CN107614648B - 金属箔与树脂膜的层压用粘接剂、叠层体、电池外装用包装材料以及电池壳体及其制造方法 - Google Patents

金属箔与树脂膜的层压用粘接剂、叠层体、电池外装用包装材料以及电池壳体及其制造方法 Download PDF

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CN107614648B
CN107614648B CN201680028381.1A CN201680028381A CN107614648B CN 107614648 B CN107614648 B CN 107614648B CN 201680028381 A CN201680028381 A CN 201680028381A CN 107614648 B CN107614648 B CN 107614648B
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resin film
adhesive
metal foil
laminating
polyol
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CN107614648A (zh
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深濑一成
江夏宽人
中川康宏
土井满
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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Abstract

一种金属箔与树脂膜的层压用粘接剂,其具有多元醇(A)、多异氰酸酯的多聚体(B)以及金属化合物(C),所述金属化合物(C)是第7族和第12族中的至少1种金属的化合物,上述多异氰酸酯的多聚体(B)包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2),金属箔与树脂膜的层压用粘接剂具有优异的粘接力,耐热性、耐电解液性优异。

Description

金属箔与树脂膜的层压用粘接剂、叠层体、电池外装用包装材 料以及电池壳体及其制造方法
技术领域
本发明涉及锂离子电池等二次电池的外装材料(packing material)用的粘接剂所适合的金属箔与树脂膜的层压用粘接剂、使用该金属箔与树脂膜的层压用粘接剂来制造的叠层体、使用了该叠层体的电池外装用包装材料、将该电池外装用包装材料成型而得的电池壳体以及该电池壳体的制造方法。
背景技术
近年来,笔记本个人电脑、便携电话等电子设备的小型化、轻量化、薄型化进展。因此,对于电子设备用的二次蓄电池,也要求高能量密度化、轻量化,代替以往的铅蓄电池、镍氢电池而具有高能量密度的锂离子电池的开发广泛地进行着。进一步,在电动汽车、混合动力汽车的电源中也能够使用的锂离子电池被实用化。
对于锂离子电池而言,作为正极材料,使用了包含锂的化合物,作为负极材料,使用了石墨、焦炭等碳材料。进一步,在正极和负极之间具备有电解质层,所述电解质层是由在碳酸亚乙酯、碳酸亚丙酯、碳酸二乙酯等具有渗透力的非质子性的溶剂中溶解有作为电解质的LiPF6、LiBF4等锂盐的电解液形成的,或由含浸有该电解液的聚合物凝胶形成的。
一直以来,作为电池壳体用包装材料,已知依次叠层有作为外侧层的耐热性树脂拉伸膜层、铝箔层、作为内侧层的热塑性树脂未拉伸膜层的叠层体。在使用这样的结构的电池壳体用包装材料来获得的电池壳体的情况下,如果电解液那样的具有渗透力的溶剂通过电池的外装所使用的叠层体中的作为密封材料的膜层,则铝箔层与树脂膜层之间的层压强度降低,有可能成为电解液漏出的原因。因此,开发了一种电池壳体用包材,其中,在铝箔层与内侧层之间,经由包含含有酸酐基或羧基、羟基等与异氰酸酯具有反应性的官能团的树脂与多官能异氰酸酯化合物的粘接剂层来粘接。
例如,专利文献1中记载了下述方法,使用使在丙烯的均聚物或丙烯与乙烯的共聚物中接枝聚合有烯属不饱和羧酸或其酐的改性聚烯烃树脂、和多官能异氰酸酯化合物溶解或分散在有机溶剂中的溶剂型粘接剂来形成粘接剂层的方法。
然而,专利文献1的改性聚烯烃树脂有在长期保存中、溶剂溶解后的经时变化,有时经常涂布时的操作性变得不稳定,此外,所形成的粘接剂层的粘接力有可能产生偏差。此外,还有假定为车载用途等的高温下的粘接力差这样的问题。
另一方面,专利文献2中记载了,将聚烯烃多元醇和多官能异氰酸酯固化剂作为必须成分,进一步添加热塑性弹性体和/或增粘剂的粘接剂组合物,专利文献3中记载了一种粘接剂组合物,其包含:选自具有来源于二聚体脂肪酸或其氢化物的疏水性单元的聚酯多元醇、和该聚酯多元醇的异氰酸酯伸长物中的1种以上的主剂;以及由选自粗甲苯二异氰酸酯、粗二苯基甲烷二异氰酸酯和聚合二苯基甲烷二异氰酸酯中的1种以上多异氰酸酯化合物形成的固化剂。
现有技术文献
专利文献
专利文献1:日本特开2010-92703号公报
专利文献2:日本特开2005-63685号公报
专利文献3:日本特开2011-187385号公报
发明内容
发明所要解决的课题
在专利文献2和专利文献3的情况下,如果在长期使用时渗透至叠层体中的作为密封材料的膜层的电解液与粘接剂层接触,则粘接力降低,电池的品质有可能降低。其中,在长期与电解液接触时,有粘接力显著降低,电解液漏出的危险性进一步提高这样的问题。
本发明是在这样的背景技术下完成的,其目的在于提供具有优异的粘接力,耐热性和耐电解液性的平衡好且优异的层压用金属箔与树脂膜的层压用粘接剂。此外,本发明的其它目的在于提供耐热性和耐电解液性的平衡好且优异,电池外装用包装材料所适合的金属箔与树脂膜的叠层体。进一步,本发明的其它目的在于提供使用包含该叠层体的电池外装用包装材料而形成的耐热性和耐电解液性的平衡好且优异的电池壳体及其制造方法。
用于解决课题的方法
即本发明涉及以下的〔1〕~〔15〕。
〔1〕一种金属箔与树脂膜的层压用粘接剂,其具有多元醇(A)、多异氰酸酯的多聚体(B)以及金属化合物(C),所述金属化合物(C)是第7族和第12族中的至少1种金属的化合物,上述多异氰酸酯的多聚体(B)包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)。
〔2〕根据上述〔1〕所述的金属箔与树脂膜的层压用粘接剂,上述多元醇(A)包含将下述成分加聚而得的聚氨酯多元醇,所述成分含有链状聚烯烃多元醇(a11)和聚酯多元醇(a12)中的至少1种、兼具饱和的环式烃结构和2个以上羟基的含羟基环式烃化合物(a2)、以及多异氰酸酯(a3)。
〔3〕根据上述〔2〕所述的金属箔与树脂膜的层压用粘接剂,上述聚酯多元醇(a12)包含具有氢化二聚酸来源的构成单元和氢化二聚二醇来源的构成单元的聚酯多元醇。
〔4〕根据上述〔1〕~〔3〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述饱和脂肪族多异氰酸酯的多聚体(b1)包含饱和脂肪族多异氰酸酯的异氰脲酸酯体。
〔5〕根据上述〔1〕~〔4〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述饱和脂环式多异氰酸酯的多聚体(b2)包含异佛尔酮二异氰酸酯的多聚体。
〔6〕根据上述〔1〕~〔5〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于上述多元醇(A)所包含的羟基数的比率为1~15。
〔7〕根据上述〔1〕~〔6〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述金属化合物(C)至少包含第7族和第12族中的至少一种羧酸盐1种以上。
〔8〕根据上述〔1〕~〔7〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述金属化合物(C)包含锌或锰的羧酸盐。
〔9〕根据上述〔1〕~〔8〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,其进一步包含溶剂(D)。
〔10〕一种叠层体,其是金属箔与树脂膜经由粘接剂层叠层而得的,所述粘接剂层由上述〔1〕~〔9〕中的任一项所述的金属箔与树脂膜的层压用粘接剂获得。
〔11〕根据上述〔10〕所述的叠层体,上述金属箔为铝箔,上述树脂膜含有热熔合性树脂膜。
〔12〕根据上述〔10〕或〔11〕所述的叠层体,上述金属箔的厚度为10~100μm,上述树脂膜的厚度为9~100μm。
〔13〕一种电池外装用包装材料,其是使用上述〔10〕~〔12〕中的任一项所述的叠层体而获得的。
〔14〕一种电池壳体,其是使用上述〔13〕所述的电池外装用包装材料而获得的。
〔15〕一种电池壳体的制造方法,将上述〔13〕所述的电池外装用包装材料进行深拉成型或鼓凸成型。
〔16〕根据上述〔2〕~〔9〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述链状聚烯烃多元醇(a11)包含聚丁二烯多元醇和氢化聚丁二烯多元醇中的至少1种,优选为聚丁二烯多元醇和氢化聚丁二烯多元醇中的至少1种,更优选包含氢化聚丁二烯多元醇,进一步优选为氢化聚丁二烯多元醇。
〔17〕根据上述〔2〕~〔9〕和〔16〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述含羟基环式烃(a2)具有具交联结构的饱和脂环结构,优选具有降冰片烷骨架、金刚烷骨架或三环癸烷骨架,更优选具有三环癸烷骨架。
〔18〕根据上述〔2〕~〔9〕、〔16〕和〔17〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述多异氰酸酯(a3)为饱和脂环式二异氰酸酯,优选为1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、1,3-双(异氰酸酯基甲基)环己烷、1,4-双(异氰酸酯基甲基)环己烷或降冰片烷二异氰酸酯,更优选为亚甲基双(4-环己基异氰酸酯)。
〔19〕根据上述〔1〕~〔9〕、〔16〕~〔18〕中的任一项所述的金属箔与树脂膜的层压用粘接剂,上述饱和脂环式多异氰酸酯的多聚体(b2)为异佛尔酮二异氰酸酯的脲基甲酸酯化多聚体和异氰脲酸酯体中的至少1种,优选为异佛尔酮二异氰酸酯的脲基甲酸酯化多聚体。
发明的效果
本发明的金属箔与树脂膜的层压用粘接剂的粘接力优异,使用该金属箔与树脂膜的层压用粘接剂而形成的金属箔与树脂膜的叠层体的耐热性和耐电解液性的平衡好且优异,因此作为锂离子电池等二次电池的制作所使用的电池外装用包装材料的原材料是适合的。此外,使用本发明的电池外装用包装材料而形成的电池壳体的耐热性和耐电解液性的平衡好且优异,可以通过使用该电池壳体来提供寿命长的安全的二次电池。
具体实施方式
[金属箔与树脂膜的层压用粘接剂]
本实施方式涉及的金属箔与树脂膜的层压用粘接剂具有多元醇(A)、多异氰酸酯的多聚体(B)以及金属化合物(C),所述金属化合物(C)是第7族和第12族中的至少1种金属的化合物,上述多异氰酸酯的多聚体(B)包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)。
在本实施方式涉及的金属箔与树脂膜的层压用粘接剂中,上述多元醇(A)相当于主剂,多异氰酸酯的多聚体(B)相当于固化剂,金属化合物(C)相当于反应促进剂。
本实施方式涉及的金属箔与树脂膜的层压用粘接剂可以适合用于金属箔与树脂膜的粘接,特别是作为金属箔与树脂膜的层压用的粘接剂是有用的,其叠层体可以适合用作电池外装用包装材料。
这里,本说明书中的“~”,是指“~”这样的记载前的值以上且“~”这样的记载后的值以下。
<多元醇(A)>
本实施方式所使用的多元醇(A)(以下,有时称为“(A)成分”或“(A)”)只要是分子结构中含有2个以上羟基的多元醇,就不受特别限制,从耐电解液性的观点出发,优选包含将下述成分加聚而得的聚氨酯多元醇(A1),所述成分含有:链状聚烯烃多元醇(a11)、聚酯多元醇(a12)和兼具饱和的环式烃结构和2个以上羟基的含羟基环式烃化合物(a2)的3种中的至少1种,以及多异氰酸酯(a3)。
从同样的观点出发,多元醇(A)更优选包含将下述成分加聚而得的聚氨酯多元醇(A2),所述成分含有链状聚烯烃多元醇(a11)和聚酯多元醇(a12)中的至少1种、以及多异氰酸酯(a3)。
从同样的观点出发,多元醇(A)进一步优选包含将下述成分加聚而得的聚氨酯多元醇(A3),所述成分含有链状聚烯烃多元醇(a11)和聚酯多元醇(a12)中的至少1种、兼具饱和的环式烃结构和2个以上羟基的含羟基环式烃化合物(a2)、以及多异氰酸酯(a3)。
上述多元醇(A)、聚氨酯多元醇(A1)、聚氨酯多元醇(A2)和聚氨酯多元醇(A3)优选包含链状聚烯烃多元醇(a11)和聚酯多元醇(a12)中的至少1种作为来源成分,从耐电解液性的观点出发,更优选包含链状聚烯烃多元醇(a11)。
在不阻碍本实施方式的效果的范围内,多元醇(A)可以包含上述聚氨酯多元醇(A1)、(A2)和(A3)以外的多元醇,从耐电解液性的观点出发,优选不包含。
在多元醇(A)包含聚氨酯多元醇(A1)的情况下,多元醇(A)中的聚氨酯多元醇(A1)的含量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,更进一步优选为100质量%。
在多元醇(A)包含聚氨酯多元醇(A2)的情况下,多元醇(A)中的聚氨酯多元醇(A2)的含量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,更进一步优选为100质量%。
在多元醇(A)包含聚氨酯多元醇(A3)的情况下,多元醇(A)中的聚氨酯多元醇(A3)的含量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,更进一步优选为100质量%。
多元醇(A)中的(a11)成分、(a12)成分、(a2)成分和(a3)成分的总含量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上,更进一步优选为100质量%。
〔链状聚烯烃多元醇(a11)〕
本实施方式的链状聚烯烃多元醇(a11)是指不含脂环结构的聚烯烃多元醇。
本实施方式所使用的链状聚烯烃多元醇(a11)(以下,也称为“聚烯烃多元醇(a11)”或“(a11)成分”或“(a11)”)只要分子中含有使1种或2种以上烯烃聚合或共聚而成的聚烯烃骨架、和2个以上羟基,并且不具有脂环结构,就不受特别限制。
链状聚烯烃多元醇(a11)可以是氢化了的物质(氢化物)也可以是未氢化的物质(非氢化物),从耐电解液性的观点出发,优选为氢化物(氢化体)。
作为链状聚烯烃多元醇(a11)的具体例,可举出聚丁二烯多元醇、聚异戊二烯多元醇等聚二烯多元醇、聚二烯多元醇与聚烯烃的接枝聚合物和它们的聚二烯多元醇、接枝聚合物的氢化物等。它们可以单独使用或2种以上混合使用。
作为它们的市售品,可举出例如,G-1000、G-3000、GI-1000、GI-3000(都是日本曹达株式会社制)、エポール(出光兴产株式会社制)等。
〔聚酯多元醇(a12)〕
本实施方式的聚酯多元醇(a12)(以下,也称为“(a12)成分”或“(a12)”)只要是分子中含有酯键和2个以上羟基的聚酯多元醇,就不受特别限制。
此外,从耐电解液性的观点出发,聚酯多元醇(a12)优选为具有氢化二聚酸来源的构成单元和氢化二聚二醇来源的构成单元的聚酯多元醇、以及蓖麻油中的至少1种,更优选包含具有氢化二聚酸来源的构成单元和氢化二聚二醇来源的构成单元的聚酯多元醇,进一步优选为具有氢化二聚酸来源的构成单元和氢化二聚二醇来源的构成单元的聚酯多元醇。
本实施方式中的所谓“二聚酸”,是指将具有烯属双键的脂肪酸(以下,也称为“不饱和脂肪酸A”)在双键部分进行反应而得的二聚酸(二聚体酸)。
不饱和脂肪酸A的碳原子数优选为14~22。认为通过具有这样比较长的烃链,从而耐电解液性提高。
上述二聚酸优选为将具有烯属双键2~4个的不饱和脂肪酸A与具有烯属双键1~4个的不饱和脂肪酸A进行反应而得的二聚体酸,更优选为将具有烯属双键2个的不饱和脂肪酸A与具有烯属双键1或2个的不饱和脂肪酸A进行反应而得的二聚体酸。作为这些二聚体酸的来源成分的2个不饱和脂肪酸A可以为不同的种类也可以为相同的种类。
作为上述不饱和脂肪酸A,可举出十四碳烯酸(粗租酸、抹香鲸酸、肉豆蔻脑酸)、十六碳烯酸(棕榈油酸等)、十八碳烯酸(油酸、反油酸、异油酸等)、二十碳烯酸(鳕油酸等)、二十二碳烯酸(芥酸、鲸蜡烯酸、巴西烯酸等)、十四碳二烯酸、十六碳二烯酸、十八碳二烯酸(亚油酸等)、二十碳二烯酸、二十二碳二烯酸、十八碳三烯酸(亚麻酸等)、二十碳四烯酸(花生四烯酸等)等,最优选为油酸或亚油酸。获得的二聚酸通常是根据双键的结合部位、异构化而结构不同的二聚酸混合物,可以分离来使用,也可以直接使用。进一步,获得的二聚酸可以含有少量的单体酸(例如6质量%以下,特别是4质量%以下)、三聚体酸以上的聚合物酸等(例如6质量%以下,特别是4质量%以下)。
本实施方式中的所谓“氢化二聚酸”,是指将上述二聚酸的碳-碳双键氢化而得的饱和二羧酸。作为氢化二聚酸的市售品,可举出例如,EMPOL1008和EMPOL1062(都是BASF制)、PRIPOL1009等(Croda制)等。
本实施方式中的所谓“氢化二聚二醇”,是指将上述二聚酸、上述氢化二聚酸及其低级醇酯中的至少1种在催化剂存在下进行还原,将二聚酸的羧酸或羧酸酯部分形成醇,在原料具有碳-碳双键的情况下将该双键氢化而得的二醇作为主成分的物质。作为氢化二聚二醇的市售品,可举出例如,Sovermol908(BASF制)、PRIPOL2033等(Croda制)。
本实施方式所使用的聚酯多元醇(a12)可以通过将以上述氢化二聚酸作为必须成分的酸成分以及以上述氢化二聚二醇作为必须成分的醇成分在二月桂酸丁基锡等酯化催化剂的存在下进行缩合反应(脱水酯化反应)来制造。或者也可以通过将以上述氢化二聚酸的低级烷基酯作为必须成分的酯成分以及以上述氢化二聚二醇作为必须成分的醇成分在酯交换催化剂的存在下进行酯交换反应来制造。
〔兼具饱和的环式烃结构和2个以上羟基的含羟基环式烃化合物(a2)〕
关于本实施方式所使用的兼具饱和的环式烃结构和2个以上羟基的含羟基环式烃化合物(a2)(以下,也称为“含羟基环式烃(a2)”或“(a2)成分”或“(a2)”),从由本实施方式的金属箔与树脂膜的层压用粘接剂获得的粘接剂层的耐电解液性的观点出发,只要是具有饱和脂环式烃结构和2个以上羟基,其它部分的结构由烃形成的化合物,就没有特别限制。
作为饱和环式烃结构,可举出环戊烷骨架、环己烷骨架、环庚烷骨架等环链烷骨架、降冰片烷骨架、金刚烷骨架、三环癸烷骨架等具有交联结构的饱和脂环结构等,作为具有这样的结构的含羟基环式烃(a2),可举出环戊二醇、环己二醇、环己烷二甲醇、降冰片烷二醇、金刚烷二醇、三环癸烷二甲醇、金刚烷三醇等。它们可以单独使用或2种以上混合使用。优选包含具有交联结构的饱和脂环结构,可举出降冰片烷二醇、金刚烷二醇、三环癸烷二甲醇、金刚烷三醇等作为优选的例子。作为它们的市售品,可举出金刚烷三醇(出光兴产株式会社制,三菱ガス化学株式会社制)、TCDアルコールDM(オクセア社制)等。
〔多异氰酸酯(a3)〕
作为本实施方式所使用的多异氰酸酯(a3)(以下,也称为“(a3)成分”或“(a3)”),只要是含有2个以上异氰酸酯基的化合物、或其多聚体,就没有特别限制。可举出例如,1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、1,3-双(异氰酸酯基甲基)环己烷、1,4-双(异氰酸酯基甲基)环己烷、降冰片烷二异氰酸酯等饱和脂环式二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、二苯基甲烷-4,4’-二异氰酸酯、1,3-苯二亚甲基二异氰酸酯、1,4-苯二亚甲基二异氰酸酯等芳香族二异氰酸酯、1,6-己二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、2,2,4-三甲基己烷亚甲基二异氰酸酯等脂肪族二异氰酸酯、以及它们的脲基甲酸酯化多聚体、异氰脲酸酯体、缩二脲改性物等。它们可以单独使用或2种以上混合使用。优选为饱和脂环式二异氰酸酯,可举出1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、1,3-双(异氰酸酯基甲基)环己烷、1,4-双(异氰酸酯基甲基)环己烷、降冰片烷二异氰酸酯等,特别优选为异佛尔酮二异氰酸酯(3-异氰酸酯甲基-3,5,5-三甲基环己基异氰酸酯)、亚甲基双(4-环己基异氰酸酯)(别名:二环己基甲烷-4,4’-二异氰酸酯)。作为它们的市售品,可举出デスモジュールI、デスモジュールW(分别为バイエル社制)、IPDI、H12MDI(分别为デグッサ社制)等。
〔聚氨酯多元醇的制造方法〕
作为本实施方式所使用的聚氨酯多元醇的制造方法的一例,通过在二月桂酸二丁基锡、二月桂酸二辛基锡、三(2-乙基己酸)铋、四乙酰丙酮锆那样的公知的氨基甲酸酯化催化剂的存在下或不存在下,使聚烯烃多元醇(a11)和/或聚酯多元醇(a12)、与多异氰酸酯(a3)和根据需要的含羟基环式烃化合物(a2)进行加聚反应来进行。为了缩短反应时间,可以并且优选在催化剂的存在下进行反应。催化剂的添加量相对于(a11)、(a12)、(a2)和(a3)成分的总量100质量份优选为0.001~1.00质量份,更优选为0.005~0.50质量份,进一步优选为0.01~0.30质量份。如果为0.001质量份以上,则反应充分地快,如果为1质量份以下,则可以保持粘接力。
此外,加聚的反应可以使聚烯烃多元醇(a11)和/或聚酯多元醇(a12)、含羟基环式烃化合物(a2)和多异氰酸酯(a3)全部同时反应,也可以将聚烯烃多元醇(a11)和/或聚酯多元醇(a12)、含羟基环式烃化合物(a2)各自分别或适当地组合来与多异氰酸酯(a3)反应之后,将全部成分进行混合,进一步进行反应。后一方法可举出例如,使含羟基环式烃化合物(a2)与多异氰酸酯(a3)进行反应来获得聚氨酯多异氰酸酯之后,使聚烯烃多元醇(a11)和/或聚酯多元醇(a12)进行反应来获得聚氨酯多元醇这样的方法。
此外,该加聚的反应可以在溶剂中进行。所使用的溶剂没有特别限制,如果使用与后述的本实施方式的金属箔与树脂膜的层压用粘接剂可以包含的溶剂(D)的相同的溶剂,则可以省略溶剂蒸馏除去等工序,可以更低成本并且抑制环境负荷来制造。
溶剂的添加量相对于(a11)、(a12)、(a2)和(a3)成分的总量100质量份优选为50~500质量份,更优选为50~200质量份,进一步优选为80~120质量份。
此外,在该加聚的反应中,可以添加氢醌单甲基醚等抗氧化剂。抗氧化剂的添加量相对于(a11)、(a12)、(a2)和(a3)成分的总量100质量份优选为0.001~1.00质量份,更优选为0.005~0.50质量份,进一步优选为0.01~0.35质量份。
制造聚氨酯多元醇时多异氰酸酯(a3)所包含的异氰酸酯基数相对于(a11)、(a12)和(a2)成分所包含的羟基数的比率(以下也称为“NCO/OH比”)优选为0.5~1.1,更优选为0.7~1.05,进一步优选为0.8~1.0。如果为0.5以上,则由本实施方式的金属箔与树脂膜的层压用粘接剂获得的粘接剂层的粘接力即使与电解液接触也不易降低,如果为1.1以下,则不易发生聚氨酯多元醇制造时的凝胶化,此外本实施方式的金属箔与树脂膜的层压用粘接剂的涂布时的操作性变得良好。
另外各多元醇成分所包含的羟基数可以利用JIS K 1557-1:2007(滴定法)的A法来求出。各异氰酸酯成分所包含的异氰酸酯基数可以利用JIS K 6806:2003(滴定法)来求出。
可以不含(a2)成分,但优选包含(a2)成分。在包含(a2)成分的情况下,制造聚氨酯多元醇时(a2)成分相对于(a11)和(a12)成分的总量100质量份的比率优选为1~100质量份,更优选为5~50质量份,进一步优选为5~20质量份。如果为1质量份以上,则由金属箔与树脂膜的层压用粘接剂获得的粘接剂层的粘接力即使与电解液接触也不易降低,如果为100质量份以下,则聚氨酯多元醇在溶剂中的溶解性以及金属箔与树脂膜的层压用粘接剂的涂布时的操作性变得良好。
<多异氰酸酯的多聚体(B)>
本实施方式中的多异氰酸酯的多聚体(B)(以下,有时称为“(B)成分”或“(B)”)在本实施方式的金属箔与树脂膜的层压用粘接剂中作为固化剂来配合。
这样,通过将多异氰酸酯制成多聚体,从而金属箔与树脂膜的层压用粘接剂的耐热性和耐电解液性变得优异。其理由还不清楚,推测是因为异氰脲酸酯体和脲基甲酸酯化多聚体等结构的耐热性和耐电解液性优异。
本实施方式中的多异氰酸酯的多聚体(B)同时包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)。在同时包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)的情况下,与单独的饱和脂肪族多异氰酸酯的多聚体(b1)相比,由金属箔与树脂膜的层压用粘接剂获得的粘接剂层与电解液接触的情况下的粘接强度变高,相反与单独的饱和脂环式多异氰酸酯的多聚体(b2)相比,高温下的粘接强度变高。
另外,关于本实施方式的多异氰酸酯的多聚体(B),在金属箔与树脂膜的层压用粘接剂的调制时,可以投入将饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)预先混合而得的物质,也可以分别投入。
本实施方式所使用的饱和脂肪族多异氰酸酯的多聚体(b1)(以下,有时称为“(b1)成分”或“(b1)”)只要是具有2个以上异氰酸酯基的饱和脂肪族化合物的多聚体,就不受特别限制。可举出例如,1,6-己二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯等脂肪族二异氰酸酯的脲基甲酸酯化多聚体、异氰脲酸酯体、缩二脲改性物等。从高温下的粘接强度的观点出发,优选包含饱和脂肪族多异氰酸酯的异氰脲酸酯体,更优选为饱和脂肪族多异氰酸酯的异氰脲酸酯体。
本实施方式所使用的饱和脂环式多异氰酸酯的多聚体(b2)(以下,有时称为“(b2)成分”或“(b2)”)只要是具有2个以上异氰酸酯基和饱和脂环结构的化合物的多聚体,就不受特别限制。优选包含例如,1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、亚甲基双(4-环己基异氰酸酯)、1,3-双(异氰酸酯基甲基)环己烷、1,4-双(异氰酸酯基甲基)环己烷、降冰片烷二异氰酸酯等饱和脂环式二异氰酸酯等多聚体,作为多聚体,可举出脲基甲酸酯化多聚体、异氰脲酸酯体、缩二脲改性物等,从耐电解液性的观点出发,优选为异佛尔酮二异氰酸酯的脲基甲酸酯化多聚体、异氰脲酸酯体、缩二脲改性物。
多异氰酸酯的多聚体(B)可以包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)以外的多异氰酸酯的多聚体,但优选不包含。
多异氰酸酯的多聚体(B)中的饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)的合计量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上。
饱和脂肪族多异氰酸酯的多聚体(b1)相对于饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)的总量的质量比[(b1)/((b1)+(b2))]优选为0.05~0.70,更优选为0.10~0.60,进一步优选为0.20~0.50,更进一步优选为0.30~0.40。
饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于多元醇(A)所包含的羟基数的比率(NCO/OH比)优选为1~15,更优选为2~13。如果NCO/OH比为1以上,则由本实施方式的金属箔与树脂膜的层压用粘接剂获得的粘接剂层的对树脂膜的粘接力变得特别良好,如果NCO/OH比为15以下,则由本实施方式的金属箔与树脂膜的层压用粘接剂获得的粘接剂层的粘接力即使与电解液接触也不易降低。
<作为第7族和第12族中的至少1种金属的化合物的金属化合物(C)>
作为本实施方式中的元素周期表的第7族和第12族中的至少1种金属的化合物的金属化合物(C)(以下,也称为“第7族和/或第12族的金属化合物(C)”或“金属化合物(C)”或“(C)成分”或“(C)”)作为用于促进本实施方式的金属箔与树脂膜的层压用粘接剂中的聚氨酯多元醇(A)和多异氰酸酯的多聚体(B)的反应的反应促进剂来进行配合。
作为本实施方式所使用的第7族和第12族中的至少1种金属的化合物的金属化合物(C)可以单独或并用包含选自锰、锝、铼中的第7族、选自锌、镉、汞中的第12族的各金属元素的化合物。
作为第7族和第12族中的至少1种金属的化合物的金属化合物(C),可举出例如,金属己酸盐、金属辛酸盐(2-乙基己酸盐)、金属新癸酸盐、金属硬脂酸盐、金属油酸盐等金属羧酸盐、金属乙酰丙酮化物等。其中从长期电解液浸渍后的粘接强度的观点出发,优选包含金属羧酸盐,更优选包含选自锰和锌中的金属的羧酸盐至少1种以上,进一步优选包含锌的羧酸盐。
具体而言,作为第7族和第12族中的至少1种金属的化合物的金属化合物(C)优选为新癸酸锌(C20H38O4Zn)、ヘキソエート亜鉛(商品名,辛酸锌、2-乙基己酸锌、C16H30O4Zn)、硬脂酸锌(C36H70O4Zn)、乙酰丙酮锌(C10H14O4Zn)、ヘキソエートマンガン(商品名,辛酸锰、2-乙基己酸锰、C16H30O4Mn),更优选为新癸酸锌(C20H38O4Zn)、ヘキソエート亜鉛(辛酸锌、2-乙基己酸锌、C16H30O4Zn)。
作为(C)成分以外的反应促进剂,可以并用作为有机锡化合物的二月桂酸二丁基锡、二月桂酸二辛基锡、二乙酸二辛基锡、作为叔胺的2,4,6-三(二甲基氨基甲基)苯酚、二甲基苯胺、二甲基对甲苯胺、N,N-二(β-羟基乙基)-对甲苯胺等。
作为第7族和第12族中的至少1种金属的化合物的金属化合物(C)相对于多元醇(A)100质量份的比率不受特别限制,相对于多元醇(A)100质量份,金属化合物(C)的含量以金属的质量换算优选为0.0001质量份~5质量份,更优选为0.001质量份~3质量份,更优选为0.01~1.5质量份,进一步优选为0.03~1.5质量份。如果为0.0001质量份以上,则由本发明的金属箔与树脂膜的层压用粘接剂获得的粘接剂层的粘接力即使长期浸渍于电解液之后也充分地变高,如果为5质量份以下,则常态的粘接强度变高。另外,第7族和/或第12族的金属化合物(C)可以在多元醇(A)的合成时添加,也可以在粘接剂的调整时添加。
<溶剂(D)>
本实施方式的金属箔与树脂膜的层压用粘接剂可以包含溶剂(D)(以下,有时称为“(D)成分”或“(D)”)。
溶剂(D)只要能够将多元醇(A)、多异氰酸酯的多聚体(B)和作为第7族和第12族中的至少1种金属的化合物的金属化合物(C)溶解或分散,就不受特别限制。可举出例如,甲苯、二甲苯等芳香族系有机溶剂、环己烷、甲基环己烷、乙基环己烷等脂环式系有机溶剂、正己烷、正庚烷等脂肪族系有机溶剂、乙酸乙酯、乙酸丙酯、乙酸丁酯等酯系有机溶剂、丙酮、甲基乙基酮、甲基丁基酮等酮系有机溶剂等。它们可以单独使用或2种以上混合使用。
其中,特别是从多元醇(A)的溶解性的观点出发,优选为乙酸乙酯、乙酸丙酯、乙酸丁酯、甲苯、甲基环己烷、甲基乙基酮,更优选为甲苯。
本实施方式涉及的金属箔与树脂膜的层压用粘接剂中的溶剂(D)的含量优选为30~80质量%,更优选为40~80质量%,进一步优选为50~80质量%,进一步优选为60~80质量%。如果为30质量%以上,则本实施方式的金属箔与树脂膜的层压用粘接剂的涂布时的操作性变得良好,如果为80质量%以下,则将本实施方式的金属箔与树脂膜的层压用粘接剂涂布、固化而得的叠层体的厚度控制性变得良好。
<其它成分>
本实施方式的金属箔与树脂膜的层压用粘接剂可以根据需要含有增粘剂、增塑剂等添加剂。
作为上述增粘剂,不受特别限定。例如,天然系时,可举出聚萜系树脂、松香系树脂等,石油系时,可举出由石脑油的分解油馏分获得的脂肪族(C5)系树脂、芳香族(C9)系树脂、共聚(C5/C9)系树脂、脂环族系树脂等。此外,可举出将这些树脂的双键部分氢化了的氢化树脂。该增粘剂可以仅使用1种,也可以并用2种以上。作为上述增塑剂,不受特别限定,可举出例如,聚异戊二烯、聚丁烯等液状橡胶、工艺油等。
此外,只要在不阻碍本实施方式的效果的范围内,就可以含有酸改性聚烯烃树脂等热塑性树脂、热塑性弹性体。作为可以配合的热塑性树脂和热塑性弹性体,可举出例如,乙烯-乙酸乙烯酯共聚树脂、乙烯-丙烯酸乙酯共聚树脂、SEBS(苯乙烯-乙烯-丁烯-苯乙烯)、SEPS(苯乙烯-乙烯-丙烯-苯乙烯)等。
本实施方式涉及的金属箔与树脂膜的层压用粘接剂中的(A)、(B)、(C)和(D)成分的合计含量优选为80质量%以上,更优选为90质量%以上,进一步优选为95质量%以上。
[叠层体]
本实施方式的叠层体是金属箔与树脂膜经由由本实施方式的金属箔与树脂膜的层压用粘接剂(以下,有时简称为“本实施方式的层压用粘接剂”。)获得的粘接剂层叠层而成的。
此外在本实施方式的叠层体中,如果包含将金属箔与树脂膜经由由本实施方式的层压用粘接剂获得的粘接剂层而接合的层,则此外可以包含金属箔彼此和/或树脂膜彼此经由由本实施方式的层压用粘接剂获得的粘接剂层而接合的层。该接合方法可以使用热层压方式、干层压方式等公知的方法。在本实施方式中,所谓热层压方式,是指将不含溶剂(D)的本实施方式的层压用粘接剂通过在与粘接剂层接触的层表面进行加热熔融、或连与粘接剂层接触的层一起加热挤出,从而使其介于叠层体的层间,形成粘接剂层的方式。此外,在本实施方式中,所谓干层压方式,是指将包含溶剂(D)的本实施方式的层压用粘接剂涂布于与粘接剂层接触的层表面,干燥后与另一层重合并压接,从而使其介于叠层体的层间,形成粘接剂层的方式。
本实施方式的叠层体的用途不受特别限定,作为有用的用途,可举出包装用途。作为该叠层体中包装的内容物,可举出包含酸、碱、有机溶剂等的液状物,例如,腻子(厚腻子、薄腻子等)、涂料(油性涂料等)、漆(透明漆等)、汽车用复合物(compound)等溶剂系的物质等。此外,该叠层体也适合于包装锂离子电池的电解液,因此可以并且优选作为电池外装用包装材料来使用。在作为电池外装用包装材料来使用的情况下,优选金属箔为铝箔,并且树脂膜包含热熔合性树脂膜,此外在铝箔的外侧设置有包含耐热性树脂膜的外层。
[电池外装用包装材料]
本实施方式的电池外装用包装材料使用本实施方式的叠层体来获得。
本实施方式的电池外装用包装材料优选在本实施方式的叠层体的金属箔的外侧设置包含树脂膜特别是耐热性树脂膜的外层。此外,根据需要,为了提高机械强度、耐电解液性等特性,可以制成附加有第1中间树脂层或/和第2中间树脂层等的构成。作为优选方式,具体而言可以制成以下那样的构成。另外,粘接剂层是指“由本实施方式的层压用粘接剂获得的粘接剂层”,将金属箔层以铝箔层的方式来例示。
(1)外层/铝箔层/粘接剂层/树脂膜层
(2)外层/第1中间树脂层/铝箔层/粘接剂层/树脂膜层
(3)外层/铝箔层/第2中间树脂层/粘接剂层/树脂膜层
(4)外层/第1中间树脂层/铝箔层/第2中间树脂层/粘接剂层/树脂膜层
(5)涂层/外层/铝箔层/粘接剂层/树脂膜层
(6)涂层/外层/第1中间树脂层/铝箔层/粘接剂层/树脂膜层
(7)涂层/外层/铝箔层/第2中间树脂层/粘接剂层/树脂膜层
(8)涂层/外层/第1中间树脂层/铝箔层/第2中间树脂层/粘接剂层/树脂膜层
(第1中间树脂层、第2中间树脂层)
在上述中,作为第1中间树脂层,聚酰胺树脂、聚酯树脂或聚乙烯树脂等以提高电池外装用包装材料的机械强度为目的来使用。作为第2中间树脂层,与第1中间树脂层同样地,聚酰胺树脂、聚酯树脂或聚乙烯树脂、聚丙烯等热粘接性挤出树脂主要以提高耐电解液性为目的来使用。树脂膜层可以使用单层的树脂膜、多层的树脂膜(通过2层的共挤出或3层的共挤出等来制造)。此外,第2中间树脂层也可以使用单层的树脂膜、多层的共挤出树脂膜。第1中间树脂层和第2中间树脂层的厚度不受特别限定,在设置它们的情况下,通常为0.1~30μm左右。
(外层)
外层所使用的树脂膜是耐热性、成型性、绝缘性等优异的树脂膜,通常使用聚酰胺(尼龙)树脂或聚酯树脂的拉伸膜。该外层膜的厚度为9~50μm左右,小于9μm时,进行包装材料的成型时拉伸膜的伸长率不足,铝箔产生颈缩,易于发生成型不良。另一方面,在超过50μm的厚度的情况下,并不会特别提高成型性的效果,相反地只是使体积能量密度降低并且导致成本上升。外层膜的厚度更优选为10~40μm左右,进一步优选为20~30μm。
作为该外层所使用的树脂膜,从获得更尖锐的形状的方面出发,优选使用将膜以在将拉伸膜的拉伸方向设为0°的情况下的0°、45°、90°的3个方向分别为拉伸方向的方式切出成规定的大小,进行拉伸试验时,其抗拉强度为150N/mm2以上,优选为200N/mm2以上,进一步优选为250N/mm2以上,并且由3个方向的拉伸得到的伸长率为80%以上,优选为100%以上,进一步优选为120%以上那样的树脂膜。通过使抗拉强度为150N/mm2以上,或使由拉伸得到的伸长率为80%以上,从而充分地发挥上述效果。另外,抗拉强度和由拉伸得到的伸长率的值是膜的拉伸试验(试验片的长度150mm×宽度15mm×厚度9~50μm,拉伸速度100mm/min)中直至断裂的值。试验片对于3方向分别切出。
(金属箔)
金属箔承担对水蒸气等的阻挡性的作用,因此作为材质,一般使用并且优选为纯铝系或铝-铁系合金的O材(软质材料)。作为铝箔的厚度,为了确保加工性和确保防止氧、水分向包装内浸入的阻挡性,优选为10~100μm左右。在铝箔的厚度小于10μm的情况下,成型时发生铝箔的断裂,或产生针孔而有氧、水分浸入的担忧。另一方面,在铝箔的厚度超过100μm的情况下,并不会特别提高成型时的断裂的改善效果、针孔发生防止效果,只是包装材料的总厚度变厚,质量增加,体积能量密度降低。铝箔通常使用30~50μm左右的厚度的铝箔,优选使用40~50μm的厚度的铝箔。另外,为了提高与树脂膜的粘接性、提高耐蚀性,优选预先对铝箔进行硅烷偶联剂、钛偶联剂等的底涂处理、铬酸盐处理等化成处理。
(树脂膜)
作为树脂膜,优选为聚丙烯、聚乙烯、马来酸改性聚丙烯、乙烯-丙烯酸酯共聚物或离子交联聚合物树脂等的热熔合性树脂膜。这些树脂具有热封性,承担提高对腐蚀性强的锂二次电池的电解液等的耐化学性的作用。它们的膜厚度优选为9~100μm,更优选为20~80μm,最优选为40~80μm。如果树脂膜的厚度为9μm以上,则获得充分的热封强度,对电解液等的耐蚀性变得良好。如果树脂膜的厚度为100μm以下,则电池外装用包装材料的强度充分,并且成型性变得良好。
(涂层)
本实施方式的电池外装用包装材料可以在外层上设置涂层。作为涂层的形成法,有涂布阻气性的聚合物的方法、将铝金属、氧化硅、氧化铝等无机氧化物进行蒸镀并涂布金属和无机物的薄膜的方法等。通过设置涂层,从而获得水蒸气及此外阻气性更优异的叠层体。
[电池壳体]
本实施方式的电池壳体使用本实施方式的电池外装用包装材料来获得。例如,通过将电池外装用包装材料进行成型来获得。
本实施方式的电池外装用包装材料的耐电解液性、耐热性、水蒸气及此外阻气性优异,适合用作二次电池、特别是锂离子电池用的电池壳体。此外,本实施方式的电池外装用包装材料的成型性非常良好,因此通过利用公知的方法来成型,从而可以简便地获得本实施方式的电池壳体。成型的方法不受特别限定,如果通过深拉成型或鼓凸成型来成型,则可以制作复杂的形状、尺寸精度高的电池壳体。
实施例
以下,通过实施例和比较例来更具体地说明本发明,但本发明不受这些实施例的任何限制。
(合成例1)
在带有搅拌机、水分离器的反应容器中,加入作为氢化二聚二醇的“Sovermol908”(BASF社制)220.00g、作为氢化二聚酸的“EMPOL1008”(BASF社制)230.00g、作为催化剂的二月桂酸丁基锡的“KS-1260”(堺化学工业株式会社制)0.10g,在约240℃,从常压下开始一边流出缩合水一边减压同时进行脱水酯化反应,获得了聚酯多元醇(以下,记为聚酯多元醇(1)。)。
(合成例2)
在具备有搅拌装置、温度计和冷凝器的反应容器中,投入作为(a11)成分的“GI-1000”(日本曹达株式会社制,氢化聚丁二烯多元醇)108.00g、作为(a2)成分的“TCDアルコールDM”(オクセア社制,三环癸烷二甲醇)12.00g、作为抗氧化剂的氢醌单甲基醚(和光纯药工业株式会社制)0.04g、作为催化剂的“KS-1260”(堺化学工业株式会社制,二月桂酸二丁基锡)0.03g、作为(a3)成分的“デスモジュールW”(バイエル社制,亚甲基双(4-环己基异氰酸酯))30.00g和作为溶剂(D)的甲苯70.00g,一边搅拌,一边使用油浴升温至85~90℃。然后,一边搅拌2.5小时一边继续反应。然后,测定红外吸收光谱,确认异氰酸酯基的吸收消失了,结束反应,进一步投入甲苯80.00g,搅拌溶解,获得了聚氨酯多元醇(以下,记为聚氨酯多元醇(1)。)的甲苯溶液(固体成分浓度50质量%)。将合成例2中的配合组成示于表1中。
(合成例3~7)
采用表1所示的配合,除此以外,利用与合成例2同样的方法进行合成,获得了聚氨酯多元醇(2)~(6)的甲苯溶液(固体成分浓度50质量%)。另外,表1中的G-1000为日本曹达株式会社制的聚丁二烯多元醇,HS 2B-5500为丰国制油株式会社制的聚酯多元醇(蓖麻油)。
另外,在合成例2~7中,基于JIS K 1557-1:2007(滴定法)的A法来测定(a11)、(a12)和(a2)成分所包含的羟基数,此外,基于JIS K 6806:2003(滴定法)来测定多异氰酸酯(a3)所包含的异氰酸酯基数。基于这些测定值,求出多异氰酸酯(a3)所包含的异氰酸酯基数相对于(a11)、(a12)和(a2)成分所包含的羟基数的比率“NCO/OH比”。将其结果示于表1中。
(实施例1)
使用由合成例2获得的聚氨酯多元醇(1)的甲苯溶液60.00g(固体成分30.00g,甲苯30.00g)作为(A)成分,在其中添加作为(b1)成分的“デュラネートTKA-100”(旭化成ケミカルズ株式会社制,1,6-己二异氰酸酯的异氰脲酸酯体)3.20g、作为(b2)成分的“デスモジュールXP 2565”(バイエル社制,异佛尔酮二异氰酸酯的脲基甲酸酯化多聚体(80质量份)和乙酸丁酯(20质量份)的混合物)7.30g、作为(C)成分的“BiCAT Z”(Shepherd Chemical社制,新癸酸锌)0.06g、作为溶剂(D)的甲苯99.44g,调制出金属箔与树脂膜的层压用粘接剂1(组合物1)。
另外,基于JIS K 1557-1:2007(滴定法)的A法测定作为(A)成分的聚氨酯多元醇(1)所包含的羟基数。此外,分别基于JIS K 6806:2003(滴定法)测定作为(b1)成分的デュラネートTKA-100和作为(b2)成分的デスモジュールXP 2565所包含的异氰酸酯基数。基于这些测定值,算出饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于多元醇(A)所包含的羟基数的比率。将其结果示于表2中。
接着,使用该层压用粘接剂1,以干层压方式制造出具有外层/外层用粘接剂/铝箔层/层压用粘接剂1/树脂膜这样的结构的电池外装用包装材料。各层的详细情况如下所示。
外层:拉伸聚酰胺膜(厚度25μm)
外层用粘接剂:氨基甲酸酯系干式层压用粘接剂(AD502/CAT10,东洋モートン株式会社制,涂布量3g/m2(涂布时))
铝箔层:铝-铁系合金的铝箔(AA规格8079-O材,厚度40μm)
层压用粘接剂1:上述层压用粘接剂1(涂布量:干燥后的厚度为2μm)
树脂膜:未拉伸聚丙烯膜(厚度40μm)
(实施例2~14、比较例1~9)
采用表2~表4所示的配合,除此以外,与实施例1同样地操作,调制出金属箔与树脂膜的层压用粘接剂2~23(组合物2~23)。
接着,代替层压用粘接剂1而使用了层压用粘接剂2~23,除此以外,与实施例1同样地操作,制造出电池外装用包装材料。
另外,表2~表4中的各成分的详细情况如下所示。
·酸改性聚丙烯:被马来酸酐和丙烯酸辛酯改性了的酸改性聚丙烯(酸值20mg/KOH)
·デュラネートTKA-100:旭化成ケミカルズ株式会社制,1,6-己二异氰酸酯的异氰脲酸酯体
·1,6-己二异氰酸酯:东京化成工业株式会社制的试剂
·デスモジュールXP 2565:バイエル社制,异佛尔酮二异氰酸酯的脲基甲酸酯化多聚体(80质量份)和乙酸丁酯(20质量份)的混合物
·デスモジュールZ 4470:バイエル社制,异佛尔酮二异氰酸酯的异氰脲酸酯体(70质量份)和乙酸丁酯(30质量份)的混合物
·异佛尔酮二异氰酸酯:东京化成工业株式会社制的试剂
·BiCAT Z:Shepherd Chemical社制,新癸酸锌
·ヘキソエート亜鉛:东荣化工株式会社制,2-乙基己酸锌(65质量份)和矿油精(35质量份)的混合物
·エフコ·ケムZNS-P:株式会社ADEKA制,硬脂酸锌
·乙酰丙酮锌:东京化成工业株式会社制的试剂
·ヘキソエートマンガン:东荣化工株式会社制,辛酸锰(42质量份)和矿油精(58质量份)的混合物
·KS-1260:堺化学工业株式会社制,二月桂酸二丁基锡
·乙酰丙酮钛:东京化成工业株式会社制的试剂
·BiCAT8210:Shepherd Chemical社制,三(2-乙基己酸)铋(三(2-乙基己酸)铋)(89质量份)和2-乙基己酸(11质量份)的混合物
<剥离强度>
使用由获得的电池外装用包装材料切出长度150mm×宽度15mm的材料作为试验片,测定电解液溶剂浸渍后的T字剥离强度、长期电解液溶剂浸渍后的T字剥离强度和85℃气氛下的T字剥离强度。测定的条件、方法如下述(1)~(3)所示。各试验以n=2来进行(对2个试验片进行测定),取其平均值。此外,将结果示于表2~表4中(单位全部是N/15mm)。
(1)电解液溶剂浸渍后的T字剥离强度
将长度150mm×宽度15mm的试验片在85℃的电解液溶剂(碳酸亚乙酯/碳酸二乙酯,质量比50/50)中浸渍1天后,取出。接着对于该试验片,使用自动绘图仪AG-X(岛津制作所制),在23℃×50%RH气氛下,在剥离速度100mm/min的条件下,测定铝箔层与未拉伸聚丙烯膜层(树脂膜)之间的180°剥离强度。将其结果示于表2~表4中。
(2)长期电解液溶剂浸渍后的T字剥离强度
将浸渍于85℃的电解液溶剂的期间从1天变更为4周,除此以外,利用与(1)相同的方法,测定铝箔层与未拉伸聚丙烯膜层之间的180°剥离强度。将其结果示于表2~表4中。
(3)85℃气氛下的T字剥离强度
使用长度150mm×宽度15mm的试验片和自动绘图仪AG-X(株式会社岛津制作所制),放置于85℃气氛下,在试验片的温度成为85℃之后以剥离速度100mm/min使其剥离,测定铝箔层与未拉伸聚丙烯膜层之间的180°剥离强度。将其结果示于表2~表4中。
[表1]
表1
Figure BDA0001470310500000241
[表2]
表2
Figure BDA0001470310500000251
*1:饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于多元醇(A)所包含的羟基数的比率。
*2:数值为直接数值。
[表3]
表3
Figure BDA0001470310500000261
*1:饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于多元醇(A)所包含的羟基数的比率。
*2:数值为直接数值。
[表4]
表4
Figure BDA0001470310500000271
*1饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于多元醇(A)所包含的羟基数的比率。
*2:数值为直接数值。
(考察)
由表2和表3的结果可知,本发明的金属箔与树脂膜的层压用粘接剂(实施例1~14)的电解液溶剂浸渍后的T字剥离强度、长期电解液溶剂浸渍后的T字剥离强度和85℃气氛下的T字剥离强度都是平衡好且优异。
与此相对,如表4所示可知,在使用不含(C)成分的金属箔与树脂膜的层压用粘接剂的情况下(比较例1、2),长期电解液溶剂浸渍后的T字剥离强度不充分,在使用不含(b1)和/或(b2)的金属箔与树脂膜的层压用粘接剂的情况下(比较例3~5),电解液溶剂浸渍后的T字剥离强度和长期电解液溶剂浸渍后的T字剥离强度不充分,在将(C)成分变更为第7族和/或第12族以外的金属化合物的情况下(比较例6~8),长期电解液溶剂浸渍后的T字剥离强度不充分,在使用将改性聚烯烃作为主剂的金属箔与树脂膜的层压用粘接剂的情况下(比较例9),85℃气氛下的T字剥离强度不充分。
产业可利用性
本发明的金属箔和树脂膜层压用金属箔与树脂膜的层压用粘接剂即使在长期电解液浸渍后、高温下也具有优异的粘接力,特别是适合于铝箔与热熔合性树脂膜的接合用。此外,本发明的叠层体由于耐热性、耐电解液性优异,因此适合用于锂离子电池等二次电池的制作所使用的电池外装用包装材料,通过将该叠层体进行成型,从而可以制造耐热性、耐电解液性优异的电池壳体。而且,通过使用该电池壳体,从而能够制造寿命长的安全的二次电池。

Claims (14)

1.一种金属箔与树脂膜的层压用粘接剂,其具有多元醇(A)、多异氰酸酯的多聚体(B)以及金属化合物(C),所述金属化合物(C)是第7族和第12族中的至少1种金属的化合物,
所述多异氰酸酯的多聚体(B)包含饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2),
所述多元醇(A)包含将下述成分加聚而得的聚氨酯多元醇,所述成分含有链状聚烯烃多元醇(a11)和聚酯多元醇(a12)中的至少1种、兼具饱和的环式烃结构和2个以上羟基的含羟基环式烃化合物(a2)、以及多异氰酸酯(a3)。
2.根据权利要求1所述的金属箔与树脂膜的层压用粘接剂,所述聚酯多元醇(a12)包含具有氢化二聚酸来源的构成单元和氢化二聚二醇来源的构成单元的聚酯多元醇。
3.根据权利要求1或2所述的金属箔与树脂膜的层压用粘接剂,所述饱和脂肪族多异氰酸酯的多聚体(b1)包含饱和脂肪族多异氰酸酯的异氰脲酸酯体。
4.根据权利要求1或2所述的金属箔与树脂膜的层压用粘接剂,所述饱和脂环式多异氰酸酯的多聚体(b2)包含异佛尔酮二异氰酸酯的多聚体。
5.根据权利要求1或2所述的金属箔与树脂膜的层压用粘接剂,饱和脂肪族多异氰酸酯的多聚体(b1)和饱和脂环式多异氰酸酯的多聚体(b2)所包含的异氰酸酯基数相对于所述多元醇(A)所包含的羟基数的比率为1~15。
6.根据权利要求1或2所述的金属箔与树脂膜的层压用粘接剂,所述金属化合物(C)至少包含第7族和第12族中的至少一种金属的羧酸盐1种以上。
7.根据权利要求1或2所述的金属箔与树脂膜的层压用粘接剂,所述金属化合物(C)包含锌或锰的羧酸盐。
8.根据权利要求1或2所述的金属箔与树脂膜的层压用粘接剂,其进一步包含溶剂(D)。
9.一种叠层体,其是金属箔与树脂膜经由粘接剂层叠层而得的,所述粘接剂层由权利要求1~8中的任一项所述的金属箔与树脂膜的层压用粘接剂获得。
10.根据权利要求9所述的叠层体,所述金属箔为铝箔,所述树脂膜含有热熔合性树脂膜。
11.根据权利要求9或10所述的叠层体,所述金属箔的厚度为10~100μm,所述树脂膜的厚度为9~100μm。
12.一种电池外装用包装材料,其是使用权利要求9~11中的任一项所述的叠层体而获得的。
13.一种电池壳体,其是使用权利要求12所述的电池外装用包装材料而获得的。
14.一种电池壳体的制造方法,将权利要求12所述的电池外装用包装材料进行深拉成型或鼓凸成型。
CN201680028381.1A 2015-06-10 2016-05-17 金属箔与树脂膜的层压用粘接剂、叠层体、电池外装用包装材料以及电池壳体及其制造方法 Active CN107614648B (zh)

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