CN106905801A - 金属电极保护液、金属电极保护层及其制备方法 - Google Patents

金属电极保护液、金属电极保护层及其制备方法 Download PDF

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CN106905801A
CN106905801A CN201510974397.9A CN201510974397A CN106905801A CN 106905801 A CN106905801 A CN 106905801A CN 201510974397 A CN201510974397 A CN 201510974397A CN 106905801 A CN106905801 A CN 106905801A
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metal electrode
acrylate
liquid
methacrylate
ester
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郑冬琛
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Beijing run LIAN Microelectronics Technology Development Co., Ltd.
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Beijing Aotuomite Electronic Co Ltd
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Abstract

本发明提供了一种金属电极保护液、金属电极保护层及其制备方法，上述金属电极保护液，以相对于所述金属电极保护液的总重量的重量百分数计，其包括：5-20％的甲基丙烯酸酯、5-15％的丙烯酸酯、2-10％的氟化甲基丙烯酸酯、1-15％的交联剂、0.001-0.5％的光引发剂、0.5-5％的填料和30-90％的有机溶剂。其用于防止金属电极被溶剂腐蚀，抑制了涂层由于应力收缩而产生的缺陷，并且确保了涂层的致密；通过将所述金属电极保护液由紫外光照射则获得金属电极保护层。

Description

金属电极保护液、金属电极保护层及其制备方法
技术领域
本发明提供了一种金属电极保护液、金属电极保护层及其制备方法。
背景技术
将金属沉积到陶瓷或塑料基材上形成金属电极在很多领域有着非常广泛的应用，如在一种液体喷射装置上，需要在陶瓷基材上沉积有金属电极，通常采用CVAD或磁控溅射技术来实现金属在陶瓷或塑料基材上的沉积，由于沉积的金属颗粒之间比较松散，另外由于在材质上较大的区别，界面结合力问题导致在使用过程中往往出现金属电极脱落的现象，尤其是在有溶剂的环境下，溶剂分子的渗透会使得金属电极和基材界面之间的剥落，因此要对金属电极进行防护处理。
可以采用电镀、真空镀膜和化学涂层法等方法来实现对金属电极的表面防护，其中化学涂层的优点是操作简便，成本低廉，适用范围广等，成为了材料表面防护的首选。通常采用具有疏水性能的防腐涂料对各类基材表面进行防护，如FEVE氟碳树脂，环氧富锌、富铝等重防腐涂料。这类防腐涂料具有高膜厚、高表面能、耐温等级低、涂装工艺复杂以及牺牲涂层其它性能换取防腐性能的特点。但是这一技术不适用于制品尺寸要求精确，在高温、酸性或碱性，以及有机溶剂等恶劣环境下的使用。也有将具有疏水特性的聚合物，如聚偏氟乙烯，聚四氟乙烯等涂覆到基材的表面，虽然能起到防止溶剂侵蚀的作用，但也带来了一些局限性。比如疏水性聚合物和基材之间的结合力相对较弱，难以制备较薄的涂层。同时在实际应用中，当有一定的滑动摩擦力时，涂层容易与基底剥离。
发明内容
针对有机聚合物涂层在涂覆时由于应力收缩会产生涂层缺陷，以及由涂层产生的针孔、微孔等易受到溶剂分子的渗透，导致涂层和基材的脱落的问题，本发明的目的是提供一种金属电极保护液，其用于防止金属电极被溶剂腐蚀，抑制了涂层由于应力收缩而产生的缺陷，并且确保了涂层的致密；所述金属电极保护液的制备方法；和通过将所述金属电极保护液由紫外光照射后获得的金属电极保护层。
为了解决上述技术问题，本发明采用以下技术方案：
一种金属电极保护液，以相对于所述金属电极保护液的总重量的重量百分数计，其包括：5-20％的甲基丙烯酸酯、5-15％的丙烯酸酯、2-10％的氟化甲基丙烯酸酯、1-15％的交联剂、0.001-0.5％的光引发剂、0.5-5％的填料和30-90％的有机溶剂。
上述甲基丙烯酸酯选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸辛酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯和甲基丙烯酸缩水甘油酯中的一种或多种。其中，优选甲基丙烯酸甲酯。
上述丙烯酸酯选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸壬酯、丙烯酸癸酯和丙烯酸缩水甘油酯中的一种或多种。
上述氟化甲基丙烯酸酯选自甲基丙烯酸三氟乙酯，甲基丙烯酸十二氟庚酯，甲基丙烯酸十三氟辛酯。其中，优选甲基丙烯酸三氟乙酯。
上述交联剂选自三羟甲基丙烷三丙烯酸酯，三丙二醇三丙烯酸酯，己二醇二丙烯酸酯，新戊二醇二甲基丙烯酸酯中的一种或多种。
上述光引发剂包括苯偶姻及衍生物，苯偶酰类和二苯甲酮类。
上述填料为纳米二氧化硅或纳米二氧化钛，粒径为10-30nm。
上述有机溶剂为酯类溶剂或者酮类溶剂，酯类溶剂如醋酸乙酯，醋酸丁酯，乙酸异戊酯，丁酸乙酯，乙二醇甲醚醋酸酯等，酮类溶剂如丙酮，丁酮，环己酮，异佛尔酮等。
也提供了一种金属电极保护液的制备方法，包括：
1)将所述甲基丙烯酸酯、所述丙烯酸酯、所述氟化甲基丙烯酸酯、所述交联剂和所述光引发剂按照所述重量百分数添加至所述有机溶剂并且完全溶解；
2)将填料分散在步骤1)获得的混合物中，从而获得所述金属电极保护液。
进一步地，步骤2)中，将填料直接分散在步骤1)获得的混合物中；或将填料分散在有机溶剂中形成填料分散液后，再将该填料分散液添加至步骤1)获得的混合物中，形成填料分散液采用的有机溶剂与步骤1)中采用的有机溶剂相同。
还提供了一种金属电极保护层，其通过将所述的金属电极保护液施涂至金属电极，然后由紫外光照射获得。
施涂方法包括：浸涂法、喷涂法、旋涂法、刮涂法、和丝网涂布法等。从均匀涂布的观点，优选刮涂法。
所述金属电极保护层的厚度是500纳米-3微米，优选500纳米-2微米，更优选500纳米-1微米。
技术效果
本发明提供的金属电极保护液能够用于防止金属电极被溶剂腐蚀，抑制了涂层由于应力收缩而产生的缺陷，与基材的结合力良好，涂层的表面疏水特性赋予保护层良好的耐溶剂性能，纳米填料的加入确保了涂层的致密。
具体实施方式
金属电极保护液
根据本发明的金属电极保护液包括甲基丙烯酸酯、丙烯酸酯、氟化甲基丙烯酸酯、交联剂、光引发剂、填料、和溶剂。以下将具体地描述各组分。
根据本发明的甲基丙烯酸酯的具体实例包括：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸辛酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯和甲基丙烯酸缩水甘油酯。其中，优选甲基丙烯酸甲酯。这些甲基丙烯酸酯可以单独或以其两种以上的组合来使用。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，甲基丙烯酸酯的含量是5-20重量％，优选5-18重量％，更优选8-15重量％。
根据本发明的丙烯酸酯的具体实例包括：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸壬酯、丙烯酸癸酯和丙烯酸缩水甘油酯。其中，优选丙烯酸乙酯，丙烯酸丁酯，丙烯酸缩水甘油酯。这些丙烯酸酯可以单独或以其两种以上的组合来使用。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，丙烯酸酯的含量是5-15重量％，优选5-12重量％，更优选5-10重量％。
根据本发明的氟化甲基丙烯酸酯的具体实例包括：甲基丙烯酸三氟乙酯，甲基丙烯酸十二氟庚酯，甲基丙烯酸十三氟辛酯。其中，优选甲基丙烯酸三氟乙酯。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，氟化甲基丙烯酸酯的含量是2-10重量％，优选2-8重量％。
根据本发明的交联剂实质上是光固化剂，其在对金属电极保护液进行紫外光照射时，进行固化从而形成致密的金属电极保护层。其具体实例包括：三羟甲基丙烷三丙烯酸酯，三丙二醇三丙烯酸酯，己二醇二丙烯酸酯，新戊二醇二甲基丙烯酸酯。这些交联剂可以单独或以其两种以上的组合来使用。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，交联剂的含量是1-15重量％，优选1-10重量％，更优选1-8重量％。
根据本发明的光引发剂包括苯偶姻及衍生物，苯偶酰类和二苯甲酮类。所述苯偶姻及衍生物的实例包括：安息香、安息香双甲醚、安息香***、安息香异丙醚、安息香丁醚。所述苯偶酰类的实例包括：二苯基乙酮、α，α-二甲氧基-α-苯基苯乙酮。所述二苯甲酮类的实例包括：二苯甲酮、2,4-二羟基二苯甲酮、米蚩酮。这些光引发剂可以单独或以其两种以上的组合来使用。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，光引发剂的含量是0.001-0.5重量％，优选0.002-0.2重量％，更优选0.002-0.1重量％。
根据本发明的填料可以是纳米二氧化硅或纳米二氧化钛。其用于防止由金属电极保护液形成的金属电极保护层由于固化时的应力收缩而产生缺陷。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，填料的含量是0.1-5重量％，优选0.5-3重量％。
根据本发明的溶剂可以是酯类或者酮类溶剂，酯类溶剂如醋酸乙酯，醋酸丁酯，乙酸异戊酯，丁酸乙酯，乙二醇甲醚醋酸酯等，酮类溶剂如丙酮，丁酮，环己酮，异佛尔酮等。这些溶剂可以单独或以其两种以上的组合来使用。在根据本发明的金属电极保护液中，相对于金属电极保护液的总重量，溶剂的含量是30-90重量％，优选30-80重量％。
金属电极保护液的制备方法
在根据本发明的金属电极保护液的制备方法中，将甲基丙烯酸酯、丙烯酸酯、氟化甲基丙烯酸酯、光引发剂添加至溶剂并且完全溶解，从而获得了混合物。该过程可以在搅拌或超声的条件下进行。
然后，填料可以直接分散在上述混合物中；或填料可以首先分散在溶剂中从而形成填料分散液，然后将该填料分散液添加至上述混合物；用于分散填料的溶剂与用于所述金属电极保护液的溶剂相同。其具体实例包括：醋酸丁酯，醋酸乙酯，丙酮，丁酮，环己酮。
金属电极保护层
在本发明中，金属电极保护层可以通过以下来获得：将根据本发明的金属电极保护液施涂至金属电极，然后由紫外光照射从而固化。其中，根据本发明的金属电极保护液可以通过以下涂布方法来施涂至金属电极。涂布方法包括：浸涂法、喷涂法、旋涂法、刮涂法、和丝网涂布法等。从均匀涂布的观点，优选刮涂法。
固化后的金属电极保护层的厚度是500纳米-3微米，优选500纳米-2微米，更优选500纳米-1微米。
对所制备的金属电极保护层进行附着力、接触角和耐溶剂腐蚀性能测试。
附着力采用划圈法。
接触角采用OCA20接触角测量仪来测量，测量水在其表面的接触角。
耐溶剂腐蚀性能测试是将制得金属电极保护层的片浸泡在80℃的环己酮溶剂中72h后观察表面腐蚀情况。
实施例1
将甲基丙烯酸甲酯5g，丙烯酸丁酯15g，甲基丙烯酸三氟乙酯2g，三羟甲基丙烷三丙烯酸酯1g，光引发剂二苯甲酮0.001g加入到76.5g醋酸乙酯中，搅拌至完全溶解，然后加入0.5g纳米二氧化钛，转移至超声发生器中，至纳米二氧化硅完全分散均匀，制得了金属电极保护液。
将金属电极保护液刮涂到沉积有金属铝电极的陶瓷基片上，在紫外光下辐射固化5min，取出陶瓷基片，得到金属电极保护层(结果如表1所示)。
实施例2
将甲基丙烯酸甲酯10g，丙烯酸乙酯10g，甲基丙烯酸三氟乙酯5g，三丙二醇三丙烯酸酯7g，光引发剂二苯甲酮0.1g加入到64.9g醋酸丁酯中，搅拌至完全溶解，然后加入1g纳米二氧化硅，转移至超声发生器中，至纳米二氧化硅完全分散均匀，制得了金属电极保护液。
将金属电极保护液刮涂到沉积有金属铝电极的陶瓷基片上，在紫外光下辐射固化5min，取出陶瓷基片，得到金属电极保护层。
实施例3
将甲基丙烯酸甲酯20g，丙烯酸丁酯15g，甲基丙烯酸三氟乙酯10g，三羟甲基丙烷三丙烯酸酯15g，光引发剂α，α-二甲氧基-α-苯基苯乙酮0.5g加入到34.5g环己酮，搅拌至完全溶解，然后加入5g纳米二氧化钛，转移至超声发生器中，至纳米二氧化硅完全分散均匀，制得了金属电极保护液。
将金属电极保护液刮涂到沉积有金属铝电极的陶瓷基片上，在紫外光下辐射固化5min，取出陶瓷基片，得到金属电极保护层(结果如表1)。
实施例4
将甲基丙烯酸丁酯20g，丙烯酸乙酯15g，甲基丙烯酸三氟乙酯10g，三丙二醇三丙烯酸酯15g，光引发剂α，α-二甲氧基-α-苯基苯乙酮0.5g加入到34.5g丙酮中，搅拌至完全溶解，然后加入5g纳米二氧化钛，转移至超声发生器中，至纳米二氧化硅完全分散均匀，制得了金属电极保护液。
将金属电极保护液刮涂到沉积有金属铝电极的陶瓷基片上，在紫外光下辐射固化5min，取出陶瓷基片，得到金属电极保护层。
实施例5
将甲基丙烯酸缩水甘油酯10g，丙烯酸庚酯10g，甲基丙烯酸三氟乙酯5g，新戊二醇二甲基丙烯酸酯7g，光引发剂二苯甲酮0.1g加入到64.9g醋酸丁酯中，搅拌至完全溶解，然后加入1g纳米二氧化硅，转移至超声发生器中，至纳米二氧化硅完全分散均匀，制得了金属电极保护液。
将金属电极保护液刮涂到沉积有金属铝电极的陶瓷基片上，在紫外光下辐射固化5min，取出陶瓷基片，得到金属电极保护层。
实施例6
1)将甲基丙烯酸缩水甘油酯10g，丙烯酸庚酯10g，甲基丙烯酸三氟乙酯5g，新戊二醇二甲基丙烯酸酯7g，光引发剂二苯甲酮0.1g加入到60g醋酸丁酯中，搅拌至完全溶解；
2)将1g纳米二氧化硅加入到4.9g醋酸丁酯中超声分散均匀；然后将分散好的纳米二氧化硅分散液加入到步骤1)中的溶液中后，制得了金属电极保护液。
将金属电极保护液刮涂到沉积有金属铝电极的陶瓷基片上，在紫外光下辐射固化5min，取出陶瓷基片，得到金属电极保护层。
对比例1(不加填料)
作为对比，只将甲基丙烯酸甲酯8g，丙烯酸丁酯10g，甲基丙烯酸三氟乙酯4g，三羟甲基丙烷三丙烯酸酯4g，光引发剂二苯甲酮0.05g加入到60g醋酸丁酯中，其他条件步骤和实施例1相同(结果如表1)。
对比例2(不加氟化甲基丙烯酸酯和填料)
作为对比，只将甲基丙烯酸甲酯8g，丙烯酸丁酯10g，三羟甲基丙烷三丙烯酸酯4g，光引发剂二苯甲酮0.05g加入到60g醋酸丁酯中，其他条件步骤和实施例1相同(结果如表1)。
表1金属电极保护层性能测试表
名称 附着力 接触角 耐溶剂
实施例1 1级 113 良
实施例2 1级 115 良
实施例3 1级 117 良
实施例4 1级 118 良
实施例5 1级 114 良
实施例6 1级 114 良
对比例1 1级 110 一般
对比例2 1级 98 差
其中：保护层的耐溶剂评价“良”表示保护层表面无任何痕迹，“一般”表示保护层表面轻微被腐蚀，无碎渣，“差”表示保护层表面被腐蚀、涂层脱落以及有碎渣。

Claims (10)

1.一种金属电极保护液，以相对于所述金属电极保护液的总重量的重量百分数计，其包括：5-20％的甲基丙烯酸酯、5-15％的丙烯酸酯、2-10％的氟化甲基丙烯酸酯、1-15％的交联剂、0.001-0.5％的光引发剂、0.5-5％的填料和30-90％的有机溶剂。
2.如权利要求1所述的金属电极保护液，其特征在于，所述的甲基丙烯酸酯选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸辛酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯和甲基丙烯酸缩水甘油酯中的一种或多种。
3.如权利要求1所述的金属电极保护液，其特征在于，所述的丙烯酸酯选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸壬酯、丙烯酸癸酯和丙烯酸缩水甘油酯中的一种或多种。
4.如权利要求1所述的金属电极保护液，其特征在于，所述的氟化甲基丙烯酸酯选自甲基丙烯酸三氟乙酯，甲基丙烯酸十二氟庚酯或甲基丙烯酸十三氟辛酯。
5.如权利要求1所述的金属电极保护液，其特征在于，所述的交联剂选自三羟甲基丙烷三丙烯酸酯，三丙二醇三丙烯酸酯，己二醇二丙烯酸酯和新戊二醇二甲基丙烯酸酯中的一种或多种；所述的光引发剂包括苯偶姻及衍生物，苯偶酰类和二苯甲酮类；所述的填料为纳米二氧化硅或纳米二氧化钛，粒径为10-30nm；所述的有机溶剂为酯类溶剂或者酮类溶剂。
6.权利要求1-5任一项所述的金属电极保护液的制备方法，包括：
1)将所述甲基丙烯酸酯、所述丙烯酸酯、所述氟化甲基丙烯酸酯、所述光引发剂按照所述重量百分数添加至所述有机溶剂并且完全溶解；
2)将填料分散在步骤1)获得的混合物中，从而获得所述金属电极保护液。
7.如权利要求6所述的金属电极保护液的制备方法，其特征在于，步骤2)中，将填料直接分散在步骤1)获得的混合物中；或将填料分散在有机溶剂中形成填料分散液后，再将该填料分散液添加至步骤1)获得的混合物中，形成填料分散液采用的有机溶剂与步骤1)中采用的有机溶剂相同。
8.一种金属电极保护层，其通过将权利要求1-5任一项所述的金属电极保护液施涂至金属电极，然后由紫外光照射获得。
9.如权利要求8所述的金属电极保护层，其特征在于，所述的施涂的方法包括：浸涂法、喷涂法、旋涂法、刮涂法和丝网涂布法。
10.如权利要求8所述的金属电极保护层，其特征在于，所述的金属电极保护层的厚度是500纳米-3微米。
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