CN1879178A - 固有导电聚合物在非离子水性聚合物中的分散液 - Google Patents
固有导电聚合物在非离子水性聚合物中的分散液 Download PDFInfo
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Abstract
本发明公开了一种固有导电聚合物和非离子水性聚合物的混合物。优选的混合物是木素磺酸接枝的聚苯胺和透气的聚氨酯。该混合物的涂层可用作船用防污涂料；抗静电织物、涂料和包装；电池；导电油墨；导电粘合剂；EMI/RFI屏蔽制品、雷达或微波吸收制品以及感应器。
Description
优先权声明
本申请要求2003年11月14日提交的美国专利临时申请60/520,026(代理案卷号12003025)的优先权。
发明领域
本发明涉及固有导电聚合物在水性聚合物中的分散液。
发明背景
固有导电聚合物早已被发现对各种电活性材料特别有用，如对船用防污涂料；抗静电织物、涂料和包装；电池；导电油墨；导电粘合剂；EMI/RFI屏蔽制品、雷达或微波吸收制品以及感应器。
固有导电聚合物可以是所述涂料的基质。根据成本而优选将固有导电聚合物分散在惰性粘合剂中，所述粘合剂用作涂料的基质或连续相。
发明概述
本领域所需要的是固有导电聚合物在粘合剂中的分散液，所述粘合剂对环境友好、相对价廉、易于施用并具有良好性能。
本发明解决了本领域存在的这个问题，方法是提供固有导电聚合物在非离子水性聚合物，较好是含丙烯酸单体或氨基甲酸酯单体的非离子水性聚合物中的混合物。更好地，非离子聚合物是水性“透气”聚氨酯粘合剂。
本发明使用的聚氨酯粘合剂最好为脂族聚醚水性氨基甲酸酯聚合物，这种聚合物具有高湿气渗透率(MVTR)。
本发明一个方面提供一种包含固有导电聚合物和非离子水性聚合物的可涂布混合物。
本发明的一个特征是所述非离子聚合物不会干扰固有导电聚合物的导电性质。
本发明的一个优点是上述可涂布混合物在常规储存和施用条件下稳定，能够更新固有导电聚合物的导电性质，因为较好的非离子聚氨酯具有高MVTR，能使水分被导电聚合物迅速吸收，这点对具有良好导电性很重要。
考虑到本发明的实施方式时，本发明的其它优点将是显而易见的。
本发明实施方式
固有导电聚合物
适合于本发明的固有导电聚合物包括：具有苯胺、噻吩、吡咯、苯硫醇等重复单体单元的聚合物。其它例子包括选自以下的导电聚合物：取代和未取代的聚对苯撑乙烯、取代和未取代的聚苯胺、取代和未取代的聚吖嗪、取代和未取代的聚噻吩、取代和未取代的聚对亚苯基、取代和未取代的对聚苯硫醚、取代和未取代的聚呋喃、取代和未取代的聚吡咯、取代和未取代的聚硒吩、取代和未取代的聚乙炔以及上述物质的混合物和它们的共聚物。这些导电聚合物披露于各种专利，包括美国专利No.5,069,820(Jen等)；5,160,457(Elsenbaumer)；5,185,100(Han等)；5,281,363(Shacklette等)；5,378,403(Shacklette)；5,422,423(Shacklette等)；5,456,862(Kwan-Yue等)；5,567,355(Wessling等)；5,700,398(Angelopoulos等)和5,911,918(Shacklette等)。如这些专利中所述，固有导电聚合物经常掺杂有酸，如盐酸或对甲苯磺酸。
特别优选的是取代的聚苯胺，如美国专利No.5,968,417(Visawanathan)中揭示的，更优选PolyOne Corporation以Teslart销售的固有导电聚合物。这种取代的聚苯胺是木素磺酸-接枝聚苯胺。
非离子水性聚合物
水性聚合物对本发明有用，因为工业上要求避免有机溶剂。非离子水性聚合物为固有导电聚合物提供了稳定的操作环境。已经发现离子水性聚合物，无论是阳离子还是阴离子，都对固有导电聚合物的电导率产生不利影响。
已知市场可购得的非离子水性聚合物包含具有丙烯酸单体或氨基甲酸酯单体的聚合物。这种类型的聚合物是对各种专门用于涂料工业的添加剂有用的非离子载体。由于这种新的非离子水性聚合物成为易得的材料，本领域技术人员不需经过试验就能决定这种新产物适用于本发明。
聚氨酯
非离子聚氨酯优选用于本发明，尤其是被称作“透气的”聚氨酯，因为这种聚氨酯具有高MVTR性质。
透气聚氨酯包含：(a)聚(环氧烷)侧链单元，其量约为聚氨酯的12-80重量％，其中(i)所述聚(环氧烷)侧链单元中的环氧烷基有2-10个碳原子，并且是未取代的、取代的，或同时有未取代和取代的，(ii)所述环氧烷基的至少约50重量％是环氧乙烷，(iii)侧链单元的量是，(i)当侧链单元分子量小于约600克/摩尔时，至少约30重量％；(ii)当侧链分子量约为600-1,000克/摩尔时，至少约15重量％；(iii)当侧链分子量大于1,000克/摩尔时，至少约12重量％；(b)聚(环氧乙烷)主链单元，其量约小于聚氨酯的25重量％。
这种透气聚氨酯详细披露于美国专利公报20030195293(Lubnin等)。
适用于本发明的聚氨酯的市售产品的非限制性例子包括PermaxTM 200和220氨基甲酸酯乳液，从Noveon Inc.，Brecksville，Ohio购得。另外的资料可在www.noveoncoatings.com查询。
固有导电聚合物和水性聚合物的混合
使用常规混合设备将固有导电聚合物完全混入非离子聚合物乳液。
固有导电聚合物加到该聚合物乳液中的量约为该混合物固体总量的5-50重量％，较好约为10-25重量％。
任选组分
本发明混合物中也可包含通常用于涂料工业的各种组分。这些任选组分的非限制例子包括：增滑剂、防粘连剂、抗氧化剂、紫外线稳定剂、猝灭剂、增塑剂、润滑剂、抗静电剂、阻燃剂、填料(如玻璃纤维、滑石、白垩或粘土)。这些填料中，纳米粘土的性质能增加刚性、韧性以及用于阻燃的炭化性质。这些韧性添加剂在本发明混合物中的含量约为0-80重量％，较好约为0.1-50重量％。该量最好约为混合物的固体总量的1-30总量％。
任何通常用于涂料和漆的着色剂也适合用于本发明。常用的着色剂包括无机颜料如二氧化钛、氧化铁、氧化铬、铬酸铅、炭黑、二氧化硅、滑石、瓷料粘土、金属氧化物、硅酸盐、铬酸盐等，有机颜料如酞青蓝、酞青绿、卡唑紫、蒽素嘧啶黄、黄烷士通黄、二氢异吲哚黄、阴丹酮蓝、喹吖啶酮紫、苝红、重氮精红等。着色剂的量约为混合物固体重量的0-30重量％，较好约为1.5-10重量％。
特别需要的任选组分是非离子增稠剂或抗沉降剂，以促进在最初混合后以及涂布该混合物为较厚的膜时更好地保持固有导电聚合物颗粒在非离子水性聚合物中的分散。市场可购得的增稠剂或流变改性剂是Elementis Specialties ofHightstown，NJ销售的Rheolate牌产品，据信其中一些是非离子缔合的氨基甲酸酯增稠剂。更多资料可在www.elementis-specialties.Com查询。增稠剂的量约为混合物固体重量的0-5重量％，较好约为1-3重量％。
本发明的用途
本发明的混合物也具有美国专利公报20030195293(Lubnin等)中揭示的透气氨酯聚合物的所有优点和用途。但是固有导电聚合物组分增加了使混合物具有电活性并能用作电子转移剂的那些性质。
采用四点探针测试(ASTMD-257-99)，表面电阻率约为1.00×103-1.00×1012Ω/sq.。
制备的可涂布混合物约含30％固体，Brookfield粘度约为125厘泊。这种粘度允许通过喷涂、刷涂、辊涂、刮涂或其它施涂方式将混合物施用在基材上。
因此，本发明混合物对各种电活性材料特别有用，如对船用防污涂料；抗静电织物、涂料和包装；电池；导电油墨；导电粘合剂；EMI/RFI屏蔽制品、雷达或微波吸收制品以及感应器。
虽然不受具体理论的限制，但是可以认为本发明中使用的水性聚合物的非离子性质抑制了混合物的凝结，否则，由于固有导电聚合物呈酸性，混合物中存在的质子必定引起混合物凝结。此外，据认为市售Permax TM聚氨酯材料的高MVTR促进了固有导电聚合物从环境迅速再吸水，这点对本发明混合物涂布在表面并干燥后，固有导电聚合物良好的电导率很重要。
由下面的实施例进一步说明实施方式。
实施例
表1列出实施例1-5以及比较例A中所用的组分。
表1
组分来源
| 组分名称 | 用途 | 牌子 | 通用名 | 来源 | 来源地点 |
| Bayhydrol 110 | 聚合物粘合剂 | Bayhydrol | 离子水性聚氨酯分散液 | Bayer | Pittsburgh，PA |
| Permax 220 | 聚合物粘合剂 | Permax | 非离子水性聚氨酯分散液 | Noveon | Brecksville，OH |
| TeslartTMWet Cake | 导电填料 | TeslartTM | 接枝到木素磺酸的聚苯胺 | PolyOne Corp. | Avon Lake，OH |
| Rheolate300 | 增稠剂抗沉降剂 | Rheolate | 非离子增稠剂 | ElementisSpecialties | Highstown，NJ |
表2列出了本发明实施例1-5的混合物、比较例A的混合物的组成、制备方法和产生的性质，比较例A使用没有高MVTR的聚氨酯。
表2
| 组成、制备和性质 | ||||||
| 组分(％) | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例A |
| Bayhydrol 110 | 0 | 0 | 0 | 0 | 0 | 89.0 |
| Permax 220 | 89.0 | 87.2 | 78.8 | 71.8 | 66.0 | 0 |
| TeslartTM湿饼(28.5％固体) | 11.0 | 10.7 | 19.3 | 26.5 | 32.4 | 11.0 |
| Rhcolate Rheolate300 | 0 | 2.1 | 1.9 | 1.7 | 1.6 | 0 |
| 制备 | ||||||
| 混合设备 | Marine Prop | Marine Prop | Marine Prop | Marine Prop | Marine Prop | Marine Prop |
| 混合温度 | 室温 | 室温 | 室温 | 室温 | 室温 | 室温 |
| 混合速度(RPM) | 200-500 | 200-500 | 200-500 | 200-500 | 200-500 | 200-500 |
| 组分添加顺序 | Permax &Teslart，充分混合 | Permax &Teslart，充分混合，然后Rheolate | Permax &Teslart，充分混合，然后Rheolate | Permax &Teslart，充分混合，然后Rheolate | Permax &Teslart，充分混合，然后Rheolate | Bayhydrol& Teslart，充分混合 |
| 混合后产物的形式 | 分散体 | 分散体 | 分散体 | 分散体 | 分散体 | 分散体 |
| 性质 | ||||||
| 室温凝结时间(天) | ＞90 | ＞90 | ＞90 | ＞90 | ＞90 | ＜1 |
| 表面电阻率(ASTM D257-99)欧姆/平方(2密耳厚(0.05mm)干燥，24小时@50％RH) | 不能测定-太多沉降 | 9*10E10 | 3*10E5 | 3*10E5 | 2*10E5 | 不能测定-分散体凝结 |
表2显示，使用非离子聚氨酯的实施例1-5在1天内都不凝结，而比较例A凝结。实施例3-5在表面电阻方面性能好于实施例2，表明本发明混合物宜存在增稠剂或抗沉降剂。表面电阻随固有导电聚合物量的增加而下降，如实施例5所示，其表面电阻小于实施例3。
本发明不限于声明的实施方式。
Claims (11)
1.一种可涂布的混合物，包含：
固有导电聚合物，
非离子水性聚合物。
2.如权利要求1所述的混合物，其特征在于，固有导电聚合物是聚苯胺。
3.如权利要求2所述的混合物，其特征在于，固有导电聚合物是木素磺酸接枝的聚苯胺。
4.如权利要求1所述的混合物，其特征在于，非离子水性聚合物选自丙烯酸类聚合物和氨基甲酸酯聚合物。
5.如权利要求4所述的混合物，其特征在于，氨基甲酸酯聚合物是脂族聚醚聚氨酯。
6.如权利要求5所述的混合物，其特征在于，聚氨酯具有高MVTR。
7.如权利要求1所述的混合物，该混合物还包含非离子增稠剂。
8.如权利要求1所述的混合物，该混合物还包含非离子抗沉降剂。
9.一种如权利要求1所述混合物的涂料。
10.一种制品，它通过涂敷权利要求9所述的混合物来保护。
11.一种使用权利要求1所述的可涂布混合物的方法，该方法包括将所述混合物施涂在制品上。
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| US52002603P | 2003-11-14 | 2003-11-14 | |
| US60/520,026 | 2003-11-14 |
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| Country | Link |
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| CN (1) | CN1879178A (zh) |
| WO (1) | WO2005050672A1 (zh) |
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| KR100757425B1 (ko) * | 2005-09-30 | 2007-09-11 | 엘지전자 주식회사 | 오프셋 인쇄용 잉크와 오프셋 인쇄기 및 오프셋 인쇄용잉크로 인쇄된 구성 소자를 구비한 플라즈마 디스플레이패널 |
| GB0905312D0 (en) | 2009-03-27 | 2009-05-13 | Qinetiq Ltd | Electromagnetic field absorbing composition |
| TWI485210B (zh) | 2011-12-09 | 2015-05-21 | Ind Tech Res Inst | 具有導電性與鐵磁性之複合材料及其混成漿料 |
| CN114375319B (zh) * | 2019-10-07 | 2024-01-05 | 伊英克公司 | 包含聚氨酯和阳离子掺杂物的粘合剂组合物 |
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| US4183836A (en) * | 1978-02-06 | 1980-01-15 | E. I. Du Pont De Nemours And Company | Aqueous polyurethane dispersions |
| JPS6172071A (ja) * | 1984-09-17 | 1986-04-14 | Yuuhoo Chem Kk | 被覆剤組成物 |
| US5068060A (en) * | 1986-08-07 | 1991-11-26 | Allied-Signal Inc. | Neutral and electrically conductive poly(heterocyclic vinylenes) and processes for preparing same |
| US5314942A (en) * | 1987-09-14 | 1994-05-24 | Ici Americas, Inc. | Aqueous dispersions |
| GB2209758B (en) * | 1987-09-14 | 1990-12-12 | Ici America Inc | Aqueous dispersions |
| US5017673A (en) * | 1989-10-12 | 1991-05-21 | Basf Corporation | Nonionically stabilized polyester urethane resin for water-borne coating compositions |
| US5217649A (en) * | 1991-01-31 | 1993-06-08 | Americhem, Inc. | Electrically conductive blends of intrinsically conductive polymers and thermoplastic polymers containing sulfonamide plasticizer and acidic surfactant |
| JPH0826231B2 (ja) * | 1991-08-16 | 1996-03-13 | インターナショナル・ビジネス・マシーンズ・コーポレイション | 導電性ポリマー材料及びその使用 |
| US5783111A (en) * | 1993-09-03 | 1998-07-21 | Uniax Corporation | Electrically conducting compositions |
| US5556518A (en) * | 1995-02-21 | 1996-09-17 | Kinlen; Patrick J. | Electrocoating compositions and methods therefor |
| US5629050A (en) * | 1995-08-30 | 1997-05-13 | The Dow Chemical Company | Process for preparing coated articles |
| US5821294A (en) * | 1996-08-30 | 1998-10-13 | National Starch And Chemical Investment Holding Corporation | Water-based laminating adhesives |
| US5968417A (en) * | 1997-03-03 | 1999-10-19 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Conducting compositions of matter |
| US6017997A (en) * | 1997-10-31 | 2000-01-25 | The B. F. Goodrich Company | Waterborne polyurethane having film properties comparable to rubber |
| US6627117B2 (en) * | 1998-06-09 | 2003-09-30 | Geotech Chemical Company, Llc | Method for applying a coating that acts as an electrolytic barrier and a cathodic corrosion prevention system |
| EP1065738A1 (en) * | 1999-06-28 | 2001-01-03 | Samhwa Paints Ind. Co., Ltd. | Coating material for shielding electromagnetic waves |
| US6596899B1 (en) * | 2000-02-16 | 2003-07-22 | Noveon Ip Holdings Corp. | S,S′BIS-(α, α′-DISUBSTITUTED-α″-ACETIC ACID)- TRITHIOCARBONATES AND DERIVATIVES AS INITIATOR-CHAIN TRANSFER AGENT-TERMINATOR FOR CONTROLLED RADICAL POLYMERIZATIONS AND THE PROCESS FOR MAKING THE SAME |
| US6384131B1 (en) * | 2000-05-01 | 2002-05-07 | The Sherwin-Williams Company | Waterborne basecoat compositions for use in basecoat/clearcoat applications |
| US6972098B1 (en) * | 2000-07-11 | 2005-12-06 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Corrosion prevention of cold rolled steel using water dispersible lignosulfonic acid doped polyaniline |
| US6897281B2 (en) * | 2002-04-05 | 2005-05-24 | Noveon Ip Holdings Corp. | Breathable polyurethanes, blends, and articles |
| EP1388345A1 (en) * | 2002-08-09 | 2004-02-11 | The Procter & Gamble Company | Polymeric compositions with enhanced vapour permeability and washability |
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- 2004-11-10 CN CNA2004800334539A patent/CN1879178A/zh active Pending
- 2004-11-10 US US10/595,692 patent/US20070051928A1/en not_active Abandoned
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| US20070051928A1 (en) | 2007-03-08 |
| WO2005050672A1 (en) | 2005-06-02 |
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