CN101591488B - 油墨及利用该油墨制作导电线路的方法 - Google Patents

油墨及利用该油墨制作导电线路的方法 Download PDF

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CN101591488B
CN101591488B CN2008103017757A CN200810301775A CN101591488B CN 101591488 B CN101591488 B CN 101591488B CN 2008103017757 A CN2008103017757 A CN 2008103017757A CN 200810301775 A CN200810301775 A CN 200810301775A CN 101591488 B CN101591488 B CN 101591488B
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silver
printing ink
agent
conducting wire
ink
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CN101591488A (zh
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林承贤
白耀文
张睿
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Peng Ding Polytron Technologies Inc
Avary Holding Shenzhen Co Ltd
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Honsentech Co Ltd
Fukui Precision Component Shenzhen Co Ltd
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Abstract

本发明涉及一种油墨,其包括银氨络合物和还原剂。本发明还涉及利用该油墨制作导电线路的方法。采用该方法有效避免了分别配制氧化性油墨和还原性油墨再分别进行打印的问题,简化了线路制作的工艺。

Description

油墨及利用该油墨制作导电线路的方法
技术领域
本发明涉及喷墨印刷技术领域,特别涉及一种油墨及利用该油墨制作导电线路的方法。
背景技术
利用喷墨打印技术制作导电线路在近年来受到了广泛关注,此方法只需将所需线路图形直接由计算机给出,再通过控制器控制喷墨印刷系统的喷嘴,将油墨颗粒由喷嘴喷出并逐点地形成线路图形,制作线路图形能够精确控制线路的位置及宽度,该方法属非接触式数码图案制程,可减少不同印刷材料间相互污染。相比于传统的线路制作方法,具有制作流程更加简化、便宜及低污染的优点。请参见文献:Murata,K.;Matsumoto,J.;Tezuka,A.;Oyama,K.;Matsuba,Y.;Yokoyama,H.;Super fine wiring by inkjet printingMicroprocesses and Nanotechnology Conference.2004.Digest of Papers.2004InternationalOct.27-29,2004Page(s):24-25。
现有技术中报道了一种采用喷墨打印含有可溶性银盐的墨水制造导电线路的方法。该方法是将可溶性银离子溶液制成可喷墨打印的墨水,在基材表面打印出含有银离子线路,然后在该线路表面打印含有还原剂如甲醛的墨水,通过氧化还原反应将银离子还原成为金属银,从而赋予线路以导电性。上述方法原理上比较简单,但实际操作并不容易,如需要大量的实验以配制氧化剂墨水和还原剂墨水;制作线路需要在基材表面同一位置反复打印,这样存在打印机的准确定位问题;另外,所形成的银线路在实际使用的过程中还存在银离子迁移,导致线路的可靠度下降。
发明内容
因此,有必要提供一种油墨利用该油墨制作导电线路的方法,以避免在基材表面的同一位置反复打印,使得制作的导电线路准确定位,并能够提升线路的可靠度。
以下将以实施例说明一种油墨及利用所述油墨制作导电线路的方法。
一种油墨,所述油墨包括银氨络合物和还原剂。
一种利用该油墨制作导电线路的方法,将包括还原剂与银氨络合物的油墨通过喷墨打印方式在基板表面形成线路图形;采用辐射照射线路图形,使所述线路图形中的银氨络合物被还原剂还原为金属银粒子,从而获得预制线路;在所述预制线路的轨迹镀覆金属,以形成导电线路。
与现有技术相比,该导电线路的制作方法避免了分别配制氧化性油墨和还原性油墨再分别进行打印的问题,简化了线路制作的工艺。
附图说明
图1是本技术方案提供的制作导电线路方法的流程图。
图2是本技术方案实施例提供的基板的结构示意图。
图3是图2中基板形成线路图形的结构示意图。
图4是图2中基板形成预制线路的结构示意图。
图5是图2中基板形成导电线路的结构示意图。
具体实施方式
下面将结合附图及实施例对本技术方案实施例提供的一种油墨及利用该油墨制作导电线路方法作进一步详细说明。
本技术方案实施例提供的油墨,其包括还原剂与银氨络合物。由于该油墨为水溶性,该银氨络合物完全溶解在溶剂中,具有较好分散性。所述油墨的配制具体如下:
首先,配制浓度为10-4mol/L至5mol/L的银盐溶液,向上述银盐溶液加入敏化剂,形成银氨络合物溶液。上述溶液的溶剂可以为水,也可以为溶于水的有机溶剂如丙酮、乙醇等的水溶液,所述的可溶性银盐可以为硝酸银、碳酸银、醋酸银及柠檬酸银等,所述敏化剂为氨水及有机胺类,有机胺类可以为甲胺、乙胺等一元和多元胺,也可为一级、二级和三级有机胺。所述敏化剂与银盐的摩尔浓度比为1比1至3比1之间,配得溶液中的银氨络合物的浓度为10-4mol/L至5mol/L。
其次,向上述混合溶液中加入还原剂,还原剂可为柠檬酸钠或酒石酸钾钠。所述还原剂的浓度为10-7mol/L至5mol/L。
再次,加入连接料、分散剂、保湿剂,表面活性剂等助剂,用以调节油墨的稳定性、表面张力、粘度等性能。所述连接料可为聚氨酯、聚乙烯醇等树脂,所述分散剂可为聚乙烯基吡咯烷酮及聚乙烯醇等水溶性聚合物,所述保湿剂可为乙二醇、乙二醇醚、二甘醇及甘油等高沸点醇类,所述表面活性剂可以为阳离子表面活性剂、阴离子表面活性剂或两性活性剂。上述各助剂的加入量为体积比0.1%至50%。还可以加入防腐剂和杀菌剂等其它助剂。
最后,充分搅拌上述混合溶液,使得全部助剂溶于溶剂中,得到配制完成的油墨。
所述油墨还原剂具有较弱的还原性,没有辐射照射的状态下,还原剂不与银氨络合物发生反应,所述油墨可以长时间稳定存在。在辐射照射下,银氨络合物中的银被还原成单质银。
请参阅图1,本实施例提供的利用所述油墨制作导电线路的方法。
第一步,将所述油墨通过喷墨打印的方式印刷在基板100表面以形成线路图形。
如图2所示,本实施例中,基板100为电路板制作过程中需要进行线路制作的半成品。根据所要制作的电路板的结构可以选择不同结构的基板100。例如,当待制作的电路板为单层板时,所述基板100为一层绝缘层;当待制作的电路板为多层电路板时,所述基板100为一由多层板和一绝缘层压合后所形成的结构,还可为硅基板或玻璃基板。本实施例中,基板100为需要制作单面线路的单层板。该基板100具有用于形成导电线路的表面110。当然,该基板100也可用于制作双面板,只要在基板100相对设置的两个表面上制作即可。
为增加形成的线路图形200与基板100的表面110的结合强度,在基板100形成线路图形200之前,可通过清洗、微蚀等方法对基板110进行表面处理,以除去附着于表面110的污物、氧化物、油脂等。
如图3所示,分别在基板100的表面110通过喷墨印刷方式形成线路图形200。具体地,喷墨打印系统在控制器的控制下根据所需制作的导电线路的图形,将所述油墨自喷嘴逐点喷洒到表面110,使沉积在表面110的油墨形成线路图形200。该油墨形成的线路图形200与所需制作的导电线路的图形相同。
第二步:采用辐射照射线路图形200,使所述线路图形200中的银氨络合物被还原剂还原为金属银粒子,从而获得预制线路300。
如图3及图4所示,将形成于基板100表面110的线路图形200转变成预制线路300。即,表面110上形成线路图形200的银氨络合物和所述还原剂经化学反应,使银氨络合物中的银以单质形式析出,从而在表面110上由银单质形成预制线路300。
常温状态下,银氨络合物与所述还原剂不发生化学反应,需要对线路图形200进行具有辐射照射,使得银氨络合物与还原剂发生氧化还原反应,析出银单质,从而形成预制线路300,所述的辐射可为紫外光、激光或γ射线等。
本实施例中,将形成线路图形200的基板100置于紫外灯箱中,使得紫外光源距离表面110的距离为8厘米,光照10分钟后,取出基材100,对基材100进行水洗,然后烘干。通过上述过程,即可使得线路图形200转化为单质银的预制线路300。实际操作中,可以跟实际情况的需要,对照射光的强度和照射时间进行调节。
第三步:在预制线路300的轨迹镀覆金属,以形成导电线路400。
前一步骤中,包括还原剂与银氨络合物的油墨经喷墨印刷系统喷射至基板100的表面110形成线路图形200时,该线路图形200为分布于表面110的还原剂与银氨络合物形成。该银氨络合物中金属离子间可能没有完全结合,其连续性较差,使银经反应生成的金属银粒子也为分布在表面110的连续性较差的金属银粒子,从而降低由该金属银粒子形成的预制线路300的导电性,使整个预制线路300可能无法达到良好的电性导通。
因此,如图5所示,在预制线路300的金属银粒子表面经过电镀或化学镀的方法镀覆金属,使所镀覆金属完全包裹于预制线路300的金属银粒子外并填充相邻两个金属银粒子的间隙,从而形成连续的导电线路400。在镀覆金属时,形成预制线路300的每个金属银粒子作为镀覆反应的催化中心,并以该每个金属银粒子为中心在其表面生长出多个金属粒子。该多个金属粒子致密排列于每个金属银粒子的表面,使该每个金属银粒子完全被多个金属粒子包裹,同时没有完全结合的相邻两个金属银粒子的表面分别生长出的多个金属粒子将该相邻两个金属银粒子电性连接,从而在基板100的表面110形成具有良好的电性导通的导电线路400。所述镀覆的金属可以为铜或镍等,镀覆金属可以采用电镀或化学镀的方式。
本实施例中,对包括金属银粒子的预制线路300进行化学镀铜,在基板100的表面110形成导电线路400。具体地,将形成预制线路300的基板100置于化学镀铜溶液中,在50摄氏度的温度下进行化学镀铜2分钟,即可使预制线路300形成完全电连通的导电线路400。导电线路400中的铜粒子的粒径为50至150纳米。该镀液还可包括铜化合物、还原剂与络合剂。铜化合物可为硫酸铜、氯化铜等;还原剂可为甲醛、乙醛酸等;络合剂可为乙烯二胺四乙酸二钠盐、酒石酸钾钠等络合物。当然,还可在渡液中加入稳定剂、光亮剂等,以满足化学镀的需要。具体地,该镀铜溶液的组分为:硫酸铜10g/L、酒石酸钾钠22g/L、乙烯二胺四乙酸二钠盐50g/L、甲醛15mL/L及甲醇10mL/L。其中,固体采用质量体积比,即,单位体积溶液中含该固体的质量,单位g/L;液体采用体积体积比,即,单位体积溶液中含该液体的体积,单位mL/L。
由此完成基板100的表面110具有较高导电性及均匀性的导电线路300的制作,以供后续加工使用。该制作方法采用同时含有氧化剂银氨络合物和弱还原剂的油墨,所述的银氨络合物与弱还原剂在常温状态下稳定存在,在高能量光的照射下,迅速发生化学反应。这样避免了分别配制氧化性油墨和还原性油墨再分别进行打印的问题,在保证了线路质量的情况下,简化了线路制作的工艺。本制作方法中的油墨的主要成分易溶于水,不必考虑分散稳定的问题。本方法中银氨络合物和弱还原剂的反应在辐射照射条件下进行,所需设备简单,而且方便进行控制。此外,镀覆金属提高了线路的导电性,并对银线路进行了保护,避免了银离子迁移的问题。
可以理解的是,对于本领域的普通技术人员来说,可以根据本发明的技术构思做出其它各种相应的改变与变形,而所有这些改变与变形都应属于本发明权利要求的保护范围。

Claims (12)

1.一种油墨,其包括银氨络合物和还原剂,所述银氨络合物由银盐和氨水或有机胺类配制,所述银盐的浓度为10-4mol/L至5mol/L,所述氨水或有机胺类与银盐摩尔浓度比在1∶1至3∶1之间,所述有机胺类为为一级、二级和三级有机胺。
2.如权利要求1所述的油墨,其特征在于,所述银氨络合物的浓度为10-4mol/L至5mol/L。
3.如权利要求1所述的油墨,其特征在于,所述还原剂的浓度为10-7mol/L至5mol/L。
4.如权利要求1所述的油墨,其特征在于,所述还原剂为酒石酸钾钠或柠檬酸钠。
5.如权利要求1所述的油墨,其特征在于,所述银盐为硝酸银、硫酸银、醋酸银或柠檬酸银。
6.如权利要求1所述的油墨,其特征在于,所述油墨进一步包括连接料、分散剂、保湿剂和表面活性剂。
7.如权利要求6所述的油墨,其特征在于,所述连接料可为聚氨酯或聚乙烯醇,所述分散剂为聚乙烯基吡咯烷酮或聚乙烯醇,所述保湿剂为乙二醇、乙二醇醚、二甘醇或甘油,所述表面活性剂为阳离子表面活性剂、阴离子表面活性剂或两性活性剂。
8.如权利要求6所述的油墨,其特征在于,所述连接料的体积含量为0.1%至50%,所述分散剂的体积含量为0.1%至50%、所述保湿剂的体积含量为0.1%至50%,所述表面活性剂的体积含量为0.1%至50%。
9.一种制作导电线路的方法,其包括以下步骤:
将油墨通过喷墨打印方式在基板表面形成线路图形,所述油墨包括银氨络合物和还原剂,所述银氨络合物由银盐和氨水或有机胺类配制,所述银盐的浓度为10-4mol/L至5mol/L,所述氨水或有机胺类与银盐摩尔浓度比在1∶1至3∶1之间,所述有机胺类为一级、二级和三级有机胺;
采用辐射照射线路图形,使所述线路图形中的银氨络合物被还原剂还原为金属银粒子,从而获得预制线路;
在所述预制线路的轨迹镀覆金属,以形成导电线路。
10.如权利要求9所述的制作导电线路的方法,其特征在于,所述辐射为紫外光、激光或γ射线。
11.如权利要求9所述的制作导电线路的方法,其特征在于,所述镀覆金属为铜或镍。
12.如权利要求9所述的制作导电线路的方法,其特征在于,镀覆金属采用电镀或化学镀的方式。
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