CN101597440A - 油墨、利用该油墨制作导电线路的方法及线路板 - Google Patents
油墨、利用该油墨制作导电线路的方法及线路板 Download PDFInfo
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Abstract
本发明提供一种油墨，其包括贵金属离子与感光单体，该感光单体分子式为：MC≡C－C≡CN，M为亲水性基团，N为亲油性基团，多个该感光单体的分子形成囊体，该贵金属离子一部分包裹于该囊体内，另一部分吸附于囊体的外壁。本发明还提供一种制作导电线路的方法及一种线路板。
Description
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、利用该油墨制作导电线路的方法及线路板。
背景技术
喷墨印刷(也称之为：喷墨打印)作为一种印刷工艺，其与平版印刷、丝网印刷一样可用于图形的转移。喷墨印刷为非接触印刷工艺，不需要像活字以及由照相方法制作的印版或软片那样印刷表面，只需将所需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图形。喷墨印刷可应用在电路板线路制作中，即喷墨打印线路图形。该方法制作线路图形能够精确控制线路的位置及宽度，还降低原料浪费，是一种环保的印刷工艺。
目前，喷墨打印线路图形是将以单分散的纳米颗粒为核心的纳米金属油墨直接喷射在基板表面形成导电线路。请参阅文献：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.27-29，2004 Page(s)：24-25。然而，铜较金或银活泼，且纳米铜的比表面积比一般金属铜大，在空气中纳米铜极易被氧化失去金属的导电性，所以纳米铜不适合作为油墨，也不能满足采用喷墨打印的方式制作铜线路。另外，喷射在基板表面的纳米金属油墨干燥后，还需经过300度高温烧结，使纳米金属颗粒烧结在一起，从而形成连续的导电线路。但是，烧结过程中，温度控制不佳会影响导电线路的连续性及导电性。如烧结温度过低，纳米金属颗粒不能完全被烧结在一起；相反地，烧结温度过高，则基板必须采用耐高温且不易受热变形材料制成。
发明内容
因此，有必要提供一种油墨、导电线路的制作方法及线路板，以提高导电线路的连续性及导电性。
以下将以实施例说明一种油墨及导电线路的制作方法。
一种油墨，其包括贵金属离子与感光单体，该感光单体分子式为：MC≡C-C≡CN，M为亲水性基团，N为亲油性基团，多个该感光单体的分子形成囊体，该贵金属离子一部分包裹于该囊体内，另一部分吸附于囊体的外壁。
一种制作导电线路的方法，首先将油墨印刷在基板表面形成线路图形，该油墨包括贵金属离子与感光单体，该感光单体分子式为：MC≡C-C≡CN，M为亲水性基团，N为亲油性基团，多个该感光单体的分子形成囊体，该贵金属离子一部分包裹于该囊体内，另一部分吸附于囊体的外壁。采用高能光束照射线路图形，该线路图形中的感光单体分子发生聚合物反应，使该线路图形中的贵金属离子被还原为相对应的贵金属粒子，从而获得预制线路。再次，在该预制线路的轨迹镀覆金属，以形成导电线路。
一种线路板，其包括基板及形成与该基板上的导电线路，该导电线路包括贵金属粒子、由感光单体聚合而成的聚合物以及包裹于贵金属粒子与聚合物外的用于电气连通的导电金属。该聚合物分子式为：
与现有技术相比，该油墨包括贵金属离子与感光单体，该感光单体中的多个分子形成囊体使一部分贵金属离子包裹于该囊体内，而另一部分吸附于该囊体的外壁，从而形成胶囊体，该感光单体分子作为载体使贵金属离子均匀的分散于油墨中，提高油墨的分散性，用其制作的线路图形分布均匀。该方法还通过光束照射线路图形，引发形成线路图形的感光单体分子与贵金属离子反应，使油墨中贵金属离子被还原成贵金属粒子，并由该贵金属粒子作为催化中心镀覆金属，从而形成连续性好的导电线路，避免采用高温烧结形成导电线路，从而使导电线路的制作不必再考虑烧结温度的影响。
附图说明
图1是本技术方案实施例提供的基板的结构示意图。
图2是图1中基板形成线路图形的结构示意图。
图3是图1中基板形成预制线路的结构示意图。
图4是图1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、利用该油墨制作导电线路的方法及线路板作进一步详细说明。
本技术方案实施例提供的油墨，其包括感光单体与贵金属离子。该感光单体分子式为：MC≡C-C≡CN，M为羧基、磺酸基、氨基等亲水性基团，N为烷烃基等亲油性基团。该感光单体同时包括亲水性与亲油性基团，使感光单体具有既亲水又亲油的双亲性质，从而使该感光单体在高能光束照射下可发生聚合反应。该贵金属离子为银离子、金离子、铂离子、钯离子或其他贵金属离子。本实施例中，贵金属离子为银离子。
该感光单体与贵金属离子在油墨的分布情况为：多个感光单体的分子形成囊体，该贵金属离子一部分包裹于该囊体内，另一部分吸附于囊体的外壁。油墨中感光单体分子作为载体使贵金属离子均匀的分散于油墨中，提高油墨的分散性，同时使感光单体分子周围均有贵金属离子存在，利于后续感光单体分子与贵金属离子的充分反应。
感光单体分子与贵金属离子形成胶囊体的原理为：包括贵金属离子与感光单体分子的混合溶液中，由于吸附作用，贵金属离子吸附于感光单体分子的周围。当感光单体的浓度大于该感光单体临界胶束浓度(Critical Micelle Concentration，CMC)时，感光单体分子在油墨溶液中聚集形成多个囊体，使分布于感光单体分子周围的贵金属离子一部分被包裹于该感光单体分子形成的囊体内，而另一部分吸附于该感光单体分子形成的囊体的外壁，从而形成感光单体分子的囊体内包裹贵金属离子而感光单体分子的囊体外吸附贵金属离子的胶囊体。其中，该临界胶束浓度是表征溶液表面活性的物理参数，也是具有表面活性的溶液的一种特性浓度。本实施例中，油墨中的感光单体的浓度为10-7至10-1mol/L时，即可使油墨中的感光单体与贵金属离子形成胶囊体。
例如，将1.5×10-1mol/L的10，12-二十五碳二炔酸(分子式为CH3(CH2)11C≡C-C≡C(CH2)8CO2H)溶液与硝酸银(分子式为AgNO3)溶液的混合物经超声波振荡1小时，即获得感光单体分子与贵金属离子形成的胶囊体。然后，将上述包括胶囊体的溶液与水、有机溶剂或其他印刷需要的水溶性介质均匀混合，从而制成油墨。
该感光单体MC≡C-C≡CN，其分子中具有两个碳碳三键(即C≡C)的共价键，在高能光束的照射下，该感光单体分子中的C≡C键打开，使每个感光单体分子中打开的C≡C与其他感光单体分子中打开的C≡C键发生键合，从而形成聚合物。同时，该C≡C键在打开时会释放出自由基，该自由基相当于氧化还原反应中的电子，当贵金属离子俘获到该自由基，即可使该贵金属离子得到电子被还原为相对应的贵金属粒子。
另外，在制备过程中还可向该油墨中加入粘度调节剂、连接料、其他表面活性剂或其他试剂，用以调节油墨的表面张力、粘度等性能，从而提高油墨与待打印物体表面的结合力。有机溶剂可以为乙醇、丙酮、甘油等可与水相溶的极性溶剂，水溶性介质可以为去离子水、水溶性有机物或两者的混合物。而表面活性剂可为阴离子型、阳离子型、非离子型等，连接料可为聚氨酯、聚乙烯醇等高分子材料。
请参阅图1至图4，本实施例提供的采用该油墨制作导电线路的方法。
第一步：提供基板100。
如图1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，还可为半导体基片。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具有用于形成预制线路的表面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。
第二步：形成线路图形200于基板100的表面110。
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，可通过采用酸、碱溶液或等离子体微蚀基板110、清洗等方法对基板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2所示，分别在基板100的表面110通过喷墨或其他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，将油墨自喷嘴逐点喷洒到表面110，使其沉积在表面110形成线路图形200。该油墨为本技术方案提供的油墨，其包括感光单体与银离子，该银离子被包裹于多个感光单体分子形成的囊体内，并在油墨中形成胶囊体。
但是，该胶囊体只能存在于液态溶液中，干燥状态时该胶囊体会破裂，其中，多个感光单体分子形成的囊体破裂，银离子依然分布于组成该破裂囊体的感光单体分子周围。而包括胶囊体的液态油墨被沉积在表面110后经加热烘干或长时间放置于空气中的自然烘干的方式，最终在表面110在表面形成干燥的线路图形200，此时线路图形200中的已经没有感光单体分子与银离子形成的胶囊体，只有感光单体分子与分布于该感光单体分子周围的银离子。即，最终表面110上是由感光单体分子与分布于该感光单体分子周围的银离子形成与所需制作的导电线路的图形相同的线路图形200。当然，该油墨也可通过其他印刷方式在基板100的表面110形成线路图形200
第三步：形成预制线路300于基板100的表面110。
如图2及图3所示，采用高能光束照射形成于基板100表面110的线路图形200，使形成该线路图形200的贵金属离子被还原为相应的贵金属粒子，从而在表面110上由该贵金属粒子形成预制线路300。
该光束可以为紫外光、激光、γ射线等高能光束。本实施例中，油墨包括银离子与感光单体分子形成的胶囊体，从而由感光单体分子与分布于该感光单体分子周围的银离子形成线路图形200。紫外光照射线路图形200，线路图形200的感光单体分子中的C≡C键打开，使每个感光单体分子中打开的C≡C键与其他感光单体分子中C≡C键打开，使感光单体发生聚合反应形成聚合物，同时释放出自由基(即电子)。贵金属离子俘获该自由基，使该贵金属离子得到电子被还原为金属银粒子，再于光照后经干燥形成预制线路300。
优选地，光束照射时间在1分钟至12分钟之间。光束照射时间越长或光束的强度越大使感光单体分子中的C≡C键越容易打开，相应地释放出自由基的几率也越大且速率越快，因此贵金属离子俘获该自由基的几率增大，使贵金属离子充分反应生成相应的贵金属粒子。
第四步：在预制线路300上镀覆金属形成导电线路400。
前一步骤中，由感光单体分子与分布于该感光单体分子周围的银离子形成线路图形200时，该线路图形200为分布于表面110的感光单体分子与银离子形成。该分布于感光单体分子周围的银离子间可能没有完全结合，其连续性较差，使银离子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，而光照后感光单体分子聚合生成的聚合物也会存在于该预制线路300中，使金属银粒子不能完全结合，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4所示，在预制线路300的贵金属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的贵金属粒子外并填充相邻两个贵金属粒子的间隙，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的每个贵金属粒子作为镀覆反应的催化中心，并以该每个贵金属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贵金属粒子的表面，使该每个贵金属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贵金属粒子的表面分别生长出的多个金属粒子将该相邻两个贵金属粒子电性连接，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。
本实施例中，对包括金属银粒子的预制线路300进行化学镀，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置于化学镀液中，在50度的温度下进行化学镀2分钟，即可使预制线路300形成完全电连通的导电线路400。该镀液可为包括铜离子、镍离子或其他所需镀覆金属对应的金属离子的盐溶液。优选地，镀液为硫酸盐或氯化盐。该镀液还可包括还原剂、配合剂、酸碱度调节剂及其他添加剂。该还原剂可为二甲胺甲硼烷、N羟乙基亚乙基二胺三乙酸、硼氢化物、乙醛酸、二羟乙酸、次亚磷酸盐、甲醛等，优选甲醛或次亚磷酸盐。该配合剂可为乙二胺四乙酸等提高溶液的稳定性以及金属的沉积速度的配合剂。酸碱度调节剂为氢氧化钠、碳酸钠、氢氧化钾等。当然，还可在渡液中加入稳定剂、光亮剂、界面活性剂等其他添加剂，以满足化学镀的需要。
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400的制作，从而完成线路板的制作，以供后续加工使用。该线路板包括基板100及形成与该基板100表面110的导电线路400。该导电线路400包括贵金属粒子、由感光单体聚合而成的聚合物以及包裹于贵金属粒子与聚合物外用于实现电气连通的导电金属。该聚合物分子式为：
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 (15)
1.一种油墨，其特征在于：所述油墨包括贵金属离子与感光单体，该感光单体分子式为：MC≡C-C≡CN，M为亲水性基团，N为亲油性基团，多个所述感光单体的分子形成囊体，所述贵金属离子一部分包裹于该囊体内，另一部分吸附于囊体的外壁。
2.如权利要求1所述的油墨，其特征在于，所述贵金属离子为银离子、金离子、铂离子或钯离子。
3.如权利要求1所述的油墨，其特征在于，该感光单体的浓度为10-7至10-1mol/L。
4.如权利要求1所述的油墨，其特征在于，所述亲水性基团为羧基、磺酸基或氨基，亲油性基团为烷烃基。
5.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、粘度调节剂、保湿剂及表面活性剂。
6.一种制作导电线路的方法，其包括以下步骤：
将如权利要求1至5所述的任意一种油墨印刷在基板表面形成线路图形；
采用高能光束照射线路图形，所述线路图形中的感光单体分子发生聚合反应，使所述线路图形中的贵金属离子被还原为相对应的贵金属粒子，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。
7.如权利要求6所述的制作导电线路的方法，其特征在于，所述光束为紫外线、激光、γ射线。
8.如权利要求6所述的制作导电线路的方法，其特征在于，在所述预制线路镀覆金属采用化学镀的方法进行。
9.如权利要求6所述的制作导电线路的方法，其特征在于，所述化学镀采用的镀液包括铜离子或镍离子。
10.如权利要求6所述的制作导电线路的方法，其特征在于，所述化学镀采用的镀液包括二甲胺甲硼烷、N-羟乙基亚乙基二胺三乙酸、硼氢化物、乙醛酸、二羟乙酸、次亚磷酸盐或甲醛。
11.如权利要求6所述的制作导电线路的方法，其特征在于，所述高能光束照射时间在1分钟至12分钟之间。
12.如权利要求6所述的制作导电线路的方法，其特征在于，所述制作导电线路的方法进一步包括在将油墨印刷在基板表面形成线路图形之后，对线路图形进行干燥的步骤。
13.一种线路板，其包括基板及形成于该基板上的导电线路，其特征在于，所述导电线路由如权利要求1至5所述的任意一种油墨制成，所述导电线路包括贵金属粒子、感光单体聚合而成的聚合物以及包裹于贵金属粒子与聚合物外的用于电气连通的导电金属，所述聚合物分子式为：M为亲水性基团，N为亲油性基团。
14.如权利要求13所述的线路板，其特征在于，所述贵金属粒子为银粒子、金粒子、铂粒子或钯粒子。
15.如权利要求13所述的线路板，其特征在于，所述导电金属为铜或镍。
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| CN103571269A (zh) * | 2012-07-30 | 2014-02-12 | 比亚迪股份有限公司 | 油墨组合物、线路板及其制备方法 |
| CN104902689A (zh) * | 2014-03-05 | 2015-09-09 | 立诚光电股份有限公司 | 制造线路的方法及具有电路图案的陶瓷基板 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010012204B4 (de) * | 2010-03-19 | 2019-01-24 | MacDermid Enthone Inc. (n.d.Ges.d. Staates Delaware) | Verbessertes Verfahren zur Direktmetallisierung von nicht leitenden Substraten |
| AT523607B1 (de) * | 2020-03-04 | 2021-11-15 | Univ Linz | Verfahren zur Herstellung zumindest einer Leiterbahn |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6610351B2 (en) * | 2000-04-12 | 2003-08-26 | Quantag Systems, Inc. | Raman-active taggants and their recognition |
| US6322620B1 (en) * | 2000-11-16 | 2001-11-27 | National Starch And Chemical Investment Holding Corporation | Conductive ink composition |
| WO2004005413A1 (en) * | 2002-07-03 | 2004-01-15 | Nanopowders Industries Ltd. | Low sintering temperatures conductive nano-inks and a method for producing the same |
| CN1730574B (zh) * | 2005-08-18 | 2011-09-14 | 杨永树 | 辐射硬化型导电油墨以及利用辐射硬化型导电油墨制成导电基材之方法 |
| JP5050249B2 (ja) * | 2005-11-08 | 2012-10-17 | テンプタイム コーポレーション | 組み合わせ型温度露出インジケータ |
| US8067483B2 (en) * | 2006-06-29 | 2011-11-29 | Temptime Corporation | Adjuvant-mediated reactivity enhancement of polymerizable diacetylenic materials |
-
2008
- 2008-06-05 CN CN200810302036XA patent/CN101597440B/zh not_active Expired - Fee Related
- 2008-12-10 US US12/331,481 patent/US20090301763A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571269A (zh) * | 2012-07-30 | 2014-02-12 | 比亚迪股份有限公司 | 油墨组合物、线路板及其制备方法 |
| CN103571269B (zh) * | 2012-07-30 | 2016-08-03 | 比亚迪股份有限公司 | 油墨组合物、线路板及其制备方法 |
| CN104902689A (zh) * | 2014-03-05 | 2015-09-09 | 立诚光电股份有限公司 | 制造线路的方法及具有电路图案的陶瓷基板 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20090301763A1 (en) | 2009-12-10 |
| CN101597440B (zh) | 2011-07-27 |
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