CN102449016B - 用于电光显示器的粘结剂和粘合剂 - Google Patents

用于电光显示器的粘结剂和粘合剂 Download PDF

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CN102449016B
CN102449016B CN201080011210.0A CN201080011210A CN102449016B CN 102449016 B CN102449016 B CN 102449016B CN 201080011210 A CN201080011210 A CN 201080011210A CN 102449016 B CN102449016 B CN 102449016B
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L·曹
D·D·米勒
R·M·韦伯
S·N·法泽勒
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Abstract

由异氰酸酯、聚醚二醇和聚酯二醇形成的聚氨酯,所述聚酯二醇的分子量小于约2000,或包括由位阻基团连接的两个聚酯二醇片段,每个聚酯二醇片段的分子量小于约2000,聚醚二醇对聚酯二醇的摩尔比为1∶9至9∶1。该聚氨酯可被用作电光显示器及用以形成这种显示器的部件中的层压粘结剂。

Description

用于电光显示器的粘结剂和粘合剂
本申请涉及以下美国专利:No.6,120,588、6,124,851、6,312,304、6,657,772、6,727,881、6,831,769、6,982,178、7,012,600、7,106,296、7,110,163、7,110,164、7,236,292和7,561,324,阅读者可以参考以上内容获得关于电光显示器的背景资料。
技术领域
本发明涉及电光显示器,且涉及用在其中的材料,尤其是粘合剂和层压粘结剂。本发明部分地涉及具有电学或其他性能的粘合剂和粘结剂,这些性能使它们特别适于用在电光显示器中。本发明还涉及提供一种可被用于除电光显示器外的其他用途中的聚氨酯。本发明还涉及一些用于制造电光显示器的制品。
背景技术
在美国专利No.7,012,600中详细地论述了关于电光显示器的背景术语和现有技术,读者可参照该美国专利获得进一步信息。相应地,将本领域的术语和现有技术简要概括如下。
作为应用于材料或者显示器的术语“电光”,其在此使用的是其在成像领域中的常规含义,指的是具有第一和第二显示状态的材料,该第一和第二显示状态的至少一个光学性质不同,通过向所述材料施加电场使该材料从其第一显示状态改变到第二显示状态。一些电光材料为固态,该固态是指在该材料具有固态外表面的意义下的固态,尽管该材料可以并且通常具有由液体或气体填充的内部空间。为了方便,下文将这种采用固态电光材料的显示器称为“固态电光显示器”。由此,术语“固态电光显示器”包括旋转双色部件显示器、封装的电泳显示器、微囊电泳显示器以及封装的液晶显示器。
术语“双稳的”和“双稳定性”在此处使用其在本领域中的常规含义,指的是包括具有第一和第二显示状态的显示元件的显示器,所述第一和第二显示状态至少有一种光学性质不同,从而在利用具有有限持续时间的寻址脉冲驱动任何给定元件以呈现其第一或第二显示状态之后,在该寻址脉冲终止后,该状态将持续至少几倍于(例如至少4倍于)改变该显示元件的状态所需的寻址脉冲的最小持续时间的时间。
已知几种类型的电光显示器,例如:
(a)旋转双色部件显示器(例如参见美国专利No.5,808,783;5,777,782;5,760,761;6,054,071;6,055,091;6,097,531;6,128,124;6,137,467以及6,147,791);
(b)电致变色显示器(例如参见O’Regan,B.等人的Nature 1991,353,737;Wood,D.的Information Display,18(3),24(2002年3月);Bach,U.等人的Adv.Mater.,2002,14(11),845;以及美国专利No.6,301,038;6,870,657和6,950,220);
(c)电湿润显示器(例如参见Hayes,R.A.等人在Nature,425,383-385(2003年9月25日)中发表的名称为“Video-Speed Electronic Paper Based onElectrowetting”一文以及美国专利公开No.2005/0151709);
(d)基于粒子的电泳显示器,其中多个带电粒子在电场的影响下移动经过流体(参见美国专利No.5,930,026;5,961,804;6,017,584;6,067,185;6,118,426;6,120,588;6,120,839;6,124,851;6,130,773和6,130,774;美国专利申请公开No.2002/0060321;2002/0090980;2003/0011560;2003/0102858;2003/0151702;2003/0222315;2004/0014265;2004/0075634;2004/0094422;2004/0105036;2005/0062714和2005/0270261;以及国际专利申请公开No.WO 00/38000;WO 00/36560;WO 00/67110和WO 01/07961;以及欧洲专利No.1,099,207B1和1,145,072B1;以及在前述美国专利No.7,012,600中论述的其它MIT和E Ink的专利和申请)。
存在电泳介质的几种不同的变形。电泳介质可以使用液态或者气态流体;对于气态流体例如参见Kitamura,T.等人2001年在IDW Japan,PaperHCS1-1中发表的名称为“Electrical toner movement for electronic paper-likedisplay”以及Yamaguchi等人2001年在IDW Japan,Paper AMD4-4)中发表的名称为“Toner display using insulative particles charged triboelectrically”;美国专利公开No.2005/0001810;欧洲专利申请1,462,847;1,482,354;1,484,635;1,500,971;1,505,194;1,536,271;1,542,067;1,577,702;1,577,703和1,598,694;以及国际申请WO 2004/090626;WO 2004/079442和WO 2004/001498。介质可以为封装的,包含大量的小囊(capsule),每一个小囊本身包含内相以及环绕内相的囊壁,该内相包含悬浮在流体悬浮介质中的电泳移动粒子。一般地,这些囊本身被保持在聚合物粘合剂内以形成位于两个电极之间的粘结层(coherent layer);参见上述的MIT和E Ink专利和申请。可替代地,在封装的电泳介质中围绕离散的微囊的壁可以由连续相代替,因而产生所谓的聚合物分散的电泳显示器,其中电泳介质包含电泳流体的多个离散的微滴以及聚合物材料的连续相;例如参见美国专利No.6,866,760。为了本申请的目的,将这样的聚合物分散的电泳介质看作是封装的电泳介质的子类。另一种变形是所谓的“微单元电泳显示器”,其中带电粒子和流体被保留在形成在载体介质内的多个腔内,该载体介质通常是聚合物膜;例如参见美国专利No.6,672,921和6,788,449。
尽管电泳介质通常是不透明的(例如,由于在许多电泳介质中,粒子基本上阻挡可见光通过显示器的透射)并且工作在反射模式下,但是可以使许多电泳显示器工作在所谓的“快门模式”下,在该模式下一种显示状态是基本上不透明的而一种显示状态是光透射的。例如参见前述的美国专利No.6,130,774和6,172,798,以及美国专利No.5,872,552;6,144,361;6,271,823;6,225,971;和6,184,856。与电泳显示器类似但是依赖于电场强度变化的介电泳显示器可以工作在类似的模式下;参见美国专利No.4,418,346。其他类型的电光显示器也能工作在快门模式下。
封装的电泳显示器通常不受传统电泳设备的聚集和沉淀的失效模式的影响并且具有另外的优点,例如可以在各种不同柔性和刚性衬底上印刷或者涂覆该显示器。(使用“印刷”一词旨在包括印刷和涂覆的所有形式,包括但并不局限于:预调式涂覆,例如小块模具型涂覆(patch die coating),狭缝式或挤压式涂覆,坡流式或阶式涂覆,淋幕式涂覆;压辊涂覆,例如辊式刮刀涂覆、前向和反向辊涂覆;凹版印刷涂覆;浸渍涂覆;喷涂;弯液面涂覆;旋涂;刷涂;气刀涂覆;丝网印刷工艺;静电印刷工艺;热印刷工艺;喷墨印刷工艺;电镀沉积(参见美国专利No.7,339,715);以及其它类似的技术。因而,所得到的显示器可以为柔性。另外,由于显示器媒质可以是印刷的(使用各种方法),显示器本身可以比较低廉地制造。
诸如聚合物分散液晶的其他类型的电光媒质也可以用在本发明的显示器中。
在考虑选择用在电光显示器中的材料时,必须要关注显示器通过什么方法被组装。现有技术中,用于最终制造电泳显示器的绝大部分方法实质上是批量的方法,其中只有在马上进行最终组装之前才把电泳媒质、层压粘结剂和背板放在一起,因此期望提供更适于大量生产的方法。前述的美国专利No.6,982,178描述了组装固态电光显示器(包括封装的电泳显示器)的方法,该方法能较好地适于大量生产。该专利实质上描述了所谓的“前平面层压(front panel laminate)”(FPL),该“前平面层压”顺序地包括透光导电层、与该导电层电接触的固态电光媒质层、粘结剂层和释放板。一般地,透光导电层由透光基板所承载,该基板优选地为柔性的,这种柔性的含义是该基板能够被手动地卷绕在(比方说)一直径为10英寸(254毫米)的圆筒上而不会出现永久变形。此处所使用的术语“透光”表示所指定的层能够使足够的光透过,以使穿过该层进行观看的观察者能够观察到电光媒质在显示状态上的变化,而通常这种变化是通过导电层和相邻的基板(如果有的话)所观看到的。基板一般为聚合物膜,并且通常其厚度在约1至约25密耳(25至634μm)范围内,优选地约2至约10密耳(51至254μm)。适合地,导电层可以为诸如铝或氧化铟锡(ITO)的薄的金属氧化物层,或者可以为导电聚合物。涂覆有铝或ITO的聚对苯二甲酸乙二酯(PET)膜是商业可得到的,例如来自特拉华州威尔明顿的杜邦公司(E.I.du Pont de Nemours & Company,Wilmington DE)的“铝化Mylar”(″Mylar″为注册商标),在前平面层压中可以使用这种商业材料并具有良好的效果。
采用这样的前平面层压可以通过下述步骤实现电光显示器的组装:从该前平面层压上移开释放板,并且在足以引起粘结剂层粘结到背板的有效条件下使该粘结剂层和背板相接触,由此将粘结剂层、电光媒质层和导电层固定到背板上。由于该前平面层压可以大量生产,一般采用辊对辊涂覆技术并随后切成与特定背板一起使用所需的任意尺寸的片,所以该工艺较好地适用于大量生产。
前述的美国专利No.6,982,178还描述了在将前平面层压引入电光显示器之前用于测试前平面层压中电光媒质的方法。在该测试方法中,释放板配有导电层,并且在该导电层和该电光媒质的相对侧的导电层之间施加足以改变电光媒质的光学状态的电压。随后,对电光媒质的观察可显现出存在于该媒质中的任何瑕疵,这就避免了将有瑕疵的电光媒质层压到显示器中,而导致最终成本是废弃整个显示器而不仅仅是有瑕疵的前平面层压。
前述的美国专利No.6,982,178还描述了通过在释放板上放置静电电荷,从而在电光媒质上形成图像的用于测试电光媒质的第二种方法。随后以与前面相同的方式观察该图像用以检测在电光媒质中的任何瑕疵。
前述的美国专利No.7,561,324描述了所谓的“双释放板”,该“双释放板”实质上为前述的前平面层压的简化版。其中一种双释放板的形式包括夹在两个粘结剂层之间的固态电光媒质层,释放板覆盖在其中一个粘结剂层或两个粘结剂层上。双释放层的另一种形式包括夹在两个释放板之间的固态电光媒质层。这两种形式的双释放膜均旨在用于与已经描述的用于从前平面层压组装电光显示器的方法基本上类似的方法中,但其包括两个单独的层压。通常,在第一次层压中是将双释放板层压到前电极以形成前子组件,然后在第二次层压中将前子组件层压到背板以形成最终的显示器。
前述的美国专利No.7,110,164描述了一种组装电光显示器的方法。其中电光媒质层被涂覆在第一释放板上,层压粘结剂层被涂覆在第二释放板上,然后将两个得到的结构层压在一起以形成按顺序包括以下层的结构:第一释放板、电光层、粘结剂层和第二释放板。
考虑到前述的美国专利No.6,982,178中所描述的采用前平面层压的组装方法的优点,期望能将一种用在电光显示器的材料引入到这样的前平面层压中。还期望能将该材料引入到前述的双释放板中,以及前面在美国专利No.7,110,164中所描述的结构中。
如已说明,当采用前平面层压或双释放膜制造电光显示器时,层压粘结剂层一般位于最终显示器的电极之间(可以在电极间有一个以上的粘结剂层;例如参见美国专利公开No.2007/0109219,其中描述了一种被称为“倒置的前平面层压”形式的双释放膜)。如前述的美国专利No.6,831,769中所讨论,层压粘结剂的电学性能对显示器的电光性能有显著影响。然而,层压粘结剂并不一定是存在于电光显示器的电极之间的唯一聚合物组分。例如前述的美国专利No.6,839,158所述,在封装的电泳显示器中,通常电光层除包括囊本身外,还包括聚合物粘合剂,在其干燥或固化时,把囊形成到机械粘结层内,尤其在该专利中所教导的当囊以理想的单层囊形式存在时。粘合剂也可位于最终显示器的电极之间,所以粘合剂也影响显示器的电光性能。在粘合剂比层压粘结剂更靠近封装的电泳显示器的囊的条件下(一般通过一定厚度的粘合剂与内部相分离),粘合剂甚至比层压粘结剂对显示器电光性能的影响更大。类似地,旋转双色部件显示器的连续基材、聚合物分散的电泳显示器的连续相以及用在微囊显示器中的壁材料(所有这些实质上对应于封装的电泳显示器的粘合剂,并且所有这些在下文中均被认为是粘合剂)主要影响着显示器的电光性能。本发明的一个方面涉及用于电光显示器中具有改善的电学和机械性能的粘合剂,且涉及引入这样的粘合剂的显示器、前平面层压、倒置的前平面层压和双释放膜。
美国专利No.7,477,444描述了一种用在电光显示器中的粘合剂,该粘合剂包括聚氨酯,其由异氰酸酯和小于约2000的分子量的聚酯二醇制成,或由包含两个通过位阻基团相连的聚酯二醇片段的聚酯二醇制成,其中每个聚酯二醇片段具有小于约2000的分子量。使电光显示器的粘合剂和层压粘结剂具有相同或相似的化学性质可以给制造和储存稳定方面带来好处。然而,由于前述的粘合剂没有足够的粘结性能且过于刚性,导致层压中具有诸如层压空隙的缺陷,因此层压质量较低,不能用作层压粘结剂。
发明内容
现已发现,对前述聚氨酯粘合剂进行化学改性后可形成具有改善粘结性能的且刚性较低的材料,因此使其适于用作电光显示器中的层压粘结剂。另外还发现,可将得到的粘结剂直接涂覆到干燥的电泳层上,从而简化了电光显示器的制造方法。
因此,本发明提供由异氰酸酯、聚醚二醇和聚酯二醇形成的聚氨酯,所述聚酯二醇的分子量小于2000,或包括由位阻基团连接的两个聚酯二醇片段,每个聚酯二醇片段的分子量小于2000,聚醚二醇对聚酯二醇的摩尔比为1∶9至9∶1。
此处使用的术语“位阻基团”定义为能将两个聚酯二醇片段连接在一起且足够庞大以给聚酯片段的晶化提供位阻的任何基团。该位阻基团例如可包括季碳原子;具体使用的基团为-C(CH3)2-基团。
在这样的聚氨酯中,聚醚二醇对聚酯二醇的摩尔比可以为1∶4至4∶1。所述聚酯二醇可以是分子量小于1500的聚己酸内酯二醇,或是包括通过弯曲基团(bending group)连接的两个聚己酸内酯片段的聚己酸内酯二醇,每个聚己酸内酯片段的分子量不大于1500。也可以用聚(己二酸)二醇来形成本发明的聚氨酯。所述异氰酸酯可以是4,4′-亚甲基双(异氰酸环己酯),在聚氨酯工业中一般公知为“H12MDI”。聚醚二醇可以是聚(环氧丙烷)二醇,优选的一种的分子量为1000至3000。聚氨酯中异氰酸酯对羟基基团的摩尔比优选为小于1.3。聚氨酯在1Hz下的交叉温度(在该温度时其储能模量等于其损耗模量)为10至90℃的范围内,且优选在40至80℃的范围内。所述聚氨酯可具有水性乳胶形式。
本发明还提供用在构造电光显示器的子组件,该子组件包括固态电光材料层、和粘附于该电光材料层的层压粘结剂层,所述层压粘结剂层包括本发明的第三种聚氨酯。这样的子组件还可包括在所述电光材料层的与所述层压粘结剂层相对侧上的透光导电层;以及在所述层压粘结剂层的与所述电光材料层相对侧上的释放板(使子组件具有前平面层压的形式)。可替代地,这样的子组件还可包括在所述电光材料层的与所述层压粘结剂层相对侧上的第二粘结剂层;以及置于所述第二粘结剂层的与所述电光材料层相对侧上的释放板(使该子组件具有双释放膜的形式)。该子组件的第三种形式还包括在所述层压粘结剂层的与所述电光材料层相对侧上的透光保护层和透光导电层中的至少一个;以及在所述电光材料层的与所述层压粘结剂层相对侧上的释放板(使该子组件具有倒置的前平面层压的形式)。最后,这样的子组件还可包括覆盖在所述电光材料层和层压粘结剂层的暴露面的第一和第二释放板。
本发明还可涉及包括这样的子组件和被布置用以施加电场至电光材料层的至少一个电极的电光显示器,且涉及包括这样的显示器的电子书阅读器、便携式计算机、平板计算机、手机、智能卡、标示牌、手表、货架标签或闪存驱动器。
附图说明
图1为通过本发明前平面层压的截面示意图;
图2为通过本发明双释放膜的截面示意图;
图3示出在下面示例3中进行差示扫描量热测试的结果;
图4示出在下面示例4中进行储存稳定性测试的结果;
图5示出在下面示例7中制备的聚氨酯的DSC曲线。
具体实施方式
现在仅以示意的方式,参照图1和图2,描述一种将本发明的聚氨酯当作电光显示器制造中的粘合剂和层压粘结剂而使用的方式。图1为通过一个在该过程中被使用的子组件(前平面层压,或FPL)的示意图;该子组件包括基板、导电层、电光层和粘结剂层,所示意的子组件处于在将该子组件层压到第二子组件之前的过程的中间阶段。
图1所示的前平面层压(总体示为100)包括透光基板110、透光电极层120、电光层130、层压粘结剂层180和释放板190;所示意的释放板正处于被从层压粘结剂层180去除,准备把FPL 100层压到背板的过程中。
基板110一般为透明塑料膜,例如5密耳(127μm)的聚(对苯二甲酸乙二醇酯)(PET)板,然而也可以使用更薄的塑料膜,例如3密耳(76μm)或0.5-1(13-25μm)密耳。当期望电极具有更好的机械保护性时,还可以使用更厚的膜,例如7密耳(177μm)。形成最终显示器观察面的基板110的下表面(图1)可具有一个或多个附加层(未示出),例如,用以吸收紫外辐射的保护层,用以防止氧气或水分进入最终显示器的阻挡层,以及用以改善显示器光学性能的防反射涂层。涂覆到基板110上表面的是薄的透光导电层120,优选为ITO的,其普遍用作最终显示器内的前电极。涂覆有ITO的PET膜可商业购得。
一般通过狭缝式涂覆可将电光层130沉积到导电层120上,使这两层电接触。图1所示的电光层130为封装的电泳媒质,且包括微囊140,每个微囊包括在基于碳氢化合物的流体中带负电荷的白色颗粒150和带正电荷的黑色颗粒160。微囊140被保持在聚合物粘合剂170内。当将电场施加到电光层130上时,白色颗粒150向正电极移动,而黑色颗粒160向负电极移动,以使电光层130根据导电层120相对于背板内相邻像素电极为正或为负,向穿过基板110观察显示器的观察者呈现白或黑。
FPL 100可以通过以下方式制成:适宜采用狭缝式涂覆将层压粘结剂180以常规的液态形式涂覆到释放板190上,干燥(或另外固化)该粘结剂以形成固态层,然后将粘结剂和释放板层压到电光层130,该电光层在之前已被涂覆到具有导电层120的基板110上;上述层压可方便地使用热辊层压来实现。可替代地,根据本发明,尤其在将本发明的第三种聚氨酯用作层压粘结剂时,可将层压粘结剂涂到电光层130上方,并在用释放板190覆盖其之前,对其进行干燥或另外的固化。释放板190适宜为5密耳(127μm)的膜;根据所使用的电光媒质的性质,可期望在该膜上涂有释放剂,例如硅树脂。如图1所示,在将FPL 100层压到背板(未示出)以形成最终显示器之前,释放板190被剥掉或以其他方式从层压粘结剂180上去除。显然,如果将层压粘结剂180直接涂覆到电光层130上并干燥,且马上将得到的前平面层压层压到背板上,那么释放板190可以省去。
关于前平面层压及其制备方法和使用的进一步细节,阅读者可参考前述的美国专利No.6,982,178。
图2示出了本发明的双释放板(总体示为300)。双释放板300包括电光材料的中间层302,特别地,在图2的层中,包括聚合物粘合剂306内的囊304。囊304可与前面参考图1所描述的囊相似。板300还包括第一粘结剂层308,覆盖在该第一粘结剂层308上的第一释放板310,置于电光层302的与第一粘结剂层308相对侧上的第二粘结剂层312,以及覆盖在该第二粘结剂层312上的第一释放板314。
板300可通过以下方式形成:首先在释放板310上涂覆一层粘结剂,然后将该层粘结剂干燥或固化以形成第一粘结剂层308。接下来,将囊304和粘合剂306的混合物印制或以其他方式沉积到该第一粘结剂层308上,然后干燥或固化该混合物以形成粘附层302。最后,将一层粘结剂沉积到层302上,干燥或固化以形成第二粘结剂层312,然后将第二释放板314覆盖到第二粘结剂层312上。
对于涂覆技术领域内的普通技术人员来说,显然上述用以形成板300的操作顺序很适于连续生产,并且通过对材料和工艺条件的认真选择,有可能通过常规辊对辊涂覆装置在单次通过内实现整个操作步骤。
为了使用诸如膜300的双释放膜来组装显示器,需要剥离一个释放板(一般是将电光材料涂覆到其上的那个释放板),然后利用诸如热、辐射、或基于化学的层压方法将双释放膜的其余层结合到前基板。前基板一般包括将形成最终显示器的前电极的导电层。前基板可包括附加层,例如紫外滤光层或旨在保护导电层免受机械损伤的保护层。之后,将另一释放板剥离,从而暴露第二粘结剂层,其用以将电光材料涂层组件结合到背板。可再次使用热、辐射、或基于化学的层压方法。尽管实际上首先将双释放膜层压到前基板、然后将得到的前子组件层压到背板的层压顺序几乎总是更加便利,但应理解,所描述的这两个层压的顺序实质上为任意的,因此也可以颠倒。
关于双释放膜及其制备方法和使用的进一步细节,阅读者可参考前述的美国专利No.7,561,324。
本发明的显示器可用在现有技术中的电光显示器已应用到的任何用途中。因此,本发明显示器例如可用在电子书阅读器、便携式计算机、平板计算机、手机、智能卡、标示牌、手表、货架标签以及闪存驱动器。
如已提到过,本发明涉及“定制”的聚氨酯,其所具有的性能能使它们特别用作封装的电泳或其他类型的电光显示器中的粘合剂和层压粘结剂。以上已概述了聚氨酯为何优选作为电光显示器内的粘合剂的一般原因,对于商业上购得的聚氨酯,NeoRez R 9314和R 9621特别有用,优选的共混物包括重量百分比为75的前者和重量百分比为25的后者。
然而,尽管该75/25的共混物为显示器提供了优良的整体性能,但仍存在一些关于其应用上的缺陷。首先,由于聚酯片段在R 9314中的重量百分比更高,该材料经历了在40℃左右的熔化/晶化转变。该聚合物晶化导致材料在电学性能上发生变化,从而随时间的流逝影响了显示器的性能。第二,通常不期望使用聚合物共混物,因为共混物中的聚合物潜在经历了宏观相分离,从而形成异质材料。第三,商品聚氨酯很少用于电光显示器中,使得这种材料的制造商通过折衷其在用作电光显示器粘合剂时的效果的这种方式来改变聚氨酯以改善其在绝大部分应用中的性能。因此,需要一种已知组合物的单一组分的“定制”的聚氨酯,其具有被优化用作电光显示器中粘合剂的性能。
在本发明的第一和第二种(或“粘合剂”)聚氨酯中,聚氨酯片段的长度是受控制的。已知诸如R 9314的聚氨酯的晶化转变归因于位于聚合物主链上的氨酯键之间的长聚酯片段。通过减少氨酯基团间聚酯片段的长度(局部分子量在2000以下),使聚酯片段不能进行链折叠晶化,从而从整体上消除聚合物的晶化。为了合成这种聚合物,有人使用链长度相对短的聚酯二醇。二醇可以是分子量不大于1500的聚己酸内酯二醇。
可在粘合剂聚氨酯中使用两种不同类型的聚酯二醇。第一类型一般通过下式I表示:
其中m+n<13。
该第一类型的聚酯二醇包含通过基团连接的两个聚酯片段(式I中的聚己酸内酯片段),所述基团没有提供对聚酯片段的晶化的任何位阻。这种类型的聚酯二醇的分子量不应超过2000。
第二类型的聚酯二醇一般通过下式Ⅱ表示:
其中m<13且n<13。
该第二类型的聚酯二醇包含通过位阻基团连接的两个聚酯片段(式Ⅱ中的聚己酸内酯片段),该位阻基团足够庞大,从而提供了足够的位阻以阻碍聚酯片段的晶化。在该类型的聚酯二醇中,这两个聚酯片段实际上被位阻基团彼此隔离且每个片段的分子量最高可达2000。
如已说明,本发明还提供了用作电光显示器中层压粘结剂的第三种聚氨酯。如以上所讨论,迄今为止,当期望提供一层靠近电光材料层的层压粘结剂层时,一般需要使用“间接方法”,其中层压粘结剂被涂覆到释放板上,干燥或固化以形成粘附层,然后将该层压粘结剂/释放板子组件层压到电光材料层。尽管第一眼感觉这比“直接方法”(其中层压粘结剂被直接涂覆到电光材料层上)要简单,但经验证明,很多在间接方法中获得较好效果的层压粘结剂在直接方法中面临多个严重问题。例如,当把美国专利No.7,342,068中描述的聚氨酯作为层压粘结剂通过间接方法应用到封装的电泳显示器中时,其提供了较好效果,如前述的美国专利No.7,012,735所述。然而,经验证明,当把相同的层压粘结剂应用到直接方法中时,最终的电泳显示器在转换效果上非常差。此外,如已提到的本发明第一种和第二种聚氨酯,尽管它们在电泳显示器中提供了较好的效果,但其并不适合用作这种显示器中的层压粘结剂,因为它们缺少足够的粘结性能且过于刚性,在1Hz下的交叉温度高于180℃。
经验发现,对于分子量恒定的聚氨酯,通过降低异氰酸酯对羟基的摩尔比可明显降低高的交叉温度,在本发明优选的粘合剂聚氨酯中,异氰酸酯对羟基的摩尔比为约1.4(比照下面示例1和2)至约1.3,且优选为约1.2;证明摩尔比为约1.2的经改性的示例1的聚氨酯的交叉温度为约60℃,这与美国专利No.7,342,068所描述的聚氨酯相当。(对于异氰酸酯对羟基的摩尔比基本恒定的聚氨酯,交叉温度倾向于随分子量的增加而升高。)这种示为“H12MDI-高PCL”的聚氨酯的合成,将在下面的示例5中作具体描述。然而,当采用直接方法将该聚氨酯作为层压粘结剂应用时,发现在室温下储存24小时后,显示器在15V时显示出差的转换。随着升高施加电压或显示器的操作温度,显示器的切换有明显改善,这表明层压粘结剂可能正在晶化。该晶化通过差示扫描量热法得到证实,其示出在重复的加热/冷却循环期间,在大约30-40℃处有熔化/晶化转变。
为了降低交叉温度并由此减少趋向晶化的趋势,引入聚(环氧丙烷)(PPO)二醇对聚氨酯作进一步改性,使聚己酸内酯对PPO的摩尔比为1∶1(如下面示例6所描述,该聚合物被示为“H12MDI-high PCL/PPO”),这样能有效降低聚酯二醇的浓度,且潜在改善粘结性能。然而,获得的材料在DSC测试期间仍显示有晶化;因为在第一次加热时显示有熔化转变,在第二次加热时却没有,但尽管如此,与没有PPO二醇的聚氨酯相比,该聚氨酯的晶化趋势大大减少。
相应地,把上式I的聚己酸内酯二醇替换为上式Ⅱ的分子量为2000的基于新戊二醇的二醇,对测试用聚氨酯作进一步改性(如下面示例7所描述;该聚氨酯示为“H12MDI-NPGD/PPO”)。从该示例中报告的DSC数据中可看出,在两个加热循环中都没有熔化转变,这暗示聚合物晶化已被彻底消除。
看起来,在保持聚合物分子量以及异氰酸酯对羟基的摩尔比恒定的情况下,提高聚醚多元醇对聚酯多元醇的比例,能增强与给定基板的粘结性(通过测量剥离力),并降低聚合物水解的速率。并且实际中,可采用较小量的N-甲基吡咯烷酮来合成含有比例较高的聚醚多元醇的聚氨酯,N-甲基吡咯烷酮是一种易在一些电光显示器中引发问题的材料,因此在把聚氨酯用作电光显示器中的层压粘结剂之前,可能必须要把其去除。
下面仅通过示意的方式给出一些示例,以进一步示出本发明优选的聚氨酯。
示例1:具有短聚酯片段的定制聚氨酯
在氮气氛下,在配备机械搅拌器、温度计和进氮口的500毫升夹套玻璃反应器中合成聚氨酯预聚物。将4,4′-亚甲基双(异氰酸环己酯)(20.99克,Bayer Desmodur W)、聚己酸内酯二醇(31.25克,Aldrich,平均Mn约1250)以及二月桂酸二丁基锡(0.04克,Aldrich)装入反应器内,并在80℃下将混合物加热2小时。之后,将1-甲基-2-吡咯烷酮(10克,Aldrich)的2,2-双(羟甲基)丙酸(3.35克,Aldrich)溶液加入至反应器中,并且使得反应在80℃下再持续1小时以得到末端为异氰酸酯的预聚物。然后将反应器温度降低至60℃持续30分钟,并加入三乙胺(2.4克,Aldrich)以中和羧酸。然后将反应器温度进一步降低至30℃,并加入去离子水(105克)以将预聚物转化为水性分散体。在分散步骤之后,在30℃下使用溶于少量去离子水的六亚甲基二胺(3.5克,Aldrich)超过1小时,立即进行链增长。最后,在60℃下加热分散体1小时以保证所有残留的异氰酸酯基团已反应。
示例2:具有包含位阻基团的聚酯的定制聚氨酯
在氮气氛下,在配备机械搅拌器、温度计和进氮口的夹套玻璃反应器中合成聚氨酯预聚物。将4,4′-亚甲基双(异氰酸环己酯)(18.3克)加入至反应器内,随后加入1-甲基-2-吡咯烷酮(27克)、聚己酸内酯二醇(分子量2000,49.3克),以及2,2-双(羟甲基)丙酸(3.4克)。加热反应器至95℃持续4小时,随后再冷却至70℃以形成末端为异氰酸酯的预聚物。将三乙胺(2.0克)缓慢加入至预聚物,并将得到的混合物混合30分钟。将水(84克)加入至配备机械搅拌器和温度计的第二反应器中。随后,在搅拌下将预聚物(80克)从第一反应器缓慢转移至第二反应器。将六亚甲基二胺(2.7克的70%溶液)加入第二反应器用于链增长,并且将得到的分散体加热至80℃1小时以完成反应。
示例3:聚氨酯的热学性能
利用差示扫描量热法测试以上示例1和2制备的聚氨酯。为提供对照,以相同方式还测试了前述的75∶25R9314/R 9621共混物(简单示为图3中的“共混物”)。结果在图3中示出。
从图3中可以看出,共混物在约40℃处显示有标记的放热峰,对应于R9314中聚酯片段的熔化;当再次加热时,该峰消失。在本发明的聚氨酯的曲线中没有可比对的峰,这说明使用有或没有位阻基团的短聚酯片段,的确能有效地消除R 9314中看到的热转变,且确保本发明的聚氨酯粘合剂具有长期的热稳定性。
示例4:聚氨酯的储存稳定性
进行该测试是为了确定示例2的聚氨酯是否具有比前述的R9314/R 9621共混物更好的储存稳定性。为此,将干燥后的每种粘合剂的膜层压到两个涂覆有ITO的聚酯聚(对苯二甲酸乙二醇酯)膜之间,ITO层自然直接与聚氨酯相接触。为了保证所有样品具有相同的热历史,将它们放在炉中于70℃下加热数小时,然后在25℃和50%的相对湿度下保持5天。在下面描述的测试中,时间零点取自这段储存期的结束。
然后,将样品在25℃和50%的相对湿度下保持6周,间隔地测量粘合剂层的电阻。结果在图4中示出。从该图中可以看出,在实验过程中,共混物的电阻增大了约百分之50,而本发明示例2的聚氨酯的电阻从初始值变化了不超过约百分之10。该聚氨酯的显著变化可能的确是实验误差的结果;因为该实验在电阻测量期间没有控制相对湿度,可理解有一些随机的变化,最高到大约百分之10,可能由上述原因所引起。
图4中的结果暗示了避免现有技术中的聚氨酯混合物所经历的聚合物晶化能帮助稳定粘合剂的电学性能。如之前已说明,粘合剂的电学性能显著影响电光显示器的电光性能,因此,图4中的结果说明采用本发明的聚氨酯粘合剂应能帮助在这种显示器中提供时间稳定的电光性能。
示例5:H12MDI-高PCL(对照)的合成
在氮气氛下、在配备机械搅拌器、隔膜和进氮口的三颈圆底烧瓶中合成聚氨酯预聚物。将4,4′-亚甲基双(异氰酸环己酯)(31.4克,Bayer DesmodurW)、聚己酸内酯二醇(100克,Aldrich,平均Mn大约2000)、2,2-双(羟甲基)丙酸(6.7克,Aldrich)、1-甲基-2-吡咯烷酮(56克,Aldrich)以及二月桂酸二丁基锡(0.04克,Aldrich)装入烧瓶,在95℃下加热该混合物5小时,以得到末端为异氰酸酯的预聚物。然后将反应器温度降低至70℃,并加入三乙胺(5克,Aldrich)以中和羧酸,并使反应混合物稳定30分钟。将水(210克)加入配备机械搅拌器、进氮口和温度计的500毫升夹套反应器中。然后在搅拌下,将预聚物转移至含水反应器中,以形成水性分散体。在分散步骤之后,在室温下使用溶于少量去离子水的六亚甲基二胺(3.2克,Aldrich)超过30分钟,立即进行链增长。最后,将分散体在70℃下加热1小时以保证所有残留的异氰酸酯基团已反应。
示例6:H12MDI-PCL/PPO的合成
在氮气氛下、在配备机械搅拌器、隔膜和进氮口的三颈圆底烧瓶中合成聚氨酯预聚物。将4,4′-亚甲基双(异氰酸环己酯)(31.4克,Bayer DesmodurW)、聚己酸内酯二醇(50克,Aldrich,平均Mn大约2000)、聚(环氧丙烷)二醇(50克,Aldrich,平均Mn大约2000)、2,2-双(羟甲基)丙酸(6.7克,Aldrich)、1-甲基-2-吡咯烷酮(40克,Aldrich)以及二丁基二月桂酸(0.04克,Aldrich)装入烧瓶内,并在95℃下将混合物加热6小时,以形成末端为异氰酸酯的预聚物。然后将反应器温度降低至70℃,加入三乙胺(3.79克,Aldrich)以中和羧酸,然后使反应混合物稳定30分钟。将水(220克)加入配备机械搅拌器、进氮口和温度计的500毫升夹套反应器中。然后在搅拌下,将预聚物转移至含水反应器中,以形成水性分散体。在分散步骤之后,在室温下使用溶于少量去离子水的六亚甲基二胺(4.6克,Aldrich)超过30分钟,立即进行链增长。最后,将分散体在70℃下加热1小时以保证所有残留的异氰酸酯基团已反应。
示例7:H12MDI-NPGD/PPO的合成
在氮气氛下、在配备机械搅拌器、隔膜和进氮口的三颈圆底烧瓶中合成聚氨酯预聚物。将4,4′-亚甲基双(异氰酸环己酯)(31.4克,Bayer DesmodurW)、CPAP的2200A的二醇(50克,购于Solvay SA,Brussels,Belgium,平均Mn大约2000)、聚(环氧丙烷)二醇(50克,Aldrich,平均Mn大约2000)、2,2-双(羟甲基)丙酸(6.7克,Aldrich)、1-甲基-2-吡咯烷酮(40克,Aldrich)以及二月桂酸二丁基锡(0.04克,Aldrich)装入反应器内,并在95℃下将混合物加热6小时,以得到末端为异氰酸酯的预聚物。然后将反应器温度降低至70℃,并加入三乙胺(3.79克,Aldrich)以中和羧酸,并使反应混合物稳定30分钟。将水(220克)加入配备机械搅拌器、进氮口和温度计的500毫升夹套反应器中。然后在搅拌下,将预聚物转移至含水反应器中,以形成水性分散体。在分散步骤之后,在室温下使用溶于少量去离子水的六亚甲基二胺(4.6克,Aldrich)超过30分钟,立即进行链增长。最后,将分散体在70℃下加热1小时以保证所有残留的异氰酸酯基团已反应。
图5为干燥后的所得聚合物的膜的DSC扫描,示出干燥后的膜不含结晶材料。
尽管本发明前面主要关于具有离散的囊的封装的电泳媒质进行了描述,但将本发明粘合剂用在之前讨论的其他类型的电光显示器中时,可以获得类似的优点。

Claims (17)

1.一种由异氰酸酯、聚醚二醇和聚酯二醇形成的聚氨酯,所述聚酯二醇的分子量小于2000,或包括由位阻基团连接的两个聚酯二醇片段,每个聚酯二醇片段的分子量小于2000,聚醚二醇对聚酯二醇的摩尔比为1:9至9:1,其中所述聚醚二醇为聚(环氧丙烷)二醇。
2.根据权利要求1所述的聚氨酯,其中聚醚二醇对聚酯二醇的摩尔比为1:4至4:1。
3.根据权利要求1所述的聚氨酯,其中所述聚酯二醇为分子量小于1500的聚己酸内酯二醇。
4.根据权利要求1所述的聚氨酯,其中所述聚酯二醇为包括由弯曲基团连接的两个聚己酸内酯片段的聚己酸内酯二醇,每个聚己酸内酯片段的分子量不大于1500。
5.根据权利要求1所述的聚氨酯,其中所述异氰酸酯为4,4'-亚甲基双(异氰酸环己酯)。
6.根据权利要求1所述的聚氨酯,其中所述聚醚二醇的分子量为1000至3000。
7.根据权利要求1所述的聚氨酯,所述聚氨酯具有小于1.3的异氰酸酯:羟基的比。
8.根据权利要求1所述的聚氨酯,所述聚氨酯在1Hz下具有10至90℃范围内的交叉温度。
9.根据权利要求8所述的聚氨酯,所述聚氨酯在1Hz下具有在40至80℃范围内的交叉温度。
10.根据权利要求1所述的聚氨酯,所述聚氨酯为水性乳胶的形式。
11.一种用在构造电光显示器的子组件,所述子组件包括固态电光材料层、和粘附于该电光材料层的层压粘结剂层,所述层压粘结剂层包括根据权利要求1所述的聚氨酯。
12.一种电光显示器,包括根据权利要求11所述的子组件以及被布置用以施加电场至电光材料层的至少一个电极。
13.一种包括根据权利要求12所述的显示器的电子书阅读器、便携式计算机、平板计算机、手机、智能卡、标示牌、手表、货架标签或闪存驱动器。
14.根据权利要求11所述的子组件,还包括:
在所述电光材料层的与所述层压粘结剂层相对侧上的透光导电层;以及
在所述层压粘结剂层的与所述电光材料层相对侧上的释放板。
15.根据权利要求11所述的子组件,还包括:
在所述电光材料层的与所述层压粘结剂层相对侧上的第二粘结剂层;以及
置于所述第二粘结剂层的与所述电光材料层相对侧上的释放板。
16.根据权利要求11所述的子组件,还包括:
在所述层压粘结剂层的与所述电光材料层相对侧上的透光保护层和透光导电层中的至少一个;以及
在所述电光材料层的与所述层压粘结剂层相对侧上的释放板。
17.根据权利要求11所述的子组件,还包括:覆盖在所述电光材料层和层压粘结剂层的暴露面的第一和第二释放板。
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