CN114959669B - 热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜 - Google Patents
热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜 Download PDFInfo
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Abstract
本发明提供了一种热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜。钝化处理乳液为水包油型乳液,其中,水相包括三价铬盐、水和水相助溶剂;油相包括酸改性聚烯烃和油相助溶剂;所述钝化处理乳液通过一步烘烤在铝箔表面依次形成钝化膜和酸改性聚烯烃薄膜。本发明通过独特的水包油乳液,将原本的两步工艺合并为一步,既减少了两步工艺区间内对铝箔表面的摩擦等损伤,同又减少了热法工艺下前处理所需预热时间。在此基础之上,油相中的低熔点酸改性聚烯烃树脂具有数量较多的非极性片段,可在热法淋膜过程中与熔融体PP更好的相容,使得产品在获得热法耐电解液性能的基础上,不损失冲壳性能。
Description
技术领域
本发明涉及锂电池软包钝化技术领域,尤其涉及一种热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜。
背景技术
锂离子电池在近几年飞速发展,其中,软包电池以其便利性与突出的安全性受到了3C电池产品及动力电池两方面的青睐。
锂电池铝塑膜包装主要由PA、铝箔及PP三种材料组成,部分亦会使用PET材料。具体来看铝塑膜膜层结构为外侧PA、中层铝箔、内层PP。其中外侧主要起到防油污、美观及保护铝箔的作用。而内层主要起到阻隔作用,是锂电池安全性与功能的主要保障。而铝塑膜内层的耐电解液性能,即能有效反映该产品的安全性能。
市面上常见的铝塑膜,主要分为干法和热法两种工艺,干法的复合方式可以简单概述为在铝箔上涂胶水后复合聚丙烯薄膜固化成型的方法。这种方法整套工艺流程简单可控,对铝箔损伤小。另一种热法复合工艺则是加热已经表面处理完毕的铝箔,随后直接将熔融的聚丙烯颗粒流延成型为复合薄膜,这种方法制备的铝塑膜耐电解液性能相对较为突出,理论上是动力电池等大功率电池的优选产品。但由于热法工艺中需要对铝箔进行长时间的高温老化处理,导致铝箔受热老化延展性能下降,在产品上则体现为冲壳性能下降,不适用于制作大体积电池。与此相对,干法铝塑膜冲壳性能好,但耐电解液性能相对较差。因此,如何同时提高铝塑膜的冲壳性能和耐电解液性能,是亟待解决的问题。
有鉴于此,有必要设计一种改进的热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜,以解决上述问题。
发明内容
为了克服上述现有技术的不足,本发明的目的在于提供一种热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜,通过制备水相主要为三价铬盐类物质,油相主要为酸改性低熔点聚烯烃类材料的水包油乳液,实现一部烘烤法得到钝化膜和胶膜,从而减少热法工艺下前处理所需预热时间,并同时赋予铝塑膜良好的冲壳性能和耐电解液性能。
为实现上述发明目的,本发明提供了一种热法铝塑膜用铝箔表面钝化处理乳液,所述钝化处理乳液为水包油型乳液,其中,水相包括三价铬盐、水和水相助溶剂;油相包括酸改性聚烯烃和油相助溶剂;所述钝化处理乳液通过一步烘烤在铝箔表面依次形成钝化膜和酸改性聚烯烃薄膜。
作为本发明的进一步改进,所述三价铬盐为硝酸铬、磷酸铬、硫酸铬、醋酸铬中的一种或多种;所述水相助溶剂为甲醇、乙醇、异丙醇中的一种或多种;
所述酸改性聚烯烃为酸或酸酐接枝改性聚烯烃;所述油相助溶剂为异辛烷、环己烷、异己烷、甲基环己烷、石油醚类、丁酮中的一种或多种。
作为本发明的进一步改进,所述酸改性聚烯烃的熔点在60-100℃,熔融指数MFR在30-60g/10min区间,酸或酸酐的接枝率在1.8-4%区间,分子量在60000-120000区间。
作为本发明的进一步改进,所述水相还包括pH调节剂,所述油相还包括消泡剂、阳离子表面活性剂、辅助树脂;
所述pH调节剂包括磷酸、盐酸、低分子量有机羧酸中的一种或多种;
所述阳离子表面活性剂包括十二烷基三甲基氯化铵、十二烷基硫酸铵、十六烷基氯化吡啶中的一种或多种;
所述辅助树脂包括双酚A环氧树脂、甲苯二异氰酸酯或六亚甲基二异氰酸酯或二苯基甲烷二异氰酸酯中的一种或多种。
作为本发明的进一步改进,所述钝化处理乳液的制备方法包括:
S1.配制酸改性聚烯烃质量浓度为15%-30%的油相溶液;
S2.配制三价铬盐浓度为0.15-0.50mol/L的水相溶液;
S3.向步骤S1得到的所述油相溶液中逐滴加入步骤S2得到的所述水相溶液,当体系粘度突降时,再补充所述油相溶液质量0.5%-2%的所述水相溶液,搅拌得到水包油钝化处理乳液。
作为本发明的进一步改进,所述油相溶液的溶剂为异辛烷、环己烷、异己烷、甲基环己烷中的一种或多种与石油醚类或丁酮组成的混合溶剂,优选为异辛烷、环己烷、异己烷、甲基环己烷中的一种与丁酮组成的混合溶剂,两者体积比为(5-12):1;
所述水相溶液中水和水相助溶剂的体积比为(2-4):1;所述水相助溶剂优先为异丙醇。
一种热法铝塑膜,由外至内依次包括防护层、铝箔层、钝化层、粘结层和阻隔层,所述钝化层、粘结层采用权利要求1至6中任一项所述的热法铝塑膜用铝箔表面钝化处理乳液通过一步烘烤法得到。
作为本发明的进一步改进,所述一步烘烤法包括:将所述钝化处理乳液在铝箔表面涂覆后,在80-90℃下风干,然后在60-80℃下老化24h,或者常温静置14天进行老化。
作为本发明的进一步改进,所述钝化处理乳液的涂覆量为20-33g/m2。
作为本发明的进一步改进,所述阻隔层为流延聚丙烯薄膜。
本发明的有益效果是:
1.本发明提供的热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜,基于相反转法制备热法铝塑膜专用铝箔处理乳液,该乳液以水包油的形式存在,水相主要为三价铬盐类物质及其体系,油相主要为酸改性低熔点聚烯烃类材料及辅助体系。此种乳液油相部分形成胶膜提供粘接性能,水相部分则与铝箔表面进行钝化反应。通过使用这种乳液,将原本的两步工艺操作合并为一步,既减少了两步工艺区间内对铝箔表面的摩擦等损伤,同时可以以一步烘烤代替两道工序,减少热法工艺下前处理所需预热时间。在此基础之上,油相中的低熔点酸改性聚烯烃树脂具有数量较多的非极性片段,可在热法淋膜的过程中与熔融体PP更好的相容,反应条件更为简单,能够减少高温老化步骤所需要的温度,缩短高温老化时长,使得产品在获得热法耐电解液性能的基础上,不损失冲壳性能。
2.此表面处理液首先通过水相中的三价铬体系下发生钝化配位成膜,而后在油相树脂的作用下,在钝化膜上再呈现一层聚合物薄膜,由于钝化面不直接接触空气或腐蚀环境,因此对无机盐的使用幅度大大减少,减少对环境的污染,在钝化同时形成酸改性聚烯烃薄膜,亦能有效的改进钝化膜层间界面与PP粘接层界面的界面状况,形成少量物理嵌合,提高膜间强度。
附图说明
图1中(a)和(b)为无钝化铝箔表面光学显微镜图;(c)和(d)为本发明一步法钝化后铝箔表面光学显微镜图。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚,下面结合具体实施例对本发明进行详细描述。
在此,还需要说明的是,为了避免因不必要的细节而模糊了本发明,在具体实施例中仅仅示出了与本发明的方案密切相关的结构和/或处理步骤,而省略了与本发明关系不大的其他细节。
另外,还需要说明的是,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。
本发明提供的热法铝塑膜用铝箔表面钝化处理乳液,为水包油型乳液,其中,水相包括三价铬盐、水和水相助溶剂;油相包括酸改性聚烯烃和油相助溶剂;所述钝化处理乳液通过一步烘烤在铝箔表面依次形成钝化膜和酸改性聚烯烃薄膜。此表面处理液首先通过水相中的三价铬体系下发生钝化配位成膜,而后在油相树脂的作用下,在钝化膜上再呈现一层聚合物薄膜,由于钝化面不直接接触空气或腐蚀环境,因此对无机盐的使用幅度大大减少,减少对环境的污染,在钝化同时形成酸改性聚烯烃薄膜,亦能有效的改进钝化膜层间界面与PP粘接层界面的界面状况,形成少量物理嵌合,提高膜间强度。
具体地,基本组分构成如下:
水相:
蒸馏水;
水相助溶剂:甲醇、乙醇、异丙醇;
水相主成分:三价铬盐(硝酸铬、磷酸铬、硫酸铬、醋酸铬);
pH调节剂:磷酸、盐酸、低分子量有机羧酸类等酸;
油相:
油相主树脂:酸改性聚烯烃类材料;
油相助溶剂:异辛烷、环己烷、异己烷、甲基环己烷、石油醚类、丁酮;
油相辅助树脂一:CYD-128、DYD-128、YD-128、GELR-128等标准双酚A环氧树脂(环氧当量在170-190之间);
油相辅助树脂二:甲苯二异氰酸酯或六亚甲基二异氰酸酯或二苯基甲烷二异氰酸酯;
助剂类:消泡剂;添加量为油相总质量的0.01-0.1%。
阳离子表面活性剂:十二烷基三甲基氯化铵、十二烷基硫酸铵、十六烷基氯化吡啶等。添加量为油相总质量的1-10%。
实施例
一种热法铝塑膜用铝箔表面钝化处理乳液,通过以下步骤制备:
油相:取酸改性聚烯烃类材料(熔点在60—100℃,MFR在30-60g/10min区间,酸或酸酐接枝率在1.8-4%区间,分子量在60000-120000区间)在环己烷/丁酮=9:1溶剂中于60℃加温搅拌溶解成25%质量百分数粘稠溶液。依照总质量3%添加阳离子表面活性剂,0.02%消泡剂,常温下以2000r/min进行搅拌。搅拌途中,施加总质量占1%的辅助树脂,维持搅拌不小于30分钟。
水相:准备蒸馏水与异丙醇体积比为7:3的溶剂体系,向其中溶解0.25mol/L浓度三价铬盐(摩尔浓度以铬计),向其中添加pH调节剂调节pH值为1-2.5区间。
溶解完毕后,维持40-50℃,400-3000r/min转速,向油相中逐渐滴加水相组分,滴加速度控制在油相的0.3-0.9%质量/min以内,同时检测体系粘度,当体系粘度出现突降时视为相转变临界点,额外补充1%油相质量的水相体系,并将搅拌速度提升至1.5倍,观察相由油包水相转化为水包油相时停止搅拌得到产品。
使用工艺优选上胶量为20-33克每平方米,涂覆后风干温度建议为80-90℃30s,后续老化温度为60-80℃ 24h,亦可常温静置14天替代高温老化进程。
为验证效果,对比同样组分下,不采用乳液,分步进行工艺操作的结果。以及对比不同酸接枝率的聚烯烃下,同样体系的工艺优劣。
表1 不同酸接枝率的两相分步涂覆和水包油乳液一步涂覆的参数
表2 不同成分含量的水包油乳液配比
注:两相独立使用时使用工艺参数如下,先进行水相涂膜,上胶量为9-15克每平方米,随后梯度升温于200℃下持续15s进行风干形成钝化层,第二步以15-20克每平方米上胶量对油相进行涂覆,而后于110℃下持续30s风干,得到基材后续工艺与混合乳液无差异。
依照表1和2内的参数配制乳液,使用厚度为45um的铝箔,涂布量为26g每平方米;经由烘烤后分别以40um与80um厚度流延聚丙烯薄膜进行复合,淋膜具体参数为,熔体温度275-295℃,熔体颗粒原料为W331(熔点150度、熔指7g/10min),淋膜速度为33m/min。
表3 实施例和对比例性能测试结果
表中,盐雾试验标准为GB/T6458-86,附着力测试标准为GB9791-88,效果亦满足使用效果。
表3中,对比例1、2为两组传统热法工艺(即无胶膜直接淋膜于钝化层)测试数据,对比例3、4为传统干法工艺(即分步涂胶膜后复合成品聚丙烯薄膜)。
可以看出,当只涂覆钝化层,无胶膜时,采用传统热法工艺得到的铝塑膜(对比例1和2)的冲壳深度明显低于实施例C-H。当分布涂胶膜后,采用传统热法工艺得到的铝塑膜(实施例A和B)的冲壳深度与对比例1和2相差不大,也明显低于实施例C-H,可见本发明通过制备成水包油乳液,然后一步法烘烤对提高冲壳性能具有重要作用。当分布涂胶膜后,采用传统干法工艺得到的铝塑膜(对比例3和4)的冲壳深度虽然与本发明相当,但剥离力显著低于实施例C-H。测试数据显示,本发明冲壳性能相较传统热法提升0.5-1mm,电解液性能相较传统干法工艺提升8-10N。可见,本发明能够兼顾传统热法和干法的优势。
通过实例AC、BD两组对比可知,乳液法处理液通过减少高温工序,能有效保证在剥离力相同的情况下获得更好的冲壳性能。而水相与油相分步单独使用时,造成铝箔多次高温加热,受热老化,从而使得冲壳性能下降。通过CD相比,酸改性聚烯烃接枝率在2.5-4%的两端均有较为接近的效果,4%接枝率整体粘接强度更高。
请参阅图1所示,可以看出,本发明一步烘烤钝化后,在铝箔表面形成了较均匀的钝化层和酸改性聚烯烃粘结层。
综上所述,本发明提供的热法铝塑膜用铝箔表面钝化处理乳液及热法铝塑膜,基于相反转法制备热法铝塑膜专用铝箔处理乳液,该乳液以水包油的形式存在,水相主要为三价铬盐类物质及其体系,油相主要为酸改性低熔点聚烯烃类材料及辅助体系。此表面处理液首先通过水相中的三价铬体系下发生钝化配位成膜,而后在油相树脂的作用下,在钝化膜上再呈现一层聚合物薄膜,由于钝化面不直接接触空气或腐蚀环境,因此对无机盐的使用幅度大大减少,减少对环境的污染,在钝化同时形成酸改性聚烯烃薄膜,亦能有效的改进钝化膜层间界面与PP粘接层界面的界面状况,形成少量物理嵌合,提高膜间强度。
以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围。
Claims (12)
1.一种热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述钝化处理乳液为水包油型乳液,其中,水相包括三价铬盐、水和水相助溶剂;油相包括酸改性聚烯烃和油相助溶剂;所述钝化处理乳液通过一步烘烤在铝箔表面依次形成钝化膜和酸改性聚烯烃薄膜。
2.根据权利要求1所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述三价铬盐为硝酸铬、磷酸铬、硫酸铬、醋酸铬中的一种或多种;所述水相助溶剂为甲醇、乙醇、异丙醇中的一种或多种;
所述酸改性聚烯烃为酸或酸酐接枝改性聚烯烃;所述油相助溶剂为异辛烷、环己烷、异己烷、甲基环己烷、石油醚类、丁酮中的一种或多种。
3.根据权利要求2所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述酸改性聚烯烃的熔点在60-100℃,熔融指数MFR在30-60g/10min区间,酸或酸酐的接枝率在1.8-4%区间,分子量在60000-120000区间。
4.根据权利要求1所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述水相还包括pH调节剂,所述油相还包括消泡剂、阳离子表面活性剂、辅助树脂;
所述pH调节剂包括磷酸、盐酸、低分子量有机羧酸中的一种或多种;
所述阳离子表面活性剂包括十二烷基三甲基氯化铵、十二烷基硫酸铵、十六烷基氯化吡啶中的一种或多种;
所述辅助树脂包括双酚A环氧树脂、甲苯二异氰酸酯或六亚甲基二异氰酸酯或二苯基甲烷二异氰酸酯中的一种或多种。
5.根据权利要求1所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述钝化处理乳液的制备方法包括:
S1.配制酸改性聚烯烃质量浓度为15%-30%油相溶液;
S2.配制三价铬盐浓度为0.15-0.50mol/L的水相溶液;
S3.向步骤S1得到的所述油相溶液中逐滴加入步骤S2得到的所述水相溶液,当体系粘度突降时,再补充所述油相溶液质量0.5%-2%的所述水相溶液,搅拌得到水包油钝化处理乳液。
6.根据权利要求5所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述油相溶液的溶剂为异辛烷、环己烷、异己烷、甲基环己烷中的一种或多种与石油醚类或丁酮组成的混合溶剂,两者体积比为(5-12):1;所述水相溶液中水和水相助溶剂的体积比为(2-4):1。
7.根据权利要求6所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述油相溶液的溶剂为异辛烷、环己烷、异己烷、甲基环己烷中的一种与丁酮组成的混合溶剂。
8.根据权利要求6所述的热法铝塑膜用铝箔表面钝化处理乳液,其特征在于,所述水相助溶剂为异丙醇。
9.一种热法铝塑膜,其特征在于,由外至内依次包括防护层、铝箔层、钝化层、粘结层和阻隔层,所述钝化层、粘结层采用权利要求1至8中任一项所述的热法铝塑膜用铝箔表面钝化处理乳液通过一步烘烤法得到。
10.根据权利要求9所述的热法铝塑膜,其特征在于,所述一步烘烤法包括:将所述钝化处理乳液在铝箔表面涂覆后,在80-90℃下风干,然后在60-80℃下老化24h,或者常温静置14天进行老化。
11.根据权利要求10所述的热法铝塑膜,其特征在于,所述钝化处理乳液的涂覆量为20-33g/m2。
12.根据权利要求9所述的热法铝塑膜,其特征在于,所述阻隔层为流延聚丙烯薄膜。
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