CN116376464A - 一种高粘接强度、高耐热性的热熔胶膜及其制备方法和应用 - Google Patents
一种高粘接强度、高耐热性的热熔胶膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种高粘接强度、高耐热性的热熔胶膜，所述热熔胶膜包括封闭异氰酸酯单体和热熔胶基材，所述封闭异氰酸酯单体的用量为热熔胶膜质量的0.1‑50％。本发明还提供了一种高粘接强度、高耐热性的热熔胶膜的制备方法：将封闭异氰酸酯单体与热熔胶基材混合成热熔胶膜。本发明还提供了一种高粘接强度、高耐热性的热熔胶膜的应用，将热熔胶膜与被粘接物贴合并热压，从而完成粘接。本发明提供的热熔胶膜在应用时无需其它任何额外交联试剂，即具有良好的粘接强度和耐热性；且制备方法简单。
Description
技术领域
本发明涉及热熔胶膜技术领域，更具体涉及一种高粘接强度、高耐热性的热熔胶膜及其制备方法和应用。
背景技术
热熔胶膜是一类可直接贴附在被粘接物上、加热加压即能粘合的薄膜状胶粘剂，主要包括热塑性聚氨酯(TPU)、聚酰胺(PA)、乙烯-醋酸乙烯酯(EVA)、聚烯烃(PO)等。它操作简单，无溶剂，易进行连续化胶合，对于织物、塑料、橡胶、纸张、金属、陶瓷、玻璃等都具有一定的粘接力，广泛用于服装鞋帽、家居建材、汽车内饰、电子产品、日用品等领域。
然而，由于热熔胶膜为热塑性材料，导致其粘接强度低、耐热性差(高温粘结力差)。引入交联结构是提高其粘接强度和耐热性的重要手段，例如，引入硅烷偶联剂(专利号200910038212.8)、多烯单体(专利号202210480936.3)、过氧化物(专利号202210879692.6)、丙烯酸-2-羟乙酯接枝改性共聚物(专利号202210827488.X)等。但目前报道的这些交联剂往往只是针对一种热熔胶膜，普适性有限。
异氰酸酯是一种常用的交联剂，通常与羟基、胺基、水反应形成交联网络结构。由于其非常活泼，易与空气中的湿气发生湿固化反应，因此通常用封闭剂将其活性临时封闭起来，使其在室温下失去活性，防止与水或其它活性物质反应；而当使用时，可在一定温度下释放出异氰酸酯基团，并参与反应。目前的封闭异氰酸酯的形式多为分子链段中含有大分子醇的封闭聚氨酯预聚物，也有少量为封闭异氰酸酯单体。相对于具有较高分子量的封闭聚氨酯预聚物而言，封闭异氰酸酯单体的分子量非常小，具有更高的活性和官能团含量，更有利于快速、高效地形成交联分子网络。然而目前的封闭异氰酸酯单体主要用于液态(专利号200810246160.9)或不干胶(专利号201010242705.6、专利号201010242879.2、专利号201010242786.X)形式的聚氨酯胶黏剂和涂料，产品是以浆料形式进行应用。此外，也有将封闭异氰酸酯单体用于热熔胶膜的交联(例如专利号201811489991.9)，但需要涂布操作；需要加入额外的交联剂(例如环氧树脂、咪唑)进行辅助，方能形成交联；且适用的热熔胶膜种类仅限一种，未显示出对TPU、PA、EVA、PO等不同分子结构胶膜的广泛交联和相应的粘接强度和耐热性提高作用。
发明内容
本发明的目的在于提供一种高粘接强度、高耐热性的热熔胶膜及其制备方法和应用，本发明提供的热熔胶膜在应用时无需其它任何额外交联试剂，即具有良好的粘接强度和耐热性；且制备方法简单。
本发明提供如下技术方案：
一种高粘接强度、高耐热性的热熔胶膜，所述热熔胶膜包括封闭异氰酸酯单体和热熔胶基材，所述封闭异氰酸酯单体的用量为热熔胶膜质量的0.1-50％。
所述热熔胶基材选自固体膜态的TPU、PA、EVA、或PO中的一种或至少两种的组合。也可以选自其他固体膜态的热熔胶基材。固体膜态是指形态结构均一的固体膜(非浆料态，也非多层复合态)，在使用时无需任何涂布操作(不需要涂布在被粘接物上，也不需要在胶膜表面涂布其辅助粘接试剂)，可直接通过简单的热压而完成粘接。
所述封闭异氰酸酯单体由异氰酸酯单体和封闭剂反应而成，反应温度为25-100℃。所述异氰酸酯单体选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯三聚体、二环己基甲烷二异氰酸酯或三苯甲烷三异氰酸酯等，所述封闭剂选自丙酮肟、丁醛肟、环己酮肟、甲醇、N-甲基苯胺、3,5-二甲基吡唑、1,2,4-三氮唑或丙二酸二乙酯等。
优选地，所述封闭异氰酸酯单体的用量为热熔胶膜质量的10-50％。通过调控封闭异氰酸酯单体的用量，可以进一步提高热熔胶膜的粘接强度和耐热性。
本发明还提供了一种高粘接强度、高耐热性的热熔胶膜的制备方法：将封闭异氰酸酯单体与热熔胶基材混合成热熔胶膜。
优选地，所述混合成热熔胶膜的方式选自流延法、吹塑法或压延法等。
优选地，在混合时同时加入添加剂，添加剂选自碳纳米管、石墨烯、银纳米线、氧化铝、硅酸盐或荧光染料等中的一种或多种。在制作热熔胶膜时，可根据后端应用场景的需要，选择性复配一定量的添加剂，额外赋予其导电、导热、荧光等功能或者美饰效果。
本发明还提供了一种高粘接强度、高耐热性的热熔胶膜的应用，将热熔胶膜与被粘接物贴合并热压，从而完成粘接。
所述热熔胶膜与被粘接物贴合并热压的温度为100-250℃，热压时间为1-120min。
所述被粘接物为织物、塑料、橡胶、纸张、金属、陶瓷或玻璃等中的一种或多种。
所述热熔胶膜与被粘接物粘结成型后，应用于服装鞋帽、家居建材、汽车内饰、电子产品或日用品领域。
在本发明中，热熔胶膜与被粘接物进行粘结时，可以粘结到一个界面，也可以同时粘结到多个界面；可以粘结同一种基材，也可以粘结不同种类的基材。
在热压过程中，封闭异氰酸酯可通过反应，与热熔胶膜(TPU、PA、EVA、PO)形成一定的交联网络结构，从而大幅提高热熔胶膜对被粘接物的粘接强度。所形成的交联作用因热熔胶膜的种类差异而有所不同，具体如下所示。
当热熔胶膜的胶种为TPU时，热压过程中，封闭异氰酸酯可与TPU分子中的氨酯甲酸酯键发生反应，生成交联网络结构(如反应式I所示)。
当热熔胶膜的胶种为PA时，热压过程中，封闭异氰酸酯可与PA分子中的酰胺键发生反应，生成交联网络结构(如反应式II所示)。
当热熔胶膜的胶种为EVA时，热压过程中，封闭异氰酸酯可与EVA分子侧链的酯键发生反应，生成交联网络结构(如反应式III所示)。
当热熔胶膜的胶种为PO时，热压过程中，封闭异氰酸酯可与热固性胶膜中的吸附水、被粘接物表面的吸附水、空气中的湿气发生反应，形成聚脲交联网络；所形成的聚脲交联网络与PO分子链段通过分子互穿，进一步形成具有交联位点的分子互穿双网络结构(如反应式IV所示)。该交联互穿反应不仅可发生于PO热熔胶膜，也可发生于TPU、PA、EVA等热熔胶膜。
与现有技术相比，本发明提供的热熔胶膜具有以下优点：1、仅需封闭异氰酸酯单体，而无需其它任何额外交联试剂，即可与热熔胶基体形成交联作用，所需试剂种类少，也可简化操作、成本低廉，具有重要的经济和应用价值；2、普适性强，可对热塑性聚氨酯(TPU)、聚酰胺(PA)、乙烯-醋酸乙烯酯(EVA)、聚烯烃(PO)等不同种类的热熔胶基体具有广泛的交联作用形成不同的交联网络结构，以及相应的粘接强度和耐热性的提高作用。因此，本发明提供的热熔胶膜及其制备方法和应用对提高多种热熔胶膜粘接强度和耐热性具有普适性。
具体实施方式
下面结合具体实施例，进一步阐述本发明。需要指出的是，这些实施例仅用于加深对本发明的理解，而不用于限制本发明的范围。
实施例1
将11份二苯基甲烷二异氰酸酯加入到9份N-甲基苯胺中，室温反应2h，即可得N-甲基苯胺封闭的二苯基甲烷二异氰酸酯单体。然后将所得封闭异氰酸酯单体与80份EVA(购买于北京华威锐科化工有限公司)一起加入到混合机中进行混合；再将混合料加入到流延机中，于140℃流延得到热熔胶膜。将所得热熔胶膜与铝片进行热压复合(185℃，5min)，即可完成粘接。热熔胶膜对铝片的粘接强度(T剥离强度)和耐热性如表1所示(对比样为不加封闭异氰酸酯单体的试样)。
表1被粘接器件的粘接强度(T剥离强度)和耐热性
实施例2
将22份甲苯二异氰酸酯加入到8份甲醇中，40℃反应1h，即可得甲醇封闭的甲苯二异氰酸酯单体。然后将所得封闭异氰酸酯单体与70份聚乙烯树脂(购买于Sigma-Aldrich)一起加入到混合机中进行混合；再将混合料加入到流延机中，于130℃流延成热熔胶膜。将所得热熔胶膜与鞋底进行热压复合(170℃，3min)，即可完成粘接。热熔胶膜对鞋底的粘接强度(180°剥离强度)和耐热性如表2所示(对比样为不加封闭异氰酸酯单体的试样)。
表2被粘接器件的粘接强度(180°剥离强度)和耐热性
实施例3
将8份甲苯二异氰酸酯加入到7份丙酮肟中，室温反应6h，即可得丙酮肟封闭的甲苯二异氰酸酯单体。然后将所得封闭异氰酸酯单体与85份聚酰胺(源自南通协鑫热熔胶有限公司)一起加入到混合机中进行混合；再将混合料于140℃压延成热熔胶膜。将所得热熔胶膜与不锈钢片进行热压复合(190℃，3min)，即可完成粘接。热熔胶膜对不锈钢片的粘接强度(拉伸剪切强度)和耐热性如表3所示(对比样为不加封闭异氰酸酯单体的试样)。
表3被粘接器件的粘接强度(拉伸剪切强度)和耐热性
实施例4
将聚己内酯二醇-2000(40份)、聚四氢呋喃醚二醇-2000(40份)加入反应釜中，于110℃的真空条件下除水1h。然后加入二苯基甲烷二异氰酸酯(10份)，于110℃下反应2.5h，即得聚氨酯热熔胶。
将5份六亚甲基二异氰酸酯加入到5份丙二酸二乙酯中，70℃反应6h，即可得丙二酸二乙酯封闭的六亚甲基二异氰酸酯单体。然后将所得封闭异氰酸酯单体与90份上述聚氨酯热熔胶一起加入到混合机中进行混合；再将混合料于120℃压延成热熔胶膜。将所得热熔胶膜与聚碳酸酯片进行热压复合(180℃，5min)，即可完成粘接。热熔胶膜对聚碳酸酯片的粘接强度(拉伸剪切强度)和耐热性如表4所示(对比样为不加封闭异氰酸酯单体的试样)。
表4被粘接器件的粘接强度(拉伸剪切强度)和耐热性
Claims (10)
1.一种高粘接强度、高耐热性的热熔胶膜，其特征在于，所述热熔胶膜包括封闭异氰酸酯单体和热熔胶基材，所述封闭异氰酸酯单体的用量为热熔胶膜质量的0.1-50％。
2.根据权利要求1所述的高粘接强度、高耐热性的热熔胶膜，其特征在于，所述热熔胶基材选自固体膜态的TPU、PA、EVA或PO中的一种或至少两种的组合。
3.根据权利要求1所述的高粘接强度、高耐热性的热熔胶膜，其特征在于，所述封闭异氰酸酯单体由异氰酸酯单体和封闭剂反应而成，反应温度为25-100℃；所述异氰酸酯单体选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯三聚体、二环己基甲烷二异氰酸酯或三苯甲烷三异氰酸酯，所述封闭剂选自丙酮肟、丁醛肟、环己酮肟、甲醇、N-甲基苯胺、3,5-二甲基吡唑、1,2,4-三氮唑或丙二酸二乙酯。
4.一种高粘接强度、高耐热性的热熔胶膜的制备方法，其特征在于，所述制备方法为：将封闭异氰酸酯单体与热熔胶基材混合成热熔胶膜。
5.根据权利要求4所述的高粘接强度、高耐热性的热熔胶膜的制备方法，所述混合成热熔胶膜的方式选自流延法、吹塑法或压延法。
6.根据权利要求4所述的高粘接强度、高耐热性的热熔胶膜的制备方法，在混合时同时加入添加剂，添加剂选自碳纳米管、石墨烯、银纳米线、氧化铝、硅酸盐或荧光染料中的一种或多种。
7.一种高粘接强度、高耐热性的热熔胶膜的应用，其特征在于，将热熔胶膜与被粘接物贴合并热压，从而完成粘接。
8.根据权利要求7所述的高粘接强度、高耐热性的热熔胶膜的应用，其特征在于，所述热熔胶膜与被粘接物贴合并热压的温度为100-250℃，热压时间为1-120min。
9.根据权利要求7所述的高粘接强度、高耐热性的热熔胶膜的应用，其特征在于，所述被粘接物为织物、塑料、橡胶、纸张、金属、陶瓷或玻璃中的一种或多种。
10.根据权利要求7所述的高粘接强度、高耐热性的热熔胶膜的应用，其特征在于，所述热熔胶膜与被粘接物粘结成型后，应用于服装鞋帽、家居建材、汽车内饰、电子产品或日用品领域。
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