CN106883811B - 一种环氧改性聚氨酯底座胶组合物及一种热固化贴合片 - Google Patents

一种环氧改性聚氨酯底座胶组合物及一种热固化贴合片 Download PDF

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CN106883811B
CN106883811B CN201710156293.6A CN201710156293A CN106883811B CN 106883811 B CN106883811 B CN 106883811B CN 201710156293 A CN201710156293 A CN 201710156293A CN 106883811 B CN106883811 B CN 106883811B
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吴朝森
谢志明
谢梦兴
韦思其
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Abstract

本发明涉及一种环氧改性聚氨酯底座胶组合物及一种热固化贴合片，所述底座胶组合物由如下质量百分比的组分组成：环氧改性聚氨酯共聚物60～80%；增粘树脂5～15%；潜伏型固化剂2%～8%；热固化剂2%～8%；热固化促进剂0.2%～2%；填充剂1%～10%；稀释剂5%～15%。本发明提供的环氧改性聚氨酯底座胶组合物在室温条件下通过湿气固化成型能够制备得到热固化贴合片，将该热固化贴合片用于后视镜底座的粘接可实现快速定位；并且贴合片在后续的高温加热过程中不会出现形态变化和位移现象，其还具有优异的抗震动性能。

Description

一种环氧改性聚氨酯底座胶组合物及一种热固化贴合片
技术领域
本发明涉及胶粘剂技术领域，具体涉及一种环氧改性聚氨酯底座胶组合物及一种热固化贴合片。
背景技术
日常生活中常见的轿车、公交车、长途大巴等交通工具，在其前挡玻璃的装配过程中的一个重要环节即为后视镜的装配，后视镜的装配首先就是对后视镜底座的定位粘接。
目前后视镜底座定位粘接所用的胶黏剂一般为双组份的环氧粘接胶。这些双组份环氧粘接胶用于后视镜的常用工艺有两种：第一种，将双组分的胶粘剂充分混合均匀后涂饰于后视镜底座上，然后经过短暂的手工压合，使其初步固化定位，待底座胶完全固化后将挡风玻璃经过130～150℃的高温烘道以对挡风玻璃的双片玻璃进行贴合；第二种，先将挡风玻璃经过高温烘道，再使用双组份环氧粘接胶对底座进行定位粘接，最后可进行后视镜的装配。在将挡风玻璃过高温烘道的这个过程中要求后视镜底座不能发生任何位移。这两种工艺都存在粘接时间长，加工效率低的问题，并且前一种处理方法还存在后视镜底座高温位移的风险。除此之外，现有的双组份环氧粘接胶往往由于使用环氧树脂体系而表现出相当的脆性，在汽车行驶过程中经受长期震荡容易出现脆性破坏；另外，双组份环氧粘接胶还存在粘接强度低、抗震动性能差的缺点。
因此，仍需研发一种柔韧性和粘接强度高、抗震动抗位移的环氧改性聚氨酯底座胶组合物。
发明内容
本发明的目的在于克服现有技术的不足，提供一种环氧改性聚氨酯底座胶组合物，本发明提供的环氧改性聚氨酯底座胶组合物在室温条件下通过湿气固化成型制备得到一种热固化贴合片，将该热固化贴合片用于后视镜底座的粘接可实现快速定位；并且在后续的高温加热过程中不会出现位移现象。
本发明的另一目的在于提供上述环氧改性聚氨酯底座胶组合物的制备方法。
本发明的另一目的在于提供上述环氧改性聚氨酯底座胶组合物在汽车后视镜底座粘接中的应用。
本发明的另一目的在于提供上述环氧改性聚氨酯底座胶组合物制备得到的热固化贴合片。
为实现上述目的，本发明采用如下技术方案：
一种环氧改性聚氨酯底座胶组合物，所述底座胶组合物由如下质量百分比的组分组成：
Figure BDA0001246715470000021
其中，所述环氧改性聚氨酯共聚物为环氧树脂对聚氨酯预聚体进行改性所得，所述聚氨酯预聚体为羟基树脂和多异氰酸酯反应得到的端NCO化合物；所述环氧改性聚氨酯共聚物的游离NCO值为1～3％，所述环氧树脂为双酚A型环氧树脂；所述羟基树脂为聚醚多元醇、聚酯多元醇、聚四氢呋喃二醇、端羟基聚丁二烯树脂、端羟基氢化聚丁二烯树脂、端羟基环氧化聚丁二烯树脂、端羟基聚丁二烯-丙烯晴树脂、端羟基聚异戊二烯树脂或端羟基氢化聚异戊二烯树脂中的一种或几种；
所述热固化剂为熔点为80～200℃、粒径小于20um的双氰胺微粉；所述稀释剂为非活性稀释剂或含环氧基团的活性稀释剂。
本发明以环氧改性的聚氨酯共聚物为主体树脂，同时采用湿固化型潜伏型固化剂和热固化剂相配合，得到了一种环氧改性聚氨酯底座胶组合物。该底座胶组合物可以在常温下经过湿气固化成型得到稳定性好的热固化贴合片，该贴合片可满足后视镜底座快速定位的要求，并且热固化贴合片在经高温热固化后不会出现形态变化和位移现象。本发明提供的热固化贴合片经过高温热固化后具有较好的柔韧性和粘结性能，其还具有较高的抗冲击性能和抗震动性能。
在本发明中，合成聚氨酯预聚体的羟基树脂的选择对热固化贴合片的抗位移性能影响较大，只有当选用上述羟基树脂来合成聚氨酯预聚体时，以经环氧改性后的聚氨酯共聚物为原料制备的底座胶组合物才具有良好的抗位移性能。
因此，优选地，所述羟基树脂为分子量为700～5000的聚醚二元醇、分子量为1000～8000的聚醚三元醇、分子量为1000～5000的端羟基氢化聚丁二烯、端羟基环氧化聚丁二烯或端羟基聚丁二烯-丙烯腈中一种或几种。
最为优选地所述羟基树脂为分子量为1000～3000的聚醚二元醇、分子量在3000～6000的聚醚三元醇、分子量为2000～3000的端羟基氢化聚丁二烯、端羟基环氧化聚丁二烯或端羟基聚丁二烯-丙烯腈中一种或几种。
在本发明中，环氧树脂的环氧值的大小会直接影响到底座胶组合物的粘接性能和抗冲击性能。优选地，所述双酚A型环氧树脂为环氧值在180～500之间的双酚A型环氧树脂。
优选地，所述环氧改性聚氨酯共聚物的制备方法如下：
将羟基树脂混合升温至90～120℃，在真空度为-0.09～-0.1MPa条件下除水2～6h；降温至60～80℃并加入多异氰酸酯充分混合反应2～4h；加入催化剂继续反应0.5～1h，控制反应条件不变加入环氧树脂继续反应1～2h，直至游离的NCO值为1～3％，终止反应即得环氧改性聚氨酯共聚物。
在本发明中，所述多异氰酸酯为官能度为2及以上的异氰酸酯化合物。优选地，所述多异氰酸酯为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、异佛尔酮二异氰酸酯三聚体(IPDI三聚体)、甲苯二异氰酸酯三聚体(TDI三聚体)、六亚甲基二异氰酸酯三聚体(HDI三聚体)中的一种或几种。
在本发明中，所述羟基树脂和多异氰酸酯的比例按OH：NCO摩尔比1.8～2.2:1的比例进行设计。
优选地，所述湿固化型潜伏型固化剂为酮亚胺化合物、醛亚胺化合物或含至少两个噁唑烷基的多氧氮杂环戊烷官能基潜伏固化剂。其中，所述多氧氮杂环戊烷官能基潜伏固化剂优选含有2～6个噁唑烷官能基的潜伏固化剂，特别是含2～4个噁唑烷官能基的潜伏固化剂。
双氰胺室温条件下为固体，其与体系中的增粘树脂相容性不好，分散性能较差，需要碾压成微粉后才可在体系中稳定存在。因此优选地，所述双氰胺微粉的熔点为100～170℃，粒径为5～10um。
本发明中的热固化促进剂可以选择有机脲、咪唑和咪唑盐、咪唑啉、酰胺基胺、亚氨基胺或路易斯酸的胺络合物。其中有机脲类促进剂可以选择非芳香族的脲；所述酰胺基胺促进剂由邻苯二甲酸酐与具有伯氨基的多元胺反应得到，多元胺可以选择二亚乙基三胺(DETA)或三亚乙基四胺(TETA)。
在本发明中，所述填充剂可以选择炭黑、气相二氧化硅、非结晶型的二氧化硅微粉、活性碳酸钙等。
优选地，所述稀释剂为邻苯二酸酯类、脂肪酯类非活性稀释剂或含环氧基团的环氧化合物类活性稀释剂。更为优选地，所述稀释剂为邻苯二甲酸二丁酯、二辛酯非活性稀释剂或缩水甘油醚类单环氧基、双环氧基活性稀释剂。
上述环氧改性聚氨酯底座胶组合物的制备方法，所述方法为：将环氧改性聚氨酯共聚物、增粘树脂、潜伏型固化剂、热固化剂、热固化促进剂、填充剂以及稀释剂在真空度为-0.09～-0.1MPa，温度为60～80℃的高速分散机中，研磨分散2～4h，最后通氮气回压即得底座胶组合物。
所述催化剂可以选择二月桂酸二丁基锡。
上述环氧改性聚氨酯底座胶组合物在汽车后视镜底座粘接中的应用也在本发明的保护范围之内。
上述环氧改性聚氨酯底座胶组合物制备得到的热固化贴合片也在本发明的保护范围之内。
上述热固化贴合片的制备方法为：
将所述底座胶组合物倒入根据贴合片厚度要求设计的模具中，使其填满模具并使之自流平(当温度低于20℃时可适当加热)，于无尘室中放置24h以上，使胶膜可以从模具中完全脱落；取下胶膜后在其两面贴上背衬底材，根据底座尺寸裁剪即得底座胶贴合片。
本发明提供的热固化贴合片对基面具有极佳的吸附和浸润能力，同时热固化贴合片已经过湿气固化，其具备一定的交联网状结构，这使得在后续的高温加热固化过程中不会出现形态变化和位移现象。
与现有技术相比，本发明具有如下有益效果：
本发明提供的环氧改性聚氨酯底座胶组合物可以在常温下经过湿气固化成型得到热固化贴合片，该贴合片性能稳定，可满足后视镜底座快速定位的要求，并且热固化贴合片在经高温热固化后不会出现形态变化和位移现象；同时，该贴合片具有较好的柔韧性和粘结性能，还具有较高的抗冲击性能和抗震动性能。
本发明提供的环氧改性聚氨酯底座胶组合物为一种单组份的底座胶，与双组份环氧粘接胶相比，其具有较好的流动性、操作方便、施工过程无需增加称量仪器和搅拌设备，能够显著提高装配效率，具有较广阔的应用前景。
具体实施方式
下面结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
以下各实施例底座胶组合物所用的原料如下表所示：
Figure BDA0001246715470000051
Figure BDA0001246715470000061
实施例1～6
实施例1～6提供了一种环氧改性聚氨酯底座胶组合物，所述底座胶组合物由如下质量百分比的组分组成：
Figure BDA0001246715470000062
其中，所述环氧改性聚氨酯共聚物为环氧树脂对聚氨酯预聚体进行改性所得，所述聚氨酯预聚体为羟基树脂和多异氰酸酯反应得到的端NCO化合物；所述环氧改性聚氨酯共聚物的游离NCO值为1～3％，所述环氧树脂为双酚A型环氧树脂；所述羟基树脂为聚醚多元醇、聚酯多元醇、聚四氢呋喃二醇、端羟基聚丁二烯树脂、端羟基氢化聚丁二烯树脂、端羟基环氧化聚丁二烯树脂、端羟基聚丁二烯-丙烯晴树脂、端羟基聚异戊二烯树脂或端羟基氢化聚异戊二烯树脂中的一种或几种；
所述热固化剂为熔点为80～200℃、粒径小于20um的双氰胺微粉；所述稀释剂为非活性稀释剂或含环氧基团的活性稀释剂。
实施例1～6的环氧改性聚氨酯底座胶组合物的配方如下
Figure BDA0001246715470000071
Figure BDA0001246715470000081
Figure BDA0001246715470000091
(1)环氧改性聚氨酯共聚物的制备
将羟基树脂混合升温至90～120℃，然后在真空度-0.09～-0.1MPa条件下，除水2～6h；然后将温度降至60～80℃，与多异氰酸酯在反应釜中充分混合反应2～4h后，加入0.05～0.1质量份的催化剂(二月桂酸二丁基锡)继续反应0.5～1h；控制条件不变，加入环氧树脂，继续反应1～2h，直至游离的NCO值为1～3％，终止反应，制得预聚体。
(2)底座胶组合物的制备
按配方量将上述共聚物、湿固化型潜伏型固化剂、热固化剂、热固化促进剂、无机粉体填充剂、稀释剂在真空度-0.09～-0.1MPa，温度60～80℃环境的高速分散机中，研磨分散2～4h，最后通氮气回压即制得底座胶组合物。
(3)底座胶贴合片的制备：
按照1mm厚度的贴合片制成PP材质磨具，往往磨具中导倒入底座胶胶液，刮满后自流平，然后将磨具放置于无尘室中，24h后，胶膜可完全脱模，贴上背衬底材，按底座尺寸裁剪后即得底座胶贴合片。
对实施例1～6的环氧改性聚氨酯底座胶制得的热固化贴合片的性能进行测试，测试方法如下，测试结果见下表2。
(1)底座胶贴合片的粘接力测试
将贴合片撕下一面背衬底材，然后合对贴在底座上，再撕下另一面背衬底材，施加一定的力将底座压在挡风玻璃黑边上，然后在底座上边缘和下边缘分别画上边界线，接着竖放立于烘箱中，设置烘箱温度为145℃。升温至所设温度后烘烤30min，然后关烘箱自然降温至常温，取出试样，观察贴合片是否位移、测试扭矩及观察界面破坏情况，扭矩能够直观的表现出贴合片的粘接性能。
表2实施例1～6制得的热固化贴合片的性能测试
Figure BDA0001246715470000101
由上表1中的实验数据可知，本发明各实施例制备得到的热固化贴合片在经过高温烘道后均未产生高温位移现象，并且具有较好的粘接性能、抗冲击性能、柔韧性和抗震动性能。实施例6中存在部分胶层破坏，但是其依然能够满足使用要求。
相比之下，对比例1中选用双酚F型的环氧树脂，以其改性后的聚氨酯共聚物为原料制得的热固化贴合片的胶层强度和对基材的粘接性能均较差，并且高温后有位移现象；对比例2中选择熔点较高的双氰胺热固化剂，其分散性能较差，使得热固化后的胶层强度下降并存在高温位移现象；对比例3中选择具有较高挥发性的溶剂作为稀释剂，制得的热固化贴合片在受热过程中易在胶层间产生气泡和流淌现象，粘接强度也大幅度下降。

Claims (7)

1.一种热固化贴合片，其特征在于，
所述热固化贴合片的制备方法为：
将底座胶组合物倒入根据贴合片厚度要求设计的模具中，使其填满模具并使之自流平，于无尘室中放置24h以上，使胶膜可以从模具中完全脱落；取下胶膜后在其两面贴上背衬底材，根据底座尺寸裁剪即得底座胶贴合片；
所述底座胶组合物由如下质量百分比的组分组成：
环氧改性聚氨酯共聚物 60～80%；
增粘树脂 5～15%；
湿固化型潜伏型固化剂 2%～8%；
热固化剂 2%～8%；
热固化促进剂 0.2%～2%
填充剂 1%～10%；
稀释剂 5%～15%；
其中，所述环氧改性聚氨酯共聚物为环氧树脂对聚氨酯预聚体进行改性所得，所述聚氨酯预聚体为羟基树脂和多异氰酸酯反应得到的端NCO化合物；所述环氧改性聚氨酯共聚物的游离NCO值为1～3%，所述环氧树脂为双酚A型环氧树脂；所述羟基树脂为聚醚多元醇、聚酯多元醇、端羟基聚丁二烯树脂、端羟基氢化聚丁二烯树脂、端羟基环氧化聚丁二烯树脂、端羟基聚丁二烯-丙烯腈树脂、端羟基聚异戊二烯树脂或端羟基氢化聚异戊二烯树脂中的一种或几种；
所述热固化剂为熔点为80～200℃、粒径小于20um的双氰胺微粉；所述稀释剂为二辛酯非活性稀释剂、烯丙基缩水甘油醚或缩水甘油醚类双环氧基活性稀释剂。
2.根据权利要求1所述热固化贴合片，其特征在于，所述羟基树脂为分子量为700～5000的聚醚二元醇、分子量为1000～8000的聚醚三元醇、分子量为1000～5000的端羟基氢化聚丁二烯、端羟基环氧化聚丁二烯或端羟基聚丁二烯-丙烯腈中一种或几种。
3.根据权利要求1所述热固化贴合片，其特征在于，所述双酚A型环氧树脂的环氧值在180～500之间。
4.根据权利要求1所述热固化贴合片，其特征在于，所述环氧改性聚氨酯共聚物的制备方法如下：
将羟基树脂混合升温至90～120℃，在真空度为-0.09～-0.1MPa条件下除水2～6h；降温至60～80℃并加入多异氰酸酯充分混合反应2～4h；加入催化剂继续反应0.5～1h，控制反应条件不变加入环氧树脂继续反应1～2h，直至游离的NCO值为1～3%，终止反应即得环氧改性聚氨酯共聚物。
5.根据权利要求1所述热固化贴合片，其特征在于，所述湿固化型潜伏型固化剂为酮亚胺化合物、醛亚胺化合物或含至少两个噁唑烷基的多氧氮杂环戊烷官能基潜伏固化剂。
6.权利要求1～5任一所述热固化贴合片的制备方法，其特征在于，所述环氧改性聚氨酯底座胶组合物的制备方法：将环氧改性聚氨酯共聚物、增粘树脂、湿固化型潜伏型固化剂、热固化剂、热固化促进剂、填充剂以及稀释剂在真空度为-0.09～-0.1MPa，温度为60～80℃的高速分散机中，研磨分散2～4h，最后通氮气回压即得底座胶组合物。
7.权利要求1～5任一所述热固化贴合片在汽车后视镜底座粘接中的应用。
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