CN111334199A - 一种锂电池用耐腐蚀型胶黏剂 - Google Patents
一种锂电池用耐腐蚀型胶黏剂 Download PDFInfo
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Abstract
本发明提供了一种锂电池用耐腐蚀型胶黏剂,包括20质量份‑40质量份基底树脂,1质量份‑5质量份交联剂,1质量份‑5质量份增粘树脂,0.1质量份‑1质量份硅烷偶联剂,0.1质量份‑1质量份纳米氧化锰,70质量份‑90质量份溶剂;所述基底树脂为有机硅烷改性的聚烯烃和丙烯酸改性的聚烯烃的混合物;所述有机硅烷改性的聚烯烃与丙烯酸改性的聚烯烃的比例为1:3‑3:1;所述纳米氧化锰的粒径为1‑50nm。本发明的胶黏剂用于锂电池封装铝塑膜的制备,具有增强的耐腐蚀性能和粘结力,并且大幅提高生产效率,降低了生产成本。
Description
技术领域
本发明涉及一种胶黏剂,特别涉及一种锂电池用耐腐蚀型胶黏剂。
背景技术
锂离子电池由于其重量轻、容量大、循环寿命长以及无记忆效应等优势,在数码电子领域广泛应用,近年来,更是在新能源汽车、储能等新兴领域快速发展。传统锂电池使用的铝壳、钢壳等刚性材料包装,除了轻便型问题外,也存在压力过大爆炸等安全隐患。针对锂电池金属包装存在的一系列问题,一种新的铝塑复合膜包装材料应运而生。该包装材料一般由三层膜材料复合而成,从外到内依次是保护层、铝箔层、耐腐蚀热封层,通常保护层是双向拉伸的尼龙膜(BOPA膜)、耐腐蚀层是流延聚丙烯膜(CPP膜)。
目前,在行业内,铝箔和外层尼龙膜的粘结方式,均是干式复合工艺,是铝箔表面涂布常规聚氨酯或丙烯酸酯胶黏剂,再烘干溶剂进行干式复合。干式复合用到的常规丙烯酸或聚氨酯胶黏剂,耐溶剂/耐酸性差,容易出现脱层/腐蚀铝箔等质量问题,因此开发一种耐酸耐溶剂腐蚀的锂电铝塑膜用胶水十分必要。
发明内容
针对上述问题,本发明提供了一种锂电池用耐腐蚀型胶黏剂,包括20质量份-40质量份基底树脂,1质量份-5质量份交联剂,1质量份-5质量份增粘树脂,0.1质量份-1质量份硅烷偶联剂,0.1质量份-1质量份纳米氧化锰,70质量份-90质量份溶剂;所述基底树脂为有机硅烷改性的聚烯烃和丙烯酸改性的聚烯烃的混合物;所述有机硅烷改性的聚烯烃与丙烯酸改性的聚烯烃的比例为1:3-3:1;所述纳米氧化锰的粒径为1-50nm。
进一步地,所述的交联剂为选自醛类、酮类、醌类、噻吨酮,均三嗪类,异氰酸酯低聚物,环氧树脂中的一种或者混合物。
进一步地,所述增粘树脂为萜烯树脂。
进一步地,所述的硅烷偶联剂为甲基丙烯酰氧基丙基三甲氧基硅烷。
进一步地,所述的聚烯烃为聚苯乙烯,聚丙烯,聚丁二烯弹性体的一种或者几种。
进一步地,所述有机硅烷改性的聚烯烃与丙烯酸改性的聚烯烃的比例为1:1。
进一步地,所述纳米氧化锰的粒径为20nm。
本发明还提供了一种锂电池用耐腐蚀型胶黏剂的制备方法,包括
(1)配料:根据权利要求1所述的耐腐蚀型胶黏剂进行精准称重;
(2)将基底树脂,增粘树脂,硅烷偶联剂加入到溶剂中,加热至60℃,搅拌混合1-2h,直至成均相溶液;
(3)将交联剂,纳米氧化锰加入步骤2得到的溶液中,保持60℃,进一步加入溶剂控制固相含量小于5%,搅拌混合2-4h,直至成均相溶液;
(3)使用前,充分搅拌后,使用PP滤芯进行过滤,除去不溶物,即可上涂布机使用。
本发明还提供了一种制备锂电池封装铝塑膜的方法,其中使用上述的耐腐蚀型胶黏剂粘结铝箔与塑料薄膜。
改性可以通过聚合物与例如有机硅烷,丙烯酸在自由基产生剂(如有机过氧化物)的存在下以反应性挤出的简单的方式制备。通过对聚烯烃聚合物体系使用有机硅烷基团,丙烯酸进行接枝改性,可以使胶黏剂的分散性更好,同时具有增强的耐溶剂性能,与CPP和铝箔这两种不同的相态具有更强的结合力。本发明还发现胶黏剂中同时具有有机硅烷改性的聚烯烃和丙烯酸改性的聚烯烃的混合体系,对增强耐溶剂和粘结力具有更优选的效果。为了更好的实现本发明的效果,基底树脂的含量约20质量份-40质量份,优选20-30质量份,更优选为25质量份;所述有机硅烷改性的聚烯烃与丙烯酸改性的聚烯烃的比例为1:3-3:1,为了更好的实现本发明的效果,比例优选为1:2-2:1,更优选为1:1。
常见的硅烷偶联剂包括氨丙基三乙氧基硅烷(KH550),缩水甘油迷氧基丙基三甲氧基硅烷(KH560),甲基丙烯酰氧基丙基三甲氧基硅烷(KH570),乙烯基三乙氧基硅烷(A151),乙烯基三乙氧基硅烷(A171),巯丙基三甲(乙)氧基硅烷(KH580,KH590),乙二胺丙基三乙氧基硅烷(KH792),乙二胺丙基甲基二甲氧基硅烷(KBM602),硅烷偶联剂可以提高纳米氧化锰和固相的分散性,并提高铝箔与聚合物之间粘结力,为了更好的实现本发明的效果,硅烷偶联剂优选为KH570。纳米氧化锰分散在胶黏剂中,在胶黏剂施用后,将进一步提高胶黏剂的耐腐蚀性能。氧化锰的粒径优选为1-50nm,越小越好,考虑到实现成本问题更优选为20nm,过大的粒径将导致降低胶黏剂的粘合力。氧化锰可以使用通常的制备方法制备得到,如气相沉积,水热,高能研磨等等。
硅烷偶联剂,交联剂,纳米氧化锰按本发明所述的上述比例范围添加,可进一步增强本发明的胶黏剂的粘合力和耐腐蚀性能,还与混合改性聚烯烃一起具有协同增强之效果。过大的助剂添加量,将降低其粘结力,影响胶黏剂的使用效果,不能更好实现本发明的目的,过小的助剂添加量,将降低耐腐蚀性能,也不能实现本发明的目的。
本发明提供了一种新型耐腐蚀型胶黏剂,添加一定比例范围的混合改性聚烯烃和助剂,增强了本发明的胶黏剂的粘合力和耐腐蚀性能,并具有协同增强之效果。将其应用于锂电池封装铝塑膜的制备,克服了干式复合工艺中用到的常规丙烯酸或聚氨酯胶黏剂,耐溶剂/耐酸性差,容易出现脱层/腐蚀铝箔等质量问题,同时在性能发明具有增强的耐腐蚀性能和粘结力,并且大幅提高生产效率,降低了生产成本。
具体实施方式
下面结合具体实施例解释本发明。
表1实施例与对比例的配方
对比例7-9,分别使用A151,KH550,KH560替代实施例1中的KH570。
对比例10,使用200nm的氧化锰替代实施例1中的纳米氧化锰。
根据表1的配方,按以下步骤制备胶黏剂和铝塑膜。
(1)配胶时,先将基底树脂,增粘树脂,硅烷偶联剂加入到溶剂中,加热60℃,搅拌混合1-2h,直至成均相溶液,固含量约20%。
(2)将交联剂,纳米二氧化锰加入到步骤1的溶液中,进一步加入溶剂,加热60℃,搅拌混合2-4h,直至成均相溶液。
(3)使用前,充分搅拌,使用PP滤芯进行过滤,除去不溶物,即可上涂布机使用。
(4)用凹版或辊式涂布,将步骤(3)制备得到的胶黏剂涂布在铝箔表面,经烘箱烘干溶剂后,再使CPP膜放卷加压贴合。烘箱温度控制在90-130℃,干胶涂布量2-5克/平米,生产速度控制在80~120m/min。
(5)贴合完成后,产品放熟化室熟化6-9天即可,熟化温度40~60℃。
性能测试:
选取一张锂电池用铝箔与等面积大小的CPP膜,在铝箔均匀涂抹上厚度约为5um的粘胶剂层后,将铝箔贴和CPP膜,静置30分钟后进行测试。
根据GB T 10125—1997标准,对胶黏的试验片进行在酸性盐雾下放置6h后,测试剥离强度。将试验片浸泡于10%的NaOH溶液中6h,测试剥离强度。上述两种剥离强度,分别与未腐蚀前的剥离强度进行比较。
表2实施例与对比例的性能测试结果
测试结果发现,对比实施例1,2,3与对比例1,2可知,有机硅烷改性与丙烯酸改性比例在一定范围内的技术方案可以有效提高产品的初始粘结力和耐腐蚀性能。对比实施例1与对比例3,4,5,6,本发明的实施例添加一定比例范围的混合改性聚烯烃和增粘树脂,硅烷偶联剂,交联剂,纳米氧化锰,增强了本发明的胶黏剂的粘合力和耐腐蚀性能,并具有协同增强之效果,保证了铝箔和CPP膜的粘结力和提升了铝塑膜产品的耐腐蚀腐蚀性。对比实施例1与对比例7,8,9,可知本发明的硅烷偶联剂优选为KH570。对比实施例1与对比例10,可知本发明的纳米氧化锰,优选为20nm。
以上内容不能认定本发明具体实施只局限于这些说明,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思前提下,还可以做出若干简单推演或替换,都应当视为属于本发明由所提交的权利要求书确定的专利保护范围。
Claims (9)
1.一种锂电池用耐腐蚀型胶黏剂,其特征在于,包括20质量份-40质量份基底树脂,1质量份-5质量份交联剂,1质量份-5质量份增粘树脂,0.1质量份-1质量份硅烷偶联剂,0.1质量份-1质量份纳米氧化锰,70质量份-90质量份溶剂;所述基底树脂为有机硅烷改性的聚烯烃和丙烯酸改性的聚烯烃的混合物;所述有机硅烷改性的聚烯烃与丙烯酸改性的聚烯烃的比例为1:3-3:1;所述纳米氧化锰的粒径为1-50nm。
2.根据权利要求1所述的耐腐蚀型胶黏剂,其中,所述的交联剂为选自醛类、酮类、醌类、噻吨酮,均三嗪类,异氰酸酯低聚物,环氧树脂中的一种或者混合物。
3.根据权利要求1所述的耐腐蚀型胶黏剂,其中,所述增粘树脂为萜烯树脂。
4.根据权利要求1所述的耐腐蚀型胶黏剂,其中,所述的硅烷偶联剂为甲基丙烯酰氧基丙基三甲氧基硅烷。
5.根据权利要求1所述的耐腐蚀型胶黏剂,其中,所述的聚烯烃为聚苯乙烯,聚丙烯,聚丁二烯弹性体的一种或者几种。
6.根据权利要求1所述的耐腐蚀型胶黏剂,其中,所述有机硅烷改性的聚烯烃与丙烯酸改性的聚烯烃的比例为1:1。
7.根据权利要求1所述的耐腐蚀型胶黏剂,其中,所述纳米氧化锰的粒径为20nm。
8.一种锂电池用耐腐蚀型胶黏剂的制备方法,包括
(1)配料:根据权利要求1所述的耐腐蚀型胶黏剂进行精准称重;
(2)将基底树脂,增粘树脂,硅烷偶联剂加入到溶剂中,加热至60℃,搅拌混合1-2h,直至成均相溶液;
(3)将交联剂,纳米氧化锰加入步骤2得到的溶液中,保持60℃,进一步加入溶剂控制固相含量小于5%,搅拌混合2-4h,直至成均相溶液;
(4)使用前,充分搅拌后,使用PP滤芯进行过滤,除去不溶物,即可上涂布机使用。
9.一种制备锂电池封装铝塑膜的方法,其中使用权利要求1所述的耐腐蚀型胶黏剂粘结铝箔与塑料薄膜。
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