CN1274869A - 导电聚合物层印制图案的方法 - Google Patents
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Abstract
一种用衬底上的导电高聚物制作电极图案的方法,该方法包括以下步骤:－涂敷含有10—5000mg/m2导电高聚物的聚合物层,以制备导电层,并且－使用一种含氧化剂的印刷溶液在所述层上印制电极图案,该氧化剂选自ClO－,BrO－,MnO4 －,Cr2O7 －－,S2O8 －－,和H2O2。
Description
本发明涉及本身导电的高聚物。尤其是，此类聚合物层的图案印制，以在所述聚合物层上形成电极。
在柔性LC(液晶)显示器、场致发光装置等产品的制造技术中，采用由本身导电的高聚物如聚乙炔，聚吡咯，聚苯胺，聚噻吩等制造的透明电极替代透明ITO(indium-tinoxide)(铟-锡氧化物)电极，这在本领域是公知的。其优点主要在于导电高聚物制成的电极比ITO电极要柔韧得多且脆性小，因此尤其在需要高柔性电极的接触屏的制造上，装置的使用寿命会延长。
已发现不同的方法来制作本身导电的高聚物电极线路(tracks of electrodes)。在WO-A-97 18944中，将一导电高分子的连续层涂敷于衬底上，将一掩膜应用于所述层上并且刻蚀未遮盖部分。洗去掩膜后即制得电极图案。在US-A-5 561 030中图案是形成于尚不能导电的预聚物连续层上并且洗去掩膜后，残余的预聚物因氧化而具有导电性，除此之外采用同样的步骤制作图案。
在US-A-4 699 804中公开了用一种聚合催化剂描绘图案于衬底上，并且在图案上应用一种可聚合化合物。在聚合催化剂和可聚合化合物之间反应后形成导电高分子图案。
以上所述的方法使用典型PCB生产所用的某种平板印刷术和刻蚀的方法，并且要进行多个步骤。因此有必要采用简单的方法，只需要较少步骤即可制得带有电极图案的衬底。
本发明的目的在于提供一种在衬底上制备电极线路的方法，所述衬底上的电极采用本身导电的高聚物仅通过少数加工步骤制得。
本发明的另一目的还在于提供一种在衬底上制备电极线路的方法，所述电极由本身导电的高聚物制得，电极上所述线路通过数字式印刷手段形成。
本发明更进一步的目的和本发明的优点通过以下描述将变得更清楚。
本发明的目的是通过提供一种用衬底上的导电高聚物制作电极图案的方法而实现，该方法包括：
—在衬底上涂敷含有10-5000mg/m2导电高聚物的聚合物层，以制备导电层，并且
—使用一种含氧化剂的印刷溶液在所述层上印制电极图案，该氧化剂选自ClO-，BrO-，MnO4 -，Cr2O7 --，S2O8 --，和H2O2。
已经发现，由导电高聚物形成电极于衬底上的电极图案，能通过涂敷一导电高分子层于衬底上然后在所述层上使用一种含有氧化剂的印刷溶液而制得。已经发现通过涂刷一种含有氧化剂的溶液，能够使聚合层的导电性以103-1011的因数改变(减低)而无需改变层片的厚度。这是有利的，尤其电极图案被用于显示器，如LDC’s，因为它可以使用很少量的间隔粒子。
优选使用一种选自ClO-，BrO-，MnO4 -，Cr2O7 --，S2O8 --，和H2O2的氧化剂。更优选使用ClO-或MnO4 -作为氧化剂。使用MnO4 -的优点在于对导电高聚物导电性的影响作用处于3-10的pH范围，几乎与含有MnO4 -离子的印刷溶液pH值无关，因此在印刷溶液的使用寿命(ageing)方面不存在问题。使用ClO-作为氧化剂其优点在于可以使用低浓度印刷溶液，或者印刷溶液浓度相当高，只须使用很少量的印刷溶液，因而避免了印刷溶液的干燥和铺层(spreading)问题，这使得印刷窄至5μm的线路成为可能。因此，最优选使用ClO-。
印刷可采用胶版印刷，丝网印刷或喷墨印刷的方法来进行。
使用低浓度ClO-氧化剂的印刷溶液，可以制备一种油墨，该油墨具有足够的氧化强度以改变导电层的导电性，但是其腐蚀性也不会太强以致于在喷墨印刷装置中不能使用。使用喷墨印刷装置，其优点在于无须丝网，电极线路图(electrode layout)可以由计算机直接印刷到导电层上。
为了调整溶液粘度，可加入增稠剂，增稠剂选自硅石、硅酸盐、粘土、合成粘土，如商标名为LAPONITE的粘土，和高分子增稠剂。
为便于印刷，印刷溶液还可包括表面活性剂。
虽然图案印刷可以使用含任何本领域公知的本身导电高聚物如聚乙炔，聚吡咯，聚苯胺，聚噻吩等的层片，但是优选使用通过涂敷一种混合物制备的层片，该混合物包括(a)一种下述通式表示的聚噻吩
其中，R1和R2分别表示氢原子或C1-C4的烷基，或者一起表示任选取代的C1-C4的亚烷基或亚环烷基，优选亚乙基，任选烷基取代的亚甲基，任选C1-C12烷基或苯基取代的1，2-亚乙基，1，3-亚丙基或1，2-亚环己基，
(b)一种多阴离子化合物和
(c)一种有机化合物，含有2个或更多个羟基(OH)和/或羧基(COOH)或酰胺基或内酰胺基。在EP-A-686 662中已描述了此类层片。
可以在层片上进行图案印刷，层片含有聚亚乙基二氧噻吩和聚苯乙烯磺酸，其中存在10-5000mg/m2聚噻吩，优选使用的层片含有50-1000mg/m2聚噻吩，更优选使用的层片其中含75-500mg/m2聚噻吩。包含导电高聚物并用本发明方法印刷的层片，可具有任意的导电性。本发明方法能够，比如，应用于导电性为1-105S/cm的图案层片。本发明方法印制的导电层片优选具有5-104S/cm的导电性，更优选10-1000S/cm。
实施例
1聚噻吩分散液(PT)(以下简称PT分散液)的制备
a)向14g数均分子量(Mn)为40,000的聚苯乙烯磺酸(218毫摩尔SO3H基团)的1000ml水溶液中加入12.9g过硫酸钾(K2S2O8)，0.1g的Fe2(SO4)3和5.68g的3，4-亚乙基二氧噻吩。由此获得的反应混合物在20℃下搅拌24小时并且进行脱盐处理。
b)将500ml上述制备的反应混合物用500ml水稀释，并且于室温下在一种粒状弱碱性离子交换树脂LEWATIT H 600(Bayer AG的商标名，Leverkusen，德国)和一种强酸性离子交换树脂LEWATIT S 100(Bayer AG的商标名，Leverkusen，德国)存在下搅拌6小时。完成上述处理后，过滤掉离子交换树脂，测量钾离子和硫酸根离子含量，分别为0.4gK+和0.1g(SO4)2-每升。
实施例1
将417ml的PT分散液和50g甲基吡咯烷酮(化合物A)与一种粘合剂(8.5ml(偏二氯乙烯/丙烯酸甲酯/衣康酸88/10/2)共聚物的30％分散液)和一种表面活性剂(0.5ml的FLUORAD，3M的商标名)混合，并将混合物加入1000ml蒸馏水中。
将该混合物涂覆于100μm厚的聚对苯二甲酸乙二酯膜上，该膜上有一底层片(subbing layer)(通常在光学材料的支撑物上)。将混合物以40μm潮湿厚度涂覆，并在35℃下干燥。
干燥的层片含有200mg/m2的聚噻吩。
电阻率(欧姆/平方(Ω/square))用上述方法测量，为680欧姆/平方。
印刷实施例1
使用一种含ClO-的印刷溶液在所述层上用丝网印刷方式印刷图案，从而其中存在25mg/m2的NaClO。印刷后，洗去印刷溶液。印刷的图案其导电性比导电层的导电性要低1011倍。
印刷实施例2
使用一种含有pH＝3的MnO4 -的印刷溶液，在所述层上用丝网印刷方式印刷图案，从而其中存在667mg/m2的KMnO4。印刷后，洗去印刷溶液。印刷的图案其导电性比导电层的导电性要低107倍。
印刷实施例3
使用一种含pH＝10的MnO4 -的印刷溶液，在所述层上用丝网印刷方式印刷图案，从而其中存在667mg/m2的KMnO4。印刷后，洗去印刷溶液。印刷的图案其导电性比导电层的导电性要低107倍。
印刷实施例4
使用一种包含pH＝10的过硫酸铵((NH4)2S2O8)的印刷溶液，在所述层上用丝网印刷方式印刷图案，从而其中存在125mg/m2的过硫酸铵。印刷后，洗去印刷溶液。印刷的图案其导电性比导电层的导电性要低106倍。
印刷实施例5
使用一种包含pH＝2.6的过硫酸铵(NH4)2S2O8)的印刷溶液，在所述层上用丝网印刷方式印刷图案，从而其中存在125mg/m2的过硫酸铵。印刷后，洗去印刷溶液。印刷的图案其导电性比导电层的导电性要低103倍。
印刷实施例6
使用一种包含pH＝2的KIO3的印刷溶液，在所述层上用丝网印刷方式印刷图案，从而其中存在1250mg/m2的KIO3。印刷后，洗去印刷溶液。印刷的图案其导电性比导电层的导电性仅低4倍。因而这种氧化剂在本发明的方法中不适用。
Claims (7)
1、一种用衬底上的导电高聚物制作电极图案的方法，包括以下步骤：
—涂敷含有10-5000mg/m2导电高聚物的聚合物层，以制备导电层，并且
—使用一种含氧化剂的印刷溶液在所述层上印制电极图案，该氧化剂选自ClO-，BrO-，MnO4 -，Cr2O7 --，S2O8 --，和H2O2。
2、如权利要求1所述的方法，其中所述导电层具有1-105S/cm的导电性。
3、如权利要求1或2所述的方法，其中所述导电高聚物具有通式：
其中，R1和R2分别表示氢原子或C1-C4的烷基，或者一起表示任选取代的C1-C4的亚烷基或一种亚环烷基，优选亚乙基，任选烷基取代的亚甲基，任选C1-C12烷基或苯基取代的1，2-亚乙基，1，3-亚丙基或1，2-亚环己基。
4、如权利要求3所述的方法，其中，以含多阴离子化合物的水溶液形式涂敷所述导电高聚物。
5、如权利要求1至4中任一项所述的方法，其中所述印刷以选自平版印刷，丝网印刷和喷墨印刷中的印刷方法进行。
6、如权利要求1至5中任一项所述的方法，其中，实施所述的印刷方法使得涂敷有25-800mg/m2的氧化剂。
7、如权利要求1至6中任一项所述的方法，其中，所述印刷溶液包括一种选自硅石，硅酸盐，粘土，合成粘土和高分子增稠剂的增稠剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP99201645.1 | 1999-05-20 | ||
| EP99201645A EP1054414B1 (en) | 1999-05-20 | 1999-05-20 | Method for patterning a layer of conductive polymer |
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| CN1274869A true CN1274869A (zh) | 2000-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN00119218A Pending CN1274869A (zh) | 1999-05-20 | 2000-05-20 | 导电聚合物层印制图案的方法 |
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| Country | Link |
|---|---|
| EP (1) | EP1054414B1 (zh) |
| JP (1) | JP4553448B2 (zh) |
| KR (1) | KR100623237B1 (zh) |
| CN (1) | CN1274869A (zh) |
| DE (1) | DE69905860T2 (zh) |
| TW (1) | TW552591B (zh) |
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| DE3843412A1 (de) * | 1988-04-22 | 1990-06-28 | Bayer Ag | Neue polythiophene, verfahren zu ihrer herstellung und ihre verwendung |
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| EP0615256B1 (en) * | 1993-03-09 | 1998-09-23 | Koninklijke Philips Electronics N.V. | Method of manufacturing a pattern of an electrically conductive polymer on a substrate surface and method of metallizing such a pattern |
| EP1007349B1 (en) * | 1995-11-22 | 2004-09-29 | THE GOVERNMENT OF THE UNITED STATES OF AMERICA, as represented by THE SECRETARY OF THE NAVY | Patterned conducting polymer surfaces and process for preparing the same and devices containing the same |
-
1999
- 1999-05-20 EP EP99201645A patent/EP1054414B1/en not_active Expired - Lifetime
- 1999-05-20 DE DE69905860T patent/DE69905860T2/de not_active Expired - Lifetime
-
2000
- 2000-05-11 TW TW089108960A patent/TW552591B/zh not_active IP Right Cessation
- 2000-05-17 JP JP2000144729A patent/JP4553448B2/ja not_active Expired - Lifetime
- 2000-05-19 KR KR1020000026889A patent/KR100623237B1/ko active IP Right Grant
- 2000-05-20 CN CN00119218A patent/CN1274869A/zh active Pending
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| CN103772727A (zh) * | 2013-11-08 | 2014-05-07 | 长兴化学工业股份有限公司 | 钝化组合物及其应用 |
| CN103772727B (zh) * | 2013-11-08 | 2016-10-05 | 长兴材料工业股份有限公司 | 钝化组合物及其应用 |
| CN108922656A (zh) * | 2018-06-19 | 2018-11-30 | 九睿海创（深圳）科技有限公司 | 一种导电聚合物薄膜及其图案化制作方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4553448B2 (ja) | 2010-09-29 |
| JP2001035276A (ja) | 2001-02-09 |
| DE69905860T2 (de) | 2003-11-06 |
| TW552591B (en) | 2003-09-11 |
| KR100623237B1 (ko) | 2006-09-11 |
| DE69905860D1 (de) | 2003-04-17 |
| KR20010020856A (ko) | 2001-03-15 |
| EP1054414A1 (en) | 2000-11-22 |
| EP1054414B1 (en) | 2003-03-12 |
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