CN1438656A - 高电导率的透明聚噻吩层 - Google Patents
高电导率的透明聚噻吩层 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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Abstract
一种制备比电导率至少为500S/cm的透明导电层的方法,该方法是通过化学氧化法使一种噻吩或多种噻吩的混合物进行聚合,其中所用的氧化剂是脂环族磺酸的铁(III)盐,用这种方法制备的导电层及其应用。
Description
技术领域
本发明涉及一种透明导电层的制备方法,该导电层的电导率至少为500S/cm,还涉及相应的导电层及其应用。
背景技术
聚噻吩层是已知的,用电化学或化学方法氧化合适的噻吩制备聚噻吩层以及其用于不导电或导电性差的基质的抗静电精加工也是已知的。
EP 206 133 A1描述了将导电聚合杂环化合物层应用于不导电或导电性差的基质的方法,该化合物是使用氧化剂制备的。按照EP 206133 A1可以制备的聚合物的电导率最大值是100S/cm。
EP 253 594 A2特别描述了3-位和/或4-位被烷基和/或烷氧基选择性取代的噻吩,以及用化学或电化学氧化得到的导电聚合物。EP 253594 A2中描述的通过化学方法氧化制备的聚合物和共聚物的电导率最高仅达到0.05S/cm。如果这种聚合物和共聚物是用电化学方法氧化制备的,则其电导率可高达1050S/cm。然而,电化学法氧化的缺点是所需的装置使电化学法氧化过程明显比化学法氧化过程更复杂。另外,电化学法氧化得到的聚合物基本上是不溶解的,这极大地限制了此种聚合物的潜在应用。电化学法氧化一般仅能形成层厚最大约200nm的均匀聚合物薄膜,超过此数值时,其机械强度低且十分粗糙。
US-A-4,521,589描述了在惰性有机溶剂中,在镍化合物存在下,使3-烷基-2,5-二卤代噻吩与镁反应来制备聚3-烷基噻吩的方法。这种方法得到的聚噻吩的电导率为9×10-14S/cm。通过与碘反应,电导率可提高到约0.5S/cm。
EP 203 438 A1和EP 257 573 A1描述了制备可溶于有机溶剂的有取代的导电聚噻吩的方法及将这种可溶的聚噻吩溶液用于不导电或导电性差的基质的抗静电精加工的用途。EP 203 438 A1中所述的聚噻吩的电导率优选大于10-2S/cm,但只有通过在聚合物中掺杂电子给体,例如碘,才可能达到上述的电导率。即使掺杂后,所述最大电导率仅达到15S/cm。按照EP 257 573 A1,使用电化学法聚合可制备电导率高达100S/cm的聚噻吩。
EP 339 340 A2描述了3,4-取代的聚噻吩,其制备是将相应的噻吩氧化聚合。所用氧化剂包括有机酸的铁(III)盐和含有有机基团的无机酸的铁(III)盐。例如可以提及C1-C20-烷基磺酸的铁(III)盐和芳族磺酸的铁(III)盐。用此种聚噻吩制备的层的电导率仅为0.01-10S/cm。同样,如果不用化学方法氧化,而用电化学方法氧化,则电导率可升至200S/cm。但其缺点已在上文中描述了。
EP 820 076 A2描述了含有固体电解质的电容器,其电解质包括导电聚合物。固体电解质由吡咯、噻吩、呋喃、苯胺或其衍生物的聚合物组成,还掺杂了聚磺酸、带羟基或羧基的有机磺酸、脂环磺酸或苯醌磺酸。EP 820 076 A2描述了将具有很大表面积且可散射光的钽箔进行浸渍的方法。因此,EP 820 076 A2描述的固体电解质不是透明的,而是不透明的。EP 820 076 A2中没有说明所述固体电解质的具体电导率。根据EP 820 076 A2,对于聚合物层用作固体电解质而言,聚合物层的电导率为10-100S/cm就足够了。没有具体地说明更高电导率聚合物层的制备方法。
然而,很多应用场合需要特别高的电导率,因此本发明的目的是提供具有很高电导率的导电层,另外,这种导电层的特征还在于具有高透明度。
令人惊奇的是,使用由适当的噻吩通过化学氧化制备的聚合物可以生产出透明的、具有特别高电导率的导电层,所用氧化剂为脂环族磺酸的铁(III)盐。
发明内容
R1和R2相互独立,是任选取代的含有1至10个碳原子的直链或支化的烷基、芳基、烷基芳基或杂环基团,
或R1和R2结合在一起成为直链或支化的、取代或未取代的1至18个碳原子的亚烷基,
其中采用化学氧化法进行聚合,且所用的氧化剂是脂环族磺酸的铁(III)盐。
R1和R2相互独立,优选是含1至6个碳原子的直链或支化的烷基、C6-C10-芳基或C1-C6-烷基-C6-C10-芳基,或R1和R2结合在一起成为直链的、含1至10个碳原子的任选取代的亚烷基。
本发明还涉及用此种方法得到的导电层及其应用。
本发明的方法优选使用通式(II)的化合物来进行其中
R3是-(CH2)m-CR4R5-(CH2)n-,其中
R4和R5相同和不同,是氢、含1至18个碳原子的直链或支化烷基、OH、O-CH2-CH2-CH2-SO3H或含1-18个碳原子的O-烷基,并且
n和m相互独立,各为0-9的整数,且n+m≤9。
R4和R5相互独立,优选为氢、含1至6个碳原子的直链烷基、OH、O-CH2-CH2-CH2-SO3H或含1-6个碳原子的O-烷基。R4和R5特别优选氢。
可用于本发明方法的化合物的实例有二甲氧基噻吩、二乙氧基噻吩、二丙氧基噻吩、二丁氧基噻吩、亚甲二氧基噻吩、亚乙二氧基噻吩、亚丙二氧基噻吩、亚丁二氧基噻吩、如US-A-5,111,327中描述的被羟基或烷氧基取代的噻吩、带有CH2-O-(CH2)n-SO3H基团的噻吩,其中n为2至10的整数、以及被烷基取代,优选被C1-C10-烷基取代的亚乙二氧基噻吩。
可用于本发明方法的铁(III)盐是脂环族磺酸的铁(III)盐。该铁(III)盐的磺酸部分是含有一个4至20个碳原子的脂环和一个或多个磺酸基团的磺酸。
可用于本发明方法的脂环族磺酸的实例是环己烷磺酸、甲基环己烷磺酸、环庚烷磺酸、樟脑磺酸和例如可通过芳族磺酸加氢制备的磺酸。
本发明的方法优选用樟脑磺酸的铁(III)盐,可以使用(+)-樟脑磺酸铁(III)、(-)-樟脑磺酸铁(III)、(+)-樟脑磺酸铁(III)和(-)-樟脑磺酸铁(III)的外消旋体、或任何所需的(+)-樟脑磺酸铁(III)与(-)-樟脑磺酸铁(III)的混合物。
不必添加其它氧化剂和/或掺杂剂,并且优选避免使用这些物质。
实施本发明的方法可得到导电的透明层,其含有聚合物链中带正电荷和抵消这些电荷的反离子的聚噻吩。可用式(III)对本发明方法制备的层中所存在的聚合物进行简化的和图示的方式加以说明。其中
R1和R2的定义如上,
X-是本发明方法所用脂环族磺酸的铁(III)盐对应的磺酸离子,
n的平均值为1至20,m的平均值为2至10,000。
用化学氧化法使式I和II的噻吩进行氧化聚合的反应,依所要求的反应时间不同,通常可在-10至+250℃的温度下,优选温度为0至200℃的温度进行。
在反应条件下将惰性有机溶剂不断加入到要用的噻吩中,得到一种可施涂到基片上的涂布溶液。可提及的惰性有机溶液的实例,尤其是:脂肪族醇,如甲醇、乙醇和丙醇;脂肪族酮,如丙酮和丁酮;脂肪族羧酸酯,如乙酸乙酯和乙酸丁酯;芳香烃,如甲苯和二甲苯;脂肪族烃,如己烷、庚烷和环己烷;氯代烃,如二氯甲烷和二氯乙烷;脂肪族腈,如乙腈;脂肪族亚砜和砜,如二甲基亚砜和环丁砜;脂肪族酰胺,如二甲基乙酰胺、二甲基甲酰胺和N-甲基吡咯烷酮;脂肪族和芳脂族醚,如二乙基醚和苯甲醚。使用的溶剂还可以是水或水和上述有机溶剂的混合物,只要后者与水是互溶的。
式I和II的噻吩进行氧化聚合,理论上每摩尔噻吩需要2.25当量的氧化剂(参见如J.Polym.Sc.Part A,Polymer Chemistry Vol.26,p.1287(1988))。而实际上,使用的氧化剂有一定的过量,例如每摩尔噻吩过量0.1至2当量。
可以通过噻吩和氧化剂的结合使用或分开使用制备透明导电层。对于分开使用,欲被涂布的基质首先用氧化剂溶液处理,然后再用噻吩溶液处理。如果是噻吩和氧化剂结合使用,则欲被涂布的基质一般仅用含噻吩和氧化剂的溶液涂布。由于在结合使用时,一部分噻吩蒸发了,因此相应于预计的噻吩损失量,可以减少向溶液中加入的氧化剂的量。
在生产涂层之前,涂布溶液中可以加入粘合剂和/或交联剂,例如聚氨基甲酸酯、聚丙烯酸酯、聚烯烃、如3-环氧丙氧丙基三烷氧基硅烷之类的环氧硅烷。另外,为了提高涂层的抗刮痕性,可以添加硅烷或硅烷的水解产物,例如基于四乙氧基硅烷的硅烷或硅烷的水解产物。
涂布到待涂布基质上的涂布溶液优选含1-30重量%相应于式I和/或II的噻吩和0-30%重量的粘合剂,两者的重量百分数均基于溶液的总重量。可使用常用的方法,如喷涂、刮涂、旋涂、刷涂或印刷等方法将涂布溶液涂布于基质上。
施涂涂布溶液之后,只需在室温下蒸发即可除去溶剂。而为了获得相对较高的加工速度,有利的方法是提高除去溶剂的温度,例如在20-250℃的温度下除去溶剂,优选在40-200℃的温度下除去溶剂。
在升高的温度下除去溶剂是有益的,因为已经发现可通过在50-250℃,优选100-200℃对涂层进行热处理来提高本发明的层的电导率。此热处理可以在除去溶剂后立即进行,也可以在制备涂层后间隔一段时间再进行。
溶剂除去(干燥)后,最好洗去涂层中过量的氧化剂。为此可使用水,其可任选地与有机磺酸或低级醇,例如甲醇和乙醇混合。
可用本发明方法涂布的基质尤其是,由玻璃、二氧化硅和陶瓷材料制成的无机透明基质,由有机塑料制成的片状透明基质,例如由聚碳酸酯、聚酰胺、聚烯烃或聚酯制成的透明薄膜。如果需要,基质可以在实际涂布前涂布促粘附剂,例如硅烷,以便例如产生更好的粘合作用。
根据所要求的涂层的电导率和透明度,所施涂的涂层干燥后的厚度一般可为0.01至100μm。
可用本发明的方法制备的透明导电层具有至少500S/cm的比电导率,优选至少1000S/cm的比电导率。通过轮廓仪测定的层厚和表面电阻(2×2cm测定条,用商业上可购得的电阻仪测定电阻),或使用商业上可购得的四点测定仪测定比电导率。
膜层具有很高的透光度。透光度优选至少50%,特别优选至少75%。这里透光度是用商业上可购得的UV-VIS分光计在可见光区(300-800nm)用透射方法测定的,结果是至少三个独立值的算数平均值。
本发明还涉及用本发明的方法得到的透明导电层。
本发明的导电透明层适用于,例如包装电子元件的塑料膜和用于无尘室包装的塑料膜的精加工,阴极射线管的抗静电加工,照相软片、透明加热体、透明电极、电路板或可电上色的窗格玻璃的抗静电加工。
实施例
比电导率的确定是通过测定层厚(轮廓仪)和表面电阻(2×2cm测定条,用商业上可购得的电阻仪测定电阻),或使用商业上可购得的四点测定仪测定的。
实施例1
0.25g 3,4,-亚乙二氧基-噻吩(1.76mmol)和5.0g(13.3mmol)54重量%樟脑磺酸铁(III)盐的丁醇溶液相互溶解,其借助于商业上可购得的旋涂仪,以不同旋转速度施涂到玻璃板上。在室温下将带涂层的玻璃板干燥,然后在80℃下调节1小时。冷却后,用水冲洗该玻璃板并将其干燥。表1列出了涂层厚度和比电导率。
表1
转速 | 比电导率(S/cm) | 涂层厚度(nm) |
1500 | 1035 | 420 |
2000 | 1276 | 340 |
对比例1
0.25g亚乙二氧基噻吩(1.76mmol)和5.0g(3.80mmol)40重量%p-甲苯磺酸铁(III)的丁醇溶液相互溶解,其借助于商业上可购得的旋涂仪,以不同旋转速度施涂到玻璃板上。在室温下将带涂层的玻璃板干燥,然后在80℃下调节1小时。冷却后,用水冲洗该玻璃板并将其干燥。表2列出了涂层厚度和比电导率。
表2
转速 | 比电导率(S/cm) | 涂层厚度(nm) |
500 | 119 | 380 |
1000 | 122 | 240 |
对比例2
0.25g亚乙二氧基噻吩(1.76mmol)和5.0g(3.80mmol)的43.6重量%苯酚-4-磺酸铁(III)的丁醇溶液相互溶解,其借助于商业上可购得的旋涂仪,以不同旋转速度施涂到玻璃板上。在室温下将带涂层的玻璃板干燥,然后在80℃下调节1小时。冷却后,用水冲洗该玻璃板并将其干燥。表3列出了涂层厚度和比电导率。
表3
转速 | 比电导率(S/cm) | 涂层厚度(nm) |
500 | 2.5 | 1300 |
对比例3
0.25g亚乙二氧基噻吩(1.76mmol)和5.0g(3.80mmol)的25.9重量%甲磺酸铁(III)的丁醇溶液相互溶解,其借助于商业上可购得的旋涂仪,以不同旋转速度施涂到玻璃板上。在室温下将带涂层的玻璃板干燥,然后在80℃下调节1小时。冷却后,用水冲洗该玻璃板并将其干燥。表4列出了涂层厚度和比电导率。
表4
转速 | 比电导率(S/cm) | 涂层厚度(nm) |
500 | 102 | 1300 |
Claims (8)
3.按照权利要求1和2的制备透明导电层的方法,其特征在于所使用的噻吩是3,4-亚乙二氧基噻吩。
4.按照权利要求1至3的制备透明导电层的方法,其特征在于所使用的铁(III)盐是樟脑磺酸铁(III)盐。
5.按照权利要求1至4的制备透明导电层的方法,其特征在于导电层的透光率至少为50%。
6.按照权利要求1至5的制备透明导电层的方法,其特征在于透明导电层的比电导率至少为1000S/cm。
7.用权利要求1至6中的至少一种方法制备的导电层。
8.权利要求7的导电层在包装电子元件用塑料膜和无尘室包装用塑料膜的精加工,阴极射线管的抗静电加工,照相软片、透明加热体、透明电极、电路板或可电上色窗格玻璃的抗静电加工中的用途。
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CN1974628B (zh) * | 2006-11-22 | 2010-12-08 | 天津大学 | 聚乙撑二氧噻吩纳米棒的化学制备方法 |
CN102282017A (zh) * | 2009-01-16 | 2011-12-14 | Skc株式会社 | 使用导电聚合物的组合物的层和结构 |
CN102321343A (zh) * | 2011-08-30 | 2012-01-18 | 固安福爱电子有限公司 | 导电高分子材料及包括其的电容器 |
CN106297968A (zh) * | 2016-08-26 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | 一种高膜厚高电导率的pedot薄膜及其制备方法 |
CN112980299A (zh) * | 2019-12-13 | 2021-06-18 | 富士胶片商业创新有限公司 | 金属光泽膜形成用组合物、金属光泽膜及物品 |
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AT500289A1 (de) * | 2003-12-29 | 2005-11-15 | Hueck Folien Gmbh | Substrate mit elektrisch leitfähigen schichten für technische anwendungen |
DE102004012319A1 (de) * | 2004-03-11 | 2005-09-22 | H.C. Starck Gmbh | Funktionsschichten für optische Anwendungen auf Basis von Polythiophenen |
JP4852526B2 (ja) * | 2005-02-07 | 2012-01-11 | 帝人デュポンフィルム株式会社 | 導電性積層フィルム |
JP4896637B2 (ja) | 2006-09-05 | 2012-03-14 | 帝人デュポンフィルム株式会社 | 導電性フィルム |
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CN1974628B (zh) * | 2006-11-22 | 2010-12-08 | 天津大学 | 聚乙撑二氧噻吩纳米棒的化学制备方法 |
CN102282017A (zh) * | 2009-01-16 | 2011-12-14 | Skc株式会社 | 使用导电聚合物的组合物的层和结构 |
CN102321343A (zh) * | 2011-08-30 | 2012-01-18 | 固安福爱电子有限公司 | 导电高分子材料及包括其的电容器 |
CN106297968A (zh) * | 2016-08-26 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | 一种高膜厚高电导率的pedot薄膜及其制备方法 |
CN112980299A (zh) * | 2019-12-13 | 2021-06-18 | 富士胶片商业创新有限公司 | 金属光泽膜形成用组合物、金属光泽膜及物品 |
US11708450B2 (en) | 2019-12-13 | 2023-07-25 | Fujifilm Business Innovation Corp. | Composition for forming metallic luster film, metallic luster film, and article |
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US20030161941A1 (en) | 2003-08-28 |
DE10206294A1 (de) | 2003-08-28 |
TW200307954A (en) | 2003-12-16 |
JP2003286336A (ja) | 2003-10-10 |
IL154435A0 (en) | 2003-09-17 |
EP1338617A2 (de) | 2003-08-27 |
KR20030069082A (ko) | 2003-08-25 |
EP1338617A3 (de) | 2003-11-05 |
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