CN1326561A - 电致变色玻璃元件 - Google Patents
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Abstract
本发明涉及一种尤其用于汽车镜的电致变色玻璃元件,其包含一种掺杂传导离子的基础聚合物(4)作为离子传导层。该电致变色玻璃元件包括,例如玻璃底物(1)和一种层体系包括有电致变色层(2)、镜层(3)、掺杂聚合物膜(4),例如聚苯并咪唑聚合物、质子存储(5)、后电极(6)及聚酯薄膜(7)。该层体系用密封层(8)加以封闭,对玻璃底物(1)上的涂层体系进行密封。
Description
发明领域
本发明涉及一种尤其用于汽车镜的电致变色玻璃元件，其包含一种掺杂传导离子的基础聚合物作为离子传导层。
发明背景
电致变色镜，尤其是用于汽车的，在现有技术中是已知的。这些电致变色镜主要构件是一层电致变色材料。一种材料在电场作用下其光学常数(n，k)发生改变并由此其光学性质发生改变就被称为电致变色。这种电致变色材料的典型实例是WO3及MoO3，在底物上将其涂成薄层时实际上是无色的。通过氧化或还原过程，电致变色层可改变其光学性质。如果质子进入这样的层，对于氧化钨就会有一种还原成蓝色的钨青铜的作用。其着色强度则可通过流入该层电荷量加以确定。
根据现有技术来看，许多尤其是用于机动车辆的电致变色镜现都是已知的，而且在不同分层结构中就有这种类型的电致变色层。
DE 3 008 768描述了一种电致变色镜，它主要由基于玻璃底物上至少一层电致变色层、至少两个电极、至少一层质子传导层及至少一层输送质子及一层存储质子层存在的一种层体系组成。
这类镜的光变性能尤其通过质子传导层的质子传导率来确定。质子传导率越高，其反射变化率也越高。在现有技术的这类镜中，质子传导玻璃板，其经硫酸浸泡，至今已用作为质子传导层(例如德国专利公报2 504 905)或如DE 3 008 768中所谓固体离子传导层。
已经表明，至今所有现有技术所用的用于电致变色玻璃元件这些离子传导层，在离子传导率方面仍然不具有令人满意的结果。而且，目前现有技术的这类镜的不足是，其所描述的离子传导层或者太厚，或者因为其制造方式而太复杂并且太昂贵。
发明综述
因此，本发明目的在于，从如DE 3 008 768所述的电致变色镜出发，提出一种显著改进的实施方案，其特征尤其在于该离子传导层在制造及加工中有利于涂敷，且离子传导率高，并因此可能很快改变电致变色层。
根据本专利权利要求1表征的特点可实现本发明。该子权利要求表明了有利的进一步发展。
因此按照本发明，提出了使用掺杂传导离子的基础聚合物作为离子传导层。已经表明，这些掺杂传导离子的基础聚合物特别适合。这种掺杂传导离子的基础聚合物优选选自聚苯并咪唑(PBI)、聚吡啶、聚咪唑、聚苯并噻唑、聚苯并噁唑、聚喹啉、聚噻唑、聚噁二唑及聚四芘。该离子传导层由此是一层优选传导质子的层。但是，原则上该层也适合其它离子，诸如例如锂。
附图简述
采用图1及图2对本发明更详细地说明于下。
图1说明一种本发明电致变色玻璃元件，这里作为一种汽车镜。
图2说明一种镜的具体结构。
发明详述
用作汽车反射镜的电致变色玻璃元件由厚度2毫米的玻璃底物1组成。将具有以下顺序层的层体系涂敷于该底物1上。
一层厚约700纳米氧化钨的电致变色层2、一层厚约70纳米的钯的镜层3、一层厚30微米的聚苯并咪唑聚合物的聚合物膜4、一层厚700纳米的三氧化钨的质子存储层5、一层厚100纳米的金的后电极6、一层厚约175微米的聚酯薄膜7以及一层传统塑料密封层8，该密封层环绕包住整个包括玻璃底物1的涂层体系并因此密封了包括层2至7的涂层体系。密封层8仅被铜线5断开，其一侧接触镜层3，另一侧接触后电极6，以便对后者施加电压。
图2a及2b表明按照图1的电致变色玻璃元件，但这种类型的玻璃组分的功能在这里变为可见的。在按照图2的示范实施方案中，为促进粘结更好，在电致变色层2和镜层3之间也涂了底胶10。因此，图2a表示了光照部位并且图2b表示了黑暗部位。
对于本发明电致变色玻璃元件特别优选的是，该掺杂传导离子聚合物为聚合物膜型。质子传导聚合物膜微粒是优选的。应该特别强调的是，本发明的离子传导层应易于用所有传统方法进行涂敷。其实例有丝网印刷、浸渍、喷涂、刮涂或者也可涂敷凝胶。
本发明尤其优选的是，该聚合物膜是一种聚苯并咪唑。
尤其应该强调的是，对于本发明电致变色玻璃元件，只要该离子传导层掺杂了酸，特别是一种强酸，该掺杂传导离子层就会有特别好的离子传导性能。优选的是在第一离解阶段25℃时掺杂酸的pKa值≤4.5，优选≤3.5。现已证明，对于酸，如果用磷酸，尤其用多磷酸，会特别有利。在US 5 599 639中描述了对聚苯并咪唑的酸处理，显然这里是用来参考。
对于本发明电致变色玻璃元件，尤其优选的是包含聚苯并咪唑的质子传导聚合物膜。
这种类型的由聚苯并咪唑组成而且是质子传导的聚合物膜，是现有技术中所已知的，如US 5 017 681。所有上述美国专利说明书所命名的聚苯并咪唑，原则上都可用于本发明的质子传导层。尤其优选的是，该聚合物由分子量在1,000和500,000之间的聚苯并咪唑组成，它由下述结构式中的重复单元组成：
现已证明，对于电致变色玻璃元件尤其有利的是使用以上更详细描述的离子传导层，其层厚1微米至1毫米，优选5微米至100微米。涂敷这种层，尤其聚合物膜，可采用丝网印刷、浸渍、喷涂、刮涂乃至如凝胶法实现。因此，按照本发明的规定，这种层或者涂成最后薄膜，或者甚至直接涂在底物上或涂在下面的层上。这些涂敷过程还可结合使用。
这种电致变色层优选包括W03、MoO3、IrO2或其混合氧化物，其优选层厚为300纳米至8,000纳米，优选300纳米至8,000纳米。可采用溅射、溶胶-凝胶或通过蒸汽淀积方法涂敷这种电致变色层。
电极是构成本发明这种层体系所必须的，它优选其层厚为50纳米至10微米的金属层。这类层的实例是那些包含铑、钯、铂或其合金的层。
按照一种优选实施方案，规定金属电极层同时要形成可接受质子的反射层。这种反射层优选包括一层包含铑、钯、铂或其合金的其厚度为30至500纳米的层。
按DE 3 008 768中所述，对于本发明电致变色玻璃元件还优选的是，由离子输送层和离子存储层同时构成一层或一种复合材料。因此，按照本发明的优选实施方案规定，质子存储层同时也是电致变色层。在这种情况下，例如WO3层，因此同时起到氢离子存储层和电致变色层的作用。按照优选实施方案，这种复合材料由薄膜上的质子存储及同时质子输送层组成，优选是一种其具有反电极喷涂金属的聚酯薄膜。玻璃、金属或其它塑料是适合于作为这种复合材料的底物材料，可替代这种聚酯薄膜。
对本发明这种电致变色玻璃元件的可能分层构造变体，可参考DE3 008 768及其中所述分层构造。
但是，对于本发明玻璃元件优选的是由两种层压复合材料构成的玻璃元件。因此，在按照优选实施方案生产这种电致变色玻璃元件中，在玻璃底物上构成第一层体系，其上涂敷一层电致变色层和喷涂金属作为一种反射层。这些层都是用溅射方法产生的。
然后，该层体系的第二部分是一种复合材料，其包括质子存储层、喷涂金属及其上铺设的薄膜，尤其一种聚酯薄膜。这种复合材料按单独工序制造，然后与上述层体系的第一层复合材料结合。这种方法有利于电致变色玻璃元件的有效成本和简化制造。
本发明更有利的实施方案规定，若有必要，在各单层之间可涂敷为了更好粘合的促进粘合层。该实例为铬、钛或甚至硅的氧化物SiOx。对于汽车镜的场合，还规定对这种层体系外部要严密封闭。因此，这种层体系可对其端面和最后层加以密封，即从观察方向看可对玻璃底物反面层提供保护层，例如一层扩散膜。此类扩散膜透水性＜1,000，优选＜100cm3。现已证明，对于汽车镜，只要该玻璃底物是一层减弱反射的其层厚为0.1至3毫米的薄玻璃，会是特别有利的。对于汽车镜，从观察方向看，若将加热镜的透明传导层涂在底物前面也是恰当的。
Claims (22)
1、一种电致变色玻璃元件，尤其用于汽车镜，其在玻璃底物铺有一种层体系，该层体系包含至少一层电致变色层、至少两个电极、至少一层离子传导层、至少一层离子输送层及至少一层离子存储层，其中后面提到的两层也可以是同时形成的一层，其特征在于该离子传导层包含一种掺杂传导离子的基础聚合物。
2、按照权利要求1的电致变色玻璃元件，其特征在于该掺杂传导离子的聚合物选自：聚苯并咪唑即PBI、聚吡啶、聚咪唑、聚苯并噻唑、聚苯并噁唑、聚喹啉、聚噻唑、聚噁二唑及聚四芘。
3、按照权利要求1或2的电致变色玻璃元件，其特征在于该掺杂传导离子的聚合物是一种聚合物膜。
4、按照权利要求3的电致变色玻璃元件，其特征在于该聚合物膜由一种聚苯并咪唑聚合物组成。
5、按照权利要求1-4中至少一项的电致变色玻璃元件，其特征在于该离子传导层用酸掺杂。
6、按照权利要求5的电致变色玻璃元件，其特征在于该层已用磷酸掺杂。
7、按照权利要求1-5中至少一项的电致变色玻璃元件，其特征在于对于第一离解阶段该游离酸25℃时的pKa值≤4.5。
8、按照权利要求1-7中至少一项的电致变色玻璃元件，其特征在于该离子传导层的厚度为1微米至1毫米。
9、按照权利要求1-8中至少一项的电致变色玻璃元件，其特征在于将该离子传导层涂于该底物上，或涂敷于该层体系的不同层上或在其上形成。
10、按照权利要求1-9中至少一项的电致变色玻璃元件，其特征在于该离子传导层是通过丝网印刷、浸渍、刮涂、喷涂或作为一种凝胶加以涂敷或产生的，或通过其一种结合而涂敷或产生的。
11、按照权利要求1-10中至少一项的电致变色玻璃元件，其特征在于该电致变色层是一种由金属氧化物组成的氧化还原层。
12、按照权利要求11的电致变色玻璃元件，其特征在于该电致变色层是一种其层厚为100纳米至3,000纳米的WO3层。
13、按照权利要求1-12中至少一项的电致变色玻璃元件，其特征在于至少一个电极是以其层厚为100纳米至10微米的金属层型设计的。
14、按照权利要求13的电致变色玻璃元件，其特征在于该金属电极层形成一种可同时接受及传导质子的反射层。
15、按照权利要求1-14中至少一项的电致变色玻璃元件，其特征在于该离子输送及离子存储层以复合材料形式存在。
16、按照权利要求15的电致变色玻璃元件，其特征在于该复合材料由一种例如玻璃、金属或塑料的底物，例如一种聚酯薄膜，其上涂敷一种质子存储层，例如一种金属氧化物层所组成的。
17、按照权利要求16的电致变色玻璃元件，其特征在于该复合材料另外具有一层喷涂金属形式的电极层。
18、按照权利要求1-17中至少一项的电致变色玻璃元件，其特征在于从观察方向看，在玻璃底物上依次涂布一层电致变色层、作为反射层的喷涂金属、一种质子传导膜及一种由质子层、喷涂金属及其上铺设的一种薄膜尤其聚酯薄膜组成的复合材料。
19、按照权利要求18的电致变色玻璃元件，其特征在于该层体系是在端面密封的。
20、按照权利要求18或19的电致变色玻璃元件，其特征在于对玻璃底物反面的最后层提供一层保护层。
21、按照权利要求19或20任一项的电致变色玻璃元件，其特征在于用一层减弱反射的其层厚为0.3至3毫米的薄玻璃作为玻璃底物。
22、按照权利要求19-21中任一项的电致变色玻璃元件，其特征在于从观察方向看将加热该镜的一层传导层涂在该底物的前面。
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| DE19851717.3 | 1998-11-10 | ||
| DE19851717A DE19851717A1 (de) | 1998-11-10 | 1998-11-10 | Elektrochrome Glasbaugruppe |
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| CN101322069B (zh) * | 2005-07-01 | 2010-09-22 | Ppg工业俄亥俄公司 | 用于电致变色变换单元的透明电极 |
| CN102323698A (zh) * | 2003-05-06 | 2012-01-18 | 金泰克斯公司 | 车辆后视镜元件及安装有这些元件的组合件 |
| CN1938642B (zh) * | 2004-02-05 | 2012-04-04 | 法国圣戈班玻璃厂 | 具有可部分地变暗的视界的透明窗玻璃和用于控制透明窗玻璃内可以电致变色的方式褪色的表面元件的方法 |
| CN104932168A (zh) * | 2015-06-10 | 2015-09-23 | 电子科技大学 | 一种柔性电致变色器件及其制备方法 |
| CN102323698B (zh) * | 2003-05-06 | 2016-12-14 | 金泰克斯公司 | 车辆后视镜元件及安装有这些元件的组合件 |
| CN110703530A (zh) * | 2019-10-30 | 2020-01-17 | 福耀玻璃工业集团股份有限公司 | 一种具有电加热及电磁屏蔽的电致变色汽车玻璃 |
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- 1999-11-09 JP JP2000581499A patent/JP2002529794A/ja active Pending
- 1999-11-09 AT AT99955960T patent/ATE232989T1/de not_active IP Right Cessation
- 1999-11-09 CZ CZ20011636A patent/CZ20011636A3/cs unknown
- 1999-11-09 CN CN99813125A patent/CN1326561A/zh active Pending
- 1999-11-09 PL PL99348203A patent/PL348203A1/xx unknown
- 1999-11-09 ES ES99955960T patent/ES2192869T3/es not_active Expired - Lifetime
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- 1999-11-09 TR TR2001/01274T patent/TR200101274T2/xx unknown
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- 1999-11-09 KR KR1020017005927A patent/KR20010092729A/ko not_active Application Discontinuation
- 1999-11-09 DE DE69905486T patent/DE69905486T2/de not_active Expired - Lifetime
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| CN102323698A (zh) * | 2003-05-06 | 2012-01-18 | 金泰克斯公司 | 车辆后视镜元件及安装有这些元件的组合件 |
| CN102323698B (zh) * | 2003-05-06 | 2016-12-14 | 金泰克斯公司 | 车辆后视镜元件及安装有这些元件的组合件 |
| CN1938642B (zh) * | 2004-02-05 | 2012-04-04 | 法国圣戈班玻璃厂 | 具有可部分地变暗的视界的透明窗玻璃和用于控制透明窗玻璃内可以电致变色的方式褪色的表面元件的方法 |
| CN100523976C (zh) * | 2005-06-17 | 2009-08-05 | 同济大学 | 一种全固态电致变色器件及其制备方法 |
| CN101322069B (zh) * | 2005-07-01 | 2010-09-22 | Ppg工业俄亥俄公司 | 用于电致变色变换单元的透明电极 |
| CN104932168A (zh) * | 2015-06-10 | 2015-09-23 | 电子科技大学 | 一种柔性电致变色器件及其制备方法 |
| CN104932168B (zh) * | 2015-06-10 | 2017-08-08 | 电子科技大学 | 一种柔性电致变色器件及其制备方法 |
| CN110703530A (zh) * | 2019-10-30 | 2020-01-17 | 福耀玻璃工业集团股份有限公司 | 一种具有电加热及电磁屏蔽的电致变色汽车玻璃 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20012267D0 (no) | 2001-05-08 |
| EP1129387B1 (en) | 2003-02-19 |
| PL348203A1 (en) | 2002-05-06 |
| ZA200103228B (en) | 2002-01-24 |
| ATE232989T1 (de) | 2003-03-15 |
| ES2192869T3 (es) | 2003-10-16 |
| SK5982001A3 (en) | 2001-12-03 |
| KR20010092729A (ko) | 2001-10-26 |
| CZ20011636A3 (cs) | 2001-09-12 |
| AU1269700A (en) | 2000-05-29 |
| EP1129387A1 (en) | 2001-09-05 |
| TR200101274T2 (tr) | 2001-10-22 |
| BR9915189A (pt) | 2001-10-30 |
| NO20012267L (no) | 2001-07-10 |
| JP2002529794A (ja) | 2002-09-10 |
| WO2000028374A1 (en) | 2000-05-18 |
| CA2350144A1 (en) | 2000-05-18 |
| DE69905486D1 (de) | 2003-03-27 |
| DE69905486T2 (de) | 2003-09-11 |
| US6563625B1 (en) | 2003-05-13 |
| DE19851717A1 (de) | 2000-06-15 |
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