间具有充分的密合强度和膜凝聚强度，且层压强度的劣化小。
用于解决课题的方案
本发明的第一方面的阻气性膜具备：树脂膜基材，以及依次层叠于所述树脂膜基材的至少一面上的第1皮膜和第2皮膜，所述第1皮膜由含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)形成，所述第2皮膜由含有氧化钛的涂覆剂(D)形成。
在上述第一方面中，所述水系涂覆剂(C)可以含有具有水溶性或水分散性的水性聚氨酯树脂、固化剂、水溶性高分子(A)、及无机层状矿物(B)。
在上述第一方面中，所述水溶性高分子(A)可以为聚乙烯醇树脂。
在上述第一方面中，所述无机层状矿物(B)可以为水溶胀性合成云母。
本发明的第二方面的阻气性层叠体具备：上述第一方面的阻气性膜、和依次层叠于所述阻气性膜的至少一面上的粘接剂层及热密封性树脂层。
发明效果
根据本发明的上述各方面，通过在树脂膜基材的至少一面上形成兼备阻气性及对树脂膜基材的密合性的皮膜，并进而在其上形成含有氧化钛的皮膜，由此可以增强这些皮膜的膜凝聚力。因此，可以提供高湿度气氛下的阻气性优异、层间的密合性或膜凝聚力也长期间良好地保持的阻气性膜及阻气性层叠体。因此，通过将本发明的各方面的阻气性膜及阻气性层叠体用作包装用材料，可以提高内容物的品质保持性。
附图说明
[图1]是表示本发明第一实施方式的阻气性膜的一例的剖面图。
[图2]是表示本发明的第二实施方式的阻气性层叠体的一例的剖面图。
具体实施方式
对本发明第一实施方式的阻气性膜1及本发明的第二实施方式的阻气性层叠体进行说明。
予以说明，为了更好地理解发明的宗旨，对本实施方式具体地进行说明，只要没有特别指定，并不限定本发明。
“阻气性膜1”
本发明第一实施方式的阻气性膜1为具备树脂膜基材2、依次层叠于树脂膜基材2的至少一面上的由含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)形成的皮膜3(以下，有时称为“第1皮膜”或“阻气层”。)、和由含有氧化钛的涂覆剂(D)形成的皮膜4(以下，有时称为“第2皮膜”或“含氧化钛层”。)的膜。
即，本实施方式的阻气性膜1为在树脂膜基材2的一面上依次层叠阻气层3和含氧化钛层4而形成的膜。
[树脂膜基材2]
作为树脂膜基材2的材质，可举出例如由以下材料形成的膜：聚乙烯、聚丙烯、丙烯-乙烯共聚物等烯烃系树脂；聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯系树脂；尼龙6、尼龙66等脂肪族系聚酰胺；聚己二酰间苯二甲胺等芳香族聚酰胺等的聚酰胺系树脂；聚苯乙烯、聚醋酸乙烯酯、乙烯-醋酸乙烯酯共聚物、聚乙烯醇、乙烯-乙烯醇共聚物等乙烯基系树脂；聚甲基丙烯酸甲酯、聚丙烯腈等(甲基)丙烯酸系单体的均聚物或共聚物等的丙烯酸系树脂；赛璐玢等。这些树脂可使用1种或组合使用2种以上。
作为树脂膜基材2，可使用由单一的树脂构成的单层膜、使用有多个树脂的单层膜、或使用有多个树脂的层叠膜。另外，可以使用将上述的树脂层叠于其它基材(金属、木材、纸、陶瓷等)而得的层叠基材。
其中，作为树脂膜基材2，优选使用聚烯烃系树脂膜(特别是聚丙烯膜等)、或聚酯系树脂膜(特别是聚对苯二甲酸乙二醇酯系树脂膜)、聚酰胺系树脂膜(特别是尼龙膜)等。
树脂膜基材2可以为未拉伸膜，也可以为单轴或双轴拉伸取向膜，还可以为进行了表面处理(电晕放电处理等)或锚固或底涂处理的膜。进而，树脂膜基材可以为层叠有多个树脂或金属等的层叠膜。
另外，树脂膜基材2也可以是通过对待涂覆的面(形成上述皮膜的面)实施电晕处理或低温等离子体处理等从而提高了对涂覆剂的良好的湿润性和对皮膜的粘接强度的基材。
树脂膜基材2的厚度没有特别限定，一边考虑作为包装材料的适性或其它皮膜的层叠适性，一边根据价格或用途而适当选择。树脂膜基材的厚度实用上为3μm～200μm，优选为5μm～120μm，更优选为10μm～100μm。
[水系涂覆剂(C)]
对水系涂覆剂(C)要求高湿度气氛下的氧阻隔性。为了实现该要求，例如水系涂覆剂(C)含有具有水溶性或水分散性的水溶性高分子(A)、及无机层状矿物(B)作为主要构成成分。
[水溶性高分子(A)]
水溶性高分子(A)为在常温下可完全溶解或微分散于水的高分子。
作为水溶性高分子(A)，只要是可侵入、配位(嵌入)于后述的无机层状矿物(B)的单晶层间的化合物，就没有特别限定。作为水溶性高分子(A)，可举出例如：聚乙烯醇及其衍生物；羧甲基纤维素、羟乙基纤维素等纤维素衍生物；氧化淀粉、醚化淀粉、糊精等淀粉类；聚乙烯基吡咯烷酮、聚丙烯酸、聚甲基丙烯酸或其酯、盐类及它们的共聚物；磺基间苯二甲酸等含有极性基团的共聚聚酯；聚甲基丙烯酸羟基乙酯及其共聚物等乙烯基系聚合物；或者这些各种聚合物的羧基等官能团改性聚合物等。
水溶性高分子(A)优选为至少1种为聚乙烯醇系聚合物及其衍生物。水溶性高分子(A)特别优选为皂化度为95％以上且聚合度为300以上的聚乙烯醇树脂。
就聚乙烯醇树脂而言，皂化度或聚合度越高，吸湿溶胀性越低。
聚乙烯醇树脂的皂化度低于95％时，难以得到充分的阻气性。
另一方面，聚乙烯醇树脂的聚合度低于300时，导致阻气性或皮膜的凝聚强度的降低。
[无机层状矿物(B)]
无机层状矿物(B)为极薄的单晶层重叠而形成1个层状粒子的无机化合物。
作为无机层状矿物(B)，优选为在水中溶胀和裂解的化合物，其中，特别优选使用对水具有溶胀性的粘土化合物。更具体而言，无机层状矿物(B)为在极薄的单晶层间配位水且具有吸收水而溶胀的性质的粘土化合物。一般而言，无机层状矿物(B)为Si4+对O2-配位而构成四面体结构的层和Al3+、Mg2+、Fe2+及Fe3+等对O2-及OH-配位而构成八面体结构的层以1对1或者2对1的方式键合并堆叠而形成层状结构的矿物。该粘土化合物可以为天然的化合物，也可以为合成的化合物。
作为代表的无机层状矿物(B)，可以举出：层状硅酸盐矿物等含水硅酸盐，例如埃洛石、高岭石、多水埃洛石、地开石及珍珠石等高岭石族粘土矿物；叶蛇纹石及纤蛇纹石等叶蛇纹石族粘土矿物；蒙脱石、贝得石、绿脱石、皂石、锂蒙脱石、锌蒙脱石及富镁蒙脱石等蒙脱石族粘土矿物；蛭石等蛭石族粘土矿物；白云母及金云母等云母；珍珠云母、四硅云母及带云母等云母或云母族粘土矿物等。
这些无机层状矿物(B)可使用1种或组合使用2种以上。
这些无机层状矿物(B)中，特别优选蒙脱石等蒙脱石族粘土矿物、以及水溶胀性云母等云母族粘土矿物。
无机层状矿物(B)的大小优选为平均粒径10μm以下，厚度500nm以下。无机层状矿物(B)中，特别优选至少1种为平均粒径1μm～10μm、厚度10nm～100nm的水溶胀性合成云母。
使用水溶胀性合成云母作为无机层状矿物(B)时，水溶胀性合成云母与水溶性高分子(A)的相溶性高，并且与天然系的云母相比杂质少，因此，不导致源自杂质的阻气性的降低或膜凝聚力的降低。另外，水溶胀性合成云母由于在结晶结构内具有氟原子，因此，也有助于抑制由水系涂覆剂(C)形成的皮膜的阻气性的湿度依赖性使其较低。进而，水溶胀性合成云母与其它水溶胀性的无机层状矿物相比具有高的长宽比，因此，迷宫效应更有效地发挥作用，特别有助于较高地显现由水系涂覆剂(C)形成的皮膜的阻气性。
无机层状矿物(B)在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率优选为10质量％～70质量％，更优选为15质量％～50质量％。
无机层状矿物(B)的固体成分配合比率低于10质量％时，不能良好地发挥无机层状矿物(B)具有的迷宫效应，高湿度气氛下的第1皮膜的阻气性差。
另一方面，无机层状矿物(B)的固体成分配合比率超过70质量％时，涂液的涂敷性或对基材的密合性劣化。
[水性聚氨酯树脂]
水系涂覆剂(C)优选含有具有水溶性或水分散性的水性聚氨酯树脂。仅含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)相对于聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯等极性高的聚酯系树脂具有良好的涂敷性、密合性。其另一方面，仅含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)对于聚乙烯、聚丙烯、丙烯-乙烯共聚物等聚烯烃系树脂那样的无极性且表面张力低的树脂不具有密合性。
与此相对，除水溶性高分子(A)及无机层状矿物(B)之外，还含有水性聚氨酯树脂和后述的固化剂的水系涂覆剂(C)对于聚烯烃系树脂那样的无极性且表面张力低的树脂也发挥良好的密合性。
水性聚氨酯树脂没有特别限定。作为通过多元醇和异氰酸酯化合物的反应而得到的水性聚氨酯树脂，可举出例如使聚酯多元醇和聚异氰酸酯用常规方法反应而得到的水性聚氨酯树脂。另外，水性聚氨酯树脂可以根据需要含有链伸长剂。
聚酯多元醇使二羧酸和二醇利用常规方法反应而得到。
作为二羧酸，可使用对苯二甲酸、间苯二甲酸、2,6-萘二羧酸等芳香族二羧酸、己二酸、癸二酸等脂肪族二羧酸、羟基苯甲酸等羟基羧酸及它们的酯形成性衍生物等。
作为二醇，可使用乙二醇、1,4-丁二醇、二乙二醇、三乙二醇等脂肪族二醇、1,4-环己烷二甲醇等芳香族二醇、聚乙二醇、聚丙二醇、聚四亚甲基二醇等聚(氧亚烷基)二醇等。
另外，使这些二羧酸和二醇反应而得到的聚酯多元醇虽然为线状结构，但可以使用3元以上的酯形成成分来形成支链状聚酯。
作为聚异氰酸酯，可举出：六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、四亚甲基二异氰酸酯、苯二甲基二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯和三羟甲基丙烷的加成物、六亚甲基二异氰酸酯和三羟甲基乙烷的加成物等。
另外，作为链伸长剂，可举出：含侧链羧基二醇类、诸如乙二醇、二乙二醇、丙二醇、1,4-丁二醇、六亚甲基二醇、新戊二醇等二醇类、或者乙二胺、丙二胺、六亚甲基二胺、苯二胺、甲苯二胺、二苯基二胺、二氨基二苯基甲烷、二氨基二苯基甲烷、二氨基环己基甲烷等二胺类等。
作为这种构成的具有水溶性或水分散性的水性聚氨酯树脂，可举出例如日本特开昭61-228030号公报中所记载的水性聚氨酯树脂等。
[固化剂]
作为固化剂，只要是与水溶性高分子(A)及水性聚氨酯树脂的至少1种具有反应性，就没有特别限定。作为固化剂，特别优选使用水分散性(水溶性)碳化二亚胺、或水溶性环氧化合物、水分散性(水溶性)噁唑烷酮化合物、水溶性环乙亚胺系化合物、水分散性异氰酸酯系固化剂等。其中，特别是相对于水溶性聚氨酯树脂的羟基具有良好的反应性，因此，优选使用水分散性异氰酸酯系固化剂。
固化剂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率优选为5质量％～15质量％。
固化剂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率低于5质量％时，由水系涂覆剂(C)形成的第1皮膜对于树脂膜基材的密合性降低。另一方面，固化剂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率超过15质量％时，由水系涂覆剂(C)形成的第1皮膜的阻气性降低。
作为用于水分散性异氰酸酯系固化剂的聚异氰酸酯化合物，可举出：芳香族聚异氰酸酯化合物、脂环族聚异氰酸酯化合物、脂肪族聚异氰酸酯化合物等。其中，为了抑制水系涂覆剂(C)中的反应并延长可使用时间，优选使用脂环族聚异氰酸酯化合物及脂肪族聚异氰酸酯化合物。
作为构成脂环族聚异氰酸酯化合物的异氰酸酯化合物，可举出例如双(异氰酸酯)甲基环己烷(氢化XDI)、或亚甲基双(4,1-环亚己基)＝二异氰酸酯(氢化MDI)等。
作为构成脂肪族聚异氰酸酯化合物的异氰酸酯化合物，可举出例如：三亚甲基二异氰酸酯、1,2-亚丙基二异氰酸酯、亚丁基二异氰酸酯(四亚甲基二异氰酸酯)、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯等。
芳香族聚异氰酸酯化合物、脂环族聚异氰酸酯化合物及脂肪族聚异氰酸酯化合物可以混合而使用。
水性聚氨酯树脂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率优选为10质量％以上。
水性聚氨酯树脂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率低于10质量％时，由水系涂覆剂(C)形成的第1皮膜对树脂膜基材的润湿性、密合性不足。
水溶性高分子(A)、无机层状矿物(B)、水性聚氨酯树脂及固化剂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率分别特别优选为以下的范围。
水溶性高分子(A)：15质量％～60质量％
无机层状矿物(B)：10质量％～50质量％
水性聚氨酯树脂：10质量％～50质量％
固化剂：5质量％～15质量％
如果水溶性高分子(A)、无机层状矿物(B)、水性聚氨酯树脂及固化剂在水系涂覆剂(C)的总固体成分中所占的固体成分配合比率在上述的范围内，则高湿度气氛下的阻气性优异。另外，通过在由水系涂覆剂(C)形成的第1皮膜上层叠由含有氧化钛的涂覆剂(D)形成的第2皮膜，可长期间发挥作为包装用材料的充分的密合强度和膜凝聚强度。
进而，只要在不损害阻气性及作为包装用层叠膜的强度的范围内，则水系涂覆剂(C)可以含有各种添加剂。
作为添加剂，例如可以举出：抗氧化剂、耐气候剂、热稳定剂、润滑剂、晶体成核剂、紫外线吸收剂、增塑剂、抗静电剂、着色剂、填料、表面活性剂及硅烷偶联剂等。
水系涂覆剂(C)以水为主，也可以包含溶解于水或与水均匀地混合的溶剂。
作为溶剂，可举出例如：甲醇、乙醇、异丙醇等醇类；丙酮、甲基乙基酮等酮类；四氢呋喃等醚类；溶纤剂类；卡必醇类；乙腈等腈类等。
[涂覆剂(D)]
涂覆剂(D)含有氧化钛作为构成成分。
氧化钛的结晶结构存在正方晶系的金红石型、锐钛矿型、及斜方晶型的板钛矿型这3种，但将本实施方式的阻气性膜1适用于包装材料的情况下，优选使用金红石型的氧化钛。
氧化钛为硬的无机材料，通过存在于水系涂覆剂(C)上而发挥抛锚效果，可以增强由涂覆剂(D)形成的第2皮膜的凝聚强度。
另外，通过干式层压加工在水系涂覆剂(C)上涂敷粘接剂时，粘接剂浸透至水系涂覆剂(C)，在浸透的区域形成强度弱的界面，结果，有时层压强度降低。在通过干式层压加工在水系涂覆剂(C)上涂敷粘接剂时，由含有氧化钛的涂覆剂(D)形成的第2皮膜还具有防止粘接剂对水系涂覆剂(C)造成不良影响的效果。
用于涂覆剂(D)的树脂只要是与氧化钛同时稳定地分散于溶剂中的树脂，就没有特别限定。作为这种树脂，可举出例如：聚氨酯树脂、聚氨酯/脲树脂、氯乙烯-醋酸乙烯酯共聚树脂、氯化聚丙烯树脂、乙烯-醋酸乙烯酯共聚物树脂、醋酸乙烯酯树脂、聚酰胺树脂、硝基纤维素树脂、丙烯酸树脂、聚酯树脂、聚氯乙烯树脂等。这些树脂可使用1种或组合使用2种以上。
作为用于涂覆剂(D)的溶剂，可使用醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸异丁酯、丙二醇单乙醚乙酸酯、丙二醇单甲醚乙酸酯等酯系溶剂；甲醇、乙醇、正丙醇、异丙醇、正丁醇、丙二醇单甲醚等醇系溶剂；水等公知的溶剂。
涂覆剂(D)可以通过使氧化钛分散于溶剂中而制备氧化钛的分散液、进而在该分散液中添加树脂来制备。
氧化钛的分散液中的氧化钛的粒度分布可以通过使用分散机而进行调节。作为分散机，例如可使用辊磨机、球磨机、超微磨碎机、砂磨机等。
用上述的方法制备的涂覆剂(D)的粘度优选为10mPa·s以上1000mPa·s以下。
涂覆剂(D)的粘度低于10mPa·s时，氧化钛沉淀，不能使氧化钛适当地分散。另一方面，涂覆剂(D)的粘度超过1000mPa·s时，不能有效地进行涂覆剂(D)的制备或涂敷。
涂覆剂(D)的粘度可以通过适当选择所使用的树脂或溶剂的种类或量而进行调节。另外，也可以通过调节氧化钛的粒径及粒度分布而调节涂覆剂(D)的粘度。
作为由水系涂覆剂(C)或涂覆剂(D)形成的皮膜的形成方法，可使用公知的湿式涂布方法。
作为湿式涂布方法，可举出：辊涂、凹版涂布、逆转涂布、口模涂布、丝网印刷、喷涂等。
使用这些湿式涂布方法在树脂膜基材的单面(一个面，第1面)或者两面(一个面及另一个面，第1面及第2面)上涂布水系涂覆剂(C)或涂覆剂(D)，形成由水系涂覆剂(C)或涂覆剂(D)形成的涂膜。通过将其涂膜进行干燥，可得到由水系涂覆剂(C)或涂覆剂(D)形成的皮膜。
作为将由水系涂覆剂(C)或涂覆剂(D)形成的涂膜进行干燥的方法，可使用热风干燥、热辊干燥、红外线照射等公知的干燥方法。
形成于树脂膜基材2上的、由水系涂覆剂(C)形成的第1皮膜3的厚度(即由水系涂覆剂(C)形成的第1皮膜3的干燥后的厚度)根据所要求的阻气性而设定，优选为0.2μm～2μm，更优选为0.3μm～1μm。
由水系涂覆剂(C)形成的第1皮膜3的厚度低于0.2μm时，难以得到充分的阻气性。另一方面，由水系涂覆剂(C)形成的第1皮膜3的厚度超过2μm时，不仅难以形成均匀的涂膜面，而且导致干燥负荷的增大、制造成本的增大，不优选。
形成于树脂膜基材2上的、由涂覆剂(D)形成的第2皮膜4的厚度(即由涂覆剂(D)形成的第2皮膜4的干燥后的厚度)优选为0.3μm以上，更优选为0.5μm以上。
如果由涂覆剂(D)形成的第2皮膜4的干燥后的厚度为0.5μm以上，则在通过干式层压加工涂敷粘接剂时，可以防止粘接剂浸透至由水系涂覆剂(C)形成的第1皮膜3。
本实施方式的阻气性膜1可以根据需要具有结合层、印刷层、保护膜层、遮光层、粘接剂层、热密封层等。
本实施方式的阻气性膜1具备：树脂膜基材2、依次层叠于树脂膜基材的至少一面上的由含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)形成的皮膜3、及由含有氧化钛的涂覆剂(D)形成的皮膜4。因此，高湿度气氛下的阻气性优异，可以长期间良好地保持层间的密合性或膜凝聚力。因此，通过将本实施方式的阻气性膜1用作包装用材料，可以提高内容物的品质保持性。
“阻气性层叠体5”
本发明的第二实施方式的阻气性层叠体为具备本发明第一实施方式的阻气性膜1和依次层叠于阻气性膜1的至少一面上的粘接剂层6及热密封性树脂层7的层叠体。
即，本实施方式的阻气性层叠体5为在本发明第一实施方式的阻气性膜1的由含有氧化钛的涂覆剂(D)形成的皮膜4上经由粘接剂层6而至少层压加工热密封性树脂层7所形成的层叠体。
在此，作为热密封性树脂层7，可以使用低密度聚乙烯、直链低密度聚乙烯、中密度聚乙烯、聚丙烯等聚烯烃膜，聚酯系共聚膜，聚丙烯腈膜，醋酸乙烯酯系共聚膜等。在这些膜中，聚烯烃膜由于低温热密封性优异且廉价，因此特别优选。
作为层压加工方法，可以使用公知的干式层压法、挤出层压法、无溶剂层压法等。
作为用于粘接剂层6的粘接剂，可以根据各种层压加工方法选择各种各样的粘接剂，例如可以使用聚氨酯系、聚酯系、聚醚系、环氧系、聚乙烯亚胺系、聚丁二烯系等公知的粘接剂。
本实施方式的阻气性层叠体5为相对于上述的实施方式的阻气性膜1经由粘接剂层6而层叠有热密封性树脂层7的包装用层叠体，其高湿度气氛下的阻气性优异，也可以长期间良好地保持层间的密合性和膜凝聚力。因此，本实施方式的阻气性层叠体5可以长期间地提高内容物的品质保持性，可作为各种各样的包装用材料有效利用。
实施例
以下，通过实施例及比较例进一步具体地说明本发明，但本发明并不限定于以下的实施例。
[实施例]
[水系涂覆剂(C)]
作为水溶性高分子(A)(以下，有时记作“成分(A)”。)，使用聚乙烯醇树脂即“クラレ社”制的Poval PVA-105(皂化度98～99％、聚合度500)、及羧甲基纤维素(CMC)。
作为无机层状矿物(B)(以下，有时记作“成分(B)”。)，使用水溶胀性合成云母(“コープケミカル社”制的ソマシフMEB-3)、或蒙脱石(“クニミネ工業社”制的クニピア-F)。
作为水性聚氨酯树脂(以下，有时记作“成分(E)”。)，使用三井化学社制的聚氨酯分散体“タケラックWPB-341”。
将成分(A)、成分(B)及成分(E)以表1所示的固体成分配合比率进行配合，在80℃下进行加热、混合之后，冷却至室温，以溶剂中的10质量％为异丙醇且成为表1所示的固体成分浓度的方式用离子交换水和异丙醇稀释，从而制备涂液。
将没有配合固化剂的涂液直接涂敷。
关于配合固化剂的涂液，在即将涂敷之前添加表1中记载的固化剂(三井化学社制的水分散性聚异氰酸酯タケネートWD-725)，从而制备实施例1～6的水系涂覆剂(C)。
[聚氨酯树脂合成例]
首先，准备具有搅拌机、温度计、回流冷却器及氮气导入管的四口烧瓶。在该四口烧瓶内装入具有3-甲基-1,5-戊二醇和己二酸的分子量2000的聚酯(羟基值56,1mgKOH/g)18.500质量份、分子量2000的聚丙二醇(羟基值56.1KOH/g)3.971质量份、异佛尔酮二异氰酸酯5.874质量份、2-乙基己酸锡(II)0.003质量份、及醋酸乙酯7.500质量份。将该混合物在氮气流下在90℃下反应3小时。在反应物中加入醋酸乙酯7.500质量份并冷却，得到末端异氰酸酯预聚物的溶液43.347质量份。
接着，在得到的末端异氰酸酯预聚物的溶液43.347质量份中，在室温下缓慢地添加将异佛尔酮二胺1.575质量份、2-氨基乙醇0.081质量份、异丙醇20.000质量份、及醋酸乙酯20.000质量份混合成的混合物，进一步添加异丙醇15.000质量份。使得到的溶液在50℃下反应1小时，得到固体成分30.0质量％、重均分子量30000的聚氨酯树脂溶液(PUO)。
[涂覆剂(D)]
作为氧化钛，使用“テイカ社”制的JR-805。
将30质量份JR-805、11.5质量份氯乙烯-醋酸乙烯酯共聚物(单体组成比：氯乙烯84质量％/醋酸乙烯酯3质量％/乙烯醇13质量％，数均分子量22000，固体成分30质量％，溶剂成分：醋酸乙酯)进行搅拌混合，用砂磨机进行混炼。其后，在得到的混合物中加入上述的聚氨酯树脂溶液(PUO)30质量份、醋酸正丙酯/异丙醇混合溶剂(质量比50/50)13.5质量份并进行搅拌混合，得到氧化钛的分散液。在该分散液100质量份中添加醋酸正丙酯/异丙醇混合溶剂(质量比50/50)50质量份作为稀释溶剂，得到涂覆剂(D)。
使用凹版印刷机，在作为树脂膜基材的双轴拉伸聚对苯二甲酸乙二醇酯膜(商品名：P-60、厚度12μm、东丽社制)的电晕处理面上涂敷实施例1～4的水系涂覆剂(C)。另外，使用凹版印刷机，在双轴拉伸聚丙烯膜(商品名：U-1、厚度20μm、“三井化学東セロ社”制)的电晕处理面上涂敷实施例5～6的水系涂覆剂(C)。由此，以膜厚成为0.5μm的方式形成由实施例1～6的水系涂覆剂(C)形成的皮膜。
进而，使用凹版印刷机，在由实施例1～6的水系涂覆剂(C)形成的皮膜上涂敷涂覆剂(D)，以膜厚成为1μm的方式形成由实施例1～6的涂覆剂(D)形成的皮膜，得到实施例1～6的阻气性膜。
予以说明，利用扫描型电子显微镜(Scanning ElectronMicroscope，SEM)确认由水系涂覆剂(C)形成的皮膜及由涂覆剂(D)形成的皮膜的膜厚。
[比较例]
以表2所示的固体成分配合比率配合成分(A)、成分(B)及成分(E)，在80℃下进行加热、混合之后，冷却至室温，以溶剂中的10质量％为异丙醇且成为表2所示的固体成分浓度的方式用离子交换水和异丙醇稀释，从而制备涂液。
将没有配合固化剂的涂液直接涂敷。
关于配合固化剂的涂液，在即将涂敷之前添加表2所示的固化剂(三井化学社制的水分散性聚异氰酸酯タケネートWD-725)，从而制备比较例1～8的水系涂覆剂(C)。
[比较例1～6]
使用凹版印刷机，在作为树脂膜基材的双轴拉伸聚对苯二甲酸乙二醇酯膜(商品名：P-60、厚度12μm、东丽社制)的电晕处理面上涂敷比较例1～4的水系涂覆剂(C)，或在双轴拉伸聚丙烯膜(商品名：U-1、厚度20μm、“三井化学東セロ社”制)的电晕处理面上涂敷比较例5～6的水系涂覆剂(C)，以膜厚成为0.5μm的方式形成由比较例1～6的水系涂覆剂(C)形成的皮膜，得到比较例1～6的阻气性膜。
予以说明，利用扫描型电子显微镜(SEM)确认由水系涂覆剂(C)形成的皮膜的膜厚。
[比较例7]
将聚氨酯树脂溶液(PUO)30质量份、醋酸正丙酯/异丙醇混合溶剂(质量比50/50)13.5质量份进行搅拌混合，得到分散液。在该分散液100质量份中添加醋酸正丙酯/异丙醇混合溶剂(质量比50/50)50质量份作为稀释溶剂，得到比较例7的涂覆剂(D)。
使用凹版印刷机，在作为树脂膜基材的双轴拉伸聚对苯二甲酸乙二醇酯膜(商品名：P-60、厚度12μm、东丽社制)的电晕处理面上涂敷比较例7的水系涂覆剂(C)，以膜厚成为0.5μm的方式形成由比较例7的水系涂覆剂(C)形成的皮膜。
进而，使用凹版印刷机，在由比较例7的水系涂覆剂(C)形成的皮膜上涂敷比较例7的涂覆剂(D)，以膜厚成为1μm的方式形成由比较例7的涂覆剂(D)形成的皮膜，得到比较例7的阻气性膜。
予以说明，利用扫描型电子显微镜(SEM)确认由水系涂覆剂(C)形成的皮膜及由涂覆剂(D)形成的皮膜的膜厚。
[比较例8]
将颜料红81：2(BASF制FANAL PINK D4830)7.4质量份、聚氨酯树脂溶液(PUO)33质量份、乙酸正丙酯20质量份及异丙醇4质量份进行搅拌混合，用砂磨机进行混炼。其后，添加聚氨酯树脂溶液(PUO)20质量份、乙酸正丙酯12质量份及异丙醇3.6质量份，得到分散液。在该分散液100质量份中添加醋酸正丙酯/异丙醇混合溶剂(质量比50/50)50质量份作为稀释溶剂，得到比较例8的涂覆剂(D)。
使用凹版印刷机，在作为树脂膜基材的双轴拉伸聚对苯二甲酸乙二醇酯膜(商品名：P-60、厚度12μm、东丽社制)的电晕处理面上涂敷比较例8的水系涂覆剂(C)。由此，以膜厚成为0.5μm的方式在膜上形成由比较例8的水系涂覆剂(C)形成的皮膜。
进而，使用凹版印刷机，在由比较例8的水系涂覆剂(C)形成的皮膜上涂敷比较例8的涂覆剂(D)，以膜厚成为1μm的方式形成由比较例8的涂覆剂(D)形成的皮膜，得到比较例8的阻气性膜。
予以说明，利用扫描型电子显微镜(SEM)确认由水系涂覆剂(C)形成的皮膜及由涂覆剂(D)形成的皮膜的膜厚。
[评价]
(1)氧气阻隔性
对实施例1～6及比较例1～8的阻气性膜，使用氧透过度测定装置(商品名：OXTRAN-2/20、MOCON社制)，在20℃、湿度80％的气氛下测定氧透过度。将结果示于表1及表2。
(2)层压强度
在实施例1～6及比较例1～8的阻气性膜的涂布面上，通过干式层压加工经由聚酯聚氨酯系粘接剂(商品名：タケラックA-525、タケネートA-52，三井化学社制)层压厚度30μm的未拉伸聚丙烯膜(商品名：CPP GLC，“三井化学東セロ社”制)。将得到的层叠体在40℃下老化48小时，得到层叠膜。
将该层叠膜切割成15mm宽度的条状，利用拉伸试验机Tensilon以300mm/分钟的速度，以未拉伸聚丙烯膜和阻气性膜的剥离角度成为90°的方式由层叠膜剥离阻气性膜，测定层压强度。将结果示于表1及表2。
(3)40℃、湿度75％、放置2个月后的层压强度
在实施例1～6及比较例1～8的阻气性膜的涂布面上，通过干式层压加工经由聚酯聚氨酯系粘接剂(商品名：タケラックA-525、タケネートA-52，三井化学社制)层压厚度30μm的未拉伸聚丙烯膜(商品名：CPP GLC，“三井化学東セロ社”制)，在40℃下老化48小时，得到层叠膜。
将该层叠膜在40℃、湿度75％的条件下的恒温槽中保管2个月。
将在上述的条件下保管了2个月的层叠膜切割成15mm宽度的条状，利用拉伸试验机Tensilon，以300mm/分钟的速度，以未拉伸聚丙烯膜和阻气性膜的剥离角度成为90°的方式由层叠膜剥离阻气性膜，测定层压强度。将结果示于表1及表2。
从表1的结果来看，实施例1～6的阻气性膜由于具备由含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)形成的皮膜和由含有氧化钛的涂覆剂(D)形成的皮膜，且水系涂覆剂(C)在高湿度气氛下具有优异的氧气阻隔性，因此，可以兼备20℃、湿度80％的气氛下的氧气阻隔性和经过2个月后的层压强度。
另外，实施例5及6中，由于含有作为水系涂覆剂(C)的成分的水性聚氨酯树脂和固化剂，因此，即使对于聚丙烯树脂那样的无极性且表面张力低的树脂也发挥良好的密合性。
就比较例1～6而言，由于没有涂敷由含有氧化钛的涂覆剂(D)形成的皮膜，因此，与实施例1～6相比，为层压强度差的结果。另外，如比较例7及8那样，即使在层叠由不含有氧化钛的涂覆剂(D)形成的皮膜的情况下，也为层压强度差的结果。
予以说明，作为用于食品或医药品等的包装的阻隔性包装材料，20℃、湿度80％的气氛下的氧气阻隔性优选为100cm3/m2/day/MPa以下，40℃、湿度75％、放置2个月后的层压强度优选为1N/15mm以上。
工业实用性
本发明的阻气性膜及阻气性层叠体其高湿度气氛下的阻气性优异，也可以长期间良好地保持层间的密合性和皮膜的凝聚力。因此，通过将本发明的阻气性膜及阻气性层叠体用作包装用材料，可以提高内容物的品质保持性，可作为各种各样的包装用材料有效利用。
符号说明
1 阻气性膜
2 树脂膜基材
3 皮膜(第1皮膜，阻气层)
4 第2皮膜(第2皮膜，含氧化钛层)
5 阻气性层叠体
6 粘接剂层
7 热密封性树脂层

Claims (5)

1.一种阻气性膜，其具备：
树脂膜基材、以及
依次层叠于所述树脂膜基材的至少一面上的第1皮膜和第2皮膜，所述第1皮膜由含有水溶性高分子(A)及无机层状矿物(B)的水系涂覆剂(C)形成，所述第2皮膜由含有氧化钛和树脂的涂覆剂(D)形成，并且所述第2皮膜的厚度大于0.5μm。
2.根据权利要求1所述的阻气性膜，其中，
所述水系涂覆剂(C)含有具有水溶性或水分散性的水性聚氨酯树脂、固化剂、水溶性高分子(A)、及无机层状矿物(B)。
3.根据权利要求1或2所述的阻气性膜，其中，
所述水溶性高分子(A)为聚乙烯醇树脂。
4.根据权利要求1或2所述的阻气性膜，其中，
所述无机层状矿物(B)为水溶胀性合成云母。
5.一种阻气性层叠体，其具备：
根据权利要求1至4中任一项所述的阻气性膜，以及
依次层叠于所述阻气性膜的至少一面上的粘接剂层及热密封性树脂层。
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JP6287064B2 (ja) * 2013-10-28 2018-03-07 凸版印刷株式会社 ガスバリア性フィルム
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