CN114410267A - 一种铝塑膜用聚氨酯复合胶及其制备方法 - Google Patents
一种铝塑膜用聚氨酯复合胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及胶黏剂技术领域,具体涉及一种铝塑膜用聚氨酯复合胶及其制备方法,该聚氨酯复合胶为包含主剂和固化剂的双组分聚氨酯胶水,其中主剂选用含支链型的苯酐聚酯多元醇和结晶型聚酯多元醇复配,可以在保证耐高温和粘接性能的基础上,提高其耐水性能,并改善了复合胶的初始粘度,增大胶黏剂对基材的附着力,选用环氧树脂作为助剂,使其在固化的时候,形成IPN网络形态,进一步提高复合胶的耐湿热性能,并引入适量的硅烷偶联剂,不仅提高了尼龙与铝箔的粘接力,且进一步增强了其耐高温高湿的能力,可更好地满足应用需求;本发明的制备方法,其工艺流程简单,制备容易,满足大批量生产制造的需求。
Description
技术领域
本发明涉及胶黏剂技术领域,特别是涉及一种铝塑膜用聚氨酯复合胶及其制备方法。
背景技术
软包锂电池所用的封装材料是铝塑复合膜,简称铝塑膜,主要应用于软包锂离子电池电芯外包装封装。铝塑膜的厚度有不同规格,其结构主要是由三种材料复合而成,由内到外分别为CPP层、Al层、尼龙层。铝塑膜的制造方法主要有热法和干法两种,热法工艺是铝层和CPP层之间用MPP粘结,在一定温度下热压合成。干法工艺为在PP和铝层中间加粘结剂直接复合。
如现有技术,专利CN110437785A,采用聚酯和聚醚复配的原则,与多异氰酸酯,通过一步法合成羟基封端的聚氨酯主剂。该方法,可以显著的提高聚氨酯的耐水性能,但聚醚的引入,势必会降低其粘接性能。此外,用一步法制备聚氨酯胶黏剂,会导致反应不完全,极易出现批次稳定性问题。
专利CN111635716A,通过溶剂法将聚烯烃,聚碳酸酯,丙烯酸树脂等热塑性高分子溶解,外加固化剂,附着力促进剂等制备可同时复合CPP与铝层,尼龙与铝层的胶黏剂。此方法,尚未考虑CPP与尼龙基材的差异性,且能溶于有机溶剂的热塑性高分子,本身分子量不可能太大,从而导致出现粘接强度不够的风险。
专利CN109852265A,采用聚酯或聚醚多元醇,与异氰酸酯固化剂,活性稀释剂,光引发剂等制备成热固化和紫外光双重固化的复合胶。该方法,虽然可以避免VOC的排放,但依旧存在着胶体强度过硬,导致冲深性能下降的风险。
综合以上可知,现有技术中的聚氨酯复合胶及其制备方法,由于原料组分配伍及其制备工艺的限制,导致最终得到的复合胶并不能很好的满足应用需求。
鉴于此,本发明旨在提出一种新的铝塑膜用聚氨酯复合胶及其制备方法,以更好地解决上述技术问题。
发明内容
为解决上述问题,本发明提供一种铝塑膜用聚氨酯复合胶及其制备方法,其制备工艺简单,制备容易,制得的聚氨酯复合胶高固含,低粘度,并具有优异的粘接性能和耐冲深性能,可更好地满足应用需求。
本发明采用的技术方案是:
一种铝塑膜用聚氨酯复合胶,该聚氨酯复合胶为包含主剂和固化剂的双组分聚氨酯胶水,其中主剂包括如下重量份数的组分:
含支链结构的苯酐聚酯多元醇70-90份,
结晶型聚酯多元醇10-30份,
醇类扩链剂0.6-2.7份,
异氰酸酯15-20份,
有机铋催化剂0.04份,
环氧树脂10-20份,
终止剂0.15-0.3份,
硅烷偶联剂0.1-0.3份,
乙酸乙酯36-42份,
丁酮80-100份;
其中固化剂为多异氰酸酯,含量为主剂重量的15-25%。
进一步地,所述含支链结构的苯聚酯酐类多元醇为聚对苯二甲酸新戊二醇己二醇二元醇、聚间苯二甲酸葵二酸新戊二醇二元醇和聚间苯二甲酸己二酸甲基丙二醇中的一种或多种。
进一步地,所述结晶型聚酯多元醇为聚己二酸乙二醇二元醇、聚己二酸丁二醇二元醇和聚己二酸己二醇二元醇中的一种或多种。
进一步地,所述异氰酸酯为二苯基甲烷二异氰酸酯和/或碳化二亚胺改性二苯基甲烷二异氰酸酯。
进一步地,所述扩链剂为乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇和一缩二乙二醇中的一种或多种。
进一步地,所述的终止剂为乙二醇。
进一步地,所述有机铋催化剂为8188;
所述环氧树脂为E-44和/或E-51;
所述硅烷偶联剂为KH-560。
进一步地,所述多异氰酸酯为75%固含量的TDI-TMP,溶剂为乙酸乙酯。
上述铝塑膜用聚氨酯复合胶的制备方法,其特征在于,包含如下步骤:
S1:按重量份数,将苯酐类聚酯多元醇70-90份,己二酸类聚酯多元醇10-30份,扩链剂0.6-2.7份,环氧树脂10-20份,催化剂0.04份,36-42份乙酯在50-60℃混合10-20min,接着加入异氰酸酯10.5-14份,将温度缓慢升至70-80℃,反应1-1.5h,然后视溶液反应粘度增加情况,逐步加入剩下的4.5-6份异氰酸酯和36-42份的丁酮,继续反应3-4h,加入终止剂0.15-0.3份,继续反应0.5h,取样测试NCO,待无NCO残留,加入剩余48-56份丁酮和0.1-0.3份的硅烷偶联剂混合5-10min,降温收料,得到主料;
S2:按重量份数,取上述主料100份,加入多异氰酸酯固化剂15-25份,用适量乙酸乙酯稀释成30-40%的溶液,即为聚氨酯复合胶。
进一步地,S1中,加入终止剂反应后,取样测试NCO,待无NCO残留后,再加入剩余的丁酮和硅烷偶联剂反应。
本发明的有益效果如下:
1、本发明的聚氨酯复合胶,其组分中的苯酐类聚酯多元醇,具有较为优异的耐高温和粘接性能,并具体选用含支链型的苯酐类聚酯多元醇,可以在保证耐高温和粘接性能的基础上,有效提高其耐水性能;
2、本发明的聚氨酯复合胶,通过苯酐类聚酯多元醇与具有高初粘力和粘接强度的结晶型己二酸类聚酯多元醇复配,改善了复合胶的初始粘度,增大胶黏剂对基材的附着力;
3、本发明的聚氨酯复合胶,选用环氧树脂作为助剂,使其在固化的时候,形成IPN网络形态,进一步提高复合胶的耐湿热性能;
4、本发明的聚氨酯复合胶,通过引入适量的硅烷偶联剂,不仅提高了尼龙与铝箔的粘接力,且进一步增强了其耐高温高湿的能力;
5、本发明的制备方法,通过-NCO欠量法制备溶剂型OH封端的聚氨酯复合胶,再通过多异氰酸酯固化剂进行进一步增加树脂的分子量,给予胶水以极好的复合性能和抗冲深性能;同时,本发明的制备方法,其工艺流程简单,制备容易,满足大批量生产制造的需求。
附图说明
图1为本发明的实施例1-4中的制备流程图。
具体实施方式
为了便于理解本发明,下面将参照实施例对本发明进行更全面的描述,以下给出了本发明的较佳实施例。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施例。提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。实施例中使用到的各类原料,除非另有说明,均为常见市售产品。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本发明实施例中揭露的数值是近似值,而并非确定值。在误差或者实验条件允许的情况下,可以包括在误差范围内的所有值而不限于本发明实施例中公开的具体数值。
本发明实施例中揭露的数值范围用于表示在混合物中的组分的相对量以及其他方法实施例中列举的温度或者其他参数的范围。
此处需要说明的是,下面实施例和对比例中中用到的组分的简称分别为:
含支链结构的苯聚酯酐类多元醇:聚对苯二甲酸新戊二醇己二醇二元醇(PNHA),聚间苯二甲酸葵二酸新戊二醇二元醇(PNSI),聚间苯二甲酸己二酸甲基丙二醇(PMAI)。
结晶型己二酸类聚酯多元醇:聚己二酸乙二醇二元醇(PEA),聚己二酸丁二醇二元醇(PBA),聚己二酸己二醇二元醇(PHA)。
异氰酸酯:二苯基甲烷二异氰酸酯(MDI),碳化二亚胺改性二苯基甲烷二异氰酸酯(L-MDI)。
扩链剂:乙二醇(EG),1,4-丁二醇(BDO),1,6-己二醇(HDO),新戊二醇(NPG),一缩二乙二醇(DEG)。
有机铋催化剂:8188。
环氧树脂:E-44或E-51。
终止剂:乙二醇(EG)。
硅烷偶联剂:KH-560。
多异氰酸酯:科思创的L-75(75%固含量的TDI-TMP,溶剂为乙酸乙酯)。
下面结合实施例对本发明作进一步详细说明:
实施例1:
本实施例提供一种铝塑膜用聚氨酯复合胶的制备方法,包含如下步骤:
S1:按重量份数,将70份的PNHA-2000、30份的PBA-2000、0.9份的BDO、12.78份的E-44、0.04份的8188和39.03份的乙酸乙酯加入反应釜内,50℃搅拌10-20min,接着将11.36份的L-MDI加入反应釜内,缓慢升温至70-80℃,反应1-1.5h,然后视溶液反应粘度增加情况,逐步加入剩下的4.87份L-MDI和39.03份的丁酮,继续反应3-4h,加入0.18份的EG,继续反应0.5h,取样测试NCO,待体系内无NCO残留,加入剩余的丁酮52.04份和0.15份的KH-560,搅拌5-10min待混合均匀,降温收料,得到主料,最终得到的主料产品的固含量为50±2%,粘度为1000-3000mpa.s/25℃。
S2:按重量份数,取上述主料100份,加入多异氰酸酯固化剂20份,用适量乙酸乙酯稀释成35%的溶液,即为聚氨酯复合胶。
应用测试
将上面制得的聚氨酯复合胶,作为底胶进行涂布。
涂布分两个步骤11、用线棒均匀涂布于40um的铝箔上,涂布量需控制在3-5g/m2,放进100-120℃的烤箱,烘烤1-2min,贴合25um的尼龙,制备好的样品放置85℃烘箱固化48h,待测试剥离力和冲深性能;
12、用线棒均匀涂布于离型纸上,涂布量控制在30±g/m2,放置85℃烘箱固化48h,待测试胶膜的拉伸性能。
实施例2:
本实施例提供一种铝塑膜用聚氨酯复合胶的制备方法,包含如下步骤:
S1:按重量份数,将85份的PNSI-2000、15份的PHA-2000、1.24份的EG、11.70份的E-51、0.04份的8188和39.07份的乙酸乙酯加入反应釜内,50℃搅拌10-20min,接着将11.94份的MDI-50加入反应釜内,缓慢升温至70-80℃,反应1-1.5h,然后视溶液反应粘度增加情况,逐步加入剩下的5.12份MDI-50和39.07份的丁酮,继续反应3-4h,加入0.21份的EG,继续反应0.5h,取样测试NCO,待体系内无NCO残留,加入剩余的丁酮52.10份和0.18份的KH-570,搅拌5-10min待混合均匀,降温收料,得到主料,最终得到的主料产品的固含量为50±2%,粘度为1000-3000mpa.s/25℃;
S2:按重量份数,取上述主料100份,加入多异氰酸酯固化剂20份,用适量乙酸乙酯稀释成30%的溶液,即为聚氨酯复合胶。
应用测试
同实施例1
实施例3:
本实施例提供一种铝塑膜用聚氨酯复合胶的制备方法,包含如下步骤:
S1:按重量份数,将90份的PMAI-2000、10份的PBA-2000、2.4份的BDO、17.80份的E-44、0.04份的8188和41.74份的乙酸乙酯加入反应釜内,50℃搅拌10-20min,接着将13.08份的MDI-50加入反应釜内,缓慢升温至70-80℃,反应1-1.5h,然后视溶液反应粘度增加情况,逐步加入剩下的5.61份MDI-50和41.74份的丁酮,继续反应3-4h,加入0.23份的EG,继续反应0.5h,取样测试NCO,待体系内无NCO残留,加入剩余的丁酮55.66份和0.20份的KH-560,搅拌5-10min待混合均匀,降温收料,得到主料,最终得到的主料产品的最终产品固含量为50±2%,粘度为1000-3000mpa.s/25℃;
S2:按重量份数,取上述主料100份,加入多异氰酸酯固化剂25份,用适量乙酸乙酯稀释成40%的溶液,即为聚氨酯复合胶。
应用测试
同实施例1
实施例4:
本实施例提供一种铝塑膜用聚氨酯复合胶的制备方法,包含如下步骤:
S1:按重量份数,将90份的PNSI-2000、10份的PBA-2000、1.5份的EG、14.41份的E-51、0.04份的8188和40.87份的乙酸乙酯加入反应釜内,50℃搅拌10-20min,接着将14.05份的L-MDI加入反应釜内,缓慢升温至70-80℃,反应1-1.5h,然后视溶液反应粘度增加情况,逐步加入剩下的6.02份L-MDI和40.87份的丁酮,继续反应3-4h,加入0.25份的EG,继续反应0.5h,取样测试NCO,待体系内无NCO残留,加入剩余的丁酮54.50份和0.20份的KH-570,搅拌5-10min待混合均匀,降温收料,得到主料,最终得到的主料产品的最终产品固含量为50±2%,粘度为1000-3000mpa.s/25℃;
S2:按重量份数,取上述主料100份,加入多异氰酸酯固化剂25份,用适量乙酸乙酯稀释成40%的溶液,即为聚氨酯复合胶。
应用测试
同实施例1
对比案例1:
本对比案例与实施案例1-4的区别在于,复合铝塑膜的胶黏剂为上海维凯光电新材料有限公司的VN930,固化剂为L-75,其质量配比比例为100/20,其余施工工艺与实施案例1-4相同。
对实施例1-4制得的样品,胶膜和对比案例1的样品,胶膜进行常温T剥离力、“双85”T型剥离力、拉伸性能和冲深性能测试,测试方法和测试标准如下:
①常温T型剥离力:依据GB2791-1995,样品尺寸为300mm*15mm,拉伸速率为150mm/min,单位为N/15mm;
②“双85”T型剥离力:将制备好的样条,放置85℃,85%RH的环境中,参照常温T型剥离力测试方法进行测试;
③拉伸强度测试:依据GB/T 528-2009,样品尺寸为150mm*25mm*0.03mm,原始标距为50mm,拉伸速率为150mm/min,进行测试;
④冲深性能测试:在25℃,湿度为55±5%,模具尺寸为50mm*40mm,R角为1mm,用冲坑机将熟化好的铝塑膜进行冲深性能测试。
性能测试结果如表1所示:
表1
由表1可知,实施例1-4所制备的铝塑膜用聚氨酯复合胶,表现出优异的粘结强度和冲深性能,其综合性能较VN930更加优异,本发明通过在组分中加入苯酐类聚酯多元醇,具有优异的耐高温和粘接性能,并具体选用含支链型的该类聚酯,可以在保证耐高温和粘接性能的基础上,有效提高其耐水性能,并通过苯酐类聚酯多元醇与具有高初粘力和粘接强度的结晶型己二酸类聚酯多元醇复配,解决了使用苯酐类聚酯多元醇制备的聚氨酯胶黏剂,整体硬度比较高的问题,有效改善了复合胶的初始粘度,增大胶黏剂对基材的附着力;通过选用环氧树脂作为助剂,使其在固化的时候,形成IPN网络形态,进一步提高复合胶的耐湿热性能;并通过引入适量的硅烷偶联剂,不仅提高了尼龙与铝箔的粘接力,且进一步增强了其耐高温高湿的能力;本发明的制备方法,通过-NCO欠量法制备溶剂型OH封端的聚氨酯复合胶,再通过多异氰酸酯固化剂进行进一步增加树脂的分子量,给予胶水以极好的复合性能和抗冲深性能;同时,本发明的制备方法,其工艺流程简单,制备容易,满足大批量生产制造的需求。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种铝塑膜用聚氨酯复合胶,其特征在于,该聚氨酯复合胶为包含主剂和固化剂的双组分聚氨酯胶水,其中主剂包括如下重量份数的组分:
含支链结构的苯酐聚酯多元醇70-90份,
结晶型聚酯多元醇10-30份,
醇类扩链剂0.6-2.7份,
异氰酸酯15-20份,
有机铋催化剂0.04份,
环氧树脂10-20份,
终止剂0.15-0.3份,
硅烷偶联剂0.1-0.3份,
乙酸乙酯36-42份,
丁酮80-100份;
其中固化剂为多异氰酸酯,含量为主剂重量的15-25%。
2.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,所述含支链结构的苯聚酯酐类多元醇为聚对苯二甲酸新戊二醇己二醇二元醇、聚间苯二甲酸葵二酸新戊二醇二元醇和聚间苯二甲酸己二酸甲基丙二醇中的一种或多种。
3.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,所述结晶型聚酯多元醇为聚己二酸乙二醇二元醇、聚己二酸丁二醇二元醇和聚己二酸己二醇二元醇中的一种或多种。
4.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,所述异氰酸酯为二苯基甲烷二异氰酸酯和/或碳化二亚胺改性二苯基甲烷二异氰酸酯。
5.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,所述扩链剂为乙二醇、1,4-丁二醇、1,6-己二醇、新戊二醇和一缩二乙二醇中的一种或多种。
6.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,所述的终止剂为乙二醇。
7.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,
所述有机铋催化剂为8188;
所述环氧树脂为E-44和/或E-51;
所述硅烷偶联剂为KH-560。
8.根据权利要求1所述的一种铝塑膜用聚氨酯复合胶,其特征在于,所述多异氰酸酯为75%固含量的TDI-TMP,溶剂为乙酸乙酯。
9.根据权利要求1-8任一所述的一种铝塑膜用聚氨酯复合胶的制备方法,其特征在于,包含如下步骤:
S1:按重量份数,将苯酐类聚酯多元醇70-90份,己二酸类聚酯多元醇10-30份,扩链剂0.6-2.7份,环氧树脂10-20份,催化剂0.04份,36-42份乙酯在50-60℃混合10-20min,接着加入异氰酸酯10.5-14份,将温度缓慢升至70-80℃,反应1-1.5h,然后视溶液反应粘度增加情况,逐步加入剩下的4.5-6份异氰酸酯和36-42份的丁酮,继续反应3-4h,加入终止剂0.15-0.3份,继续反应0.5h,取样测试NCO,待无NCO残留,加入剩余48-56份丁酮和0.1-0.3份的硅烷偶联剂混合5-10min,降温收料,得到主料;
S2:按重量份数,取上述主料100份,加入多异氰酸酯固化剂15-25份,用适量乙酸乙酯稀释成30-40%的溶液,即为聚氨酯复合胶。
10.根据权利要求9所述的一种铝塑膜用聚氨酯复合胶的制备方法,其特征在于,S1中,加入终止剂反应后,取样测试NCO,待无NCO残留后,再加入剩余的丁酮和硅烷偶联剂反应。
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