CN113745718A - 蓄电设备外包装材料用层叠体 - Google Patents
蓄电设备外包装材料用层叠体 Download PDFInfo
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- CN113745718A CN113745718A CN202110570681.5A CN202110570681A CN113745718A CN 113745718 A CN113745718 A CN 113745718A CN 202110570681 A CN202110570681 A CN 202110570681A CN 113745718 A CN113745718 A CN 113745718A
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- layer
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Abstract
本发明涉及蓄电设备外包装材料用层叠体,提供能够获得充分的成型性的蓄电设备外包装材料用层叠体。本发明的蓄电设备外包装材料用层叠体(1)的特征在于,具备:金属制的阻隔层(3);层叠于阻隔层(3)的外侧面的由耐热性树脂形成的基材层(2);和层叠于阻隔层(3)的内侧面的由热熔接性树脂形成的密封层(4),基材层(2)由作为外侧层的聚酯膜层(21)和作为内侧层的聚酰胺膜层(22)构成,就聚酯膜层(21)而言,MD的拉伸断裂强度与TD的拉伸断裂强度之和为500MPa~600MPa,且TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.8~1.1,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为110%~200%。其中,MD:机械流动方向,TD:与MD正交的方向。
Description
技术领域
本发明涉及由树脂层层叠于金属层而成的层合材料构成的蓄电设备外包装材料用层叠体。
背景技术
以往,收纳电池的电池用包装材料大多使用加工为圆筒型类型、方型类型的金属制材料。另外,近年来,作为多样化的能量供给源、能量贮存的一种,电池被用于多种场所,也要求轻量化、省空间化。
作为其对策之一,在金属箔的两面层叠有树脂膜的金属-树脂层合片(以下称为层合体)作为电池包装材料来使用,通过以片的状态使用、或进行与收纳空间的形状匹配的深拉深成型,从而能够在有限的空间内提供最大容量的电池。
由于使用该层合体的电池的耐腐蚀性、密封性优异,因此,也开展了例如电动汽车(EV)、插电式混合动力电动汽车(PHEV)这类汽车驱动用大型电池的包装材料的开发,作为也能够耐受严酷环境下的使用的大型电池用包装材料的构成例,提出了使配置于金属箔的外侧的基材层多层化的构成(参见下述专利文献1~3)。
需要说明的是,在本发明中,外侧表示电池包装材料中收纳空间的相反侧,内侧表示电池包装材料中的收纳空间侧。
在专利文献1中提出了,通过使基材层成为PET膜/ONY膜的2层构成,从而具有刺穿强度、抗拉强度、弯折性、耐热性及耐化学药品性的电池用包装材料。
在专利文献2中也提出了,通过使基材层成为PET膜/ONY膜的2层构成,从而具有耐热性、耐水性及耐化学药品性(防止由电解液引起的ONY膜的白化)的电池包装材料。
另外,在专利文献3中提出了,通过使基材层成为PET膜/ONY膜的2层构成并进一步规定PET膜的拉伸断裂强度及拉伸断裂伸长率的范围,从而具有考虑汽车行驶时的振动的耐振动性和成型性的车载电池用包装材料。
现有技术文献
专利文献
专利文献1:日本专利4559548号
专利文献2:日本专利5830585号
专利文献3:日本专利5453680号
发明内容
发明要解决的课题
但是,专利文献1及2中关于基材层的PET膜及ONY膜的具体物性并没有记载,并且由于使基材层多层化(2层构成),因此存在出现下述情况的问题:无法满足为了提高电池容量所要求的更为严格的成型性(更深的成型高度)。
另外,专利文献3中没有关于ONY膜的物性的具体记载,在4层构成包装材料(PET/ONY/AL/密封层)中也存在成型形状尖锐且成型高度高的情况下无法获得充分的成型性的问题。
本发明的优选实施方式是鉴于相关技术中的上述及/或其他问题而做出的。本发明的优选实施方式能够显著改善现有的方法及/或装置。
本发明是鉴于以上技术背景而做出的,目的在于提供在设想为车载电池用包装材料的4层构成电池包装材料中,即使在成型形状尖锐且成型高度高的情况下也能够获得充分的成型性的蓄电设备外包装材料用层叠体。
本发明的其他目的及优点由以下优选的实施方式获知。
用于解决课题的手段
为了实现前述目的,本发明提供以下的手段。
[1]蓄电设备外包装材料用层叠体,其具备:
金属制的阻隔层;
层叠于上述阻隔层的外侧面的由耐热性树脂形成的基材层;和
层叠于上述阻隔层的内侧面的由热熔接性树脂形成的密封层,
所述蓄电设备外包装材料用层叠体的特征在于,
上述基材层由作为外侧层的聚酯膜层和作为内侧层的聚酰胺膜层构成,
就上述聚酯膜层而言,MD的拉伸断裂强度与TD的拉伸断裂强度之和为500MPa~600MPa,且TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.8~1.1,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为110%~200%。
其中,MD:机械流动方向,TD:与MD正交的方向
[2]根据上述1所述的蓄电设备外包装材料用层叠体,其中,上述聚酰胺膜层的MD的热水收缩率及TD的热水收缩率为2.5%~6%。
[3]根据上述1或2所述的蓄电设备外包装材料用层叠体,其中,上述聚酰胺膜层MD的拉伸断裂强度与TD的拉伸断裂强度之和为550MPa~700MPa,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为90%~200%。
[4]根据上述1~3所述的蓄电设备外包装材料用层叠体,其中,在上述聚酯膜层与上述聚酰胺膜层之间层叠有基材间粘接剂层,
上述基材间粘接剂层的杨氏模量为70MPa~400MPa、断裂强度为20MPa~70MPa、断裂伸长率为50%~400%。
[5]根据上述4所述的蓄电设备外包装材料用层叠体,其中,上述基材间粘接剂层由下述粘接剂的固化物形成,所述粘接剂以从聚氨酯系树脂、聚酯聚氨酯系树脂、聚醚聚氨酯系树脂、聚醚系树脂、聚酯系树脂中选择的1种或2种以上的树脂为主剂,且以多官能异氰酸酯为固化剂。
发明效果
根据[1]的发明,基材层由作为外侧层的聚酯膜层和作为内侧层的聚酰胺膜层构成,就聚酯膜层而言,MD的拉伸断裂强度与TD的拉伸断裂强度之和为500MPa~600MPa,且TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.8~1.1,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为110%~200%,从而聚酯膜层难以破裂,因此,即使在成型形状尖锐且成型高度高的情况下也能够获得充分的成型性(能够进行更深的拉深成型)。
另外,通过在基材层的外侧层使用聚酯膜层,从而也能够提高耐化学药品性、耐冲击性。
根据[2]的发明,通过将MD的热水收缩率及TD的热水收缩率设为2.5%~6%,从而聚酰胺膜层的刺穿强度变高,因此能够更加难以破裂。
另外,在由高强度的聚酯膜层与高强度且不易破裂的聚酰胺膜层形成的基材层中,通过将聚酰胺膜层的MD的热水收缩率及TD的热水收缩率设为2.5%~6%,从而能够避免在相对于为了增大能量密度所要求的角部R小且深成型的成型条件、模具形状而被实施最严格的成型加工的冲头的肩R附近的成型加工部处产生成型裂纹。
根据[3]的发明,聚酰胺膜层的MD的拉伸断裂强度与TD的拉伸断裂强度之和为550MPa~700MPa,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为90%~200%,从而成型时聚酰胺膜层难以破裂,能够进一步提高成型性。
根据[4]的发明,在聚酯膜层与聚酰胺膜层之间层叠有基材间粘接剂层,基材间粘接剂层的杨氏模量为70MPa~400MPa、断裂强度为20MPa~70MPa、断裂伸长率为50%~400%,从而在成型加工时,能够追随聚酰胺膜层的变形行为,不易在聚酰胺膜层与基材间粘接剂层之间发生剥离,能够将聚酰胺膜层的特征(特别是伸长率、不易破裂性)向阻隔层传递(累加)。
根据[5]的发明,基材间粘接剂层由下述粘接剂的固化物形成,所述粘接剂以从聚氨酯系树脂、聚酯聚氨酯系树脂、聚醚聚氨酯系树脂、聚醚系树脂、聚酯系树脂中选择的1种或2种以上的树脂为主剂,且以多官能异氰酸酯为固化剂,从而能够更进一步抑制脱层等的发生。
附图说明
图1是示出本实施方式的蓄电设备外包装材料用层叠体的剖视图。
图2是示出使用本实施方式的蓄电设备外包装材料用层叠体形成的蓄电设备的一个实施方式的剖视图。
图3是以热封前的分离的状态示出构成图2的蓄电设备的外包装材料(平面状的外包装材料)、蓄电设备主体部及外包装壳(成型为立体形状的成型体)的立体图。
附图标记说明
1:蓄电设备外包装材料用层叠体
2:基材层
21:聚酯膜层
22:聚酰胺膜层
3:阻隔层
4:密封层
5:基材间粘接剂层
具体实施方式
本发明的蓄电设备外包装材料用层叠体构成收纳蓄电设备的外包装材料。
本实施方式的蓄电设备外包装材料用层叠体1如图1所示由下述构成形成,所述构成为在阻隔层3的内侧面介由第1粘接剂层7层叠有密封层4,且在阻隔层3的外侧面介由第2粘接剂层6层叠有基材层2。
本发明的基材层由耐热性树脂形成,为层叠在后述的阻隔层的外侧面的层。需要说明的是,形成基材层的耐热性树脂为熔点比形成后述的密封层的热熔接性树脂高10℃以上的树脂,更加优选高20℃以上的树脂。
本实施方式的基材层2由2层构造形成,由聚酯膜层21和聚酰胺膜层22构成。
本发明的聚酯膜层构成基材层的外侧层。
本实施方式的聚酯膜层21的MD及TD的拉伸断裂强度、MD及TD的拉伸断裂伸长率具有以下特征。需要说明的是,MD是指“机械流动方向”,TD是指“与MD(机械流动方向)正交的方向”。
在本实施方式的聚酯膜层21中,MD的拉伸断裂强度与TD的拉伸断裂强度之和为500MPa~600MPa,其中,优选为520MPa~580MPa。
这是由于,若MD的拉伸断裂强度与TD的拉伸断裂强度之和低于500MPa,则在被施加严格成型加工的部位(冲头的肩R附近)发生断裂,另一方面,若超过600MPa,则聚酯膜层的拉伸断裂强度变得过高,无法成型为规定形状。
另外,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.8~1.1,其中优选为0.85~0.95。
这是由于,若TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值低于0.8,则TD的拉伸断裂强度弱,因此会在被施加严格成型加工的部位发生断裂,另一方面,若超过1.1,则需要在聚酯膜层成膜时提高沿TD的拉伸,因此难以成膜且在成本上也不利。
此外,在本实施方式的聚酯膜层21中,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率均为110%~200%。
这是由于,若MD的拉伸断裂伸长率及TD的拉伸断裂伸长率低于110%,则会在被施加严格成型加工的部位(冲头的肩R附近)发生断裂,另一方面,即使超过200%,针对成型加工的效果也没有大的差异。
另外,作为本实施方式的聚酯膜层21,能够使用聚对苯二甲酸乙二醇酯(PET)膜、聚对苯二甲酸丁二醇酯(PBT)膜、聚萘二甲酸乙二醇酯(PEN)膜等,其中优选使用这些材料的拉伸膜。
另外,优选本实施方式的聚酯膜层21的厚度为6μm~50μm,其中更加优选12μm~25μm。
就本实施方式的聚酯膜层21而言,为了提高与后述的基材间粘接剂层5的密合性,优选在聚酯膜层21的至少单面层叠易粘接层、进行电晕处理等。通过层叠易粘接层,从而能够谋求优异的密合性、粘接强度的提高。层叠易粘接层的方法没有特别限定,优选通过在线涂布进行层叠。这是由于,能够在聚酯膜层21表面均匀地形成易粘接层。
另外,作为易粘接层,例如能够使用丙烯酸系树脂、聚氨酯系树脂、聚酯系树脂、烯烃系树脂、氟系树脂、乙烯基系树脂、氯系树脂、苯乙烯系树脂、各种接枝系树脂、环氧系树脂、有机硅系树脂等,也可以使用这些树脂的混合物。其中,从密合性的观点出发,优选使用丙烯酸系树脂或聚酯系树脂。
本发明的聚酰胺膜层构成基材层的内侧层。
在本实施方式的聚酰胺膜层22中,100℃、30分钟的条件下的MD的热水收缩率及TD的热水收缩率均为2.5%~6%,其中优选3%~5%。
这是由于,若MD的热水收缩率及TD的热水收缩率低于2.5%,则会在被施加严格成型加工的部位(冲头的肩R附近)发生断裂,另一方面,若超过6%,则在成型加工后或热封后,容易发生凸缘部的回弹(变形)。
通过像这样将聚酰胺膜层22的MD的热水收缩率及TD的热水收缩率设为2.5%~6%,从而聚酰胺膜层22的刺穿强度变高,因此能够更加难以破裂。
另外,在由高强度的聚酯膜层21与高强度且不易破裂的聚酰胺膜层22形成的基材层2中,通过将聚酰胺膜层22的MD的热水收缩率及TD的热水收缩率设为2.5%~6%,从而能够避免相对于为了增大能量密度所要求的角部R小且深成型的成型条件、模具形状而在被实施最严格的成型加工的冲头的肩R附近的成型加工部处产生成型裂纹。
另外,在本实施方式的聚酰胺膜层22中,MD的拉伸断裂强度与TD的拉伸断裂强度之和为550MPa~700MPa,其中优选550MPa~650MPa。
这是由于,若MD的拉伸断裂强度与TD的拉伸断裂强度之和低于550MPa,则在被施加严格成型加工的部位(冲头的肩R附近)会发生断裂,另一方面,若超过700MPa,则聚酰胺膜层的拉伸断裂强度变得过高,无法成型为规定的形状。
另外,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率均为90%~200%。
若MD的拉伸断裂伸长率及TD的拉伸断裂伸长率低于90%,则会在被施加严格成型加工的部位(冲头的肩R附近)发生断裂,另一方面,即使超过200%,针对成型加工的效果也没有大的差异。
如此使得聚酰胺膜层22的MD的拉伸断裂强度与TD的拉伸断裂强度之和为550MPa~700MPa,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为90%~200%,从而成型时聚酰胺膜层22难以破裂,能够进一步提高成型性。
作为本实施方式的聚酰胺膜层22,能够使用6尼龙膜、6,6尼龙膜等,其中优选使用这些材料的拉伸膜。
另外,优选本实施方式的聚酰胺膜层22的厚度为10μm~50μm,其中更加优选15μm~25μm。
优选对本实施方式的聚酰胺膜层22实施电晕处理、层叠易粘接层。特别是,通过将易粘接层设置在阻隔层3侧,能够谋求与阻隔层3的优异的密合性、粘接强度的提高。易粘接层的形成方法没有特别限定,例如,能够通过在聚酰胺膜层22的表面涂布选自由环氧树脂、聚氨酯树脂、丙烯酸酯树脂、甲基丙烯酸酯树脂及聚乙烯酰亚胺树脂组成的组中的1种或2种以上的树脂的水性乳液(水系乳液)并使其干燥来形成易粘接层。作为上述涂布方法并无特别限定,例如,能够举出喷涂法、凹版辊涂法、逆向辊涂布法、唇式涂布法等。需要说明的是,更加优选在对层叠易粘接层进行前预先对膜表面进行电晕处理等来预先提高润湿性。
其中,特别优选上述易粘接层含有聚氨酯树脂及环氧树脂而成的构成或含有(甲基)丙烯酸酯树脂及环氧树脂而成的构成。在该情况下,能够更进一步充分地抑制在聚酰胺膜层22与阻隔层3之间发生脱层。
在本实施方式中,如图1所示,在聚酯膜层21与聚酰胺膜层22之间层叠有基材间粘接剂层5。
本发明的基材间粘接剂层为承担聚酯膜层和聚酰胺膜层的接合的层。
在本实施方式的基材间粘接剂层5中,杨氏模量为70MPa~400MPa,其中优选为100MPa~300MPa。
这是由于,若杨氏模量小于70MPa,则成型加工时粘接剂涂膜断裂,该断裂的部位成为粘接缺陷而发生成型断裂,另一方面,若超过400MPa,则粘接剂涂膜变得过硬而粘接力下降,因此容易在成型加工时发生与拉伸膜(聚酰胺膜层)的剥离。
另外,基材间粘接剂层5的断裂强度为20MPa~70MPa,其中优选为30~50MPa。
若断裂强度低于20MPa,则成型加工时粘接剂涂膜断裂,该断裂的部位成为粘接缺陷而发生成型断裂,另一方面,若超过70MPa,则粘接剂涂膜变得过硬而粘接力下降,因此容易在成型加工时发生与拉伸膜(聚酰胺膜层)的剥离。
此外,基材间粘接剂层5的断裂伸长率为50%~400%,其中优选100%~300%。
这是由于,若断裂伸长率低于50%,则成型加工时粘接剂涂膜断裂,该断裂的部位成为粘接缺陷而发生成型断裂,另一方面,即使超过400%,针对成型加工的效果也没有大的差异。
上述杨氏模量、断裂强度及断裂伸长率的机械特性为按照JIS K7161-2(2014)对粘接剂的块状(固化物)试验片(2液固化型粘接剂的试验片为按照JIS K6878-1(2011)制得的0.5mm厚的试验片)测定得到的值。
像这样,在本实施方式中,在聚酯膜层21与聚酰胺膜层22之间层叠有基材间粘接剂层5,基材间粘接剂层5的杨氏模量为70MPa~400MPa、断裂强度为20MPa~70MPa、断裂伸长率为50%~400%,从而在成型加工时,能够追随聚酰胺膜层22的变形行为而不易在聚酰胺膜层22与基材间粘接剂层5之间发生剥离,能够将聚酰胺膜层22的特征(特别是伸长率、不易破裂性)向阻隔层3传递(累加)。
另外,作为本实施方式的基材间粘接剂层5,优选使用下述粘接剂的固化物,所述粘接剂以从聚氨酯系树脂、聚酯聚氨酯系树脂、聚醚聚氨酯系树脂、聚醚系树脂、聚酯系树脂中选择的1种或2种以上的树脂为主剂,且以多官能异氰酸酯为固化剂,也可以使用环氧系粘接剂、丙烯酸系粘接剂、聚酯酰胺系粘接剂或聚酰胺系粘接剂。
另外,优选基材间粘接剂层5的厚度为1μm~5μm。
另外,作为多官能异氰酸酯,能够举出芳香族多官能异氰酸酯、具有芳香环的脂肪族多官能异氰酸酯、脂肪族多官能异氰酸酯。
作为芳香族多官能异氰酸酯,并无特别限定,例如,能够使用甲苯二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)、三苯甲烷三异氰酸酯等。
作为具有芳香环的脂肪族多官能异氰酸酯,并无特别限定,例如,能够使用苯二亚甲基二异氰酸酯(XDI)、四甲基苯二亚甲基二异氰酸酯(TMXDI)等。
作为脂肪族多官能异氰酸酯,并无特别限定,例如,能够使用六亚甲基二异氰酸酯(HDI)。
像这样,基材间粘接剂层5由下述粘接剂的固化物形成从而能够更进一步抑制脱层等的发生,所述粘接剂以从聚氨酯系树脂、聚酯聚氨酯系树脂、聚醚聚氨酯系树脂、聚醚系树脂、聚酯系树脂中选择的1种或2种以上的树脂为主剂,且以多官能异氰酸酯为固化剂。
本发明的阻隔层承担对蓄电设备外包装材料用层叠体赋予阻止氧气、水分侵入的气体阻隔性的作用。
作为本实施方式的阻隔层3,能够使用铝箔、铜箔、不锈钢箔、镍箔、钛箔等,特别优选使用JIS H4160规定的1000系、8000系的铝箔,优选厚度为20μm~100μm。
另外,优选预先在阻隔层3的至少内侧面、即后述的密封层侧的面设置例如磷酸铬酸盐处理、锆系化学转化处理等化学转化处理层。通过实施这样的化学转化处理,从而能够充分地防止由内容物(电池的电解液等)引起的阻隔层3表面的腐蚀。例如通过以下处理来对阻隔层3实施化学转化处理。即,对例如进行脱脂处理后的金属箔的表面涂布下述水溶液后进行干燥,从而形成化学转化皮膜:
1)由磷酸、铬酸及氟化物的金属盐的混合物形成的水溶液
2)由磷酸、铬酸、氟化物金属盐及非金属盐的混合物形成的水溶液
3)由丙烯酸系树脂及/或酚系树脂、磷酸、铬酸与氟化物金属盐的混合物形成的水溶液
4)由丙烯酸系树脂及/或酚系树脂、磷酸盐或磷酸化合物、铬酸盐或铬酸化合物与氟化物金属盐的混合物形成的水溶液
在本实施方式中,在阻隔层3的外侧面层叠有第2粘接剂层6。
本实施方式的第2粘接剂层6为承担阻隔层3与聚酰胺膜层22的接合的层。
作为本实施方式的第2粘接剂层6,能够使用聚氨酯系粘接剂、环氧系粘接剂、丙烯酸系粘接剂,优选厚度为1μm~5μm。
在本实施方式中,在阻隔层3的内侧面介由第1粘接剂层7而层叠有密封层4。
本发明的密封层由热熔接性树脂形成,且构成蓄电设备外包装材料用层叠体的最内层。
作为本实施方式的密封层4,能够使用聚烯烃系膜(未拉伸聚丙烯、直链状低密度聚乙烯等),优选厚度为20μm~100μm。
本实施方式的第1粘接剂层7为承担阻隔层3与密封层4的接合的层。
作为本实施方式的第1粘接剂层7,能够使用烯烃系粘接剂、环氧系粘接剂,特别优选使用经酸改性的烯烃系粘接剂。
如上,在本实施方式中,基材层2由作为外侧层的聚酯膜层21和作为内侧层的聚酰胺膜层22构成,就聚酯膜层21而言,MD的拉伸断裂强度与TD的拉伸断裂强度之和为500MPa~600MPa,且TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.8~1.1,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为110%~200%,从而聚酯膜层21难以破裂,因此即使在成型形状尖锐且成型高度高的情况下也能够获得充分的成型性(能够进行更深的拉深成型)。
另外,通过在基材层2的外侧层使用聚酯膜层21,从而还能够提高耐化学药品性、耐冲击性。
图2是示出使用本实施方式的蓄电设备外包装材料用层叠体1形成的蓄电设备70的一个实施方式的剖视图,图3是以热封前的分离状态示出构成图2的蓄电设备70的外包装材料61(平面状的外包装材料)、蓄电设备主体部71及外包装壳62(成型为立体形状的成型体)的立体图。
由本实施方式的蓄电设备外包装材料用层叠体1构成的蓄电设备外包装材料61作为例如锂离子2次电池用外包装材料使用。该外包装材料61也可以无需实施成型而直接作为外包装材料使用,例如也可以进行深拉深成型、鼓凸成型等成型而用作外包装壳62。
在本实施方式中,如图2及3所示,由平面状的外包装材料61和对外包装材料61进行成型而得到的外包装壳62构成外包装构件60。
在外包装壳62的收容凹部内收容大致长方体形状的蓄电设备主体部71(电化学元件等),在该蓄电设备主体部71上方将外包装材料61不进行成型而以密封层4侧为内侧(下侧)的方式配置,外包装材料61中的密封层4的周缘部与外包装壳62的凸缘部63中的密封层4使用热封部81通过热熔接而接合并封固,由此构成蓄电设备70。
需要说明的是,外包装壳62中的收容凹部内表面为密封层4,收容凹部外表面为基材层2。
另外,蓄电设备主体部71并无特别限定,例如能够举出电池主体部、电容器(capicitor)主体部、冷凝器(condenser)主体部等。
在上述实施方式中,外包装构件60为由平面状的外包装材料61和对外包装材料61进行成型而得到的外包装壳62形成的构成,但并非特别限定于这样的组合,例如,外包装构件60也可以是由一对平面状的外包装材料61形成的构成,或是由一对外包装壳62形成的构成。
实施例
接下来,对本发明的具体实施例进行说明,但本发明并不特别限定于这些实施例。
<实施例1>
在厚度为40μm的铝箔(阻隔层3)的两面涂布由聚丙烯酸、三价铬化合物、水、醇形成的化学转化处理液并于180℃进行干燥,进行化学转化处理以使得铬附着量成为10mg/m2。需要说明的是,作为铝箔,使用A8021-O材料(JIS H4160(2006))。
进而,在该铝箔的一个面上通过干式层合涂覆厚度为4μm的2液固化型的聚氨酯系粘接剂(第2粘接剂层6),并贴合厚度为15μm的拉伸尼龙膜(聚酰胺膜层22)。
进而,在该拉伸尼龙膜的面上通过干式层合涂覆厚度为4μm的聚酯聚氨酯系粘接剂(基材间粘接剂层5),并贴合厚度为12μm的拉伸聚对苯二甲酸乙二醇酯(PET)膜(聚酯膜层21)。
进而,于60℃进行7天的加热熟化处理。
接下来,在铝箔的另一面涂覆厚度为3μm的烯烃系粘接剂(第1粘接剂层7),并贴合厚度为80μm的无拉伸聚丙烯(CPP)膜(密封层4)。
进而,于40℃进行10天的加热熟化处理,制备实施例1的蓄电设备外包装材料用层叠体1。
拉伸聚对苯二甲酸乙二醇酯(PET)膜使用下述膜:MD的拉伸断裂强度为305MPa、TD的拉伸断裂强度为272MPa即二者之和为577MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.89,MD的拉伸断裂伸长率为138%,TD的拉伸断裂伸长率为160%。
拉伸尼龙膜使用下述膜:MD的拉伸断裂强度为276MPa、TD的拉伸断裂强度为310MPa即二者之和为586MPa,MD的拉伸断裂伸长率为120%,TD的拉伸断裂伸长率为120%,MD的热水收缩率为3.5%,TD的热水收缩率为3.8%。
聚酯聚氨酯系粘接剂使用杨氏模量为150MPa、断裂强度为40MPa、断裂伸长率为200%的粘接剂。
<实施例2>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为280MPa、TD的拉伸断裂强度为276MPa即二者之和为556MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.99,MD的拉伸断裂伸长率为171%,TD的拉伸断裂伸长率为158%。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为280MPa、TD的拉伸断裂强度为322MPa即二者之和为602MPa,MD的拉伸断裂伸长率为140%,TD的拉伸断裂伸长率为120%,MD的热水收缩率为3.6%,TD的热水收缩率为4.2%。
除了使用上述的材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
<实施例3>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为271MPa、TD的拉伸断裂强度为254MPa即二者之和为525MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.94,MD的拉伸断裂伸长率为155%,TD的拉伸断裂伸长率为151%。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为276MPa、TD的拉伸断裂强度为320MPa即二者之和为596MPa,MD的拉伸断裂伸长率为120%,TD的拉伸断裂伸长率为110%,MD的热水收缩率为3.4%,TD的热水收缩率为4.2%。
除了使用上述材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
<实施例4>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为281MPa、TD的拉伸断裂强度为244MPa即二者之和为525MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.87,MD的拉伸断裂伸长率为112%,TD的拉伸断裂伸长率为139%。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为285MPa、TD的拉伸断裂强度为325MPa即二者之和为610MPa,MD的拉伸断裂伸长率为170%,TD的拉伸断裂伸长率为100%,MD的热水收缩率为3.5%,TD的热水收缩率为4.0%。
除了使用上述材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
<实施例5>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为306MPa、TD的拉伸断裂强度为279MPa即二者之和为585MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.91,MD的拉伸断裂伸长率为110%,TD的拉伸断裂伸长率为117%。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为276MPa、TD的拉伸断裂强度为320MPa即二者之和为596MPa,MD的拉伸断裂伸长率为120%,TD的拉伸断裂伸长率为110%,MD的热水收缩率为3.4%,TD的热水收缩率为4.2%。
除了使用上述材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
<实施例6>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为240MPa、TD的拉伸断裂强度为260MPa即二者之和为500MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为1.08,MD的拉伸断裂伸长率为140%,TD的拉伸断裂伸长率为120%。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为250MPa、TD的拉伸断裂强度为280MPa即二者之和为530MPa,MD的拉伸断裂伸长率为120%,TD的拉伸断裂伸长率为100%,MD的热水收缩率为2.1%,TD的热水收缩率为2.0%的膜。
除了使用上述材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
<比较例1>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为230MPa、TD的拉伸断裂强度为240MPa即二者之和为470MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为1.04,MD的拉伸断裂伸长率为100%,TD的拉伸断裂伸长率为90%。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为210MPa、TD的拉伸断裂强度为270MPa即二者之和为480MPa,MD的拉伸断裂伸长率为100%,TD的拉伸断裂伸长率80%,MD的热水收缩率为2.3%,TD的热水收缩率为2.2%。
除了使用上述材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
<比较例2>
作为拉伸聚对苯二甲酸乙二醇酯(PET)膜,使用下述膜:MD的拉伸断裂强度为310MPa、TD的拉伸断裂强度为295MPa即二者之和为605MPa,TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.95,MD的拉伸断裂伸长率为96%,TD的拉伸断裂伸长率85%的膜。
作为拉伸尼龙膜,使用下述膜:MD的拉伸断裂强度为210MPa、TD的拉伸断裂强度为270MPa即二者之和为480MPa,MD的拉伸断裂伸长率为100%,TD的拉伸断裂伸长率80%,MD的热水收缩率为2.3%,TD的热水收缩率为2.2%。
除了使用上述材料以外,与实施例1同样地制备蓄电设备外包装材料用层叠体1。
对于按照上述方式制备的各蓄电设备外包装材料用层叠体1,基于下述评价方法进行评价。需要说明的是,拉伸断裂强度及拉伸断裂伸长率按照JIS K7161-2(2014)进行测定。
<成型性评价方法>
使用株式会社天田制的25吨冲压机,将4层构成电池用包装材料深拉深成型为长55mm×宽35mm×各深度的长方体形状(角部为R形)。从深度5mm开始进行试验,在直到深度7mm的范围内,使成型深度每次加深0.5mm,在以各成型深度进行成型后所制得的成型品(样品数为5个)中的4个部位的角部确认是否产生针孔或裂纹。进而,确认各成型深度处未发生针孔或裂纹的个数,并确认极限成型高度。
成型性基于下述判定基准来评价。需要说明的是,是否产生针孔或裂纹在暗室中使用光透射法来调查。
(判定基准)
“◎”(合格)…在成型深度7mm处未产生针孔或裂纹
“○”(合格)…在成型深度6mm处未产生针孔或裂纹
“×”(不合格)…在成型深度6mm处产生了针孔或裂纹
将上述结果示于表1。
[表1]
表1中的“PET”为拉伸聚对苯二甲酸乙二醇酯,“ONY”为拉伸尼龙,“CPP”为无拉伸聚丙烯。
另外,表1中的“AL箔”为铝箔,作为AL箔,能够使用成型性良好的8000系合金箔(A8021H-O、A8079H-O:JIS H4160)。
从表1可知,在实施例1~6中获得了充分的成型性。
另一方面,可知在比较例1及2中无法获得充分的成型性。
产业上的可利用性
本发明的蓄电设备外包装材料用层叠体能够应用于智能手机、平板电脑等便携式电子设备、混合动力汽车、电动汽车、发电机、夜间电力的蓄电用电池(锂离子2次电池、全固态电池等)、锂离子、双电层电容器等电容器。
本申请主张2020年5月29日申请的日本专利申请日本特愿2020-094316号和2021年3月31日申请的日本专利申请日本特愿2021-060725号的优先权,其公开内容直接构成本申请的一部分。
此处使用的用语及表达是出于说明目的而使用的,而非用于进行限定性解释,并不排除此处示出及说明的特征事项的任何等同内容,应该认识到的是本发明请求保护范围内的各种变形也是允许的。
Claims (5)
1.蓄电设备外包装材料用层叠体,其具备:
金属制的阻隔层;
层叠于所述阻隔层的外侧面的由耐热性树脂形成的基材层;和
层叠于所述阻隔层的内侧面的由热熔接性树脂形成的密封层,所述蓄电设备外包装材料用层叠体的特征在于,
所述基材层由作为外侧层的聚酯膜层和作为内侧层的聚酰胺膜层构成,
就所述聚酯膜层而言,MD的拉伸断裂强度与TD的拉伸断裂强度之和为500MPa~600MPa,且TD的拉伸断裂强度相对于MD的拉伸断裂强度的比值为0.8~1.1,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为110%~200%,
其中,MD:机械流动方向,TD:与MD正交的方向。
2.根据权利要求1所述的蓄电设备外包装材料用层叠体,其中,所述聚酰胺膜层的MD的热水收缩率及TD的热水收缩率为2.5%~6%。
3.根据权利要求1或2所述的蓄电设备外包装材料用层叠体,其中,就所述聚酰胺膜层而言,MD的拉伸断裂强度与TD的拉伸断裂强度之和为550MPa~700MPa,MD的拉伸断裂伸长率及TD的拉伸断裂伸长率为90%~200%。
4.根据权利要求1~3中任一项所述的蓄电设备外包装材料用层叠体,其中,在所述聚酯膜层与所述聚酰胺膜层之间层叠有基材间粘接剂层,
所述基材间粘接剂层的杨氏模量为70MPa~400MPa、断裂强度为20MPa~70MPa、断裂伸长率为50%~400%。
5.根据权利要求4所述的蓄电设备外包装材料用层叠体,其中,所述基材间粘接剂层由下述粘接剂的固化物形成,所述粘接剂以从聚氨酯系树脂、聚酯聚氨酯系树脂、聚醚聚氨酯系树脂、聚醚系树脂、聚酯系树脂中选择的1种或2种以上的树脂为主剂,且以多官能异氰酸酯为固化剂。
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