CN109605862B - 一种具有导热和电磁屏蔽功能的复合材料及其制备方法 - Google Patents
一种具有导热和电磁屏蔽功能的复合材料及其制备方法 Download PDFInfo
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- CN109605862B CN109605862B CN201811219478.8A CN201811219478A CN109605862B CN 109605862 B CN109605862 B CN 109605862B CN 201811219478 A CN201811219478 A CN 201811219478A CN 109605862 B CN109605862 B CN 109605862B
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Abstract
一种具有导热和电磁屏蔽功能的复合材料，包括导热材料层、二维软磁复合材料层和屏蔽材料层，所述二维软磁复合材料层两侧分别设有导热材料层和屏蔽材料层。本发明所述的具有导热和电磁屏蔽功能的复合材料，所获得的复合膜材料不仅拥有优异的电磁屏蔽能力，同时可以降低电子器件表面温度，快速导出热量。该复合膜材料不仅可以应用到笔记本、GPS、ADSL和移动电话等3C产品中，也可以应用到一些对电磁屏蔽性能有更高要求的领域。根据在不同的终端电子产品的应用，复合膜材料的厚度规格可以做相应的调整。
Description
技术领域
本发明属于高分子材料技术领域，涉及一种具有导热和电磁屏蔽功能的复合材料及其制备方法。
背景技术
近些年，随着电子技术的飞速发展，电子产品正迅速向智能化、信息化、节能化及小型化、柔性化等多方面方向发展。各种电子产品在丰富了人们的物质生活需要的同时，也不可避免的带来了一些问题，例如电磁兼容（EMC）问题。电磁兼容问题的存在，往往会使电子、电气设备或系统不能正常工作，导致性能降低，甚至造成损坏。为了解决这些问题，全球各地区基本都设置了与电磁兼容相关的市场准入认证，用以保护本地区的电磁环境，如北美的FCC、NEBC认证、欧盟的CE认证、日本的VCCEI认证、澳洲的C-TICK认证及中国的3C认证等。鉴于此，如何有效地解决电子产品的电磁兼容问题，为产品赢得市场机会，成为每一个电子产品制造厂商必须予以足够重视的问题。伴随着目前消费类电子产品的便携化、小巧化、多通信系统融合及智能化等发展趋势，也使得在进行电子产品电磁兼容设计时，一些传统的设计方法无法应用，比如：使用全封闭的金属外壳，产品内添加屏蔽罩等。但是其电磁屏蔽性能有待加强，并且整体散热效果受限，市面上难以广泛的普及与应用。
发明内容
发明目的：为了克服现有技术的不足，本发明的目的是提供一种具有导热和电磁屏蔽功能的复合材料。
技术方案：本发明提供了一种具有导热和电磁屏蔽功能的复合材料，包括导热材料层、二维软磁复合材料层和屏蔽材料层，所述二维软磁复合材料层两侧分别设有导热材料层和屏蔽材料层；
所述二维软磁复合材料层以重量组分计，包括以下组分：二维软磁粉60～100份，粘结剂树脂10～30份，消泡剂1～5份，润湿剂1～5份，增稠剂1～5份，流平剂1～5份，交联剂1～5份，抗氧剂1～5份，三氧化二铝5～10份，溶剂100～150份。
本发明所述的具有导热和电磁屏蔽功能的复合材料，结构和组成合理，其中导热材料层可以提供优良的导热性能，二维软磁粉属于磁损耗型吸收剂，依靠磁滞损耗、涡流损耗和剩余损耗等极化机制衰减吸收电磁噪音。加入纳米三氧化二铝可以改善体系的绝缘性能、导热性能及机械性能，使得二维软磁复合材料层提供吸收电磁噪音的功能，屏蔽材料层在提高散热效率的同时，会把未完全吸收的电磁噪音反射至二维软磁复合材料层，被金属薄膜层反射的噪音会再次被二维软磁复合材料所吸收。也就是说，入射的噪音会在二维软磁复合材料厚度方向往返时被吸收，因此可大幅降低噪音的能量从而使复合膜材料具有优异的电磁屏蔽性能。所获得的复合膜材料不仅拥有优异的电磁屏蔽能力，同时可以降低电子器件表面温度，快速导出热量。该复合膜材料不仅可以应用到笔记本、GPS、ADSL和移动电话等3C产品中，也可以应用到一些对电磁屏蔽性能有更高要求的领域。根据在不同的终端电子产品的应用，复合膜材料的厚度规格可以做相应的调整。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述二维软磁粉包括Fe-Si合金微粉、FeNi坡莫合金微粉、Sendust合金微粉、FeSiCr铁硅铬合金微粉、FeCuB合金微粉、FeCuSiBCo合金微粉、FeCuBNi合金微粉、FeCuSiBCV合金微粉。二维软磁粉可以根据需要进行选择，其属于磁损耗型吸收剂，依靠磁滞损耗、涡流损耗和剩余损耗等极化机制衰减吸收电磁噪音，具有强吸收，效果好、厚度薄、工作频带宽、重量轻、粘结强度高等特点。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述粘结剂为树脂酚醛树脂、脲醛树脂、三聚氰胺－甲醛树脂、环氧树脂、不饱和树脂、聚氨酯、聚酰亚胺、丙烯酸树脂、呋喃树脂、聚丁二烯树脂、有机硅树脂中的一种或几种混合。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述增稠剂包括甲基纤维素、羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素；聚丙烯酸盐，丙烯酸、甲基丙烯酸的均聚物或共聚物乳液；聚氨酯类增稠剂；膨润土、凹凸棒土、硅酸铝。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述流平剂为硅油、聚二甲基硅氧烷、聚醚聚酯改性有机硅氧烷、烷基改性有机硅氧烷或丙烯酸酯类和氟改性的丙烯酸酯类的一种或几种混合；所述消泡剂包括乳化硅油、高碳醇脂肪酸酯复合物、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚、聚氧丙烯聚氧乙烯甘油醚、聚二甲基硅氧烷。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述交联剂为过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、过氧化二异丙苯、二亚乙基三胺的一种或几种混合；所述润湿剂包括硫酸盐、磺酸盐、脂肪酸或者脂肪酸酯硫酸盐、羧酸皂类、磷酸酯；聚氧乙烯烷基酚醚，聚氧乙烯脂肪醇醚，聚氧乙烯聚氧丙烯嵌段共聚物；硅醇类非离子表面活性剂。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述抗氧剂包括二烷基二硫代磷酸锌、二烷基二硫代氨基甲酸锌；N-苯基-α-萘胺和烷基吩噻嗪；苯并三氮唑衍生物和巯基苯并噻唑衍生物；所述溶剂为正己烷、二甘醇单乙基醚、4-甲基-2-戊酮、醋酸正丁酯、2-乙氧基乙醇、丁酮、甲基异丁酮、乙酸乙酯、乙酸丁酯、二甲苯、丁醇、丙二醇甲醚、二甲基甲酰胺、二甲基乙酰胺、卤代烷烃中的一种或几种的混合。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述导热材料层为导热硅胶层，以重量组分计，含有50～100份的硅胶；所述屏蔽材料层为金属薄膜，包括铜箔、铝箔、锡箔、银箔。其中，导热硅胶可以提供优良的导热性能，导热硅胶是高端的导热化合物，其不导电的特性可以避免诸如电路短路等风险，是通过空气中的水分发生缩合反应放出低分子引起交联固化，而成为高性能弹性体。具有卓越的抗冷热交变性能、耐老化性能和电绝缘性能。并且具有优于的防潮、抗震、耐电晕、抗漏电性能和耐化学介质性能。可持续使用-60℃~280℃且保持性能，不溶胀并且对于大多数金属和非金属材料都具有良好的粘结性。运用导热硅胶的性能，可以减少热源表面与散热器件接触面之间产生的接触热阻。同时可以很好的填充接触面的间隙，将空气挤出接触面，空气作为热的不良导体，其存在会严重阻碍热量在接触面之间的传递。外加的金属薄膜层在提高散热效率的同时，会把未完全吸收的电磁噪音反射至二维软磁复合材料层，被金属薄膜层反射的噪音会再次被二维软磁复合材料所吸收。
进一步的，上述的具有导热和电磁屏蔽功能的复合材料，所述三氧化二铝为纳米三氧化二铝，可以使用等量的纳米三氧化二镍替换。纳米三氧化二铝效果佳，并且作为本发明的一种改进，三氧化二镍的加入可以进一步改善体系的绝缘性能、导热性能及机械性能。
本发明还公开一种具有导热和电磁屏蔽功能的复合材料的制备方法，包括以下步骤：
1）将二维软磁粉、粘结剂树脂、消泡剂、润湿剂、增稠剂、流平剂、交联剂、抗氧剂、三氧化二铝和溶剂加入到反应釜内，以1200r/min~1800r/min的搅拌速度下高速搅拌120min~180min，制得二维软磁复合材料浆料A；
2）将浆料A均匀倒至屏蔽材料层上，使用滚筒式压延机压延制得A膜；将导热材料均匀倒至离型膜上，使用滚筒式压延机压延制得B膜；
3）以A膜在上、B膜在下的形式通过滚筒式压延机，经压延后得C膜；
4）将C膜在120℃~180℃烘干3~5分钟，冷却静置5~8h，使得复合膜材料内部交联固化，各部分充分粘合，撕掉外侧离型膜后得所述具有导热和电磁屏蔽功能的复合材料。
本发明所述的具有导热和电磁屏蔽功能的复合材料的制备方法，方法合理，采用延涂布的工艺，复合膜材料整体结构分为A、B膜，首先将二维软磁粉、粘合剂树脂、助剂和有机溶剂制得的二维软磁复合材料浆料通过压延机涂覆在金属薄膜上制得A膜，再将导热硅胶通过压延机涂覆在表面经硅油处理的PET等塑料薄膜材料上制得B膜，然后将A、B膜通过压延机和后续高温处理使其充分结合，撕掉表面塑料薄膜材料后得到目标产品。对比现有技术其具有以下特点：
1）复合膜材料具有优良的导热散热性能；
2）复合膜材料具有优异的电磁屏蔽性能；
3）制作过程简单，设备投入成本低；
4）复合膜材料结构简单，利用市场推广及应用。
上述技术方案可以看出，本发明具有如下有益效果：本发明专利的优点：
1）导热硅胶层的加入，使所获得的复合膜材料同时具备了优良的导热散热性能；
2）金属薄膜层的加入，可将未完全吸收的电磁噪音反射回二维软磁复合材料层形成多次吸收，从而提高对电磁噪音的屏蔽效果；
3）二维软磁复合材料层在内层，可以得到一定保护；
4）复合膜材料三层结构，具有良好得机械性能；
5）复合膜材料的制作工艺流程简单易行，可大批量、高效率的生产，利于其市场化的推广。
附图说明
图1为本发明所述的具有导热和电磁屏蔽功能的复合材料的结构示意图；
图2为本发明实施例1中制备具有导热和电磁屏蔽功能的复合材料的示意图；
图3为本发明所述的具有导热和电磁屏蔽功能的复合材料的工作原理示意图；
图中：1导热材料层、2二维软磁复合材料层、3屏蔽材料层。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“顺时针”、“逆时针”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，除非另有说明，“多个”的含义是两个或两个以上，除非另有明确的限定。
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。
实施例1
如图1所示的一种具有导热和电磁屏蔽功能的复合材料，包括导热材料层1、二维软磁复合材料层2和屏蔽材料层3，所述二维软磁复合材料层2两侧分别设有导热材料层1和屏蔽材料层3。
在本实施例中，以0.01mm厚度的铝箔作为A膜基材，选用0.03mm厚度的PET离型膜作为B膜基材。所述导热材料层1为导热硅胶层，以重量组分计，含有100份的硅胶。二维软磁复合材料的浆料组成及各组分的重量份数如下：
二维软磁粉 85份
粘合剂树脂 14份
消泡剂 1份
润湿剂 2份
增稠剂 2份
流平剂 1份
交联剂 2份
抗氧剂 1份
三氧化二铝 5份
溶剂 100份
具体的使用材料选择如下表：
上述具有导热和电磁屏蔽功能的复合材料的制备方法，包括以下步骤：
1）将二维软磁粉、粘结剂树脂、消泡剂、润湿剂、增稠剂、流平剂、交联剂、抗氧剂、三氧化二铝和溶剂加入到反应釜内，以1600r/min的搅拌速度下高速搅拌150min，制得二维软磁复合材料浆料A；
2）如图2所示，在滚筒式压延机①处，将浆料A均匀倒至屏蔽材料层3上，使用滚筒式压延机压延制得A膜；同时在滚筒式压延机②处，将导热材料均匀倒至离型膜上，使用滚筒式压延机压延制得B膜；
3）以A膜在上、B膜在下的形式通过滚筒式压延机③，经压延后得C膜；
4）将C膜在150℃烘干4分钟，冷却静置6h，使得复合膜材料内部交联固化，各部分充分粘合，撕掉外侧离型膜后得所述具有导热和电磁屏蔽功能的复合材料。
按照上述步骤，制得总厚度约为0.04mm的复合膜材料。
如图3所示，电磁噪音被吸收反射再吸收消耗殆尽，热能通过导热材料传导出去，减少了IC的热量堆积。
在2~18GHz频段，对复合膜材料进行测试，其最大反射系数和有效带宽如下表所
示：
| 吸收片厚度 | 最大反射系数（dB） | ≤-8dB有效带宽（GHz） |
| 0.04mm | -29 | 2~10 |
实施例2
如图1所示的一种具有导热和电磁屏蔽功能的复合材料，区别于实施例1，在本实施例中，以0.01mm厚度的铜箔作为A膜基材，所述导热材料层1为导热硅胶层，以重量组分计，含有50份的硅胶。所述二维软磁复合材料层2以重量组分计，包括以下组分：Sendust 合金微粉60份，丙烯酸树脂10份，高碳醇脂肪酸酯复合物1份，聚氧乙烯脂肪醇醚1份，甲基丙烯酸的均聚物1份，聚醚聚酯改性有机硅氧烷1份，过氧化苯甲酰1份，二甘醇单乙基醚1份，纳米三氧化二铝5份，二甲基乙酰胺100份。
上述具有导热和电磁屏蔽功能的复合材料的制备方法，包括以下步骤：
1）将Sendust 合金微粉、丙烯酸树脂、高碳醇脂肪酸酯复合物、聚氧乙烯脂肪醇醚、甲基丙烯酸的均聚物、聚醚聚酯改性有机硅氧烷、过氧化苯甲酰、二甘醇单乙基醚、纳米三氧化二铝和二甲基乙酰胺加入到反应釜内，以1200r/min的搅拌速度下高速搅拌120min，制得二维软磁复合材料浆料A；
2）将浆料A均匀倒至屏蔽材料层3上，使用滚筒式压延机压延制得A膜；将导热材料均匀倒至离型膜上，使用滚筒式压延机压延制得B膜；
3）以A膜在上、B膜在下的形式通过滚筒式压延机，经压延后得C膜；
4）将C膜在120℃烘干3分钟，冷却静置5h，使得复合膜材料内部交联固化，各部分充分粘合，撕掉外侧离型膜后得所述具有导热和电磁屏蔽功能的复合材料。
实施例3
如图1所示的一种具有导热和电磁屏蔽功能的复合材料，区别于实施例1，在本实施例中，以0.01mm厚度的银箔作为A膜基材，所述导热材料层1为导热硅胶层，以重量组分计，含有100份的硅胶。所述二维软磁复合材料层2以重量组分计，包括以下组分：FeCuSiBCV合金微粉100份，三聚氰胺－甲醛树脂30份，聚氧乙烯聚氧丙烯季戊四醇醚5份，磷酸酯5份，羟乙基纤维素5份，聚二甲基硅氧烷5份，过氧化苯甲酰5份，醋酸正丁酯5份，纳米三氧化二镍10份，二甘醇单乙基醚150份。
上述具有导热和电磁屏蔽功能的复合材料的制备方法，包括以下步骤：
1）将FeCuSiBCV合金微粉、三聚氰胺－甲醛树脂、聚氧乙烯聚氧丙烯季戊四醇醚、磷酸酯、羟乙基纤维素、聚二甲基硅氧烷、过氧化苯甲酰、醋酸正丁酯、纳米三氧化二镍和二甘醇单乙基醚加入到反应釜内，以1800r/min的搅拌速度下高速搅拌180min，制得二维软磁复合材料浆料A；
2）将浆料A均匀倒至屏蔽材料层3上，使用滚筒式压延机压延制得A膜；将导热材料均匀倒至离型膜上，使用滚筒式压延机压延制得B膜；
3）以A膜在上、B膜在下的形式通过滚筒式压延机，经压延后得C膜；
4）将C膜在180℃烘干5分钟，冷却静置8h，使得复合膜材料内部交联固化，各部分充分粘合，撕掉外侧离型膜后得所述具有导热和电磁屏蔽功能的复合材料。
实施例4
如图1所示的一种具有导热和电磁屏蔽功能的复合材料，区别于实施例1，在本实施例中，以0.01mm厚度的锡箔作为A膜基材，所述导热材料层1为导热硅胶层，以重量组分计，含有60份的硅胶。所述二维软磁复合材料层2以重量组分计，包括以下组分：FeCuSiBCo合金微粉100份，呋喃树脂10份，聚氧乙烯聚氧丙烯季戊四醇醚4份，聚氧乙烯脂肪醇醚2份，硅酸铝1份，聚二甲基硅氧烷5份，二亚乙基三胺2份，二烷基二硫代氨基甲酸锌4份，纳米三氧化二铝10份，二甲基甲酰胺100份。
上述具有导热和电磁屏蔽功能的复合材料的制备方法，包括以下步骤：
1）将FeCuSiBCo合金微粉、呋喃树脂、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯脂肪醇醚、硅酸铝、聚二甲基硅氧烷、二亚乙基三胺、二烷基二硫代氨基甲酸锌、纳米三氧化二铝和二甲基甲酰胺加入到反应釜内，以1800r/min的搅拌速度下高速搅拌150min，制得二维软磁复合材料浆料A；
2）将浆料A均匀倒至屏蔽材料层3上，使用滚筒式压延机压延制得A膜；将导热材料均匀倒至离型膜上，使用滚筒式压延机压延制得B膜；
3）以A膜在上、B膜在下的形式通过滚筒式压延机，经压延后得C膜；
4）将C膜在150℃烘干4分钟，冷却静置5h，使得复合膜材料内部交联固化，各部分充分粘合，撕掉外侧离型膜后得所述具有导热和电磁屏蔽功能的复合材料。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进，这些改进也应视为本发明的保护范围。
Claims (2)
1.一种具有导热和电磁屏蔽功能的复合材料，其特征在于：包括导热材料层（1）、二维软磁复合材料层（2）和屏蔽材料层（3），所述二维软磁复合材料层（2）两侧分别设有导热材料层（1）和屏蔽材料层（3）；
所述导热材料层（1）为导热硅胶层，以重量组分计，含有100份的硅胶；所述屏蔽材料层（3）为0.01mm厚度的铝箔；
所述二维软磁复合材料层（2）以重量组分计，包括以下组分：Fe-Si合金微粉85份，丙烯酸树脂14份，聚氧乙烯脂肪醇醚2份，膨润土2份，聚二甲基硅氧烷2份，过氧化苯甲酰2份，二烷基二硫代磷酸锌1份，三氧化二铝5份，溶剂100份。
2.用于制备权利要求1所述的具有导热和电磁屏蔽功能的复合材料的方法，其特征在于：包括以下步骤：
1）将Fe-Si合金微粉、丙烯酸树脂、聚氧乙烯脂肪醇醚、膨润土、聚二甲基硅氧烷、过氧化苯甲酰、二烷基二硫代磷酸锌、三氧化二铝和溶剂加入到反应釜内，以1600r/min的搅拌速度下高速搅拌150min，制得二维软磁复合材料浆料A；
2）将浆料A均匀倒至屏蔽材料层（3）上，使用滚筒式压延机压延制得A膜；将导热硅胶均匀倒至离型膜上，使用滚筒式压延机压延制得B膜；
3）以A膜在上、B膜在下的形式通过滚筒式压延机，经压延后得C膜；
4）将C膜在150℃烘干4分钟，冷却静置6h，使得复合膜材料内部交联固化，各部分充分粘合，撕掉外侧离型膜后得所述具有导热和电磁屏蔽功能的复合材料。
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