CN113362984A - 适用于高精密直写3d打印的纳米颗粒铜浆、制备及用途 - Google Patents
适用于高精密直写3d打印的纳米颗粒铜浆、制备及用途 Download PDFInfo
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- CN113362984A CN113362984A CN202110681236.6A CN202110681236A CN113362984A CN 113362984 A CN113362984 A CN 113362984A CN 202110681236 A CN202110681236 A CN 202110681236A CN 113362984 A CN113362984 A CN 113362984A
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- Prior art keywords
- copper
- epoxy resin
- copper paste
- precision direct
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
本发明提供一种适用于高精密直写3D打印的纳米颗粒铜浆、制备及用途，采用三芳基膦或者三烷基膦类化合物作为铜粉保护剂并将铜纳米颗粒配制成含有环氧树脂的油溶性浆料，解决纳米颗粒铜浆在制备和存放过程中容易被氧化的问题，提高纳米颗粒铜浆的导电性能，使其适用于高精密直写3D打印。
Description
技术领域
本发明涉及导电浆料，特别涉及一种适用于高精密直写3D打印的纳米颗粒铜浆、制备及用途。
背景技术
金属3D打印工艺与传统工艺相比，在缩短新产品研发及实现周期、可高效成形更为复杂的结构、实现一体化、轻量化设计、实现优良的力学性能等方面表现出了无法比拟的优势。目前，在金属3D打印工艺领域中，银纳米颗粒是应用最为广泛的，这是由于银纳米颗粒具有易烧结、导电性能高、耐氧化等特点，进而使其在金属3D打印中表现良好。然而，银材料作为金属3D打印的原材料具有一大致命缺陷：价格高昂，这也极大程度地限制了金属3D打印技术的发展和应用。
相比而言，铜材料的价格相对银材料而言更为低廉，且和银材料具有相似的导线性能。但由于铜的纳米材料在空气氛围中较易被氧化，这会导致在制备铜浆以及铜浆存放的过程中，铜的纳米颗粒的表面容易被氧化成CuO或者Cu2O，进而导致材料的导电性能显著降低，这极大的限制了铜浆在3D打印领域的应用，进而越来越多科研团队致力于研究适用于金属3D打印的铜纳米颗粒以及对应的铜浆。
比如南京工业大学公布的CN104505137A的“一种导电铜浆及其制备方法和用途”中提供了一种导电铜浆的制备方法，其在铜浆的制备中添加草酸、抗坏血酸或葡萄糖的一种作为还原剂；CN106981324B的“一种铜导电浆料及其制备方法和用途”中通过在体系中加入稳定剂，在烧结过程中还原氧化铜，获得低氧化铜含量的导线线路，其中稳定剂包括柠檬酸、抗坏血酸、戊二醛等。然而此类还原剂或稳定剂制备得到的是微米级别的铜颗粒，依旧无法满足高精密直写3D打印的需求；换言之，高精密直写3D打印中，特别是针对10μm以下线宽的打印，需要的材料往往是百nm级别或者更小尺寸的浆料作为材料，而铜颗粒的尺寸越小对应的活性越高，越容易被氧化，对应的现有技术无法达到纳米级别的铜浆的制备和保护。另外，且此类铜浆加入的还原剂或者稳定剂，对于铜纳米颗粒的保护效果有限，在存放一周以上的时间，由于表面依然会被彻底氧化，会出现烧结后电阻明显变大的问题。
具体的，以“抗坏血酸”作为还原剂为例，虽则它有一定的还原性，但实际上它本身就是一类酸，而纳米铜本身表面的铜原子反应活性就会很高，因此在长时间过程中，铜纳米颗粒表面会被抗坏血酸分解(类似于活泼金属如铁与酸发生的化学反应)，从而导致铜纳米颗粒自身的稳定性显著下降；另外，其实际起到还原效果的是由于其在高温时会分解出来一氧化碳，而一氧化碳是一类气体，其在实际烧结过程中存在和铜颗粒表面接触不充分的问题，进而带来还原效果差，无法制备和保护纳米级别的铜颗粒的效果。且，其高温分解的气体还会导致铜导线烧结后存在不致密的问题，进而影响导电性能，无法很好地适用于高精密直写3D打印中。
换言之，高精密直写3D打印需要百nm级别的铜纳米颗粒作为材料，而铜颗粒的尺寸越小对应的活性越高，导致其在制备和保存过程中极易氧化，而目前的制备导电铜浆的技术并无法解决该核心问题，进而限制了铜材料在高精密直写3D打印中的应用。
发明内容
本发明的目的在于提供一种适用于高精密直写3D打印的纳米颗粒铜浆、制备及用途，采用三芳基膦、三烷基膦类化合物作为还原剂并将铜纳米颗粒配制成含有环氧树脂的油溶性浆料，解决纳米颗粒铜浆在制备和存放过程中容易被氧化的问题，提高纳米颗粒铜浆的导电性能，使其适用于高精密直写3D打印。
第一方面，本技术方案提供一种适用于高精密直写3D打印的纳米颗粒铜浆，所述纳米颗粒铜浆包括以下原料组分以及重量份：50-90％铜粉；10-40％有机载体，所述有机载体由占原料组分1-15％环氧树脂、5-25％有机溶剂以及1-5％固化剂组成；0-2％非导电填料，各个原料组分相加的比例为100％。
在本方案中，选用的铜粉的平均粒径控制为100nm～5μm，这样的好处在于：可以更有针对性的根据不同的打印线宽要求，选择合适的铜纳米颗粒进行制备铜浆。
所述铜粉保护剂为三芳基膦、三烷基膦类化合物的任一种或其组合，其在室温和低温时和铜粉配位，在高温时和氧原子结合形成氧膦化合物。
所述环氧树脂的种类不受限制，为热固性环氧树脂，可选择为：双酚A型环氧树脂、E-44环氧树脂、联苯氧型环氧树脂的任一种或其组合，环氧树脂在反应体系中起到的作用是利用其疏水性，有效隔绝环境中水分子对铜纳米颗粒的破坏，且环氧树脂在高温下容易固结，也可有效地提高铜浆在基底的粘附性。
所述有机溶剂选择为二乙二醇单乙醚醋酸酯、二价酸酯、异氟尔酮、松油醇或二乙二醇单丁醚中的任一种或其组合，其在反应体系中的作用是溶解环氧树脂和固化剂。
所述固化剂选择为多元硫醇固化剂、双氰胺固化剂、酸酐类固化剂，其在反应体系中的作用是为了使环氧树脂高温烧结时，能够快速固化，起到与打印介质更好的粘附的目的，从而有效地提升铜线与介质材料的粘附性以及导电的稳定性。
所述有机载体的制备方式如下：将环氧树脂溶解到有机溶剂中，加热至第一温度并保持一段时间后直到环氧树脂完全溶解在有机溶剂中得到初步载体，随后将固化剂添加到初步载体中高速分散均匀，并加热至第二温度并老化一定时间后，得到有机载体。其中第一温度高于第二温度。在本方案的实施例中，第一温度控制在75-85摄氏度之间，可以是80摄氏度，第二温度控制在30-35摄氏度之间。
所述非导电填料为超细碳粉、纳米石墨烯粉末、膨润土或纳米二氧化硅粉末中的任一种或其组合，主要用于调节导电浆料的粘度与触变性，使浆料获得良好的流变性能，提高打印质量。即，可更好地将纳米颗粒铜分散，使其长时间存放时不会重新团聚。
在一些具体实施例中，所述纳米颗粒铜浆包括以下原料组分以及重量份：75％铜粉；14％有机载体，所述有机载体包括5％环氧树脂、8％有机溶剂以及1％固化剂；10％铜粉保护剂；1％非导电填料。
在一些具体实施例中，所述纳米颗粒铜浆包括以下原料组分以及重量份：60％铜粉；23％有机载体，所述有机载体包括10％环氧树脂、11％有机溶剂以及2％固化剂；15％铜粉保护剂；2％非导电填料。
在一些具体实施例中，所述纳米颗粒铜浆包括以下原料组分以及重量份：80％铜粉；15％有机载体，所述有机载体包括4％环氧树脂、10％有机溶剂以及1％固化剂；5％铜粉保护剂。
第二方面，本方案提供一种适用于高精密直写3D打印的纳米颗粒铜浆，包括如下步骤：
有机载体的制备：
将环氧树脂溶解到有机溶剂中，加热至第一温度并保持一段时间后直到环氧树脂完全溶解在有机溶剂中得到初步载体，随后将固化剂添加到初步载体中高速分散均匀，并加热至第二温度并老化一定时间后，得到有机载体，其中第一温度高于第二温度；
铜浆的配制：
将铜粉、铜粉保护剂、非导电填料及所述有机载体混合并进行分散，得到均匀的初浆料；
将初浆料辊轧至一定细度，并经滤网过滤得到铜浆成品。
在本方案提供的制备方法中，将初浆料进行棍轧直到<1μm的细度为止，并经10μm-20μm的滤网进行过滤，得到铜浆成品。在得到初步载体阶段时保持1小时的时间，在得到有机载体的阶段时保持2小时的时间，以提供充足的老化时间。
根据以上方案制备得到的纳米颗粒铜浆满足≥1μm线宽的高精密直写3D打印，铜浆成品在空气氛围下存放10天后，烧结的铜线电阻率在10μΩ·cm以下。
另外本方案制备得到纳米颗粒铜浆可用于高精密直写3D打印，可用于显示面板、电子元器件、光伏面板等电子行业的高精细导线的打印。
本方案提供一种适用于高精密直写3D打印的纳米颗粒铜浆、制备及用途，制备得到的纳米颗粒铜浆适用于高精密直写3D打印，特别是在针对10μm以下线宽打印的情况时，高精密直写3D打印需要的材料往往是百nm级别或者更小尺寸的浆料，然而铜浆的颗粒度越小进而引发的后果就是：铜颗粒表面活性增加，是更容易被氧化的；且纳米颗粒铜浆在打印过程中存在长时间接触空气中的水和氧气的问题，而长时间的环境暴露也会导致铜纳米颗粒的表面被逐渐氧化，进而影响最后的导电性能。
故此，本方案在铜浆的制备过程中，引入三芳基膦、三烷基膦类化合物作为还原剂，并将铜纳米颗粒配置成含有环氧树脂的油溶性浆料，一来可通过油溶性浆料隔绝外界水分子对铜纳米颗粒的破坏，以及提高铜浆在基底的粘附性，二来利用三芳基膦、三烷基膦类化合物配位到纳米颗粒铜表面的原理，相较于传统的一氧化碳气体接触的方式而言，提高了铜表面保护的效率；且三芳基膦、三烷基膦类化合物能够与氧原子结合形成氧膦化合物，不会影响铜纳米颗粒烧结时形成的导电的性能。换言之，本方案提供的还原剂在室温下能够长时间稳定，不易被空气中的氧气所氧化，其可有效地抑制铜纳米颗粒在制备以及打印过程中被氧化的问题，保证还原剂在浆料中的存放稳定性，另一方面，其在烧结过程中，随着烧结温度的升高，还原剂的还原性逐渐升高，可以有效地消耗烧结氛围中残留的氧气以及铜纳米颗粒表面所氧化所形成的氧化物，使得制备得到的纳米颗粒铜浆可长时间存放，且在打印过程中也不受到外界环境的影响。
本方案制备得到的纳米颗粒铜浆满足≥1μm的高精密直写3D打印，且铜浆成品在空气氛围下存放10天后，烧结的铜线电阻率在10μΩ·cm以下，三芳基膦、三烷基膦类化合物在室温或者较低的温度时，可以保护纳米铜表面不易被氧化，在高温烧结时可以将表面被氧化的铜，还原为单质铜，从而使烧结后的铜线有良好的导电性。
相较现有技术，本技术方案具有以下特点和有益效果：
1.制备适用于高精密直写3D打印的纳米颗粒铜浆以取代银浆，相较于银浆作为材料的情况而言，纳米颗粒铜浆可极大程度地减少打印材料的成本，且还可保证良好的导电性能。
2.本方案将铜纳米颗粒配置成含有环氧树脂的油溶性浆料，环氧树脂作为一类疏水性材料，能够有效的隔绝水分子对于铜纳米颗粒的破坏，且环氧树脂作为一类高温易固化的材料，能够有效的提升铜浆在基底的粘附性能。
3.本方案采用三芳基膦、三烷基膦类化合物作为还原剂，三芳基膦、三烷基膦类化合物配位到铜纳米颗粒表面起到保护铜的效果，不存在与铜颗粒发生反应的可能性，另外，三芳基膦、三烷基膦类化合物的还原性靠的是其能够与氧原子结合形成氧膦化合物，不会影响铜纳米颗粒烧结时形成的导电的性能，现有技术的铜浆在用直写3D打印出来的铜线导电性明显差于丝网印刷后烧结出来的铜线的问题。
附图说明
图1是本方案实施例1制备得到的铜浆成品A在存放1周后烧结后的铜膜的电阻率在85℃/85RH环境下的老化数据。
图2是本方案实施例1制备得到的100～200nm尺寸的铜浆成品A烧结前的扫描电镜图。
图3是本方案实施例1制备得到的100～200nm尺寸的铜浆成品A烧结后的扫描电镜图。
图4是本方案对照实施例1制备得到的100～200nm尺寸的铜浆成品D烧结前的扫描电镜图。
图5是本方案对照实施例1制备得到的100～200nm尺寸的铜浆成品D烧结后的扫描电镜图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本发明保护的范围。
可以理解的是，术语“一”应理解为“至少一”或“一个或多个”，即在一个实施例中，一个元件的数量可以为一个，而在另外的实施例中，该元件的数量可以为多个，术语“一”不能理解为对数量的限制。
以下用特定实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。应理解本发明的保护范围不局限于下述特定的具体实施方案；还应当理解，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围。下列实施例中未注明具体条件的试验方法，通常按照常规方法，或者按照各制造商所建议的条件。
实施例1
称取双酚A型环氧树脂8g，溶到15g的乙酸丁酯溶剂中，加热至80℃保持1小时，至完全溶解得到初步载体；称取酸酐类固化剂1g，加入到初步载体中，用高速分散机进行高速分散，分散均匀后加热至30-35℃老化2小时，得到有机载体；称取100～200nm的铜粉70g，还原剂三苯基膦5g，非导电填料纳米石墨烯粉末0.2g、50nm的二氧化硅粉末0.8g；与所述有机载体在混料机中充分混合，再使用高速分散机进行高速分散，得到均匀的初浆料；将初浆料在三辊机进行6遍棍轧，达到<1μm的细度为止，然后经过10μm的滤网进行过滤，得到的铜浆成品A。
实施例2
称取E-44环氧树脂6g，溶到10g的聚乙二醇溶剂中，加热至80℃保持1小时，至完全溶解得到初步载体；称取多元硫醇固化剂0.5g，加入到初步载体中，用高速分散机进行高速分散，分散均匀后加热至30-35℃老化2小时，得到有机载体；称取500～600nm的铜粉70g，还原剂三辛基膦5g，非导电填料纳米石墨烯粉末0.2g、50nm的二氧化硅粉末0.8g；与所述有机载体在混料机中充分混合，再使用高速分散机进行高速分散，得到均匀的初浆料；将初浆料在三辊机进行6遍棍轧，达到<1μm的细度为止，然后经过10μm的滤网进行过滤，得到的铜浆成品B。
实施例3
称取联苯氧型环氧树脂5g，溶到7g的二乙二醇乙醚醋酸酯溶剂中，加热至80℃保持1小时，至完全溶解得到初步载体；称取双氰胺固化剂0.5g，加入到初步载体中，用高速分散机进行高速分散，分散均匀后加热至30-35℃老化2小时，得到有机载体；称取1～2μm的铜粉70g，还原剂三对甲基苯基膦5g；与所述有机载体在混料机中充分混合，再使用高速分散机进行高速分散，得到均匀的初浆料；将初浆料在三辊机进行6遍棍轧，达到<1μm的细度为止，然后经过10μm的滤网进行过滤，得到的铜浆成品C。
对照实施例1:
称取双酚A型环氧树脂8g，溶到15g的乙酸丁酯溶剂中，加热至80℃保持1小时，至完全溶解得到初步载体；称取酸酐类固化剂1g，加入到初步载体中，用高速分散机进行高速分散，分散均匀后加热至30-35℃老化2小时，得到有机载体；称取100～200nm的铜粉70g，还原剂抗坏血酸5g，非导电填料纳米石墨烯粉末0.2g、50nm的二氧化硅粉末0.8g；与所述有机载体在混料机中充分混合，再使用高速分散机进行高速分散，得到均匀的初浆料；将初浆料在三辊机进行6遍棍轧，达到<1μm的细度为止，然后经过10μm的滤网进行过滤，得到的铜浆成品D。
对照实施例2：
称取24g乙酸丁酯作为有机载体；称取100～200nm的铜粉70g，还原剂三苯基膦5g，非导电填料纳米石墨烯粉末0.2g、50nm的二氧化硅粉末0.8g；与所述有机载体在混料机中充分混合，再使用高速分散机进行高速分散，得到均匀的初浆料；将初浆料在三辊机进行6遍棍轧，达到<1μm的细度为止，然后经过10μm的滤网进行过滤，得到的铜浆成品E。
电阻率测量实验：
把制好的导电铜浆通过3D打印设备打印在相应的基底如硅片上，在100℃下烘干后放入炉子中在氮气氛围烧结，烧结程序为30～300℃升温速率为10℃/min，300℃烧结30min。经烧结后得到导电铜膜，采用四探针电阻测试仪(Advance Riko，型号ZEM-3M10)对固化后铜膜进行电阻率测试。
得到的实验结果如下表一：
表一铜浆成品的电阻率的测量
从表一的数据可以看到，铜浆成品A/B/C的电阻率远高于铜浆成品D和铜浆成品E,说明本方案提供的条件制备得到铜浆制备得到的导电性能也更好。
存放时间测量实验：
为了验证本专利所开发的铜浆成品的存放稳定性能够满足实际商业应用的需求，将不同的铜浆成品在室温下放置一定的时间，根据上述相同的工艺，进行烧结后制得相应的铜膜，并进行电阻率测试。
得到的实验结果如下表二，存放10天后的铜浆成品A烧结后铜膜的电阻率在85℃/85RH环境下的老化数据如图1所示。
表二铜浆成品的存放时间和电阻率的关系
从表二的数据可以看到，铜浆成品A/B/C在长时间存放时的稳定性能也更好，且铜浆成品在空气氛围下存放10天后，烧结的铜线电阻率在10μΩ·cm以下。
扫描电镜实验：
将实施例1得到的铜浆成品A和对照实施例1得到的铜浆成品D作为测试样品，铜浆成品A铜浆烧结前的扫描电镜图和烧结后的扫描电镜图如图2和图3所示，铜浆成品D铜浆烧结前的扫描电镜图和烧结后的扫描电镜图如图4和图5所示。从图中可明显地看到：铜浆成品A在烧结之后形成的铜膜十分致密，表面更为光滑；相对应的，铜浆成品D铜浆由于表面被氧化而形成了CuO或者Cu2O，当相同的烧结温度下，无法形成致密的铜膜，因此扫描电镜中依然可以看到明显的C铜纳米颗粒，导致其导电性能明显差于铜浆成品A烧结之后的结果。
本发明不局限于上述最佳实施方式，任何人在本发明的启示下都可得出其他各种形式的产品，但不论在其形状或结构上作任何变化，凡是具有与本申请相同或相近似的技术方案，均落在本发明的保护范围之内。
Claims (10)
1.一种适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，包括以下重量份的原料组分：
50-90％铜粉；7-40％有机载体，所述有机载体由占原料组分1-15％环氧树脂、5-25％有机溶剂以及1-5％固化剂组成；1-20％铜粉保护剂；0-2％非导电填料，各原料组分相加的比例为100％。
2.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，所述铜粉保护剂为三芳基膦、三烷基膦类化合物的任一种或其组合，在＜100℃和铜粉配位，在≥100℃和氧原子结合形成氧膦化合物。
3.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，所述铜粉为50nm～5μm的铜纳米颗粒。
4.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，所述铜粉为50nm～500nm的铜纳米颗粒。
5.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，所述非导电填料为超细碳粉、纳米石墨烯粉末、膨润土或纳米二氧化硅粉末中的任一种或其组合。
6.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，包括如下步骤：
有机载体的制备:
将环氧树脂溶解到有机溶剂中，加热至第一温度并保持一段时间后直到环氧树脂完全溶解在有机溶剂中得到初步载体，随后将固化剂添加到初步载体中高速分散均匀，并加热至第二温度并老化一定时间后，得到有机载体，其中第一温度高于第二温度；
铜浆的配制:
将铜粉、铜粉保护剂、非导电填料及所述有机载体混合并进行分散，得到均匀的初浆料；
将初浆料辊轧至一定细度，并经滤网过滤得到铜浆成品。
7.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，所述环氧树脂为热固性环氧树脂，选择为双酚A型环氧树脂、E-44环氧树脂、联苯氧型环氧树脂的一种或其组合。
8.根据权利要求1所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，所述固化剂选择为多元硫醇固化剂、双氰胺固化剂、酸酐类固化剂的任一种或其组合。
9.一种根据权利要求1到8任一所述的适用于高精密直写3D打印的纳米颗粒铜浆，满足≥1μm线宽的高精密直写3D打印的用途。
10.根据权利要求9所述的适用于高精密直写3D打印的纳米颗粒铜浆，其特征在于，铜浆成品在空气氛围下存放10天后，烧结的铜线电阻率在10μΩ·cm以下。
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| CN116259435A (zh) * | 2023-01-05 | 2023-06-13 | 嘉庚创新实验室 | 导电铜浆及其制备方法、应用 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2023534343A (ja) | 2023-08-09 |
| WO2022262794A1 (zh) | 2022-12-22 |
| US20240300012A1 (en) | 2024-09-12 |
| JP7424686B2 (ja) | 2024-01-30 |
| EP4138096A4 (en) | 2023-10-18 |
| EP4138096A1 (en) | 2023-02-22 |
| TW202300598A (zh) | 2023-01-01 |
| KR20220169474A (ko) | 2022-12-27 |
| CN113362984B (zh) | 2021-11-23 |
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