CN106189689A - 一种石墨烯基抗电磁辐射双组份环氧树脂涂料 - Google Patents
一种石墨烯基抗电磁辐射双组份环氧树脂涂料 Download PDFInfo
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Abstract
本发明涉及一种石墨烯基抗电磁辐射双组份环氧树脂涂料，该涂料利用了双重防辐射手段，得到了具有优异抗辐射、耐黄变的环氧树脂涂料。涂料由A组分和B组分组成，A组分和B组分的重量比2‑6:1；A组分包括：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10‑15重量份，抗氧剂3‑10重量份，紫外吸收剂1‑3重量份，导电填料10‑22重量份，分散剂2‑5重量份，颜料1‑3重量份，溶剂20重量份；B组分包括：聚酰胺固化剂20‑30重量份，氢化腰果酚改性酚醛胺10‑30重量份，溶剂20重量份。该涂料固化产物具有优异的抗电磁辐射、耐黄变、附着力和合适的硬度，综合性能优异，优于现有技术同类产品。
Description
技术领域
本发明涉及一种环氧树脂涂料，具体涉及一种石墨烯基抗电磁辐射双组份环氧树脂涂料。
背景技术
随着生活水平的提高，各类电器在居住环境中增多，电视、电脑、冰箱、微波炉等都是常用的家用电器。但电子产品的使用伴随的是无处不在的电磁辐射，家用电器的电磁辐射的累积会一定程度对人体产生慢性影响，如何降低电磁辐射成为一个研究热点。与此同时，电器表层的老化也是影响电器使用年限的重要因素，长时间的空气和光氧化，涂层会发生失真、产生色差，影响电子产品的外观。
针对上述两点问题，急需一种兼具降低电磁辐射和涂层氧化的电子产品用涂料来解决。
发明内容
发明目的：本发明提供一种石墨烯基抗电磁辐射双组份环氧树脂涂料，该涂料利用了双重防辐射手段，得到了具有优异抗辐射、耐黄变的环氧树脂涂料。
本发明提供的石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比2-6:1；A组分包括：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10-15重量份，抗氧剂3-10重量份，紫外吸收剂1-3重量份，导电填料10-22重量份，分散剂2-5重量份，颜料0-3重量份，溶剂20重量份；B组分包括：聚酰胺固化剂20-30重量份，氢化腰果酚改性酚醛胺10-30重量份，溶剂20重量份。
A组分和B组分的重量比优选3-5:1。
所述石墨烯是通过Hummers法制备氧化石墨烯、进一步还原后制备得到。
所述导电填料由导电云母粉和导电沸石以2:1的重量比混合得到，所述导电沸石可以为镀银纳米沸石、镀铜纳米沸石或镀金纳米沸石，所述导电云母粉为片状。
本发明的电磁屏蔽中使用石墨烯，其屏蔽作用取决于表面反射，导石墨烯是片状结构，可以在涂层中形成紧密平行排列，面与面的接触实现导电通路，这就是理想中的石墨烯屏蔽材料的的导电网络，石墨烯的结构有利于提高多次反射损耗。但单纯石墨烯填充量难以实现很大，且石墨烯成本很高，石墨烯的堆叠较为松散。为了实现形成导电通路、多次反射损耗，本申请创造性的复合使用了导电云母粉，导电云母粉选择为片状，其具有与石墨烯类似的结构，其可以穿插于石墨烯堆叠的空隙，实现石墨烯更好的连接，可以更加有效的实现形成导电通路、多次反射损耗。
同时，导电填料使用导电沸石，其可以填充石墨烯与导电云母之间微小的空隙，实现更好的导电性。作为另一种降低电磁辐射的方式，导电沸石中含有充分的孔隙，电磁波进入孔隙中就像进入迷宫，难以快速穿出，实现了损耗，从而显著地提升材料的电磁屏蔽效能。
上述石墨烯-导电片状云母粉-导电沸石的混合使用，通过层状导电、层状多次反射损耗、孔隙损耗三种机理，综合提高了体系的导电性能，其综合使用比单独使用某一种的效果都要优异很多，暂未发现相关报道。
所述紫外吸收剂为 2-(2′- 羟基 -3′,5′-二戊基苯基）苯并三唑、2- (2′-羟基-3′-叔丁基-5-甲基苯基）-5-氯代苯并三唑、2-(2′-羟基 -3′，5′-叔辛基苯基）苯并三唑。所述抗氧剂为抗氧剂1010，抗氧剂168或抗氧剂1076。紫外吸收剂和抗氧剂的使用，提高了涂料对紫外、氧气等外部环境的氧化，避免了色眼的变化。
所述颜料为白色颜料、红色颜料、黑色颜料、蓝色颜料、绿色颜料、银色颜料、金色颜料、灰色颜料及其混合物。颜色根据实际需要进行适当的调整和复配。
本发明环氧树脂使用混合体系，其使用了双酚A环氧树脂和脂环族环氧树脂，其比例为20:80，双酚A环氧树脂可以有多种环氧值，通过不同环氧值的选择可以实现硬度的调节，根据不同电器使用环境的不同，可以选择不同环氧值的双酚A环氧树脂。脂环族环氧树脂不含有苯环结构，不易吸收紫外线，可以实现耐黄变性能好，但通常固化物强度不足。为了综合考量两种环氧树脂性能，本发明选择了合适的比例范围，既满足了耐黄变性能，又可以保证固化物具有一定强度，硬度根据需要在一定范围内选择。
本发明固化剂同样采用混合体系，其采用聚酰胺固化剂和氢化腰果酚改性酚醛胺，聚酰胺固化剂具有固化物弹性好，耐黄变性能好；腰果酚改性酚醛胺由于其结构特征，其可以实现对树脂、玻璃、金属良好的附着性，但由于含有酚结构，十分容易被氧化，本发明中将腰果酚改性酚醛胺进行氢化，其酚变为醇，耐氧化性能提高很多，且保持了提高附着性能的性能。聚酰胺和氢化腰果酚改性酚醛胺的连用，实现了耐黄变性能优异、对不同类型基材均具有好的附着性。
技术效果：本发明环氧树脂体系、固化剂体系、石墨烯的采用和填料体系的选择都会最终产品的性能产生了至关重要的作用。石墨烯-导电片状云母粉-导电沸石的混合使用，通过层状导电、层状多次反射损耗、孔隙损耗三种机理，综合提高了体系的导电性能，其综合使用比单独使用某一种的效果都要优异很多。本合适的比例范围双酚A环氧树脂和脂环族环氧树脂的连用，既满足了耐黄变性能，又可以保证固化物具有一定强度，硬度根据需要在一定范围内选择。聚酰胺和氢化腰果酚改性酚醛胺的连用，实现了耐黄变性能优异、对不同类型基材均具有好的附着性。上述几个体系的协调增效，最终得到了综合性能优异，现有技术没有发现类似报道。
实施方式：
实施例1：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉6.67重量份，导电沸石3.33重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
实施例2：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比4:1；A组分包括：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯15重量份，抗氧剂10重量份，紫外吸收剂3重量份，导电片状云母粉14.67重量份，导电沸石7.33重量份，分散剂5重量份，颜料3重量份，溶剂20重量份；
B组分包括：聚酰胺固化剂30重量份，氢化腰果酚改性酚醛胺30重量份，溶剂20重量份。
对比例1：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂100重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉6.67重量份，导电沸石3.33重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例2：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：脂环族环氧树脂100重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉6.67重量份，导电沸石3.33重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例3：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电沸石10重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例4：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉10重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例5：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉:3.33重量份，导电沸石6.67重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例6：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉6.67重量份，导电沸石3.33重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂30重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例7：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉6.67重量份，导电沸石3.33重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：氢化腰果酚改性酚醛胺30重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对比例8：
石墨烯基抗电磁辐射双组份环氧树脂涂料，由A组分和B组分组成，A组分和B组分的重量比3:1；A组分：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，抗氧剂3重量份，紫外吸收剂1重量份，导电片状云母粉16.67重量份，导电沸石3.33重量份，分散剂2重量份，颜料1重量份，溶剂20重量份；B组分：聚酰胺固化剂20重量份，氢化腰果酚改性酚醛胺10重量份，溶剂20重量份。A组分和B组分分别混合均匀，使用时A组分和B组分按照重量比混合均匀后即可使用。
对本发明实施例1-2和对比例1-8的涂料进行性能检测，检测结果如下：
# 相对于玻璃基片附着力；
* 涂料涂覆与玻璃基片，保证各样品厚度接近，完全固化后采用频谱分析仪频率，测定在1 MHz～1.5GHz的电磁波的衰减；
&将涂料分别涂在玻璃基片，在同样的固化条件下完全固化，在阳光下发生明显可视黄变的天数。
Claims (9)
1.一种石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：由A组分和B组分组成，A组分和B组分的重量比2-6:1；
A组分包括：双酚A环氧树脂20重量份，脂环族环氧树脂80重量份，石墨烯10-15重量份，抗氧剂3-10重量份，紫外吸收剂1-3重量份，导电填料10-22重量份，分散剂2-5重量份，颜料0-3重量份，溶剂20重量份；
B组分包括：聚酰胺固化剂20-30重量份，氢化腰果酚改性酚醛胺10-30重量份，溶剂20重量份。
2.如权利要求1所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：A组分和B组分的重量比为3-5:1。
3.如权利要求1所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述石墨烯是通过Hummers法制备氧化石墨烯、经进一步还原后制备得到。
4.如权利要求1所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述导电填料由导电云母粉和导电沸石以2:1的重量比混合得到。
5.如权利要求1所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述紫外吸收剂为 2-(2′- 羟基 -3′,5′-二戊基苯基）苯并三唑、2- (2′-羟基-3′-叔丁基-5-甲基苯基）-5-氯代苯并三唑或2-(2′-羟基 -3′，5′-叔辛基苯基）苯并三唑。
6.如权利要求1所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述抗氧剂为抗氧剂1010，抗氧剂168或抗氧剂1076。
7.如权利要求1所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述颜料为白色颜料、红色颜料、黑色颜料、蓝色颜料、绿色颜料、银色颜料、金色颜料、灰色颜料及其混合物。
8.如权利要求4所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述导电沸石可以为镀银纳米沸石、镀铜纳米沸石或镀金纳米沸石。
9.如权利要求4所述的石墨烯基抗电磁辐射双组份环氧树脂涂料，其特征在于：所述导电云母粉为片状。
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| CN108084849A (zh) * | 2017-12-26 | 2018-05-29 | 马晓洁 | 一种石墨烯基耐污环氧树脂涂料和制备方法及其应用 |
| CN111057441A (zh) * | 2019-12-19 | 2020-04-24 | 电子科技大学 | 一种改性银粉导电涂料及其制备方法 |
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| CN114410223A (zh) * | 2020-10-28 | 2022-04-29 | 中国科学院理化技术研究所 | 一种石墨烯电磁屏蔽涂料及其制备方法 |
| CN114410223B (zh) * | 2020-10-28 | 2023-02-03 | 中国科学院理化技术研究所 | 一种石墨烯电磁屏蔽涂料及其制备方法 |
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| CN108624190A (zh) | 2018-10-09 |
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