CN112585201A - 耐水性阻气膜及耐水性阻气膜的制造方法 - Google Patents
耐水性阻气膜及耐水性阻气膜的制造方法 Download PDFInfo
- Publication number
- CN112585201A CN112585201A CN201980054489.1A CN201980054489A CN112585201A CN 112585201 A CN112585201 A CN 112585201A CN 201980054489 A CN201980054489 A CN 201980054489A CN 112585201 A CN112585201 A CN 112585201A
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- Prior art keywords
- polyvinyl alcohol
- gas barrier
- film
- water
- barrier film
- 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
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Abstract
一种耐水性阻气膜(10),其中在基材膜(1)上至少设置有阻气层(2),阻气层(2)是由包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液形成的。
Description
技术领域
本发明涉及阻气膜,特别是涉及一种具有耐水性的阻气膜及其制造方法。
背景技术
以往,已经开发了多种材料作为具备氧气阻隔性等阻气性的包装材料。近年来,已经提出了许多阻气性膜,其是通过在塑料基材上以纳米尺度的方式设置诸如氧化硅、氧化铝之类的金属氧化物膜而得到的。
然而,为了形成金属氧化物膜,通常需要用于实施蒸镀法或离子镀法等的真空成膜装置和相关的制造设备,因此在成本方面是昂贵的。
近年来,包装材料已经成为全球性的需求,而为了低价地提供包装材料,利用印刷机等可以进行加工的低价的阻隔性材料成为需求。为了表现出氧气阻隔性,以往使用聚偏二氯乙烯,但是从焚烧过程中产生有害物质的观点出发,其使用量正在减少。另外,乙烯乙烯醇膜也广泛地用于包装,但是其价格昂贵。
因此,例如,如专利文献1所示,提出了薄膜涂布使用了聚乙烯醇和无机层状矿物的材料的方法。尽管通过这种构成获得了优异的阻气性,但是需要进一步的研究以获得具有耐水性的密合性。
现有技术文献
专利文献
专利文献1:国际公开第2013/129520号
发明内容
发明所要解决的问题
鉴于上述问题,本发明的目的在于提供一种在具有氧气阻隔性的同时还具有耐水性的新型阻气膜。本发明的另一个目的在于提供该耐水性阻气膜的制造方法。
用于解决问题的方法
根据本发明的一个方面的耐水性阻气膜是在基材膜上至少设置有阻气层的阻气膜,该阻气层是由包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液形成的。
在一个实施方式中,部分皂化的聚乙烯醇和完全皂化的聚乙烯醇的聚合度可以为3000以下。
在一个实施方式中,以阻气层的总量为基准,聚乙烯亚胺的含量可以为10质量%以下。
在一个实施方式中,聚乙烯亚胺的重均分子量可以为500以上。
在一个实施方式中,羧基改性的聚乙烯醇可以是乙烯基酯类单体和含羧基的单体的共聚物的皂化产物。
在一个实施方式中,耐水性阻气膜可以是逐次拉伸膜。
根据本公开的一个方面的耐水性阻气膜的制造方法具备:在基材膜上涂布包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液的步骤;以及对所涂布的涂液进行加热使其干燥以在基材膜上形成涂膜的步骤。
在一个实施方式中,耐水性阻气膜的制造方法可以进一步具备将基材膜与涂膜一起拉伸的步骤。
在一个实施方式中,拉伸步骤中的拉伸倍率可以为2倍至20倍。
发明的效果
根据本发明,可以提供一种在具有氧气阻隔性的同时还具有耐水性的新型阻气膜。另外,根据本发明,可以提供该耐水性阻气膜的制造方法。通过使用包含聚乙烯醇和聚乙烯亚胺的涂液,其中该聚乙烯醇的至少一部分是羧基改性的聚乙烯醇或部分皂化的聚乙烯醇,从而可以提供具有耐水密合性的阻气膜。具备能够拉伸的聚乙烯醇类的涂膜的本发明阻气膜作为包装材料是低价的,并且可以利用印刷机等加工。
附图简要说明
[图1]图1是表示根据一个实施方式的耐水性阻气膜的示意性截面图。
具体实施方式
<耐水性阻气膜>
以下,参照附图对本发明的一个实施方式进行说明。图1是表示根据一个实施方式的耐水性阻气膜的示意性截面图。耐水性阻气膜10在基材膜1上具备用于对基材膜赋予阻气性的阻气层2。阻气层2由特定组分构成,具有优异的耐水性。
(基材膜)
作为基材膜1,可列举出(例如)由聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚丙烯、聚碳酸酯、环烯烃等构成的膜,但是不限于这些。这些材料也可以是无定形的。基材膜可以是拉伸膜,也可以是非拉伸膜。但是,若基材膜是拉伸膜,则其具有拉伸强度等力学特性和耐热性优异的特性,因此是优选的。根据需要,基材膜可以是仅在一个轴方向(例如MD方向)上拉伸的膜。
基材膜1的厚度没有特别的限定,但是期望为约3μm以上100μm以下的常规厚度。
(阻气层)
阻气层2包含聚乙烯醇和聚乙烯亚胺,并且聚乙烯醇的至少一部分包括羧基改性的聚乙烯醇或部分皂化的聚乙烯醇。即,阻气层2是由包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液形成的。更具体地,可以认为阻气层2是通过对该涂液进行加热和干燥而得的(加热干燥产物)。
通常,在只有仅含羟基(完全皂化)的聚乙烯醇的涂膜中,即使可以通过离子键而与基材密合,但是存在有该结合由于水的介入而容易剥离的问题。因此,需要引入具有其他官能团的物质以与基材形成牢固的结合,但是若简单地添加容易与羟基成键的材料,则会导致沉淀或适用期的减少。
作为解决上述问题的方法,本发明人除了完全皂化的聚乙烯醇以外,还使用了羧基改性的聚乙烯醇或部分皂化的聚乙烯醇。然后,据认为,经由这些羧基或乙酸基而将涂膜和基材结合起来,从而在保持膜本身的聚乙烯醇特性的同时可以获得牢固的密合性。通过在涂膜与基材的结合中采用聚乙烯亚胺,并且将聚乙烯亚胺***至羧基或乙酸基与基材之间,从而发现可以获得涂膜与基材的牢固结合,由此完成了本发明。
根据需要,耐水性阻气膜的基材膜1和/或阻气层2中可以包含诸如抗静电剂、紫外线吸收剂、增塑剂、润滑剂之类的添加剂。此外,可以至少对基材膜1的阻气层2一侧的表面进行电晕处理、火焰处理、等离子体处理、易粘接处理等改性处理。另外,根据膜的用途,耐水性阻气膜10还可以进一步具备印刷层、密封剂层、粘接层、保护层等功能层。
阻气层2的厚度优选为0.01μm至20μm。若厚度小于0.01μm,则阻隔性容易降低,若厚度大于20μm,则在形成层时干燥容易变得不充分,有时会存在卷取涂布适应性差的情况。
(聚乙烯醇)
作为聚乙烯醇,可以使用普通的聚乙烯醇。聚乙烯醇可以通过使乙烯基酯类单体聚合、接着进行皂化而得。作为乙烯基酯类单体,可列举出甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、异丁酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等,并且通常使用乙酸乙烯酯。
聚乙烯醇可以是共聚改性或后改性的改性聚乙烯醇。共聚改性的聚乙烯醇可以通过使乙烯基酯类单体与能够和乙烯基酯类单体共聚的其他单体(不饱和单体)共聚、然后进行皂化而得。后改性的聚乙烯醇可以通过在使乙烯基酯类单体聚合之后进行皂化以获得聚乙烯醇、并且在聚合催化剂的存在下使其他单体与所得的聚乙烯醇共聚而得。
作为这样的其他单体,可列举出(例如)乙烯、丙烯、异丁烯等烯烃类;丙烯腈、甲基丙烯腈等腈类;丙烯酰胺、甲基丙烯酰胺等酰胺类;氯乙烯、偏二氯乙烯、聚氧丙烯、聚氧丙烯乙烯基胺等。
另外,在获得羧基改性的聚乙烯醇的情况下,作为这样的其他单体(即含羧基的单体),可列举出丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、以及这些羧酸的单酯等。作为羧基改性的聚乙烯醇的原料,期望为乙酸乙烯酯和含羧基的单体的组合。羧基改性的聚乙烯醇中的改性量(羧基改性的聚乙烯醇中所含的全部单体单元(100摩尔%)当中的羧基改性的单体单元的含有率)没有特别的限定,可以设为1摩尔%至50摩尔%。
在原料单体的聚合中使用聚合催化剂。作为聚合催化剂,可列举出2,2-偶氮二异丁腈、过氧化苯甲酰、过氧化月桂酰等自由基聚合催化剂等。聚合方法没有特别的限定,可以采用本体聚合、乳液聚合、溶剂聚合等。
聚合后,将原料单体的聚合物供给至皂化步骤。皂化可以通过将聚合物溶解在含有醇的溶剂中、并使用碱或酸来进行,但是从皂化速度的观点出发,优选使用碱。作为碱,可列举出氢氧化钠、氢氧化钾等碱金属氢氧化物;乙醇钠、乙醇钾、甲醇锂等碱金属醇盐。将皂化后的皂化产物(聚乙烯醇)干燥,从而可以粉末形式获得。
完全皂化的聚乙烯醇的皂化度为98摩尔%以上,也可以为99摩尔%以上。完全皂化的聚乙烯醇的皂化度为98摩尔%以上,从而容易获得充分的阻隔性。另外,部分皂化的聚乙烯醇的皂化度可以设为75摩尔%以上且小于98摩尔%,也可以为80摩尔%至95摩尔%。部分皂化的聚乙烯醇的皂化度为75摩尔%以上,从而容易获得充分的阻隔性,另外,通过小于98摩尔%,从而容易获得良好的润湿性。
聚乙烯醇(部分皂化和完全皂化的聚乙烯醇)的聚合度期望在300至3000、或者300以上且小于3000的范围内。若聚合度小于300,则阻隔性容易降低,若大于3000,则粘度过高,涂布适应性容易降低。从这种观点出发,聚合物可以为300至1500。
(聚乙烯亚胺)
聚乙烯亚胺是乙烯亚胺的共聚物,可列举出仅包含仲胺的直链状共聚物、以及包含伯胺、仲胺、叔胺的支链状共聚物,可以使用它们当中的任一种。另外,也可以混合多种类型。此外,可以使用导入有阳离子基团等官能团的衍生物。
聚乙烯亚胺的重均分子量期望为500以上、或1500以上。由于重均分子量过低的聚乙烯亚胺倾向于渗透至膜内部,因此可能无法实现足够的耐水性。需要说明的是,该重均分子量的上限可以设为10万。
<耐水性阻气膜的制造方法>
耐水性阻气膜的制造方法具备:在基材膜上涂布包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液的步骤(涂布步骤);以及对所涂布的涂液进行加热并使其干燥以在基材膜上形成涂膜的步骤(加热干燥步骤)。该制造方法可以进一步具备将基材膜与涂膜一起拉伸的步骤(拉伸步骤)。
(涂布步骤)
称取必要量的羧基改性的聚乙烯醇、部分皂化的聚乙烯醇、以及完全皂化的聚乙烯醇的各个粉末,并溶解在加热至80℃以上的水中。也可以预先制备通过使各个粉末单独溶解而得的水溶液。水溶液中的固形物含量没有特别的限制,但是从处理方面考虑,期望固形物含量小于20质量%。需要说明的是,从涂布效率等观点出发,该固形物含量的下限可以设为1质量%。
通过将聚乙烯亚胺进一步添加到含有聚乙烯醇的水溶液中,从而获得涂液。根据需要,也可以向涂液中添加防腐剂、醇、流平剂、消泡剂、紫外线吸收剂、抗氧化剂、硅烷偶联剂、金属螯合剂等。
当将羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者设为(a)组分、将完全皂化的聚乙烯醇设为(b)组分、以及将聚乙烯亚胺设为(c)组分时,可以适当地调节涂液中的(a)至(c)组分的量的比例等,以使涂膜中的各组分的量的比例等成为(例如)后述的期望值。
涂布步骤可以通过使用水溶液的涂布方法来实施。作为涂布方式,可以使用公知的方法,具体而言,可列举出凹版涂布机、浸渍涂布机、反向涂布机、线棒涂布机、模头涂布机等的湿式成膜法。
需要说明的是,可以在涂布步骤之前实施将基材膜预先拉伸的预拉伸步骤。特别地,在获得后述的逐次拉伸膜的情况下,通过预拉伸步骤,仅在一个轴方向(例如,MD方向)上对基材膜进行拉伸。拉伸倍率可以设为2倍至20倍。
(加热干燥步骤)
加热干燥步骤中的干燥温度期望为90℃以上。此外,若干燥温度低于250℃,则没有问题。涂布后的干膜厚度期望为0.01μm至20μm。厚度越薄,则加工速度越快,另外,厚度越厚,则阻隔性能越好。可以根据需要进行适当调整。
当将羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者设为(a)组分、将完全皂化的聚乙烯醇设为(b)组分、以及将聚乙烯亚胺设为(c)组分时,优选如下所述地调整涂膜中的各组分的量。
在所形成的涂膜中,以涂膜的总量为基准,(a)组分和(b)组分的总量优选为90质量%至99.9质量%,更优选为95质量%至99.5质量%。另外,(a)组分的量相对于(a)组分和(b)组分的总量的比例((a)组分的量/(a)组分和(b)组分的总量)优选为0.01至0.5,更优选为0.02至0.4。由此,易于保持良好的阻隔性和润湿性。
在所形成的涂膜中,以涂膜的总量为基准,(c)组分的含量期望为10质量%以下、或5质量%以下。若添加过多,则会导致阻隔性的降低。(c)组分的含量的下限可以设为0.01质量%。
(拉伸步骤)
由于涂膜具有充分的柔软性,因此在本步骤中可以将基材膜与涂膜一起拉伸。进行拉伸以控制热收缩特性。在拉伸步骤中,将基材膜在其Tg以上的温度下拉伸至预定的倍率。拉伸倍率可以设为2倍至20倍,也可以为3倍至10倍。若拉伸倍率小于2倍,则收缩特性没怎么变化;若大于20倍,则膜可能会被撕裂。在本制造方法中,由于可以在形成涂膜之后对基材膜进行拉伸,因而能够进行在线的防渗涂布(barrier coating)。因此,通过上述制造方法,可以低成本地获得耐水性阻气膜。
通过上述制造方法获得的耐水性阻气膜也可以通过在根据需要已经预先沿一个轴方向(例如,MD方向)拉伸了的基材膜上形成涂膜、然后进一步沿另一个轴方向(例如,TD方向)进行拉伸而得。通过这种步骤得到的膜不是双轴同时进行拉伸的,而是逐次进行拉伸的膜,因而可以称为逐次拉伸膜。
在拉伸步骤之后,根据需要,可以进行后加热步骤。
实施例
以下,根据实施例对本发明进行更具体的说明,但是本发明不限于这些实施例。
<膜的制作>
[(a1)羧基改性的聚乙烯醇水溶液的制备]
使用2,2-偶氮二异丁腈作为催化剂以使乙酸乙烯酯和马来酸聚合。采用氢氧化钠水溶液(含有甲醇)对聚合物进行皂化,然后在80℃下干燥,从而得到了(a)羧基改性的聚乙烯醇粉末。在90℃下将该粉末溶解于水中。
[(a2)部分皂化的聚乙烯醇水溶液的制备]
使用2,2-偶氮二异丁腈作为催化剂以使乙酸乙烯酯聚合。采用氢氧化钠水溶液(含有甲醇)对聚合物进行皂化,然后在80℃下干燥,从而得到了聚合度为1000的(a)部分皂化的聚乙烯醇粉末。皂化度为87摩尔%。在90℃下将该粉末溶解于水中。
[(b)完全皂化的聚乙烯醇水溶液的制备]
使用2,2-偶氮二异丁腈作为催化剂以使乙酸乙烯酯聚合。采用氢氧化钠水溶液(含有甲醇)对聚合物进行皂化,然后在80℃下干燥,从而得到了聚合度为500的(b)完全皂化的聚乙烯醇粉末。皂化度为98摩尔%以上。在90℃下将该粉末溶解于水中。
[(c)聚乙烯亚胺的准备]
准备了重均分子量不同的多种聚乙烯亚胺。
[涂液的制备]
称量各种聚乙烯醇水溶液和聚乙烯亚胺以使得各种聚乙烯醇和聚乙烯亚胺的量成为表1所示的比例,并将它们混合10分钟以上。由此,得到了各例子中使用的涂液。以涂液的总量为基准,将涂液中的(a1)羧基改性的聚乙烯醇或(a2)部分皂化的聚乙烯醇、以及(b)完全皂化的聚乙烯醇的总含量(固形物含量)调整成为10质量%。
(实施例1)
将(a1)羧基改性的聚乙烯醇和(b)完全皂化的聚乙烯醇混合,使得以质量比计的比例为约1:2,向其中添加重均分子量为1800的聚乙烯亚胺,从而制备了涂液。调整聚乙烯亚胺的添加量,以使得涂膜中的含量为2质量%。通过棒涂法将该涂液涂布在厚度为12μm的聚对苯二甲酸乙二醇酯膜基材(P60,“東レ株式会社”制)上。然后,在150℃下将涂液干燥固化3分钟,由此在基材上形成了厚度为200nm的涂膜。
(实施例2)
将(a1)羧基改性的聚乙烯醇和(b)完全皂化的聚乙烯醇混合,使得以质量比计的比例为约1:2,向其中添加重均分子量为10000的聚乙烯亚胺,从而制备了涂液。调整聚乙烯亚胺的添加量,以使得涂膜中的含量为1质量%。随后,与实施例1同样地在基材上形成了涂膜。
(实施例3)
除了使用(a2)部分皂化的聚乙烯醇以代替(a1)羧基改性的聚乙烯醇以外,与实施例2同样地在基材上形成了涂膜。
(实施例4)
除了使用厚度为20μm的未拉伸聚丙烯膜基材以代替厚度为12μm的聚对苯二甲酸乙二醇酯膜基材以外,与实施例2同样地在基材上形成了涂膜。随后,将未拉伸聚丙烯膜基材与涂膜一起在TD方向上拉伸。拉伸倍率设为3倍。
(实施例5)
除了使用重均分子量为10000的聚乙烯亚胺以代替重均分子量为1800的聚乙烯亚胺、以及使用厚度为150μm的未拉伸聚对苯二甲酸乙二酯膜基材以代替厚度为12μm的聚对苯二甲酸乙二醇酯膜基材以外,与实施例1同样地在基材上形成了涂膜。随后,将未拉伸聚对苯二甲酸乙二醇酯膜基材与涂膜一起在TD方向上拉伸。拉伸倍率设为3倍。
(实施例6)
除了使用重均分子量为600的聚乙烯亚胺以代替重均分子量为1800的聚乙烯亚胺以外,与实施例1同样地在基材上形成了涂膜。
(实施例7)
除了调整聚乙烯亚胺的添加量以使得涂膜中的含量成为10质量%以外,与实施例2同样地在基材上形成了涂膜。
(比较例1)
除了使用仅包含(b)完全皂化的聚乙烯醇的涂液以外,与实施例1同样地在基材上形成了涂膜。
[表1]
<膜的性能评价>
根据下述方法,对膜的性能进行评价。结果示出于表2中。
[耐水密合性]
经由粘接剂将所制作的膜的涂膜面与CPP膜贴合,然后将其切出15mm×100mm以作为样品。在将剥离面暴露以后,将样品浸入水中,并根据JIS Z1707测定层压强度。测定条件设为:剥离速度为300m/分钟、剥离角度为180度。若层压强度为1.0N以上,则耐水密合性可以评价为良好。
[氧透过率]
通过依照JIS-K7129 C方法的差分气相色谱法,在30℃、70RH%的条件下,测定了所制作的膜的氧透过率。若氧透过率为50(cc/m2·天·atm)以下,则阻隔性可以评价为良好,若氧透过率为15(cc/m2·天·atm)以下,则阻隔性可以评价为特别良好。
[表2]
如表2所示,实施例的膜的耐水密合性和阻隔性均良好。另一方面,虽然比较例的膜的阻隔性良好,但是耐水密合性差。
由上述结果可知,本发明的耐水性阻气膜的耐水密合性良好,且具有优异的阻隔性。
符号的说明
1···基材膜;2···阻气层;10···耐水性阻气膜
Claims (9)
1.一种耐水性阻气膜,其中在基材膜上至少设置有阻气层,
所述阻气层是由包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液形成的。
2.根据权利要求1所述的耐水性阻气膜,其中,所述部分皂化的聚乙烯醇和所述完全皂化的聚乙烯醇的聚合度为3000以下。
3.根据权利要求1或2所述的耐水性阻气膜,其中,以所述阻气层的总量为基准,所述聚乙烯亚胺的含量为10质量%以下。
4.根据权利要求1至3中任一项所述的耐水性阻气膜,其中,所述聚乙烯亚胺的重均分子量为500以上。
5.根据权利要求1至4中任一项所述的耐水性阻气膜,其中,所述羧基改性的聚乙烯醇是乙烯基酯类单体和含羧基的单体的共聚物的皂化产物。
6.根据权利要求1至5中任一项所述的耐水性阻气膜,其中,所述耐水性阻气膜是逐次拉伸膜。
7.一种耐水性阻气膜的制造方法,具备:
在基材膜上涂布包含(a)羧基改性的聚乙烯醇和部分皂化的聚乙烯醇中的至少一者、(b)完全皂化的聚乙烯醇、以及(c)聚乙烯亚胺的涂液的步骤;以及
对所涂布的所述涂液进行加热使其干燥以在所述基材膜上形成涂膜的步骤。
8.根据权利要求7所述的制造方法,进一步具备将所述基材膜与所述涂膜一起拉伸的步骤。
9.根据权利要求8所述的制造方法,其中,所述拉伸步骤中的拉伸倍率为2倍至20倍。
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