CN107408644B - 电池用包装材料和电池 - Google Patents

电池用包装材料和电池 Download PDF

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Publication number
CN107408644B
CN107408644B CN201680018029.XA CN201680018029A CN107408644B CN 107408644 B CN107408644 B CN 107408644B CN 201680018029 A CN201680018029 A CN 201680018029A CN 107408644 B CN107408644 B CN 107408644B
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China
Prior art keywords
layer
packaging material
battery
base material
battery packaging
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CN201680018029.XA
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CN107408644A (zh
Inventor
天野真
山下力也
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP2015063402A external-priority patent/JP6710894B2/ja
Priority claimed from JP2015063403A external-priority patent/JP6710895B2/ja
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Publication of CN107408644A publication Critical patent/CN107408644A/zh
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
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Abstract

本发明提供基材层表面的油墨的印刷特性优异的电池用包装材料。该电池用包装材料包括至少依次具有基材层、金属层和热熔接性树脂层的叠层体,上述基材层由包含亚乙基双硬脂酰胺、亚乙基双油酰胺的聚酰胺树脂形成。

Description

电池用包装材料和电池
技术领域
本发明涉及电池用包装材料和电池。
背景技术
以往,开发有各种类型的电池,而在所有电池中,为了封装电极、电解质等的电池元件,包装材料成为不可缺少的部件。以往,作为电池用包装,普遍使用金属制的包装材料,但是近年来,伴随电动汽车、混合动力电动汽车、电脑、照相机、移动电话等的高性能化,对于电池,要求多样的形状,并且要求薄型化、轻质化。然而,以往普遍使用的金属制的电池用包装材料存在难以应对形状的多样化,而且轻质化也有局限这样的缺点。
于是,作为容易加工成多样的形状、且能够实现薄型化、轻质化的电池用包装材料,提出了依次叠层有基材层/粘接层/金属层/热熔接性树脂层的膜状的叠层体(例如,参照专利文献1)。这种膜状的电池用包装材料形成为能够通过使热熔接性树脂层彼此对置并将边缘部利用热封进行热熔接来封装电池元件。
在由如上所述的叠层体形成的各式各样的包装材料中,广泛采用通过在基材层的表面印刷油墨,形成条码、纹样、文字等,在进行了印刷的一侧的基材层上叠层粘接剂、金属箔的方法,在包装材料进行印字的方法(一般称为背面印刷)。然而,在基材层与金属层之间存在这种印刷面时,基材层与金属层的密合性降低,容易在层间发生脱层。特别是对使用电池用包装材料的电池要求高的安全性,因此在电池用包装材料中避免采用通过这种背面印刷进行印字的方法。由此,以往在电池用包装材料形成条码等的印字时,一般采用将形成有印字的贴层粘贴在基材层的表面的方法。
然而,将形成有印字的贴层粘贴在基材层的表面时,电池用包装材料的厚度、重量增加。由此,出于对电池用包装材料近年来进一步的薄型化、轻质化的倾向,研究了通过直接油墨印刷在电池用包装材料的基材层的表面进行印字的方法。
作为在电池用包装材料的基材层的表面直接印刷油墨的方法,已知有移印(也被称为TAMPO印刷)。移印是指如下的印刷方法。首先,使油墨流入到蚀刻有想要印刷的图案的平板的凹部。接下来,从该凹部的上面贴压硅垫,使油墨转移到硅垫。接下来,使转移在硅垫表面的油墨转印至印刷对象物,在印刷对象物涂布油墨。这种移印利用有弹性的硅垫等来使油墨转印至印刷对象物,因此也容易在成型后的电池用包装材料的表面进行印刷,具有能够在利用电池用包装材料封装电池元件后对电池进行印刷这样的优点。
在此,在电池用包装材料的基材层中,广泛使用尼龙等聚酰胺树脂膜,在聚酰胺树脂膜中,一般包含亚乙基双油酰胺作为拨水剂。通过包含拨水剂,在制造膜时,熔融树脂相对于水的浸润性得以调整,能够在原膜的表面形成适度的凹凸(表面粗糙度),在原膜的拉伸后也留有该凹凸形状,能够成为表面的滑性得到调整的聚酰胺树脂膜。
现有技术文献
专利文献
专利文献1:日本特开2008-287971号公报
发明内容
发明所要解决的技术问题
但是,本发明的发明人进行研究的结果得知,在将包含亚乙基双油酰胺作为拨水剂的聚酰胺树脂膜用于基材层的情况下,通过在将电解液等的电池元件封入电池用包装材料后的烧制(baking)工序等进行加热,亚乙基双油酰胺在基材层表面渗出,通过移印等在基材层表面印刷油墨时,油墨在基材层表面被排斥,油墨难以固定,出现没有形成油墨的漏印部分。确认到特别是通过移印进行印刷时存在印刷适应性不充分的倾向。
这种状况下本发明主要目的在于,提供一种由聚酰胺树脂膜形成的基材层表面的油墨印刷特性优异的电池用包装材料。另外,本发明的目的还在于,提供该电池用包装材料的制造方法和使用该电池用包装材料的电池。
用于解决技术问题的方法
本发明的发明人为了解决上述技术问题进行了深入研究。其结果发现,在包括至少依次具有基材层、金属层和热熔接性树脂层的叠层体的电池用包装材料中,基材层由包含亚乙基双硬脂酰胺的聚酰胺树脂形成,由此能够有效提高基材层表面的油墨的印刷特性。本发明的第一发明基于这些见解通过进一步重复研究而完成。
另外,本发明的发明人为了解决上述技术问题进行了进一步深入研究。其结果发现,在包括至少依次具有基材层、金属层和热熔接树脂层的叠层体的电池用包装材料中,基材层由包含亚乙基双油酰胺的聚酰胺树脂形成,并且将该基材层中的亚乙基双油酰胺的含量设为 400ppm以下,由此能够有效提高基材层表面的油墨的印刷特性。本发明的第二发明基于这些见解通过进一步重复研究而完成。
即,本发明提供以下列举的方式的发明。
项1.一种电池用包装材料,其包括至少依次具有基材层、金属层和热熔接性树脂层的叠层体,其中,
上述基材层由包含亚乙基双硬脂酰胺的聚酰胺树脂形成。
项2.如项1所述的电池用包装材料,其中,将上述电池用包装材料在100℃的恒温槽中静置24小时后,在210mm×297mm的范围的上述基材层表面存在的亚乙基双硬脂酰胺的量为30μg以下。
项3.一种电池用包装材料,其包括至少依次具有基材层、金属层和密封层的叠层体,其中,
上述基材层由包含亚乙基双油酰胺的聚酰胺树脂形成,
上述基材层中的亚乙基双油酰胺的含量为400ppm以下。
项4.如项3所述的电池用包装材料,其中,将上述电池用包装材料在100℃的恒温槽中静置24小时后,在210mm×297mm的范围的上述基材层表面存在的亚乙基双油酰胺为380μg以下。
项5.如项1~4中任一项所述的电池用包装材料,其中,上述基材层表面的至少一部分为油墨接受面。
项6.如项1~4中任一项所述的电池用包装材料,其中,上述基材层表面的至少一部分具有由油墨构成的印刷层。
项7.如项1~6中任一项所述的电池用包装材料,其中,上述基材层表面的湿润张力为32mN/m以上。
项8.如项1~7中任一项所述的电池用包装材料,其中,上述聚酰胺树脂为双轴拉伸尼龙。
项9.如项1~8中任一项所述的电池用包装材料,其中,在上述基材层与上述金属层之间具有粘接层。
项10.如项1~9中任一项所述的电池用包装材料,其中,在上述金属层与上述热熔接性树脂层之间具有粘接层。
项11.如项1~10中任一项所述的电池用包装材料,其中,上述金属层为铝箔或不锈钢箔。
项12.一种电池,在由项1~11中任一项所述的电池用包装材料形成的包装体中收容有至少具有正极、负极和电解质的电池元件。
发明的效果
根据本发明,能够提供基材层表面的油墨印刷特性优异的电池用包装材料。另外,根据本发明,也能够提供使用该电池用包装材料的电池。
附图说明
图1为表示本发明的电池用包装材料的截面结构的一例的图。
图2为表示本发明的电池用包装材料的截面结构的一例的图。
图3为表示本发明的电池用包装材料的截面结构的一例的图。
具体实施方式
第一发明的电池用包装材料的特征在于:其包括至少依次具有基材层、金属层和热熔接性树脂层的叠层体,基材层由包含亚乙基双硬脂酰胺的聚酰胺树脂形成。以下,对第一发明的电池用包装材料、该电池用包装材料的制造方法、使用该电池用包装材料的电池进行详述。
第二发明的电池用包装材料的特征在于:其包括至少依次具有基材层、金属层和热熔接树脂层的叠层体,基材层由包含亚乙基双油酰胺的聚酰胺树脂形成,并且将该基材层中的亚乙基双油酰胺的含量设为400ppm以下。以下,对第二发明的电池用包装材料、该电池用包装材料的制造方法、使用该电池用包装材料的电池进行详述。
此外,第一发明和第二发明中除基材层1的构成以外的构成是共通的。
1.电池用包装材料的叠层结构
如图1所示,本发明的电池用包装材料包括至少依次具有基材层 1、金属层3和热熔接性树脂层4的叠层体。在本发明的电池用包装材料中,基材层1成为最外层,热熔接性树脂层4成为最内层。即,组装电池时,通过位于电池元件的边缘的热熔接性树脂层4彼此热熔接而密封电池元件,从而封装电池元件。
如图2所示,本发明的电池用包装材料中,在基材层1与金属层3 之间,也可以以提高它们的粘接性为目的根据需要设有粘接剂层2。另外,如图3所示,在金属层3与热熔接性树脂层4之间,也可以以提高它们的粘接性为目的根据需要设有粘接层5。
2.形成电池用包装材料的各层的组成
[基材层1]
在第一发明的电池用包装材料中,基材层1是位于最外层的层。在第一发明中,基材层1由包含亚乙基双硬脂酰胺的聚酰胺树脂形成。
另一方面,在第二发明的电池用包装材料中,基材层1也是位于最外层的层。在第二发明中,关于基材层1,基材层1由包含亚乙基双油酰胺的聚酰胺树脂形成,并且将基材层1中的亚乙基双油酰胺的含量设为400ppm以下。
作为聚酰胺树脂,优选列举尼龙。作为聚酰胺树脂的具体例,可以列举:尼龙6、尼龙66、尼龙610、尼龙12、尼龙46、尼龙6与尼龙6,6的共聚物等脂肪族系聚酰胺;包含来自对苯二甲酸和/或间苯二甲酸的结构单元的尼龙6I、尼龙6T、尼龙6IT、尼龙6I6T(I表示间苯二甲酸、T表示对苯二甲酸)等六亚甲基二胺-间苯二甲酸-对苯二甲酸共聚聚酰胺、聚己二酰间苯二甲胺(MXD6)等包含芳香族的聚酰胺;聚氨基甲基环己基己二酰二胺(PACM6)等脂环系聚酰胺;以及将内酰胺成分、4,4’-二苯甲烷-二异氰酸酯等异氰酸酯成分共聚而得到的聚酰胺、作为共聚聚酰胺和聚酯、聚亚烷基醚二醇的共聚物的聚酯酰胺共聚物、聚醚酯酰胺共聚物;它们的共聚物等。这些聚酰胺树脂可以单独使用1种,或者也可以组合2种以上使用。
基材层1可以由单轴或双轴拉伸后的聚酰胺树脂膜形成,或者也可以由未拉伸的聚酰胺树脂膜形成。拉伸聚酰胺树脂膜的拉伸性优异,能够防止由成型时的基材层1的树脂破裂导致的白化发生,适合作为基材层1的形成原材料使用。拉伸聚酰胺树脂膜中,单轴或双轴拉伸后的聚酰胺树脂膜、特别是双轴拉伸后的聚酰胺树脂膜(特别是,双轴拉伸尼龙)通过取向结晶化而提高了耐热性,因此适合用作基材层1。
在第一发明中,聚酰胺树脂包含亚乙基双硬脂酰胺。亚乙基双硬脂酰胺在形成基材层1的聚酰胺树脂中,作为拨水剂合适地发挥功能。具体而言,通过聚酰胺树脂包含亚乙基双硬脂酰胺,在制造聚酰胺树脂膜时,熔融树脂相对于水的浸润性得以调整,能够在原膜的表面形成适度的凹凸(表面粗糙度),在原膜的拉伸后也留有该凹凸形状,能够制成表面的滑性得到调整的聚酰胺树脂膜。此外,形成基材层1的聚酰胺树脂也可以包含以往广泛使用的亚乙基双油酰胺作为拨水剂,从提高基材层表面的印刷适应性的观点考虑,优选实质上不含亚乙基双油酰胺。
在第一发明的形成基材层1的聚酰胺树脂中,作为亚乙基双硬脂酰胺的含量没有特别限制,优选列举1ppm以上600ppm以下左右、更优选列举50ppm以上500ppm以下左右、进一步优选列举100ppm以上 400ppm以下左右。此外,在第一发明中,形成基材层1的聚酰胺树脂中的亚乙基双硬脂酰胺的含量,为存在于聚酰胺树脂的内部和表面的亚乙基双硬脂酰胺的总量。构成电池用包装材料的基材层1的聚酰胺树脂中的亚乙基双硬脂酰胺的含量,能够通过将基材层1从电池用包装材料剥离,将基材层1溶解于六氟异丙醇后,添加二甲基乙烷进行溶剂沉淀,使树脂成分分离,制作亚乙基双油酰胺的提取溶液,对该提取溶液进行GC-MS分析,由此进行定量。
另外,在第一发明的电池用包装材料中,将电池用包装材料在 100℃的恒温槽中静置24小时后,在210mm×297mm的范围(A4尺寸)的上述基材层表面存在的亚乙基双硬脂酰胺的量优选为30μg以下。将电池用包装材料在100℃的恒温槽中静置24小时的操作是模拟制造电池单元时的烧制工序的处理,使通过该处理在基材层1表面渗出的亚乙基双硬脂酰胺的量为30μg/A4尺寸以下,由此在基材层1的表面油墨不易被排斥,能够制成印刷适应性进一步优异的电池用包装材料。与亚乙基双油酰胺相比,亚乙基双硬脂酰胺难以发生由加热而引起的渗出,因此,例如聚酰胺树脂中的亚乙基双硬脂酰胺的含量处于上述那样的范围时,能够使由于上述的烧制处理而在基材层1表面渗出的亚乙基双硬脂酰胺的量合适地成为30μg/A4尺寸以下。此外,具体而言,电池用包装材料中的该亚乙基双硬脂酰胺量,为通过后述的实施例所记载的方法测得的值。
在第二发明中,聚酰胺树脂包含亚乙基双油酰胺。另外,聚酰胺树脂中的亚乙基双油酰胺的含量为400ppm以下。亚乙基双油酰胺在形成基材层1的聚酰胺树脂中作为拨水剂合适地发挥功能。具体而言,通过聚酰胺树脂包含400ppm以下的亚乙基双油酰胺,在制造聚酰胺树脂膜时,熔融树脂相对于水的浸润性得以调整,能够在原膜的表面形成适度的凹凸(表面粗糙度),在原膜的拉伸后也留有该凹凸形状,能够制成表面的滑性得到调整的聚酰胺树脂膜。
在第二发明的形成基材层1的聚酰胺树脂中,作为亚乙基双油酰胺的含量没有特别限制,优选列举1ppm以上400ppm以下左右、更优选列举50ppm以上350ppm以下左右、进一步优选列举100ppm以上 300ppm以下左右。此外在第二发明中,形成基材层1的聚酰胺树脂中的亚乙基双油酰胺的含量,为存在于聚酰胺树脂的内部和表面的亚乙基双油酰胺的总量。另外,构成电池用包装材料的基材层1的聚酰胺树脂中的亚乙基双油酰胺的含量,能够通过将基材层1从电池用包装材料剥离,将基材层1溶解于六氟异丙醇后,添加二甲基乙烷进行溶剂沉淀,将树脂成分分离,制作亚乙基双油酰胺的提取溶液,对该提取溶液进行GC-MS分析,由此进行定量。
另外,在第二发明的电池用包装材料中,将电池用包装材料在 100℃的恒温槽中静置24小时后,在210mm×297mm的范围(A4尺寸)的上述基材层表面存在的亚乙基双油酰胺的量优选为380μg以下。将电池用包装材料在100℃的恒温槽中静置24小时的操作是模拟制造电池单元时的烧制工序的处理,使通过该处理在基材层1表面渗出的亚乙基双油酰胺的量为380μg/A4尺寸以下,由此在基材层1的表面油墨不易被排斥,能够制成印刷适应性进一步优异的电池用包装材料。此外,具体而言,第二发明的电池用包装材料中的该亚乙基双油酰胺量,为通过后述的实施例所记载的方法测得的值。
在本发明(第一和第二发明)中,基材层1中,为了提高耐针孔性和制成电池的包装体时的绝缘性,也能够将与聚酰胺树脂不同的树脂和聚酰胺树脂进行叠层化。例如可以列举将聚酯膜和尼龙膜叠层而得到的多层结构、将双轴拉伸聚酯和双轴拉伸尼龙叠层而得到的多层结构等。此外,在本发明中,将基材层1制成多层结构时,在最表面侧(与金属层3相反侧)配置聚酰胺树脂。另外,将基材层1制成多层结构时,各树脂膜可以通过粘接剂粘接,也可以不通过粘接剂直接叠层。不通过粘接剂粘接时,可以列举例如共挤出法、夹层层压法、热层压法等在热熔融状态下粘接的方法。另外,通过粘接剂粘接时,所使用的粘接剂可以为双液固化型粘接剂,或者也可以为单液固化型粘接剂。另外,对于粘接剂的粘接机制也没有特别限制,化学反应型、溶剂挥发型、热熔融型、热压型、UV、EB等电子射线固化型等任意方式均可。作为粘接剂的成分,可以列举聚酯系树脂、聚醚系树脂、聚氨酯系树脂、环氧系树脂、酚醛树脂系树脂、聚酰胺系树脂、聚烯烃系树脂、聚乙酸乙烯酯系树脂、纤维素系树脂、(甲基)丙烯酸系树脂、聚酰亚胺系树脂、氨基树脂、橡胶、硅系树脂。
在第一发明的电池用包装材料中,基材层1的表面的湿润张力优选为32mN/m以上。通过基材层1的表面的湿润张力为32mN/m以上,在基材层1的表面油墨不易被排斥,能够进一步提高印刷适应性。特别是对于通过使滑剂存在于基材层表面来提高成型性的电池用包装材料,通过移印印刷油墨时,在基材层1的表面油墨被排斥,有时出现印刷不良,但是即使在这种情况下,如果基材层1由包含亚乙基双硬脂酰胺的聚酰胺树脂形成,并且基材层1的表面的湿润张力为32mN /m以上,则油墨不易被排斥,从而特别适合作为通过移印在基材层表面形成印字等的电池用包装材料。如此在本发明中,基材层1表面的至少一部分能够成为油墨接受面。
在第二发明的电池用包装材料中,基材层1的表面的湿润张力优选为32mN/m以上。通过基材层1的表面的湿润张力为32mN/m以上,在基材层1的表面油墨不易被排斥,能够进一步提高印刷适应性。特别是对于通过使滑剂存在于基材层表面来提高成型性的电池用包装材料,通过移印印刷油墨时,在基材层1的表面油墨被排斥,有时出现印刷不良,但是即使在这种情况下,如果基材层1由包含规定量以下的亚乙基双油酰胺的聚酰胺树脂形成,并且基材层1的表面的湿润张力为32mN/m以上,则油墨不易被排斥,从而特别适合作为利用移印在基材层表面形成印字等的电池用包装材料。
在第一和第二发明的电池用包装材料中,从提高成型性并且提高印刷适应性的观点考虑,作为基材层1的表面的湿润张力,更优选列举32mN/m以上50mN/m以下左右、进一步优选列举35mN/m以上45mN/m以下左右。
此外,在第一和第二发明中,电池用包装材料的湿润张力是通过按照JIS K6768:1999的规定的方法测得的值,具体的方法如实施例所记载。
在第一和第二发明中,作为基材层1的厚度,例如可以列举10μm 以上50μm以下左右、优选列举12μm以上30μm以下左右。
在第一和第二发明的电池用包装材料中,能够合适地在基材层1 的表面的至少一部分印刷油墨。即,在本发明中,在基材层1的表面印刷了油墨的电池用包装材料中,印刷在基材层1的表面的油墨(油墨的固化物、干燥物等)露出。印刷后的油墨能够形成例如条码、纹样、文字等的印字。作为用于印刷的油墨没有特别限制,能够使用公知的油墨,能够使用例如通过照射紫外线等固化的光固化性油墨等。
[粘接剂层2]
在本发明的电池用包装材料中,粘接剂层2是为了将基材层1和金属层3粘接而根据需要设置的层。
粘接剂层2由能够将基材层1和金属层3粘接的粘接剂形成。用于形成粘接剂层2的粘接剂可以为双液固化型粘接剂,或者也可以为单液固化型粘接剂。另外,对于用于形成粘接剂层2的粘接剂的粘接机制也没有特别限制,化学反应型、溶剂挥发型、热熔融型、热压型等任意方式均可。
作为能够用于形成粘接剂层2的粘接剂的树脂成分,具体而言可以列举: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、聚萘二甲酸丁二醇酯、聚间苯二甲酸乙二醇酯、聚碳酸酯、共聚聚酯等聚酯系树脂;聚醚系粘接剂;聚氨酯系粘接剂;环氧系树脂;酚醛树脂系树脂;尼龙6、尼龙66、尼龙12、共聚聚酰胺等聚酰胺系树脂;聚烯烃、酸改性聚烯烃、金属改性聚烯烃等聚烯烃系树脂;聚乙酸乙烯酯系树脂;纤维素系粘接剂;(甲基)丙烯酸系树脂;聚酰亚胺系树脂;尿素树脂、三聚氰胺树脂等氨基树脂;氯丁二烯橡胶、丁腈橡胶、苯乙烯-丁二烯橡胶等橡胶;有机硅系树脂;氟化乙烯丙烯共聚物等。这些粘接剂成分可以单独使用1种,或者也可以组合2种以上使用。对于2种以上的粘接剂成分的组合方式没有特别限制,例如,作为其粘接剂成分,可以列举聚酰胺和酸改性聚烯烃的混合树脂、聚酰胺和金属改性聚烯烃的混合树脂、聚酰胺和聚酯、聚酯和酸改性聚烯烃的混合树脂、聚酯和金属改性聚烯烃的混合树脂等。其中,从延展性、高湿度条件下的耐久性和应变抑制作用、热封时的热劣化抑制作用等优异、抑制基材层1与金属层3之间的脱层强度的降低而有效抑制脱层的发生这样的观点考虑,优选列举聚氨酯系双液固化型粘接剂;聚酰胺、聚酯、或它们和改性聚烯烃的掺混树脂。
另外,粘接剂层2也可以由不同的粘接剂成分而多层化。粘接剂层2由不同的粘接剂成分而多层化时,从提高基材层1与金属层3的脱层强度这样的观点考虑,优选作为配置于基材层1侧的粘接剂成分选择与基材层1的粘接性优异的树脂,作为配置于金属层3侧的粘接剂成分选择与金属层3的粘接性优异的粘接剂成分。粘接剂层2由不同的粘接剂成分而多层化时,具体而言,作为配置于金属层3侧的粘接剂成分优选列举酸改性聚烯烃、金属改性聚烯烃、聚酯和酸改性聚烯烃的混合树脂、包含共聚聚酯的树脂等。
对于粘接剂层2的厚度,例如可以列举2μm以上50μm以下左右、优选列举3μm以上25μm以下左右。
[金属层3]
在本发明的电池用包装材料中,金属层3是为了提高包装材料的强度、以及作为为了防止水蒸气、氧、光等侵入电池内部的阻隔层发挥功能的层。作为形成金属层3的金属,具体而言,可以列举铝(铝合金)、不锈钢、钛等金属箔。其中,适合使用铝或不锈钢。为了在制造包装材料时防止褶皱、针孔,在本发明中作为金属层3,优选使用软质铝,例如经退火处理后的铝(JIS A8021P-O)或(JIS A8079P-O) 等。
对于金属层3的厚度,例如可以列举10μm以上200μm以下左右、优选列举20μm以上100μm以下左右。
另外,为了粘接的稳定化、防止溶解和腐蚀等,优选金属层3的至少一侧的面、优选至少热熔接性树脂层4侧的面、进一步优选两面被施以化学法表面处理。其中,化学法表面处理是指在金属层3的表面形成耐酸性覆膜的处理。化学法表面处理例如可以列举:利用硝酸铬、氟化铬、硫酸铬、乙酸铬、草酸铬、磷酸二氢铬、铬酸乙酰乙酸酯、氯化铬、硫酸钾铬等铬酸化合物的铬酸铬酸盐处理;利用磷酸钠、磷酸钾、磷酸铵、多磷酸等磷酸化合物的磷酸铬酸盐处理;利用包括下述通式(1)~(4)所示的重复单元的氨基化酚聚合物的铬酸盐处理等。此外,在该氨基化酚聚合物中,下述通式(1)~(4)所示的重复单元既可以单独包含1种,也可以为2种以上的任意组合。
Figure GDA0002895418790000111
Figure GDA0002895418790000121
在通式(1)~(4)中,X表示氢原子、羟基、烷基、羟基烷基、烯丙基或苄基。另外,R1和R2相同或不同,表示羟基、烷基或羟基烷基。在通式(1)~(4)中,作为X、R1、R2所示的烷基,例如可以列举甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等碳原子数1~4的直链或支链状烷基。另外,作为X、R1、R2所示的羟基烷基,例如可以列举羟基甲基、1-羟基乙基、2-羟基乙基、1-羟基丙基、2-羟基丙基、3-羟基丙基、1-羟基丁基、2-羟基丁基、3-羟基丁基、4-羟基丁基等取代有1个羟基的碳原子数1~4的直链或支链状烷基。在通式(1)~(4)中,X优选为氢原子、羟基和羟基烷基中的任一种。包括通式(1)~(4)所示的重复单元的氨基化酚聚合物的数均分子量例如可以列举约500以上约100万以下、优选为约 1000以上约2万以下。
另外,作为对金属层3赋予耐蚀性的化学法表面处理方法,可以列举:通过涂敷在磷酸中分散氧化铝、氧化钛、氧化铈、氧化锡等金属氧化物、硫酸钡的微粒而得到的物质,并在150℃以上进行烧结处理,由此在金属层3的表面形成耐蚀处理层的方法。另外,在耐蚀处理层之上,也可以形成有将阳离子性聚合物用交联剂交联而得到的树脂层。其中,作为阳离子性聚合物,例如可以列举聚乙烯亚胺、包括聚乙烯亚胺和具有羧酸的聚合物的离子高分子配位化合物、在丙烯酸主骨架接枝伯胺而得到的伯胺接枝丙烯酸树脂、聚烯丙胺或其衍生物、氨基苯酚等。这些阳离子性聚合物可以单独使用1种,或者也可以组合2 种以上使用。另外,作为交联剂,例如可以列举具有选自异氰酸酯基、缩水甘油基、羧基和噁唑啉基中的至少1种官能团的化合物、硅烷偶联剂等。这些交联剂可以单独使用1种,或者也可以组合2种以上使用。
这些化学法表面处理可以单独进行1种化学法表面处理,也可以组合2种以上化学法表面处理来进行。另外,这些化学法表面处理可以单独使用1种化合物进行,或者也可以组合使用2种以上化合物来进行。其中,优选列举铬酸铬酸盐处理、进一步优选列举组合铬酸化合物、磷酸化合物和氨基化酚聚合物的铬酸盐处理。
对于化学法表面处理中在金属层3的表面形成的耐酸性覆膜的量,没有特别限制,如果例如是在组合铬酸化合物、磷酸化合物和氨基化酚聚合物进行铬酸盐处理的情况下,则对于金属层3的表面每1m2,优选以如下比例含有:铬酸化合物以铬换算计为约0.5mg以上约50mg 以下,优选为约1.0mg以上约40mg以下;磷化合物以磷换算计为约 0.5mg以上约50mg以下,优选为约1.0mg以上约40mg以下;以及氨基化酚聚合物为约1mg以上约200mg以下,优选为约5.0mg以上150mg 以下。
化学法表面处理可以通过如下方法进行:利用棒涂法、辊涂法、凹版涂敷法、浸渍法等将包含用于形成耐酸性覆膜的化合物的溶液涂布在金属层3的表面后,将金属层3的温度加热至70℃以上200℃以下左右,从而进行化学法表面处理。另外,对金属层3实施化学法表面处理之前,也可以预先对金属层3实施利用碱浸渍法、电解清洗法、酸清洗法、电解酸清洗法等进行的脱脂处理。通过如此进行脱脂处理,能够使金属层3的表面的化学法表面处理进一步高效进行。
[热熔接性树脂层4]
在本发明的电池用包装材料中,热熔接性树脂层4对应于最内层,为组装电池时热熔接性树脂层彼此热熔接而密封电池元件的层。
对于用于热熔接性树脂层4的树脂成分,只要能够热熔接,就没有特别限制,例如可以列举聚烯烃、环状聚烯烃、羧酸改性聚烯烃、羧酸改性环状聚烯烃。
作为上述聚烯烃,具体而言可以列举低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线状低密度聚乙烯等聚乙烯;均聚丙烯、聚丙烯的嵌段共聚物(例如,丙烯和乙烯的嵌段共聚物)、聚丙烯的无规共聚物(例如,丙烯和乙烯的无规共聚物)等聚丙烯;乙烯-丁烯-丙烯的三聚物等。这些聚烯烃中,优选列举聚乙烯和聚丙烯。
上述环状聚烯烃为烯烃和环状单体的共聚物,作为成为上述环状聚烯烃的构成单体的烯烃,例如可以列举乙烯、丙烯、4-甲基-1-戊烯、苯乙烯、丁二烯、异戊二烯等。另外,作为成为上述环状聚烯烃的构成单体的环状单体,例如可以列举降冰片烯等环状烯烃;具体而言可以列举环戊二烯、二环戊二烯、环己二烯、降冰片二烯等环状二烯等。这些聚烯烃中,优选列举环状烯烃、进一步优选列举降冰片烯。
上述羧酸改性聚烯烃是指,将上述聚烯烃利用羧酸通过嵌段聚合或接枝聚合而改性的聚合物。作为用于改性的羧酸,例如可以列举马来酸、丙烯酸、衣康酸、巴豆酸、马来酸酐、衣康酸酐等。
上述羧酸改性环状聚烯烃是指,通过将构成环状聚烯烃的单体的一部分替换成α,β-不饱和羧酸或其酸酐进行共聚、或者通过对于环状聚烯烃将α,β-不饱和羧酸或其酸酐进行嵌段聚合或接枝聚合而得到的聚合物。对于被羧酸改性的环状聚烯烃,与上述例子相同。另外,作为用于改性的羧酸,与用于上述酸改性环烯烃共聚物的改性的例子相同。
这些树脂成分中,优选列举羧酸改性聚烯烃;进一步优选列举羧酸改性聚丙烯。
热熔接性树脂层4既可以由1种树脂成分单独形成,或者也可以由组合2种以上树脂成分而得到的掺混聚合物形成。另外,热熔接性树脂层4既可以仅由1层形成,也可以由相同或不同的树脂成分形成为2层以上。
在本发明的电池用包装材料中,热熔接性树脂层4也可以包含滑剂。作为滑剂的种类没有特别限制,例如可以列举在上述的[基材层1] 的项目中例示的滑剂。在热熔接性树脂层4包含滑剂的情况下,其含量适宜选择即可,优选列举700ppm以上1200ppm以下左右、更优选列举800ppm以上1100ppm以下左右。此外,在本发明中,热熔接性树脂层4中的滑剂的含量,为存在于热熔接性树脂层4的内部的滑剂和存在于热熔接性树脂层4的表面的滑剂的总量。
另外,作为热熔接性树脂层4的厚度,能够适宜选择设定,可以列举10μm以上100μm以下左右、优选列举15μm以上50μm以下左右。
[粘接层5]
在本发明的电池用包装材料中,粘接层5是为了将金属层3与热熔接性树脂层4牢固粘接而在它们之间根据需要设置的层。
粘接层5由能够将金属层3与热熔接性树脂层4粘接的粘接剂形成。对于用于形成粘接层5的粘接剂,其粘接机制、粘接剂成分的种类等与上述粘接剂层2的情况相同。作为用于粘接层5的粘接剂成分,优选列举聚烯烃系树脂、进一步优选列举羧酸改性聚烯烃、特别优选列举羧酸改性聚丙烯。
对于粘接层5的厚度,例如可以列举2μm以上50μm以下,优选为15μm以上30μm以下。
3.电池用包装材料的制造方法
对于本发明的电池用包装材料的制造方法,只要能够得到叠层有规定组成的各层的叠层体,就没有特别限制,例如可以例示以下的方法。
首先,形成依次具有基材层1、粘接剂层2、金属层3的叠层体(以下,有时也标记为“叠层体A”)。具体而言,叠层体A的形成能够通过利用挤出法、凹版涂敷法、辊涂法等涂布方法将用于形成粘接剂层2 的粘接剂涂布在基材层1上或根据需要表面经化学法表面处理后的金属层3并进行干燥后,将该金属层3或基材层1叠层并使粘接剂层2 固化的干式叠压法来进行。
接下来,在叠层体A的金属层3上叠层热熔接性树脂层4。在金属层3上直接叠层热熔接性树脂层4时,利用凹版涂敷法、辊涂法等方法将构成热熔接性树脂层4的树脂成分涂布在叠层体A的金属层3 上即可。另外,在金属层3与热熔接性树脂层4之间设置粘接层5时,例如可以列举:(1)将粘接层5和热熔接性树脂层4通过共挤出叠层在叠层体A的金属层3上的方法(共挤出叠层法);(2)另外形成叠层有粘接层5和热熔接性树脂层4的叠层体,利用热层压法将其叠层在叠层体A的金属层3上的方法;(3)利用挤出法或以溶液涂敷的高温进行干燥进而进行烧结的方法等将用于形成粘接层5的粘接剂叠层在叠层体A的金属层3上,利用热层压法将预先成膜为片状的热熔接性树脂层4叠层在该粘接层5上的方法;(4)在叠层体A的金属层3与预先成膜为片状的热熔接性树脂层4之间,一边流入熔融的粘接层5、一边经由粘接层5将叠层体A和热熔接性树脂层4贴合的方法(夹层层压法)等。此外,为了使粘接剂层2与根据需要设置的粘接层5的粘接性变得牢固,也可以进一步实施热辊接触式、热风式、近红外线式或远红外线式等的加热处理。作为这种加热处理的条件,可以列举例如在150℃以上250℃以下进行1分钟以上5分钟以下。
在本发明的电池用包装材料中,构成叠层体的各层,根据需要,为了使成膜性、叠层化加工、最终制品2次加工(包装化、压花成型) 适应性等提高或稳定化,也可以实施电晕放电处理、喷砂处理、氧化处理、臭氧处理等表面活性化处理。
另外,在第一发明中,在电池用包装材料的表面印刷油墨时,作为印刷方法没有特别限制,在对成型后的电池用包装材料进行印刷的情况下,优选移印。利用本发明的制造方法得到的电池用包装材料由于基材层由包含亚乙基双硬脂酰胺的聚酰胺树脂形成,所以油墨不易被排斥,通过移印也能够合适地进行油墨的印刷。由此,能够在基材层1的表面的至少一部分合适地形成例如条码、纹样、文字等的印字。作为用于印刷的油墨如上所述。
另外,在第二发明中,在电池用包装材料的表面印刷油墨时,作为印刷方法没有特别限制,在对成型后的电池用包装材料进行印刷的情况下,优选移印。利用第二发明的制造方法得到的电池用包装材料由于基材层由包含亚乙基双油酰胺的聚酰胺树脂形成并且基材层中的亚乙基双油酰胺的含量为400ppm以下,所以油墨不易被排斥,通过移印也能够合适地进行油墨的印刷。由此,能够在基材层1的表面的至少一部分合适地形成例如条码、纹样、文字等的印字。作为用于印刷的油墨如上所述。
4.电池用包装材料的用途
本发明的电池用包装材料作为用于密封并收容正极、负极、电解质等的电池元件的包装材料使用。
具体而言,利用本发明的电池用包装材料,将至少具有正极、负极和电解质的电池元件在与上述正极和负极各自连接的金属端子向外侧突出的状态下、以能够在电池元件的边缘形成凸缘部(热熔接性树脂层彼此相接触的区域)的方式进行包覆,通过将上述凸缘部的热熔接性树脂层彼此热封来进行密封,从而提供使用了电池用包装材料的电池。此外,在使用本发明的电池用包装材料收容电池元件时,以本发明的电池用包装材料的密封部分成为内侧(与电池元件接触的面) 的方式使用。
本发明的电池中使用了上述本发明的电池用包装材料,因此,能够在成型电池用包装材料并封装电池元件后的电池的表面合适地印刷油墨。即,本发明的电池由于电池用包装材料的基材层由包含亚乙基双硬脂酰胺的聚酰胺树脂形成,所以通过通常油墨容易被排斥的移印,也能够合适地进行油墨的印刷,能够在电池的表面的至少一部分合适地形成例如条码、纹样、文字等的印字。
本发明的电池用包装材料可以用于一次电池、二次电池的任意种,优选为二次电池。对于本发明的电池用包装材料所适用的二次电池的种类,没有特别限制,例如可以列举锂离子电池、锂离子聚合物电池、铅蓄电池、镍-氢蓄电池、镍-镉蓄电池、镍-铁蓄电池、镍-锌蓄电池、氧化银-锌蓄电池、金属空气电池、多价阳离子电池、电容器 (condenser)、电容器(capacitor)等。这些二次电池中,作为本发明的电池用包装材料的合适的适用对象,可以列举锂离子电池和锂离子聚合物电池。
实施例
以下示出实施例和比较例详细说明本发明。但是,本发明并不限定于实施例。
实施例1A-5A和比较例1A
<电池用包装材料的制造>
对于依次具有基材层1/粘接剂层2/金属层3的叠层体,利用共挤出法将粘接层5和热熔接性树脂层4叠层,从而制造包括依次具有基材层1/粘接剂层2/金属层3/粘接层5/热熔接性树脂层4的叠层体的电池用包装材料。电池用包装材料的具体的制造条件如下所述。
在实施例1A-5A和比较例1A中,分别使用构成基材层1的双轴拉伸尼龙膜(厚度15μm)和构成金属层3的铝箔(铝合金)或不锈钢箔(分别为35μm)。构成基材层1的双轴拉伸尼龙膜中,分别配合表 1A所记载的含量的亚乙基双硬脂酰胺或亚乙基双油酰胺作为拨水剂。另外,关于铝箔和不锈钢箔,利用辊涂法将包括酚醛树脂、氟化铬化合物(三价)和磷酸的处理液以铬的涂布量成为10mg/m2(干燥重量) 的方式涂布在金属层的两面,在覆膜温度成为180℃以上的条件下进行 20秒烧结,从而进行化学法表面处理。
首先,制作依次具有基材层1/粘接剂层2/金属层3的叠层体。具体而言,在基材层1的一个面(电晕放电处理面),将包括聚酯系的主剂和异氰酸酯系固化剂的双液型聚氨酯粘接剂的粘接剂层2形成为 3μm,利用干式叠压法将其与金属层3叠层,从而制作依次具有基材层 1/粘接剂层2/金属层3的叠层体。
接下来,如表1A所示,使构成粘接层5的酸改性聚丙烯树脂〔用不饱和羧酸接枝改性而得到的不饱和羧酸接枝改性无规聚丙烯(酸改性PP)〕或酸改性聚乙烯树脂〔用不饱和羧酸接枝改性而得到的不饱和羧酸接枝改性无规聚乙烯(酸改性PE)〕、和构成热熔接性树脂层4的聚丙烯〔无规共聚物(PP)〕或聚乙烯(PE)熔融,在上述叠层体的金属层3的表面共挤出,从而叠层厚度20μm的粘接层5和厚度15μm的热熔接性树脂层4。如上操作,得到依次具有基材层1/粘接剂层2/ 金属层3/粘接层5/热熔接性树脂层4的叠层体。将所得到的叠层体暂时冷却后,加热至180℃,将该温度保持1分钟,实施热处理,由此得到电池用包装材料。
<通过模拟制造电池单元时的烧制工序的处理在基材层表面渗出的拨水剂的量的测定>
模仿制造电池单元时在100℃进行的烧制工序,将实施例1A-5A 和比较例1A所得到的电池用包装材料在100℃的恒温槽中静置24小时,利用30ml的甲醇清洗基材层表面(A4尺寸:210mm×297mm),利用吹氮使清洗后的甲醇挥发、干燥。接下来,向干燥固体成分添加1.5ml的甲醇使其再溶解,利用GC-MS(岛津制作所制的QP2010、离子化法:电子冲击离子化法(EI法)、检测器:四重极型检测器、色谱柱:Inert Cap 5MS)测定拨水剂(亚乙基双硬脂酰胺或亚乙基双油酰胺)的量。将结果示于表1A(表面渗出量)。此外,拨水剂的检测界限为30μg/A4尺寸。
<印字性评价>
对于进行了上述的模拟烧制工序的处理的实施例1A-5A和比较例1A的电池用包装材料,通过移印在基材层表面印刷图纹。移印机使用MISHIMA株式会社制SPACE PAD 6GX,油墨使用NAVITAS株式会社制的UV油墨PJU-A黑色。另外,使用AS ONE制的Handy UV LampSUV-4以紫外线波长:254nm从10cm的距离照射30秒UV,使油墨固化。根据以下的基准评价印字性。此外,印字适应性测定在 24℃、相对湿度50%的环境下进行。将结果示于表1A。
5:完全没有印字的漏印
4:印字的漏印为2.5%以下
3:印字的漏印超过2.5%且为5.0%以下
2:印字的漏印超过5.0%且为10%以下
1:印字的漏印超过10%
<浸润性评价>
对于进行了上述的模拟烧制工序的处理的实施例1A-5A和比较例1的电池用包装材料,以印字正确合适的比较验证为目的,实施利用符合JIS标准的湿润试剂的电池用包装材料外包装材料的基材面的达因值判定。试验方法按照“JIS K6768塑料-膜和片-湿润张力试验法”。使用NACALAI TESQUE公司制的湿润张力试验用混合液,将含于球状的脱脂绵的试剂在电池用包装材料外包装材料的基材面线状涂布5cm左右,2秒后判定液膜是否破裂,将没有破裂的达因值作为该基材的浸润性。此外,湿润张力的测定在24℃、相对湿度50%的环境下进行。将结果示于表1A。
[表1A]
Figure GDA0002895418790000201
表1A中,EBS是指亚乙基双硬脂酰胺,EBO是指亚乙基双油酰胺。
如表1A所示,在形成基材层的尼龙中使用亚乙基双硬脂酰胺作为拨水剂的实施例1A-5A中,拨水剂的表面渗出被抑制,通过移印的油墨的印刷特性优异。特别是,实施例1A-2A非常优异。另一方面,在形成基材层的尼龙中使用亚乙基双油酰胺作为拨水剂的比较例1A 中,拨水剂大量渗出,通过移印的油墨的印刷特性差。另外,任一电池用包装材料的成型性均为良好。
实施例1B-5B和比较例1B
<电池用包装材料的制造>
对于依次具有基材层1/粘接剂层2/金属层3的叠层体,利用共挤出法将粘接层5和热熔接树脂层4叠层,从而制造包括依次具有基材层1/粘接剂层2/金属层3/粘接层5/热熔接树脂层4的叠层体的电池用包装材料。电池用包装材料的具体的制造条件如下所示。
在实施例1B-5B和比较例1B中,分别使用构成基材层1的双轴拉伸尼龙膜(厚度15μm)和构成金属层3的铝箔(铝合金)或不锈钢箔(分别35μm)。构成基材层1的双轴拉伸尼龙膜中,分别配合有表 1B所记载的含量的亚乙基双油酰胺作为拨水剂。另外,关于铝箔和不锈钢箔,利用辊涂法将包括酚醛树脂、氟化铬化合物(三价)和磷酸的处理液以铬的涂布量成为10mg/m2(干燥重量)的方式涂布在金属层的两面,在覆膜温度成为180℃以上的条件下烧结20秒,从而进行化学法表面处理。
首先,制作依次具有基材层1/粘接剂层2/金属层3的叠层体。具体而言,在基材层1的一个面(电晕放电处理面),将包括聚酯系的主剂和异氰酸酯系固化剂的双液型聚氨酯粘接剂的粘接剂层2形成为3μm,利用干式层压法将其与金属层3叠层,从而制作依次具有基材层1/粘接剂层2/金属层3的叠层体。
接下来,如表1B所示,使构成粘接层5的酸改性聚丙烯树脂〔用不饱和羧酸接枝改性而得到的不饱和羧酸接枝改性无规聚丙烯(酸改性PP)〕或酸改性聚乙烯树脂〔用不饱和羧酸接枝改性而得到的不饱和羧酸接枝改性无规聚乙烯(酸改性PE)〕、和构成热熔接树脂层4的聚丙烯〔无规共聚物(PP)〕或聚乙烯(PE)熔融,在上述叠层体的金属层3的表面共挤出,叠层厚度20μm的粘接层5和厚度15μm的热熔接树脂层4。如上操作,得到依次具有基材层1/粘接剂层2/金属层3/ 粘接层5/热熔接树脂层4的叠层体。将所得到的叠层体暂时冷却后,加热至180℃,将该温度保持1分钟,实施热处理,由此得到电池用包装材料。
<通过模拟制造电池单元时的烧制工序的处理在基材层表面渗出的拨水剂的量的测定>
模仿制造电池单元时在100℃进行的烧制工序,将实施例1B-5B 和比较例1B所得到的电池用包装材料在100℃的恒温槽中静置24小时,利用30ml的甲醇清洗基材层表面(A4尺寸:210mm×297mm),利用吹氮使清洗后的甲醇挥发、干燥。接下来,向干燥固体成分添加1.5ml的甲醇使其再溶解,利用(GC-MS岛津制作所制的QP2010、离子化法:电子冲击离子化法(EI法)、检测器:四重极型检测器、色谱柱:Inert Cap 5MS)测定拨水剂(亚乙基双油酰胺)的量。其结果,在实施例1B-5B中,渗出的拨水剂的量均被抑制在380μg/A4尺寸以下。另一方面,比较例1B中,远远超过380μg/A4尺寸。
<印字性评价>
对于进行了上述的模拟烧制工序的处理的实施例1B-5B和比较例1B的电池用包装材料,通过移印在基材层表面印刷图纹。移印机使用MISHIMA株式会社制SPACE PAD 6GX,油墨使用NAVITAS株式会社制的UV油墨PJU-A黑色。另外,使用AS ONE制的Handy UV LampSUV-4以紫外线波长:254nm从10cm的距离照射30秒UV,使油墨固化。根据以下的基准评价印字性。此外,印字适应性测定在 24℃、相对湿度50%的环境下进行。将结果示于表1B。
5:完全没有印字的漏印
4:印字的漏印为2.5%以下
3:印字的漏印超过2.5%且为5.0%以下
2:印字的漏印超过5.0%且为10%以下
1:印字的漏印超过10%
<浸润性评价>
对于进行了上述的模拟烧制工序的处理的实施例1B-5B和比较例1B的电池用包装材料,以印字正确合适的比较验证为目的,实施利用符合JIS标准的湿润试剂的电池用包装材料外包装材料的基材面的达因值判定。试验方法按照“JIS K6768塑料-膜和片-湿润张力试验法”。使用NACALAI TESQUE公司制的湿润张力试验用混合液,将含于球状的脱脂绵的试剂在电池用包装材料外包装材料的基材面线状涂布5cm左右,2秒后判定液膜是否破裂,将没有破裂的达因值作为该基材的浸润性。此外,湿润张力的测定在24℃、相对湿度50%的环境下进行。将结果示于表1B。
[表1B]
Figure GDA0002895418790000221
表1B中,EBO是指亚乙基双油酰胺。
如表1B所示,在形成基材层的尼龙中包含400ppm以下的亚乙基双油酰胺作为拨水剂的实施例1B-5B中,通过移印的油墨的印刷特性优异。特别是,实施例1B-2B非常优异。另一方面,在形成基材层的尼龙中包含超过400ppm的亚乙基双油酰胺作为拨水剂的比较例1B 中,通过移印的油墨的印刷特性差。另外,任一电池用包装材料的成型性均为良好。
符号说明
1 基材层
2 粘接剂层
3 金属层
4 热熔接性树脂层
5 粘接层

Claims (9)

1.一种电池用包装材料,其特征在于:
该电池用包装材料包括至少依次具有基材层、金属层和热熔接性树脂层的叠层体,
所述基材层由包含亚乙基双硬脂酰胺的聚酰胺树脂形成,
所述聚酰胺树脂中的亚乙基双硬脂酰胺的含量为200ppm以上400ppm以下,
所述基材层表面的湿润张力为32mN/m以上45mN/m以下,
将所述电池用包装材料在100℃的恒温槽中静置24小时后,在210mm×297mm的范围的所述基材层表面存在的亚乙基双硬脂酰胺的量为30μg以下。
2.一种电池用包装材料,其特征在于:
该电池用包装材料包括至少依次具有基材层、金属层和密封层的叠层体,
所述基材层由包含亚乙基双油酰胺的聚酰胺树脂形成,
所述基材层中的亚乙基双油酰胺的含量为400ppm以下,
所述基材层表面的湿润张力为32mN/m以上45mN/m以下,
将所述电池用包装材料在100℃的恒温槽中静置24小时后,在210mm×297mm的范围的所述基材层表面存在的亚乙基双油酰胺为380μg以下。
3.如权利要求1或2所述的电池用包装材料,其特征在于:
所述基材层表面的至少一部分为油墨接受面。
4.如权利要求1或2所述的电池用包装材料,其特征在于:
所述基材层表面的至少一部分具有由油墨构成的印刷层。
5.如权利要求1或2所述的电池用包装材料,其特征在于:
所述聚酰胺树脂为双轴拉伸尼龙。
6.如权利要求1或2所述的电池用包装材料,其特征在于:
在所述基材层与所述金属层之间具有粘接层。
7.如权利要求1或2所述的电池用包装材料,其特征在于:
在所述金属层与所述热熔接性树脂层之间具有粘接层。
8.如权利要求1或2所述的电池用包装材料,其特征在于:
所述金属层为铝箔或不锈钢箔。
9.一种电池,其特征在于:
在由权利要求1~8中任一项所述的电池用包装材料形成的包装体中收容有至少具有正极、负极和电解质的电池元件。
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