CN115558442A - 聚烯烃类粘接剂组合物 - Google Patents
聚烯烃类粘接剂组合物 Download PDFInfo
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- CN115558442A CN115558442A CN202211266830.XA CN202211266830A CN115558442A CN 115558442 A CN115558442 A CN 115558442A CN 202211266830 A CN202211266830 A CN 202211266830A CN 115558442 A CN115558442 A CN 115558442A
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- CN
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- Prior art keywords
- adhesive composition
- modified polyolefin
- mass
- propylene
- curing agent
- Prior art date
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Abstract
提供一种可以在低温下进行贴合及熟化、粘接性、耐电解液性、耐热性、耐久性、成形性优异的粘接剂组合物。一种粘接剂组合物,其为海岛结构,在海中含有改性聚烯烃(A)和固化剂(C)的反应物,在岛中含有热塑性树脂(B)和固化剂(C)的反应物。
Description
本申请是基于以下中国专利申请的分案申请:
原案申请日:2019年03月13日
原案申请号:201980023372.7(PCT/JP2019/010256)
原案申请名称:聚烯烃类粘接剂组合物
技术领域
本发明涉及粘接剂组合物、层叠体及锂离子电池用包装材料。
背景技术
近年来,作为用于个人计算机、手机等便携终端装置、摄影机、卫星等的电池,可超薄型化、小型化的锂离子电池正被积极开发。该锂离子电池的包装材料与以往使用的金属制罐不同,由于轻量且可自由地选择电池的形状的优点,正渐渐开始使用如基材层/阻挡层/密封剂层的构成的层叠体。
锂离子电池含有正极材料及负极材料,同时还含有将锂盐溶解于碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸乙基甲酯等非质子性溶剂而得的电解液或由含浸有该电解液的聚合物凝胶构成的电解质层作为电池内容物。这样的强渗透性溶剂若通过密封剂层,则会使阻挡层与密封剂层之间的层压强度降低,发生分层,最终会产生诸如电解液漏出这样的问题。此外,作为电池的电解质即锂盐,使用LiPF6、LiBF4等物质,但这些盐会因与水分的水解反应而产生氢氟酸,氢氟酸会腐蚀阻挡层,从而使层压强度降低。如此地,电池用包装材料需具有对电解质的耐受性。
此外,假设在各种环境下使用锂离子电池的情况,需具备更加严苛的耐受性。例如用于移动设备时,要求诸如在车内等的60~70℃的高温环境下的耐漏液性。此外,假定用于手机而误掉入水中的情况,需要水分不会浸入的耐水性。
基于这样的情况,有人提出了各种改善耐电解液性的锂电池用包装材料(例如参照专利文献1~2)。
背景技术文献
专利文献
专利文献1:国际公开第2014/123183号单行本
专利文献2:国际公开第2017/187904号单行本
发明内容
发明所要解决的问题
但是,前述提出的锂电池用包装材料在成形性及加工性方面还不充分。具体地,当将包装材料加工成软包状时,有时粘接剂层不遵循基材之间的延伸而剥离。而且,耐热性方面仍然不充分。
本发明提供一种与聚烯烃树脂基材及金属基材具有良好的粘接性及对基材的显著的追随性,且具有优异的耐热性及耐电解液性的粘接剂组合物。并且,还提供一种含有该粘接剂组合物的层叠体及含有该层叠体的电池用包装材料。
解决问题的技术方案
为了实现上述技术问题,本发明的发明人进行了深入研究,发现在含有改性聚烯烃的粘接剂组合物中,与热塑性树脂具有海岛型结构作为粘接剂非常有效,从而提出了以下发明。
即,本发明是一种粘接剂组合物,其为海岛结构,在海中含有改性聚烯烃(A)和固化剂(C)的反应物,在岛中含有热塑性树脂(B)和固化剂(C)的反应物。
所述海岛结构的岛相的粒径优选为0.001~5μm。
所述改性聚烯烃(A)的酸值优选为2~50mgKOH/g。
所述改性聚烯烃(A)优选含有丙烯及1-丁烯作为烯烃成分,且丙烯与1-丁烯的摩尔比为丙烯/1-丁烯=98~60/2~40。
所述热塑性树脂(B)优选为苯乙烯类弹性体。
所述热塑性树脂(B)优选具有2~50mgKOH/g的酸值。
所述热塑性树脂(B)的含量优选相对于100质量份所述改性聚烯烃(A)为5~30质量份。
所述固化剂(C)优选为环氧固化剂或异氰酸酯固化剂中的任一种。
所述固化剂(C)的含量优选相对于100质量份所述改性聚烯烃(A)为0.5~40质量份。
所述改性聚烯烃(A)优选包含熔点为50℃~155℃的改性聚烯烃(A1),及熔点为55℃~160℃的改性聚烯烃(A2)。
所述改性聚烯烃(A1)与所述改性聚烯烃(A2)的质量比优选为(A1)/(A2)=99~21/1~79。
一种层叠体,其通过在基材的至少一个表面上层叠所述粘接剂组合物而形成。
所述基材为聚烯烃基材或金属基材的层叠体。
一种锂离子电池用包装材料,其以所述层叠体作为构成部件。
发明的效果
本发明的粘接剂组合物包含改性聚烯烃和固化剂的反应物,及热塑性树脂和固化剂的反应物,由于是海岛结构,因此具有与基材的显著的追随性。因此深冲性能等加工特性优异。另外,可以表现出良好的粘接性和耐电解液性,并且可以表现出优异的耐热性和耐软包膨胀性。
附图说明
图1是显示实施例的粘接剂组合物的海岛结构的透射型电子显微镜照片的一个例子。
具体实施方式
以下,对本发明的实施方式进行详细地说明。
<海岛结构>
本发明的粘接剂组合物需要包含海岛结构。海岛结构是指两种以上的成分的混合物中该成分彼此不发生相分离而微细地分散而成的结构。本发明的粘接剂组合物中,通过在海中包含改性聚烯烃(A)与固化剂(C)的反应产物,在岛中包含热塑性树脂(B)与固化剂(C)的反应产物而形成海岛结构,从而导入细微的弹性体区域,改善了在加工时及使用时对基材变形的跟随性,并且提高耐软包膨胀性。耐软包膨胀性是指如下的性质,例如,当本发明的粘接剂组合物用于锂离子电池中时,即使在高温条件下锂离子电池中的基材拉伸,基材的粘接面之间也会维持粘接性进行追随而不发生剥落或断裂。
本发明的粘接剂组合物的岛相的粒径优选为0.001~5μm。该岛相的粒径优选为4μm以下,更优选为2μm以下,进一步优选为1μm以下,更进一步优选为0.5μm以下,最优选为0.4μm以下。另外,优选为0.003μm以上,更优选为0.005μm以上,进一步优选为0.01μm以上,更进一步优选0.05μm以上,最优选0.09μm以上。岛的粒径小于0.001μm时,有时具有海岛结构时产生的空穴作用不充分,无法得到良好的柔软性及基材追随性。岛的粒径超过5μm时,岛存在于粘接界面时,有时会较大地阻碍海的粘接,因此无法得到良好的粘接性。岛的形状为椭圆等的情况下,设定为测定长轴的长度。
本发明的粘接剂组合物优选粘接剂组合物的10μm×10μm的每单位面积上的总岛数的80%以上的岛的粒径为0.001~5μm。更优选为85%以上,进一步优选为90%以上。更进一步优选为95%以上,最优选为100%。若小于85%,则粘接性降低。
<粘接剂组合物>
本发明的粘接剂组合物是海岛结构,是在海中包含改性聚烯烃(A)和固化剂(C)的反应物,在岛中包含热塑性树脂(B)和固化剂(C)的反应物的粘接剂组合物。本发明涉及的粘接剂组合物,可以通过将包含所述改性聚烯烃(A)、热塑性树脂(B)及固化剂(C)的组合物涂布在基材上,并进行干燥、固化而得到。求出本发明的粘接剂组合物中的海部及岛部的含有比例的方法有,例如,对粘接剂组合物的照片使用图像处理装置的方法;用描图纸复制粘接剂组合物的照片,切取岛部,测定求出纸的重量的方法。作为所述照片,例如,将本发明的粘接剂组合物用作粘接剂层制成层叠体,使用冷冻超薄切片机(cryomicrotome)由粘接剂层剖面制备切片,对实施了染色、镀碳的样品使用日本电子公司制造的JEM2100透射电子显微镜在200kV的加速电压下,并以2000的放大倍数下拍摄的照片。
在本发明的粘接剂组合物100质量份中,岛结构的含量优选为40质量份以下,更优选为30质量份以下,进一步优选为20质量份以下。另外,该含量优选为0.1质量份以上,更优选为0.5质量份以上,进一步优选为1质量份以上。超过所述值时,有时粘接性降低,低于所述值时,有时耐软包膨胀性降低。
本发明的粘接剂组合物的海结构100质量份中的改性聚烯烃(A)和固化剂(C)的反应物的含量为60质量份以上,更优选为70质量份以上,进一步优选为80质量份以上。低于所述值时,有时粘接性降低。
本发明的粘接剂组合物的岛结构100质量份中的热塑性树脂(B)和固化剂(C)的反应物的含量优选为70质量份以上,更优选为80质量份以上,进一步优选为90质量份以上。低于所述值时,有时耐软包膨胀性降低。
<改性聚烯烃(A)>
在本发明中使用的改性聚烯烃(A)没有限定,但优选在聚乙烯、聚丙烯和丙烯-α-烯烃共聚物中的至少一种实施了改性的聚烯烃。另外,改性聚烯烃(A1)及(A2)更优选在聚丙烯或丙烯-α-烯烃共聚物中实施了改性的聚烯烃。
丙烯-α-烯烃共聚物将丙烯作为主体并与α-烯烃进行共聚。作为α-烯烃,可以使用,例如,乙烯、丙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等中的1种或多种。这些α-烯烃中,优选为乙烯、1-丁烯,最优选为1-丁烯。丙烯-烯-烯烃共聚物中的丙烯成分与α-烯烃成分的摩尔比优选为99~40/1~60,更优选为98~45/2~55,进一步优选为94~60/6~40。另外,丙烯-另-烯烃共聚物中丙烯成分和1-丁烯成分的总量优选为72mol%以上,更优选为80mol%以上,进一步优选为90mol%以上,最优选为100mol%。另外,丙烯/1-丁烯的摩尔比优选为99~60/1~40,优选为98~65/2~35。另外,丙烯-另-烯烃共聚物优选乙烯含量较少。
改性聚烯烃(A)可以为单独的树脂,也可以为2种以上的不同的改性聚烯烃的混合物。组合使用2种以上的改性聚烯烃的情况下,优选为改性聚烯烃(A1)及改性聚烯烃(A2)。
改性聚烯烃中(A1)的丙烯含量优选为28mol%以上,更优选为40mol%以上,进一步优选为50mol%以上,特别优选为65mol%以上。另外,优选为100mol%以下,更优选为98mol%以下,特别优选为90mol%以下。通过含有30mol%以上的丙烯,有助于与丙烯基材的密合性变得良好。另外,可以含有丙烯以外的α-烯烃成分。
优选改性聚烯烃(A1)的丙烯与1-丁烯的摩尔比为丙烯/1-丁烯=98~40/2~60。丙烯的摩尔比优选为50%以上,进一步优选为60%以上,更优选为70%以上。丙烯的摩尔比为40%以上,由此,可显示出与聚烯烃基材、特别是与聚丙烯基材优异的密合性。另外,丙烯的摩尔比更优选为95%以下,进一步优选为93%以下,最优选为90%以下。并且,若1-丁烯的摩尔比为2%以上,则改性聚烯烃变得柔软,与基材的追随性等的加工特性提高。1-丁烯的摩尔比更优选为5%以上,进一步优选为7%以上,最优选10%以上。1-丁烯的摩尔比更优选为50%以下,进一步优选为40%以下,最优选30%以下。
改性聚烯烃中(A2)的丙烯含量优选为30mol%以上,更优选为40mol%以上,进一步优选为45mol%以上,特别优选为60mol%以上,最优选为70mol%以上。另外,优选为100mol%以下,更优选为99mol%以下,特别优选为97mol%以下。通过含有30mol%以上的丙烯,倾向于显示出与丙烯基材良好的密合性。另外,可以含有除丙烯以外的α-烯烃成分。
改性聚烯烃(A2)的丙烯与1-丁烯的摩尔比优选为丙烯/1-丁烯=99~45/1~55。丙烯的摩尔比更优选为55%以上,进一步优选为65%以上,更进一步优选为76%以上。通过丙烯的摩尔比为45%以上,可以显示出与聚烯烃基材、特别是与聚丙烯基材优异的密合性。另外,更优选丙烯的摩尔比为97%以下。进一步优选为94%以下,最优选92%以下。并且,若1-丁烯的摩尔比为1%以上,则改性聚烯烃变得柔软,对基材的追随性等加工特性提高。1-丁烯的摩尔比更优选为3%以上,进一步优选为6%以上,最优选8%以上。1-丁烯的摩尔比更优选为45%以下,进一步优选为35%以下,最优选24%以下。
作为本发明中使用的改性聚烯烃(A)的改性,具体而言,可列举:酸改性、氯改性、丙烯改性、羟基改性等。(A1)及(A2)这两者分别需要进行这些中的一种以上的改性。另外,特别优选改性聚烯烃(A1)及(A2)进行了酸改性。
本发明中使用的改性聚烯烃(A)没有限定,优选通过将α,β-不饱和羧酸及其酸酐的至少1种接枝于聚乙烯、聚丙烯及丙烯-丙-烯烃共聚物的至少1种。作为α,β-不饱和羧酸及其酸酐中的至少1种,可列举,例如,马来酸、衣康酸、柠康酸及它们的酸酐。这些之中,优选酸酐,更优选马来酸酐。具体地可列举马来酸酐改性聚丙烯、马来酸酐改性丙烯-乙烯共聚物、马来酸酐改性丙烯-1-丁烯共聚物、马来酸酐改性丙烯-乙烯-1-丁烯共聚物等,这些酸改性聚烯烃可使用1种,或可将2种以上组合使用。
从聚烯烃树脂基材及金属基材之间的粘接性及耐电解液性的观点出发,改性聚烯烃(A)的酸值优选为2~50mgKOH/g的范围。更优选为3~45mgKOH/g,进一步优选为5~40mgKOH/g,特别优选7~35mgKOH/g的范围。在所述范围内时,通过与固化剂良好地相容提高交联密度,并提高粘接强度、耐化学品性(耐电解液性)。另外,组合使用改性聚烯烃(A1)及改性聚烯烃(A2)时,优选分别具有与改性聚烯烃(A)相同的酸值。
改性聚烯烃(A)的熔点优选为50~160℃。另外,更优选改性聚烯烃(A)包含熔点为50~155℃的改性聚烯烃(A1)和熔点为55~160℃的改性聚烯烃(A2),且与改性聚烯烃(A1)相比,改性聚烯烃(A2)为高熔点。通过组合使用高熔点的改性聚烯烃和低熔点的改性聚烯烃,即使在聚烯烃基材的热收缩影响小的80℃以下这样的低温下进行贴合,在40℃以下这样的低温下进行熟化,也可发挥聚烯烃树脂基材与金属基材之间良好的粘接性和耐药品性,而且固化后具有优异的耐热性。并且,(A1)与(A2)的熔点之差优选为3~55℃,更优选为4~45℃,进一步优选为5~30℃。超过所述值时,可能无法兼顾低温加工性、耐电解液性及高温条件下的耐久性。
改性聚烯烃(A1)的熔点(Tm)优选50℃~155℃的范围,更优选为55℃~120℃的范围。进一步优选为60℃~100℃的范围,最优选70℃~90℃的范围。小于所述值时,则有时晶体来源的聚集力较弱,粘接性及耐化学品性较差。另一方面,超过所述值时,有时溶液稳定性、流动性较低,在粘接时的操作性方面产生问题。
改性聚烯烃(A2)的熔点(Tm)优选55℃~160℃的范围,更优选为60℃~125℃的范围。进一步优选为65℃~105℃的范围,最优选75℃~95℃的范围。小于所述值时,则有时晶体来源的内聚力较弱,粘接性及耐化学品性较差。另一方面,大于所述值时,有时溶液稳定性、流动性较低,在粘接时在操作性方面产生问题。
改性聚烯烃(A)的熔点可以通过改性聚烯烃的结晶性进行调整,例如,在酸改性丙烯-1-丁烯共聚物的情况下,通过增加1-丁烯成分的比率,降低共聚物中基于丙烯聚合部产生的结晶性,由此降低熔点。
改性聚烯烃(A1)及(A2)的质量比优选为(A1)/(A2)=99~21/1~79,更优选为75~25/25~75的范围。进一步优选为60~40/40~60的范围。若在所述范围内,则可以兼顾固低温加工性、耐电解液性及高温条件下的耐久性。
改性聚烯烃(A)的酸值可以通过α,β-不饱和羧酸、α,β-不饱和羧酸的酸酐及自由基产生剂的使用量进行調整。
改性聚烯烃(A)的熔解热(ΔH)优选为1J/g~60J/g的范围。更优选为3J/g~50J/g的范围,最优选为5J/g~40J/g的范围。小于所述值时,有时晶体来源的内聚力较弱,粘接性及耐化学品性较弱。另一方面,大于所述值,有时溶液稳定性、流动性较低,进行粘接时,在操作性方面产生问题。另外,组合使用改性聚烯烃(A1)及改性聚烯烃(A2)时,优选分别具有与改性聚烯烃(A)相同的熔解热。
作为改性聚烯烃(A)的制造方法没有特别限定,例如,可以列举出:自由基接枝反应(即,对作为主链的聚合物产生自由基种,以该自由基种为聚合起始点,使不饱和羧酸和酸酐接枝聚合的反应)等。
作为自由基产生剂并无特别的限定,例如可列举有机过氧化物、偶氮腈类,优选使用有机过氧化物。作为有机过氧化物,没有特别限定,可列举:过氧化苯二甲酸二叔丁酯、叔丁基过氧化氢、过氧化二异丙苯、过氧化苯甲酰、过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过氧化三甲基乙酸叔丁酯、过氧化甲乙酮、二叔丁基过氧化物、过氧化月桂酰等过氧化物;偶氮双异丁腈、偶氮双异丙腈等偶氮腈类等。
优选改性聚烯烃(A)的重均分子量(Mw)为10,000~200,000的范围,更优选为20,000~180,000的范围,进一步优选为30,000~160,000的范围,特别优选40,000~140,000的范围,最优选50,000~110,000的范围。小于所述值时,有时内聚力较弱,粘接性较差。另一方面,大于所述值时,有时流动性降低,进行粘接时在操作性方面产生问题。若在所述范围内,则能有效利用与固化剂的固化反应,故优选。另外,组合使用改性聚烯烃(A1)及改性聚烯烃(A2)时,优选分别具有与改性聚烯烃(A)相同的重均分子量。
<热塑性树脂(B)>
本发明中使用的热塑性树脂(B)没有特别限定,可以使用具有苯乙烯骨架的热塑性树脂。作为苯乙烯类热塑性树脂,具体而言可以列举:苯乙烯-乙烯-丁烯-苯乙烯共聚树脂、苯乙烯-乙烯-丙烯-苯乙烯共聚树脂、苯乙烯-丁二烯共聚树脂、苯乙烯-乙烯共聚树脂、苯乙烯-丁烯共聚树脂、苯乙烯-乙烯-苯乙烯共聚树脂、苯乙烯-丁烯-苯乙烯共聚树脂等的苯乙烯类弹性体等。另外,作为不具有苯乙烯骨架的热塑性树脂,可列举乙烯-丙烯共聚树脂、乙烯-丁烯共聚树脂、乙烯-乙酸乙烯酯共聚树脂、乙烯-丙烯酸乙酯共聚树脂等的烯烃类弹性体等。其中,从与改性聚烯烃(A)的相容性及耐热性的观点出发,优选苯乙烯-乙烯-丁烯-苯乙烯共聚树脂、苯乙烯-乙烯-丙烯-苯乙烯等的苯乙烯类弹性体。
热塑性树脂(B)可以具有酸值。优选具有2~50mgKOH/g的范围的酸值,更优选为3~45mgKOH/g,进一步优选为5~40mgKOH/g,特别优选在7~35mgKOH/g。另外,对热塑性树脂(B)进行酸改性的情况下,优选进行马来酸酐改性。通过具有所述范围的酸值,与改性聚烯烃(A)、及固化剂(C)的相容性变得良好,通过与固化剂(C)的交联,内聚力、粘接力及耐热性提高。
热塑性树脂(B)的配入量相对于改性聚烯烃共聚物(A)(组合使用改性聚烯烃(A1)和改性聚烯烃(A2)的情况下为其总量)100质量份为3~60质量份,优选为(B)/(A)=3~60(质量份)/100(质量份)。更优选为8~40(质量份)/100(质量份),进一步优选为8~30质量份的范围,特别优选10~20(质量份)/100(质量份)的范围。通过在所述范围,成为具有海岛结构的粘接剂组合物,能够具有适当的柔软性,并兼具深冲性能等加工特性及与聚烯烃基材的粘接性。
<固化剂(C)>
本发明中使用的固化剂(C)没有特别限定,例如,可列举:环氧固化剂、异氰酸酯固化剂、碳化二亚胺类固化剂、噁唑啉类固化剂等,优选使用环氧固化剂或异氰酸酯固化剂。
本发明的粘接剂组合物中含有的环氧固化剂没有特别限定,可以优选使用环氧树脂及从这些中衍生的化合物。作为具体例,可列举缩水甘油胺型环氧树脂、缩水甘油醚型环氧树脂、六氢邻苯二甲酸缩水甘油酯、二聚酸缩水甘油酯等的缩水甘油酯型,或3,4-环氧环己基甲基羧酸酯、环氧化聚丁二烯、环氧化大豆油等脂环族或脂肪族环氧化物等,可以单独使用1种,可以组合使用2种以上。
作为缩水甘油胺型环氧树脂的具体例,没有特别限定,可列举四缩水甘油基二氨基二苯基甲烷、三缩水甘油基对氨基苯酚、四缩水甘油基双氨基甲基环己酮、N,N,N’,N’-四缩水甘油基-间苯二甲胺等的缩水甘油胺类等。其中,优选N,N,N’,N’-四缩水甘油基-间苯二甲胺。这些缩水甘油胺型环氧树脂可单独使用或两种以上组合使用。
作为缩水甘油醚型环氧树脂的具体例,没有特别限定,可列举苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂,从这些与金属基板的粘接性及耐化学品性的观点出发,优选。这些缩水甘油醚型环氧树脂可以单独使用或两种以上组合使用。
作为环氧固化剂,从与金属基材的粘接性及耐化学品性这样的观点出发,优选并用缩水甘油胺型环氧树脂和缩水甘油醚型环氧树脂。优选的质量比为缩水甘油胺型环氧树脂/缩水甘油醚型环氧树脂=1~30/99~70,更优选为5~20/95~80,进一步优选为8~15/92~75。
本发明的粘接剂组合物中含有的异氰酸酯固化剂没有特别限定,可以优选使用二异氰酸酯、三异氰酸酯及从这些衍生出的化合物。例如,可列举2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、苯二甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,5-萘二异氰酸酯、六亚甲基二异氰酸酯、双(4-异氰酸酯环己基)甲烷或氢化二苯基甲烷二异氰酸酯等二异氰酸酯。进一步,可列举从上述二异氰酸酯衍生得到的化合物,即,上述二异氰酸酯的异氰尿酸酯体、加合物、缩二脲型、脲二酮体、脲基甲酸酯体、具有异氰酸酯残基的预聚物(由二异氰酸酯和多元醇获得的低聚物)、异氰尿酸三缩水甘油酯、或它们的复合体。这些可单独使用,也可两种以上任意组合使用。
作为异氰酸酯固化剂,其中,由于耐电解液性优异,优选具有上述二异氰酸酯化合物的异氰尿酸酯体。
固化剂(C)除环氧固化剂、异氰酸酯固化剂,还可以列举碳化二亚胺化合物、噁唑啉化合物、偶联剂类等。作为碳化二亚胺化合物,可列举二甲基碳化二亚胺、二异丙基碳化二亚胺、二环己基碳化二亚胺、叔丁基异丙基碳化二亚胺、二苯基碳化二亚胺、二-β-萘基碳化二亚胺等的单碳化二亚胺化合物类,或脂肪族二异氰酸酯、芳香族二异氰酸酯或脂环族二异氰酸酯等有机二异氰酸酯在缩合催化剂的存在下,无溶剂或非活性溶剂中,进行脱碳酸缩合反应而制造的聚碳二亚胺化合物类等。另外,作为噁唑啉化合物,可列举:2-噁唑啉、2-甲基-2-噁唑啉、2-苯基-2-噁唑啉、2,5-二甲基-2-噁唑啉、或2,4-二苯基-2-噁唑啉等的单噁唑啉化合物、2,2’-(1,3-亚苯基)-双(2-噁唑啉)、2,2’-(1,2-亚乙基)-双(2-噁唑啉)、2,2’-(1,4-亚丁基)-双(2-噁唑啉)、或2,2’-(1,4-亚苯基)-双(2-噁唑啉)等的二噁唑啉化合物等。另外,作为偶联剂,可列举硅烷偶联剂、钛酸酯偶联剂等。
本发明的粘接剂组合物的固化剂(C)的含量相对于改性聚烯烃(A)100质量份优选0.5~40质量份的范围,更优选为1~35质量份,进一步优选为2~30质量份,特别优选3~25质量份的范围。小于所述值时,则有时无法得到充分的固化効果,粘接性及耐化学品性较低。大于所述范围时,则有时适用期性及粘接性降低,并且追随性降低从而导致在成形时产生针孔。并且从成分方面的观点出发不优选。另外,通过在所述范围内,可以具有海岛结构。
本发明的粘接剂组合物在无损本发明的性能的范围中,可以含有所述改性聚烯烃(A)、热塑性树脂(B)及固化剂(C),还可以还有各种的增粘剂、增塑剂、固化促进剂、阻燃剂、顔料、防黏连剂等的添加剂。
本发明中的粘接剂组合物,没有特别限定,可以通过对含有所述改性聚烯烃(A)、热塑性树脂(B)及固化剂(C)及有机溶剂的组合物进行涂布并干燥而得到。作为有机溶剂,只要是可使改性聚烯烃(A)、热塑性树脂(B)及固化剂(C)溶解或分散的有机溶剂即可,没有特别限定,可示例:脂肪族烃及脂环族烃等的低极性溶剂、醇类溶剂、醚类溶剂、酮类溶剂、酯类溶剂等的高极性溶剂等。从保存稳定性及适用期的观点出发,优选组合使用低极性溶剂和高极性溶剂。高极性溶剂和低极性溶剂的含量比优选为60~3/40~97(质量比)、更优选为50~5/50~95、进一步优选为40~8/60~90、最优选为30~20/70~80。
所述的有机溶剂中,作为低极性溶剂,优选作为脂环族烃的环己烷等,作为高极性溶剂优选作为酮类溶剂的甲基乙基酮等。这些有机溶剂相对于改性聚烯烃(A)(组合使用改性聚烯烃(A1)和改性聚烯烃(A2)的情况下为其总量)及热塑性树脂(B)的总量100质量份,优选含有80~2000质量份,更优选为90~1600质量份,进一步优选为100~1200质量份,特别优选110~800质量份的范围。通过在所述范围内,溶液状态及适用期性容易变得良好。
<层叠体>
本发明的层叠体是在基材的至少一个表面上层叠粘接剂组合物得到的层叠体。另外,所述基材可以是聚烯烃基材或金属基材。另外,可以是以聚烯烃基材、粘接剂组合物和金属基材的顺序层叠的层叠体。
本发明的粘接剂组合物优选在110℃的储能模量为1.0×104Pa以上。进一步优选为1.0×105Pa以上,更优选为1.0×106Pa以上。小于1.0×104Pa时,由于耐热性较差,因此不利于在高温环境下的实用性。储能模量可以根据JIS K7244-4(1999)(ISO6721-4:1994)的实验法进行测定。
本发明的粘接剂组合物在25℃下的拉伸断裂伸长率优选为200%以上。进一步优选为250%以上,更优选为300%以上。小于200%的情况下,存在与基材的追随性较差的情况。拉伸断裂伸长率可以根据JIS K7161(2014)(ISO527)的实验法进行测定。
作为进行层压的方法,可以利用目前公知的层压制造技术。例如,没有特别限定,可以在金属基材的表面上,将改性聚烯烃(A)与热塑性树脂(B)与固化剂(C)的混合物(以下,也称为组合物)使用辊涂机及棒涂机等的适当的涂布手段进行涂布及干燥。在干燥后,在金属基材表面上形成的组合物层(粘接剂层)还处于熔融状态的情况下,将聚烯烃树脂基材层压粘接(laminate-bonded)在该涂布面上而得到层叠体。即使在所述层压温度为80℃以下这样的低温下,也可以得到具有优异的粘接性、耐电解液性及基材追随性的粘接性组合物。
通过所述粘接性组合物形成的粘接剂层的厚度没有特别限定,优选为0.5~10μm,更优选为0.8~9.5μm,进一步优选为1~9μm。
<聚烯烃树脂基材>
作为聚烯烃树脂基材,从目前的公知的聚烯烃树脂中适宜选择即可。例如,没有特别特别限定,可以使用聚乙烯、聚丙烯、乙烯-丙烯共聚物等。其中,优选使用聚丙烯的无拉伸膜(以下,也称为CPP)。其厚度没有特别限定,优选20~100μm,更优选为25~95μm,进一步优选为30~90μm。需要说明的是,聚烯烃树脂基材中可以根据需要添加颜料及各种添加物,可以进行表面处理。
<金属基材>
作为金属基材,没有特别限定,例如可以使用铝、铜、钢铁、铬、锌、硬铝、压铸件等各种金属及其合金。此外,其形状可采金属箔、压延钢板、平板、管、罐、盖等任意形状。一般而言,基于加工性等的观点,优选铝箔。此外,尽管因使用目的而有所不同,一般以0.01~10mm、优选0.02~5mm的厚度的片材形式使用。
实施例
以下列举实施例对本发明更详细地说明。只是本发明并不限定于实施例。
<酸值的测定>
本发明的酸值(mgKOH/g)是中和1g的酸改性树脂所需要的KOH量,并以JIS K0070(1992)实验法为基准进行测定。具体而言,使1g改性聚烯烃(A)或热塑性树脂(B)溶解在温度调整为100℃的二甲苯100g中,然后,在相同温度下,以酚酞作为指示剂,用0.1mol/L氢氧化钾乙醇溶液[商品名“0.1mol/L乙醇性氢氧化钾溶液”,和光纯药株式会社制造]进行滴定。此时,将滴定所需的氢氧化钾量换算成mg而算出酸值(mgKOH/g)。
<重均分子量(Mw)的测定>
本发明中的重均分子量,利用日本Waters公司制凝胶渗透色谱仪Alliance e2695(以下称为GPC,标准物质:聚苯乙烯树脂,流动相:四氢呋喃,色谱柱:Shodex KF-806+KF-803,色谱柱温度:40℃,流速:1.0ml/分钟,检测器:光二极管阵列检测器(波长254nm=紫外线))测得的值。
<熔点、熔解热的测定>
本发明中的熔点、熔解热是使用差示扫描量热仪(以下称为DSC,TA InstrumentJapan制,Q-2000),由以10℃/分钟的速度升温熔解、冷却树脂化,再次升温熔解时的熔融峰的顶部温度及面积测得的值
<海岛结构的解析>
使用冷冻超薄切片机(cryomicrotome)从制作的层叠体的粘接剂层(粘接剂组合物)截面,制作厚度为200nm的超薄切片。然后,将在四氧化钌蒸汽中进行染色后,实施镀碳得到的样品,用作透射电子显微镜观察试样。使用日本电子株式会社制造的JEM2100透射电子显微镜在加速电压200kV下,拍摄2000倍的照片。此时,含有改性聚烯烃的海结构部分为明部,含有热塑性树脂的岛结构部分为暗部。观察所述照片中粘接剂组合物的10μm×10μm单位面积中存在的岛,求出岛的最大粒径和最小粒径。此外,本发明的粘接剂组合物的海部分和岛部分的比率是通过用描图纸复制照片,切下岛部分并测量纸的重量而获得的。
<初期粘接性的评价>
将制作得到的层叠体切出100mm×15mm的尺寸,通过T型剥离试验按照以下基准评价粘接性。
T型剥离试验以ASTM-D1876-61试验法为基准,使用Orient Corporation株式会社制造的Tensilon RTM-100,在25℃环境下,测定拉伸速度为50mm/分钟下的剥离强度。金属基材/聚烯烃树脂基材间的剥离强度(N/cm)是5次试验值的平均值。
评价基准如下所述。
☆(实用上特别优异):8.0N/cm以上
◎(实用上优异):7.5N/cm以上且小于8.0N/cm
○(可以实用):7.0N/cm以上且小于7.5N/cm
×(不能实用):小于7.0N/cm
<85℃耐电解液性的评价>
为了探讨作为锂离子电池的包装材的利用性,进行耐电解液性的评价。将制作的层叠体裁切成100mm×15mm的尺寸,在85℃下浸入电解液[碳酸乙烯酯/碳酸二乙酯/碳酸二甲酯=1/1/1(容积比)100g中添加13g的六氟磷酸锂]1天。其后,取出层叠体,用离子交换水清洗,用擦拭纸擦掉水,使水分充分地干燥,并裁切成100mm×15mm尺寸,通过T型剥离试验按照以下的基准对耐电解液性进行评价。
☆(实用上特别优异):8.0N/cm以上
◎(实用上优异):7.5N/cm以上且小于8.0N/cm
○(实用可能):7.0N/cm以上且小于7.5N/cm
×(实用不可能):小于7.0N/cm
<成形性的评价>
成形性通过制作得到的层叠体的拉伸断裂伸长率及极限成形深度(深冲性能)进行评价。
极限成形深度(深冲性能)的测定
将层叠体裁切成80×120mm的尺寸,进行冷压成形。具体而言,使用株式会社Amada制造的拉伸式成形机(产品编号:TP-25C-X2),具有55mm×35mm的口径的成形模具(母模)及与其对应的成形模具(公模),在25℃氛围下以推压压力0.4MPa从0.5mm的成形深度起以0.5mm单位改变成形深度,对10个样品(层叠体)分别进行冷压成形。对冷压成形后的样品,将10个样品中均未产生皱纹、铝箔均未产生针孔、均无裂纹的最深的成形深度作为该样品的极限成形深度。由该极限成形深度根据以下基准进行电池用包装材料的成形性评价。评价结果显示于表3~2。
<判定基准>
☆(实用上特别优异):极限成形深度为6.0mm以上
◎(实用上优异):极限成形深度为4.0mm以上且小于6.0mm
○(可实用):极限成形深度2.0mm以上且小于4.0mm
×(不可实用):极限成形深度小于2.0mm
拉伸断裂伸长率的测定
本发明在25℃下的拉伸断裂伸长率(Eb)以JIS K7161(2014)试验法为基准进行测定。具体而言,使用Orientec Corporation株式会社制造的Tensilon RTM-100,在25℃环境下,测定以速度50mm/分钟进行拉伸中断裂时的伸长率(%)值。使用500μm的涂布器将得到的粘接剂组合物涂布在特氟隆片上,并将干燥后的粘接剂层的厚度调整为50μm后,使用热风干燥机在100℃的气氛中将涂覆面干燥1分钟。从特氟隆片上剥离粘接剂层,得到厚度为50μm的试验片。将试验片裁切成50mm×15mm,以与T型剥离试验相同的方式进行,并通过试验片断裂时的伸长率进行评价。
☆(实用上特别优异):300%以上
◎(实用上优异):250%以上且小于300%
○(可以实用):200%以上且小于250%
×(不可实用):小于200%
<改性聚烯烃(A)的制造例>
制造例1
在1L高压釜中加入丙烯-1-丁烯共聚物(熔点95℃、丙烯/1-丁烯=85/15(摩尔比))100质量份、甲苯233质量份及马来酸酐20质量份、二叔丁基过氧化物5质量份。一边搅拌一边加热,在140℃下反应1小时。将得到的反应液冷却到100℃后,一边搅拌一边注入到装有甲基乙基酮950质量份的容器中,冷却到25℃使树脂析出。将含有该树脂的浆液进行离心分离,来分离接枝聚合有马来酸酐的酸改性丙烯-1-丁烯共聚物与(聚)马来酸酐及低分子量物。
进一步,将进行离心分离而分离出的酸改性丙烯-1-丁烯共聚物,一边搅拌一边装入预先在25℃下保温的装有新的2000质量份的甲基乙基酮的容器中,继续搅拌1小时。然后,对浆液进行离心分离,由此进一步将酸改性丙烯-1-丁烯共聚物与(聚)马来酸酐及低分子量物分离。重复该操作2次进行纯化。
纯化后,在减压下,在70℃下干燥5小时,由此得到作为改性聚烯烃的马来酸酐改性丙烯-1-丁烯共聚物(A-1、酸值25mgKOH/g、重均分子量60,000、熔点94℃、ΔH61J/g)。
制造例2
将制造例1中使用的丙烯-1-丁烯共聚物变更为丙烯-1-丁烯共聚物(熔点80℃、丙烯/1-丁烯=80/20(摩尔比)),除此以外,与制造例1同样地操作,得到作为改性聚烯烃的马来酸酐改性丙烯-1-丁烯共聚物(A-2、酸值25mgKOH/g、重均分子量60,000、熔点80℃、ΔH56J/g)。
制造例3
将制造例1中使用的丙烯-1-丁烯共聚物变更为丙烯-1-丁烯共聚物(熔点70℃、丙烯/1-丁烯=75/25(摩尔比)),除此以外,将马来酸酐的加入量变更为15质量份,二叔丁基过氧化物的加入量变更为4质量份,除此以外,与制造例1同样地操作,得到作为改性聚烯烃的马来酸酐改性丙烯-1-丁烯共聚物(A-3、酸值25mgKOH/g、重均分子量60,000、熔点70℃、ΔH56J/g)。
制造例4
将制造例1中使用的丙烯-1-丁烯共聚物变更为丙烯-乙烯-1-丁烯共聚物(熔点132℃、丙烯/乙烯/1-丁烯=94/3/3(摩尔比)),除此以外,与制造例1同样地操作,得到作为改性聚烯烃的马来酸酐改性丙烯-乙烯-1-丁烯共聚物(A-4、酸值25mgKOH/g、重均分子量60,000、熔点126℃、ΔH73J/g)。
(主剂1的制备)
在配备有水冷回流冷凝器与搅拌机的500ml四口烧瓶中,作为树脂加入制造例1中获得的马来酸酐改性丙烯-1-丁烯共聚物(A-l)100质量份、15质量份的热塑性树脂B-1。另外作为溶剂,加入环己烷424质量份及甲基乙基酮228质量份。边搅拌边升温至80℃,继续搅拌1小时后冷却,由此得到主剂1。
(主剂2~20的制备)
将加入量变更为表1-1及表1-2,通过与主剂1相同的方法制备主剂2~20。
[表1-1]
[表1-2]
表1-1及表1-2中使用的热塑性树脂(B)为以下物质。
B-1:Clayton株式会社制造的Clayton(注册商标)FG1924(马来酸酐改性苯乙烯-乙烯-丁烯-苯乙烯树脂、酸值11mgKOH/g)
B-2:Clayton株式会社制造的Clayton(注册商标)FG1901(马来酸酐改性苯乙烯-乙烯-丁烯-苯乙烯树脂、酸值19mgKOH/g)
B-3:旭化成株式会社制造的Tuftec(注册商标)M1911(马来酸酐改性苯乙烯-乙烯-丁烯-苯乙烯树脂、酸值2mgKOH/g)
B-4:旭化成株式会社制造的Tuftec(注册商标)H1517(苯乙烯-乙烯-丁烯-苯乙烯树脂、酸值0mgKOH/g)
B-5:Clayton株式会社制造的Clayton(注册商标)G1730(苯乙烯-乙烯-丙烯-苯乙烯树脂、酸值0mgKOH/g)
B-6:三井化学株式会社制造的TAFMER(注册商标)DF640(乙烯-丁二烯树脂、酸值0mgKOH/g)
实施例1
将500质量份的主剂1、3.8质量份的固化剂C-1、0.5质量份的C-2混合得到组合物。使用该组合物,通过下述的方法制作层叠体。
金属基材与聚烯烃树脂基材层叠体的制作
金属基材使用铝箔(Sumi Light Aluminum Foil株式会社制造、8079-0、厚度40μm),聚烯烃树脂基材使用无拉伸聚丙烯膜(东洋纺株式会社制造Pyrene(注册商标)filmCT、厚度40μm)(以下,也称CPP)。
使用棒涂机将含有主剂及固化剂的组合物涂布于金属基材上,并进行调整使得干燥后的粘接剂层的膜厚为3μm。使用热风干燥机将涂布面在100℃氛围下干燥5分钟,得到层叠有膜厚为3μm的粘接剂层的金属基材。在所述粘接剂层表面上重合聚烯烃树脂基材,使用Tester Sangyo株式会社制造的小型桌上测试层压机Test laminator(SA-1010-S),在层压温度80℃下,以0.3MPa、1m/分钟进行贴合,以40℃、50%RH进行5天熟化,由此得到层叠体(聚烯烃基材/粘接剂层(粘接剂组合物)/金属基材)。
对于得到的层叠体,对粘接性、耐电解液性及成形性进行评价。结果如表2-1及表2-2所示。
实施例2~5及比较例4
将主剂及固化剂如表2-1及表2-2所示进行变更制备组合物,与实施例1相同的方法制作层叠体,实施各评价。
比较例1中未形成海岛结构而是均匀的溶液,在比较例2~4中未形成海岛结构而是分离为二层的分离结构。
实施例6~17及比较例1~3
将层亚温度变更为80℃,除此以外,与实施例1同样地制作层叠体,实施各评价。
实施例18
将固化剂变更为固化剂C-3(5质量),除此以外,与实施例5同样地制作层叠体,实施各评价。
表2-1及表2-2中使用的固化剂为以下的物质。
C-1:三菱化学株式会社制造jER(注册商标)152(缩水甘油醚型环氧树脂)
C-2:三菱瓦斯化学株式会社制造TETRAD(注册商标)-X(缩水甘油胺型环氧树脂)
C-3:Covestro株式会社制造Sumidur N(注册商标)3300(多官能异氰酸酯)
[表2-1]
[表2-2]
工业上的可利用性
本发明涉及的粘接剂组合物为海岛结构,在海中含有改性聚烯烃(A)和固化剂(C)的反应物,在岛中含有热塑性树脂(B)和固化剂(C)的反应物。通过具有海岛结构,显示出对基材显著的追随性,深冲性能等加工特性优异。此外,即使在低温的贴合条件下也显示出聚烯烃树脂基材与金属基材之间良好的粘接性,且具有高温条件下的耐电解液性。因此,由本发明的粘接剂组合物形成的聚烯烃树脂基材与金属基材的层叠体不仅可用于家电外板、家具用素材、建筑内装用部材等领域,还可作为用于电脑、手机、摄像机等的锂离子电池的包装材料(软包形态)或车载用而广泛使用。
Claims (14)
1.一种粘接剂组合物,其为海岛结构,在海中含有改性聚烯烃A和固化剂C的反应物,在岛中含有热塑性树脂B和固化剂C的反应物。
2.如权利要求1所述的粘接剂组合物,其中,所述海岛结构的岛相的粒径为0.001~5μm。
3.如权利要求1或2所述的粘接剂组合物,其中,所述改性聚烯烃A的酸值为2~50mgKOH/g。
4.如权利要求1~3中任一项所述的粘接剂组合物,其中,所述改性聚烯烃A含有丙烯及1-丁烯作为烯烃成分,且丙烯与1-丁烯的摩尔比为丙烯/1-丁烯=99~60/1~40。
5.如权利要求1~4中任一项所述的粘接剂组合物,其中,所述热塑性树脂B为苯乙烯类弹性体。
6.如权利要求1~5中任一项所述的粘接剂组合物,其中,所述热塑性树脂B具有2~50mgKOH/g的酸值。
7.如权利要求1~6中任一项所述的粘接剂组合物,其中,所述热塑性树脂B的含量相对于100质量份的所述改性聚烯烃A为5~30质量份。
8.如权利要求1~7中任一项所述的粘接剂组合物,其中,所述固化剂C为环氧固化剂或异氰酸酯固化剂中的任一种。
9.如权利要求1~8中任一项所述的粘接剂组合物,其中,所述固化剂C的含量相对于100质量份的所述改性聚烯烃A为0.5~40质量份。
10.如权利要求1~9中任一项所述的粘接剂组合物,其中,所述改性聚烯烃A包含熔点为50℃~155℃的改性聚烯烃A1,及熔点为55℃~160℃的改性聚烯烃A2。
11.如权利要求10中所述的粘接剂组合物,其中,所述改性聚烯烃A1与所述改性聚烯烃A2的质量比为A1/A2=99~21/1~79。
12.一种层叠体,其通过在基材的至少一个表面上层叠权利要求1~11中任一项所述的粘接剂组合物而形成。
13.如权利要求12记载的层叠体,其中,所述基材为聚烯烃基材或金属基材。
14.一种锂离子电池用包装材料,其将权利要求13中所述的层叠体作为构成部件。
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