CN111433020A - 用于制造柔性显示器的层合体以及使用其的柔性显示器制造方法 - Google Patents
用于制造柔性显示器的层合体以及使用其的柔性显示器制造方法 Download PDFInfo
- Publication number
- CN111433020A CN111433020A CN201980006151.9A CN201980006151A CN111433020A CN 111433020 A CN111433020 A CN 111433020A CN 201980006151 A CN201980006151 A CN 201980006151A CN 111433020 A CN111433020 A CN 111433020A
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- layer
- flexible
- flexible substrate
- dianhydride
- laminate
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Links
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Images
Classifications
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10082—Properties of the bulk of a glass sheet
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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Abstract
本发明采用在等于或高于350℃的温度下热膨胀系数(CTE)为负数的聚酰亚胺膜作为用于分离柔性基底和载体基底的脱粘层,并因此通过利用由在用于在柔性基底上生产元件的高温过程之后在柔性基底与脱粘层之间的残余应力的差异引起的分离现象,可以容易地使柔性基底从载体基底分离。因此,本发明可以分离柔性基底,而不对形成在柔性基底上的元件造成化学或物理损坏,从而使在剥离过程期间可能出现的问题最小化。
Description
技术领域
本申请要求于2018年9月11日提交的韩国专利申请第10-2018-0108219号的优先权的权益,其全部公开内容通过引用并入本文。
本发明涉及具有能够促进柔性基底与载体基底的分离的脱粘层的层合体以及使用其制造柔性显示器的方法。
背景技术
显示装置市场正在将其焦点迅速改变到大尺寸、薄化且轻质的平板显示器(FPD)上。这样的平板显示器包括液晶显示器(LCD)、有机发光显示器(OLED)、或电泳装置。
特别地,近年来,为了进一步扩展这样的平板显示器的应用和用途,注意力已集中在应用柔性基底的所谓的柔性显示装置上。主要考虑将柔性显示装置应用于诸如智能电话的移动装置,并且考虑将应用领域逐渐扩展。
然而,形成和处理显示装置结构例如塑料上TFT(TFT on plastic,TOP)的过程是制造柔性显示装置时的重要关键过程。然而,由于设置在这样的柔性显示装置中的基底的柔性,在装置的制造过程中,在通过将柔性塑料基底直接替换现有的玻璃基底来形成装置结构时仍存在许多工艺问题。
特别地,由于包括在柔性基底中的薄膜玻璃容易被冲击破坏,因此显示器基底的制造过程利用在载体玻璃上的薄玻璃来进行。常规地,在载体基底例如玻璃基底上形成a-硅牺牲层等之后,在其上形成柔性基底。此后,通过玻璃基底上的器件的现有制造过程在由载体基底支撑的柔性基底上形成装置结构例如薄膜晶体管。然后,通过用激光或光照射载体基底等来破坏牺牲层以将其上形成有装置结构的柔性基底分离,最后,制造了具有柔性基底的装置,例如柔性显示装置。
然而,在现有技术的制造过程中,在激光或光的照射期间可能影响装置结构,使得可能出现缺陷,并且此外,需要用于激光或光照射的设备和另外的过程。因此,装置的整个制造过程复杂并且制造成本也大大增加。
此外,由于a-Si牺牲层与柔性基底之间的粘合性不足,因此常常需要在牺牲层与柔性基底之间形成单独的粘合层,这可能使整个过程复杂化。此外,由于需要在较苛刻的条件下进行激光或光照射,因此越来越担心可能不利地影响装置的可靠性。
发明内容
技术问题
本发明的一个目的是提供用于制造柔性显示器的具有容易与柔性基底分离的脱粘层的层合体。
本发明的另一个目的是提供使用所述层合体制造柔性显示器的方法。
技术方案
为了解决本发明的问题,提供了层合体,所述层合体包括:
载体基底;
脱粘层,所述脱粘层涂覆在载体基底上并且包含在350℃或更高的温度下具有为负值的CTE的聚酰亚胺;以及
形成在脱粘层上的柔性基底层。
根据一个实施方案,
脱粘层可以具有第一面积,以及
柔性基底层可以具有大于第一面积的第二面积并且完全覆盖脱粘层。
根据一个实施方案,脱粘层中包含的聚酰亚胺可以包含含有联苯四羧酸二酐(BPDA)的二酐与含有苯二胺(PDA)的二胺聚合并固化的产物。
此外,二酐还可以包含均苯四酸二酐(PMDA),二胺还可以包含2,3'-双(三氟甲基)联苯胺(TFMB)。
根据一个实施方案,二酐和二胺的组合可以选自BPDA-PDA、BPDA-PMDA-PDA和BPDA-PDA-TFMB。
根据一个实施方案,脱粘层中包含的聚酰亚胺可以通过使二胺和二酐在其中二胺的当量比相对于二酐过量的条件下聚合并固化来制备。
根据一个实施方案,二酐和二胺的组合为BPDA-PDA-TFMB,并且TFMB的量可以为总的二胺的5mol%或更大。
根据一个实施方案,二酐和二胺的组合为BPDA-PMDA-PDA,并且PMDA的量可以为总的二酐的5mol%或更大。
根据一个实施方案,脱粘层中包含的聚酰亚胺的热分解温度可以为560℃或更高。
根据一个实施方案,脱粘层的厚度可以为50nm或更大且1μm或更小。
根据一个实施方案,柔性基底层可以包含在350℃或更高的温度下具有为正值的CTE的聚酰亚胺。
为了解决本发明的另一个问题,本发明提供了用于制造柔性显示器的方法,所述方法包括以下步骤:
在载体基底上形成包含在350℃以上具有为负值的CTE的聚酰亚胺的脱粘层;
在脱粘层上形成柔性基底层;
在柔性基底层上形成器件;以及
将其上形成有器件的柔性基底层从脱粘层上剥离。
根据一个实施方案,脱粘层可以在载体基底上形成为具有第一面积,柔性基底层可以形成为具有大于第一面积的第二面积并且完全覆盖脱粘层,并且器件可以形成在柔性基底层上的脱粘层与柔性基底重叠的区域中。
根据一个实施方案,剥离柔性基底层的步骤可以通过在脱粘层与柔性基底重叠的区域的内边缘处沿垂直于载体基底的方向切割以使柔性基底层与脱粘层分离来进行。
根据一个实施方案,在剥离期间将柔性基底层从脱粘层上剥离的剥离强度可以为0.05N/cm或更小。
根据一个实施方案,将聚酰亚胺基底层与其上形成有脱粘层的载体基底分离可以不包括在脱粘层与柔性基底层之间引起化学或物理变化的过程。
有益效果
在根据本发明的用于制造柔性显示器的层合体中,在用于将柔性基底与载体基底分离的脱粘层中使用在350℃或更高的温度下具有为负值的CTE(热膨胀系数)的聚酰亚胺,从而通过利用由于在高温形成过程期间柔性基底与脱粘层之间的残余应力的差异引起的分离现象来促进柔性基底与载体基底的分离。由此,可以将柔性基底分离而没有对形成在柔性基底上的器件的化学或物理损坏,从而使在剥离过程期间可能出现的问题最小化。
附图说明
图1a和1b是示出当脱粘层的CTE具有正值时,基于温度变化的尺寸变化和残余应力变化的图(图1a),以及示出层合体的翘曲变化的示意图(图1b)。
图2a和2b是示出当脱粘层的CTE具有负值时,基于温度变化的尺寸变化和残余应力变化的图(图2a),以及示出层合体的翘曲变化的示意图(图2b)。
图3a和3b是用于说明将其上形成有器件的柔性基底从根据本发明的一个实施方案的用于制造柔性基底的层合体上剥离的过程的平面图(图3a)和截面图(图3b)。
具体实施方式
由于可以在本发明中进行多种修改和变化,因此在附图中示出了特定实施方案,并且将在具体实施方式中对其进行详细描述。然而,应理解,本发明不旨在限于特定实施方案,而是包括落入本发明的精神和范围内的所有修改、等同方案和替代方案。在本发明的以下描述中,如果确定已知功能的详细描述可能使本发明的主旨不清楚,则将省略其详细描述。
在本公开内容中,除非另有说明,否则所有化合物或有机基团可以为经取代或未经取代的。在本文中,术语“经取代的”意指化合物或有机基团中包含的至少一个氢被选自以下的取代基替代:卤素原子、具有1至10个碳原子的烷基或卤代烷基、具有3至30个碳原子的环烷基、具有6至30个碳原子的芳基、羟基、具有1至10个碳原子的烷氧基、羧基、醛基、环氧基、氰基、硝基、氨基、磺酸基或其衍生物。
柔性显示器由于其自由的形式、轻质、薄且不易破碎的特性而市场需求正在增加。在实现这样的柔性显示器时,主要使用具有优异耐热性的包含BPDA-PDA的聚酰亚胺作为柔性基底。
形成这样的柔性显示器的方法主要包括在作为支撑基底的玻璃基底上形成由诸如聚酰亚胺的聚合物材料制成的柔性基底,在柔性基底上形成器件,然后用激光照射以使柔性基底与玻璃基底分离。
然而,在激光分离的情况下,设备投资成本可能增加,并且当激光透射塑料基底时,可能对TFT器件造成损坏,这可能导致产率降低。
为了解决现有技术的问题,本发明提供了层合体,所述层合体包括:
载体基底;
脱粘层,所述脱粘层涂覆在载体基底上并且包含在350℃或更高的温度下具有为负值的CTE的聚酰亚胺;以及
形成在脱粘层上的柔性基底层。
此外,本发明提供了用于制造柔性显示器的方法,所述方法包括以下步骤:
在载体基底上形成包含在350℃以上具有为负值的CTE的聚酰亚胺的脱粘层;
在脱粘层上形成柔性基底层;
在柔性基底层上形成器件;以及
将其上形成有器件的柔性基底层从脱粘层上剥离。
在用作柔性基底的聚酰亚胺膜在高温下具有为负值的CTE,即在高温下表现出收缩行为的情况下,在高温热处理过程中可能出现问题。根据本发明,通过在脱粘层中而不是在柔性基底中使用在高温下表现出这种收缩行为的聚酰亚胺,柔性基底通过高温过程例如器件的形成过程中的收缩自然地从脱粘层上剥离。以这种方式,柔性基底可以在没有任何单独的处理例如激光过程的情况下容易地与载体基底分离。
图1a示出了显示在350℃以上具有为正值的CTE的聚酰亚胺膜的基于温度的尺寸变化和残余应力变化的图。
如图1a所示,在使用在350℃以上具有正CTE的聚酰亚胺作为脱粘层的情况下,在升温范围内应力减小(①),并且在350℃以上应力减小或保持(②③)。之后,在降温范围内应力再次增加(④)。应力变化模式与一般柔性基底的根据温度变化的翘曲变化模式相同。因此,在使用在350℃以上具有正CTE的聚酰亚胺作为脱粘层的情况下,由应力变化引起的翘曲变化模式在柔性基底与脱粘层之间相同,使得不会发生柔性基底与脱粘层之间的分离,如图1b所示。
图2a示出了显示在350℃以上具有为负值的CTE的聚酰亚胺膜的根据温度的尺寸变化和残余应力变化的图。如图2a和2b所示,在在350℃以上具有为负值的CTE的聚酰亚胺的脱粘层的情况下,在低于350℃的温度下应力减小(①),这表明与柔性基底的翘曲变化相同的翘曲变化。另一方面,在350℃或更高的温度下应力增加(②),并因此在与柔性基底相反的方向上发生翘曲,并且在柔性基底与脱粘层之间可能发生分离。此后,在降温范围(③)中,应力再次减小,但是仍保持分离。这可以从温度升高期间的应力曲线与温度降低期间的应力曲线之间的大差异中看出。因此,即使在低于350℃下应力增加(④)并且在与柔性基底相同的方向上再次发生翘曲,所产生的分离也仍保持,由此可以降低对柔性基底的粘合性。以这种方式产生的分离在后续过程中可能更大或保持,并且对柔性基底的粘合性可能降低,从而促进剥离。
在本发明中,通过热机械分析仪来测量CTE(热膨胀系数),例如,从100℃至460℃以4℃/分钟的加热速率进行第一升温步骤,然后从460℃至100℃以5℃/分钟的冷却速率进行冷却,并从100℃至460℃以4℃/分钟的加热速率进行第二升温步骤。在350℃或更高的温度范围内的为负值的CTE意指在350℃或更高的温度范围内,指示试样的长度(μm)基于温度变化的变化的图的斜率具有负值。
用于脱粘层中的聚酰亚胺可以包含含有联苯四羧酸二酐(BPDA)的二酐与含有苯二胺(PDA)的二胺聚合并固化的产物。
此外,二酐还可以包含均苯四酸二酐(PMDA),二胺还可以包含2,3'-双(三氟甲基)联苯胺(TFMB)。
根据一个实施方案,酸二酐和二胺的组合可以选自BPDA-PDA、BPDA-PMDA-PDA和BPDA-PDA-TFMB。在本文中,这些缩写意指:
BPDA:联苯-四羧酸二酐
PDA:苯二胺
PMDA:均苯四酸二酐
TFMB:2,2'-双(三氟甲基)联苯胺
聚酰亚胺可以通过在二胺的当量比相对于二酐过量的条件下聚合来获得。例如,BPDA-PDA可以通过使用当量比与BPDA相比过量的二胺PDA来聚合。
BPDA-PMDA-PDA可以通过使用当量比超过BPDA与PMDA之和的PDA来聚合,BPDA-PDA-TFMB可以通过使用超过BPDA与TFMB之和的当量比的PDA来聚合。
在二胺的当量比相对于二酐过量的条件下的聚合可以为例如摩尔比为0.9:1至0.99:1的二酐与二胺的聚合。二酐相对于1摩尔二胺的摩尔比可以为0.95至0.99或0.97至0.99或0.98至0.99或0.985至0.99。
通常,通过使当量比超过二酐的二胺聚合并固化而制备的聚酰亚胺在粘度和分子量稳定性方面是有利的,但是存在负CTE的问题,即在高温下的收缩行为,这可能在高温热处理过程中导致缺陷。例如,存在这样的问题:可能出现各种缺陷,例如由在高温热处理过程之后产生的残余应力引起的形成在柔性基底上的无机膜的开裂和膜的分离。根据本发明,通过使用在350℃或更高的温度下具有为负值的CTE(热膨胀系数)的聚酰亚胺作为用于将柔性基底与载体基底分离的脱粘层,在高温过程中在其上形成器件的柔性基底可以在不经历引起化学或物理变化的过程(例如激光照射过程)或牺牲层的形成和除去过程的情况下与载体基底分离而没有损坏。
根据一个实施方案,在BPDA-PMDA-PDA的聚酰亚胺的聚合中,PMDA可以以总的二酐含量的至少5mol%或至少8mol%或至少10mol%,并且至多18mol%或至多15mol%存在。
此外,根据另一个实施方案,在BPDA-PDA-TFMB的聚酰亚胺的聚合中,TFMB可以以总的二胺含量的至少5mol%或至少8mol%或至少10mol%,并且至多18mol%或至多15mol%存在。
根据一个实施方案,用作脱粘层的聚酰亚胺的热分解温度应高于柔性显示装置的工艺温度,例如,即使在高至500℃的高温过程中,聚酰亚胺也不应分解,优选其可以具有高于560℃的热分解温度。
根据一个实施方案,脱粘层的固化温度可以为350℃或更高,优选400℃或更高。在350℃或更高的温度下固化可以形成具有与柔性基底的收缩现象不同的收缩现象的脱粘层,从而促进剥离。
脱粘层的厚度可以为50nm或更大且1μm或更小。当脱粘层的厚度小于50nm或大于1μm时,脱粘层可能由于根据温度变化的收缩不足而难以剥离。脱粘层的厚度可以为70nm或更大、80nm或更大、或者90nm或更大,并且可以为800nm或更小、600nm或更小、400nm或更小、或者200nm或更小。
根据一个实施方案,在剥离期间用于将柔性基底层从脱粘层上剥离的剥离强度可以为0.05N/cm或更小或者0.04N/cm或更小或者0.03N/cm或更小。
在涂覆用于柔性基底的聚酰亚胺前体并使其固化以在脱粘层上形成柔性基底层的过程中,可能发生脱粘层与柔性基底层之间的分离。当重复用于形成器件的热处理过程时,分离可能变得更大,从而减小柔性基底层与脱粘层之间的粘合性。在这种情况下,可以在350℃以上进行热处理过程,并且在重复的热处理过程之后,脱粘层与柔性基底层之间的粘合力(或剥离强度)可以为0.05N/m或更小。
根据一个实施方案,形成在脱粘层上的聚酰亚胺柔性基底层的CTE在350℃或更高的温度下具有正值,优选7ppm/℃或更小,更优选4ppm/℃或更小。柔性基底层在350℃或更高的温度下具有为正值的CTE,使得根据温度变化的膜变化模式与脱粘层的根据温度变化的膜变化模式不同,从而引起分离并促进将柔性基底层从脱粘层上剥离。
根据本发明的一个实施方案的用于制造柔性显示器的层合体包括:
载体基底;
形成在载体基底上并且具有第一面积的脱粘层;以及
具有大于第一面积的第二面积并且完全覆盖脱粘层的柔性基底层。
图3a和3b分别示出了根据一个实施方案的层合体的平面图和截面图。
参照图3a和3b,在载体基底上形成有脱粘层,并且脱粘层的面积被称为第一面积。在脱粘层上形成有柔性基底层,其中柔性基底层形成有大于脱粘层的第一面积的第二面积。即,由于柔性基底层形成为完全覆盖脱粘层,因此可能存在其中载体基底和柔性基底层彼此直接接触的区域A。
在这种情况下,由于载体基底与柔性基底层之间的粘合力大于柔性基底与脱粘层之间的粘合力,因此即使在器件的形成过程中,粘合力也可以提供过程稳定性。
即,即使在器件的形成过程中柔性基底层与脱粘层之间的粘合力由于在350℃或更高的过程温度下由脱粘层的CTE变化引起的翘曲而劣化,由于柔性基底层和载体基底彼此结合的区域A,柔性基底层和脱粘层也不分离或移动,并因此即使在高过程温度下也可以稳定地进行器件的形成过程。
根据本发明的用于制造柔性显示器的方法包括以下步骤:
在载体基底上形成具有第一面积的脱粘层;
形成具有大于第一面积的第二面积并且完全覆盖脱粘层的柔性基底层,
在柔性基底层上形成器件;以及
将其上形成有器件的柔性基底层从脱粘层上剥离。
剥离柔性基底层通过在脱粘层与柔性基底重叠的面积的内边缘处沿垂直于载体基底的方向切割以使柔性基底层与脱粘层分离来进行。
就过程效率而言,优选待形成在柔性基底层上的器件形成在柔性基底层上的脱粘层与柔性基底重叠的区域中。
用作柔性基底层的聚酰亚胺可以例如通过使具有下式1的结构的至少一种四羧酸二酐和具有下式2的结构的至少一种二胺聚合并固化来制备。
[式1]
[式2]
在式1中,X可以为包含具有3至24个碳原子的脂族环或具有6至30个碳原子的芳族环的四价有机基团,并且具体地,X可以为这样的包含芳族环或脂族环的四价有机基团:其中各个环结构为刚性结构即单环结构,各个环通过单键连接,或者各个环彼此直接连接以形成杂环结构,例如,而且可以为下式3a至3k的四价有机基团,但不限于此。
由式3a至3k表示的四价官能团中的至少一个氢原子可以被选自以下的取代基替代:具有1至10个碳原子的烷基(例如,甲基、乙基、丙基、异丙基、叔丁基、戊基、己基等)、具有1至10个碳原子的氟烷基(例如,氟甲基、全氟乙基、三氟甲基等)、具有6至12个碳原子的芳基(例如,苯基、萘基等)、磺酸基和羧酸基,优选经具有1至10个碳原子的氟烷基取代,并且
式3a至3k中指示的*表示键合位点。
式2中的Y为具有4至30个碳原子的脂族或脂环族二价有机基团或者具有6至30个碳原子的芳族二价有机基团或其组合,其中脂族、脂环族或芳族二价有机基团彼此直接连接或经由交联基团连接。例如,Y可以为具有6至30个碳原子的单环或多环芳族基团、具有6至30个碳原子的单环或多环脂环族基团、或者其中其两者或更多者通过单键连接的结构,更具体地,Y可以为这样的包含芳族环或脂族环的二价有机基团:其中各个环结构为刚性链结构(例如,单环结构),各个环通过单键连接,或者各个环彼此直接连接以形成杂环结构,例如,下式4a至4k的二价有机基团,但不限于此。
由式4a至4k表示的二价官能团中的至少一个氢原子可以被选自以下的取代基替代:具有1至10个碳原子的烷基(例如,甲基、乙基、丙基、异丙基、叔丁基、戊基、己基等)、具有1至10个碳原子的氟烷基(例如,氟甲基、全氟乙基、三氟甲基等)、具有6至12个碳原子的芳基(例如,苯基、萘基等)、磺酸基和羧酸基,优选经具有1至10个碳原子的氟烷基取代,并且
式4a至4k中指示的*表示键合位点。
根据一个实施方案,用于柔性基底的聚酰亚胺可以通过使由式1的酸二酐与式2的二胺以酸二酐相对于二胺的总摩尔量过量的方式聚合获得的前体固化来获得。
用于生产用于脱粘层和柔性基底的聚酰亚胺的酸二酐与二胺化合物的聚合反应可以根据聚酰亚胺或其前体的常规聚合方法例如溶液聚合来进行。
反应可以在无水条件下进行,并且聚合反应期间的反应温度可以为-75℃至50℃,优选0℃至40℃。反应可以通过向酸二酐中添加溶解在有机溶剂中的二胺化合物来进行。
此外,可以用于聚合反应的有机溶剂可以选自酮,例如γ-丁内酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、环己酮、环戊酮和4-羟基-4-甲基-2-戊酮;芳族烃,例如甲苯、二甲苯和四甲基苯;二醇醚(溶纤剂),例如乙二醇单***、乙二醇单甲醚、乙二醇单丁醚、二乙二醇单***、二乙二醇单甲醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单***、二丙二醇二***和三乙二醇单***;乙酸乙酯、乙酸丁酯、乙二醇单***乙酸酯、乙二醇单丁醚乙酸酯、二乙二醇单***乙酸酯、二丙二醇单甲醚乙酸酯、乙醇、丙醇、乙二醇、丙二醇、卡必醇、二甲基乙酰胺(DMAc)、N,N-二乙基乙酰胺(DEAc)、二甲基甲酰胺(DMF)、二乙基甲酰胺(DEF)、N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)、N-乙烯基吡咯烷酮、1,3-二甲基-2-咪唑啉酮、N,N-二甲基甲氧基乙酰胺、二甲基亚砜、吡啶、二甲基砜、六甲基磷酰胺、四甲基脲、N-甲基己内酰胺、四氢呋喃、间二烷、对二烷、1,2-二甲氧基乙烷、双(2-甲氧基乙基)醚、1,2-双(2-甲氧基乙氧基)乙烷、双[2-(2-甲氧基乙氧基)]醚、及其混合物。
此外,在合成聚酰胺酸或聚酰亚胺的情况下,为了使过量的多氨基或酸酐基失活,还可以添加封端剂,其中分子的末端与二羧酸酐或单胺反应以将聚酰亚胺的末端封端。
使用所制备的聚酰亚胺前体组合物生产聚酰亚胺的方法包括将聚酰亚胺前体组合物施加至基底的一个表面并热处理以使其酰亚胺化的固化步骤。
具体地,聚酰亚胺前体组合物可以呈溶解在有机溶剂中的溶液形式。例如,当在有机溶剂中合成聚酰亚胺前体时,聚酰亚胺前体组合物可以为聚合之后获得的聚酰亚胺前体溶液本身或者添加有相同溶液的聚酰亚胺前体溶液,或者可以通过将聚合之后获得的聚酰亚胺用另外的溶剂稀释来获得。
考虑到成膜过程中的加工性例如涂覆特性,聚酰亚胺前体组合物可以以使得聚酰亚胺前体组合物具有适当粘度的量包含固体,并且基于聚酰亚胺前体组合物的总重量,固体含量为5重量%至20重量%。或者,可以将聚酰亚胺前体组合物调节至粘度为400cP至50000cP。粘度可以通过ASTM D4287,ISO2884的标准方法来测量。聚酰亚胺前体组合物的粘度可以小于400cP,并且当聚酰亚胺前体组合物的粘度大于50000cP时,在使用聚酰亚胺前体组合物制造显示器基底期间流动性可能降低,这可能在制造过程中引起问题,例如不均匀涂覆。
作为载体基底,可以没有任何特别限制地使用玻璃基底、金属基底、塑料基底等。其中,可以优选这样的玻璃基底:其在聚酰亚胺前体的酰亚胺化和固化过程期间的热稳定性和化学稳定性优异,并且即使在没有用另外的脱模剂的任何处理的情况下也可以容易地分离,同时不损坏固化之后形成的聚酰亚胺膜。
施加或涂覆过程可以根据常规施加方法来进行。具体地,可以使用旋涂法、棒涂法、辊涂法、气刀法、凹版印刷法、反向辊法、湿润辊法、刮刀法、喷涂法、浸渍法、刷涂法等。其中,更优选通过允许连续过程并且能够增加聚酰亚胺树脂的酰亚胺化率的流延法来进行。
此外,聚酰亚胺前体溶液可以以使得最终生产的聚酰亚胺膜具有适用于脱粘层或显示器基底的厚度的厚度范围施加在基底上。
在施加聚酰亚胺前体组合物之后,可以在固化过程之前进一步任选地进行用于除去聚酰亚胺前体组合物中剩余的溶剂的干燥过程。
干燥过程可以根据常规方法进行。具体地,干燥过程可以在140℃或更低、或80℃至140℃的温度下进行。如果干燥温度低于80℃,则干燥过程变得较长。如果干燥温度超过140℃,则酰亚胺化局部地进行,使得难以形成具有均匀厚度的聚酰亚胺膜。
随后,可以通过在80℃至450℃的温度下的热处理来进行固化过程。固化过程可以在上述温度范围内以多步加热过程进行。固化过程中的固化时间没有特别限制,例如为3分钟至30分钟。
在固化过程之后,可以任选地进行后续热处理过程以增加聚酰亚胺膜中的聚酰亚胺树脂的酰亚胺化率以形成具有上述物理特性的聚酰亚胺膜。
热处理过程优选在200℃或更高、或200℃至450℃下进行1分钟至30分钟。此外,后续热处理过程可以进行一次或者可以以多个阶段进行两次或更多次。具体地,其可以以三步进行,包括在200℃至220℃下的第一热处理、在300℃至380℃下的第二热处理、以及在400℃至450℃下的第三热处理。
柔性基底层中包含的聚酰亚胺的玻璃化转变温度可以为约360℃或更高。由于其具有如此优异的耐热性,因此含有聚酰亚胺的膜相对于在器件制造过程中添加的高温热可以保持优异的耐热性和机械特性。
发明实施方式
在下文中,将详细描述本发明的实施方案使得本领域技术人员可以容易地进行本发明。然而,本发明可以以许多不同的形式实施,并且不应被解释为限于本文中所阐述的实施方案。
<制备例1>聚酰亚胺BPDA-pPDA(98.9:100)的聚合
在将100g NMP(N-甲基-2-吡咯烷酮)装入具有氮气流的反应器中之后,在将反应器的温度保持在25℃的同时将6.243g(57.726mmol)对苯二胺(p-PDA)溶解。在相同温度下,将16.797g(57.091mmol)3,3',4,4'-联苯四羧酸二酐(s-BPDA)和56.96g NMP添加至p-PDA的溶液中,并搅拌预定时间以聚合聚酰胺酸,从而制备聚酰亚胺前体。
以使由反应制备的聚酰亚胺前体的固体浓度为12.8重量%的量添加有机溶剂以制备聚酰亚胺前体溶液。
<制备例2>聚酰亚胺BPDA-PMDA-pPDA(88.9:10:100)的聚合
在将100g NMP(N-甲基-2-吡咯烷酮)装入具有氮气流的反应器中之后,在将反应器的温度保持在25℃的同时将6.364g(58.849mmol)对苯二胺(p-PDA)溶解。在相同温度下,将15.393g(52.316mmol)3,3',4,4'-联苯四羧酸二酐(s-BPDA)、1.289g(5.885mmol)均苯四酸二酐(PMDA)和56.96g NMP添加至p-PDA的溶液中,并搅拌预定时间以聚合聚酰胺酸,从而制备聚酰亚胺前体。
以使由反应制备的聚酰亚胺前体的固体浓度为12.8重量%的量添加有机溶剂以制备聚酰亚胺前体溶液。
<制备例3>聚酰亚胺BPDA-pPDA-TFMB(98.9:90:10)的聚合
在将100g NMP(N-甲基-2-吡咯烷酮)装入具有氮气流的反应器中之后,在将反应器的温度保持在25℃的同时将5.335g(49.332mmol)对苯二胺(p-PDA)和1.775g(5.481mmol)双三氟甲基联苯胺(TFMB)溶解。在相同温度下,将15.950g(54.221mmol)3,3',4,4'-联苯四羧酸二酐(s-BPDA)和56.96g NMP添加至p-PDA与TFMB的溶液中,并搅拌预定时间以聚合聚酰胺酸,从而制备聚酰亚胺前体。
以使由反应制备的聚酰亚胺前体的固体浓度为12.8重量%的量添加有机溶剂以制备聚酰亚胺前体溶液。
<制备例4>聚酰亚胺BPDA-pPDA(100:98.9)的聚合
在将100g NMP(N-甲基-2-吡咯烷酮)装入具有氮气流的反应器中之后,在将反应器的温度保持在25℃的同时将6.142g(56.800mmol)对苯二胺(p-PDA)溶解。在相同温度下,将16.898g(57.432mmol)3,3',4,4'-联苯四羧酸二酐(s-BPDA)和56.96g NMP添加至p-PDA的溶液中,并搅拌预定时间以聚合聚酰胺酸,从而制备聚酰亚胺前体。
以使由反应制备的聚酰亚胺前体的固体浓度为12.8重量%的量添加有机溶剂以制备聚酰亚胺前体溶液。
<制备例5>聚酰亚胺BPDA-pPDA/PA(98.9:100:2.2)的聚合
在将100g NMP(N-甲基-2-吡咯烷酮)装入具有氮气流的反应器中之后,在将反应器的温度保持在25℃的同时将6.192g(57.259mmol)对苯二胺(p-PDA)溶解。在相同温度下,将16.661g(56.629mmol)3,3',4,4'-联苯四羧酸二酐(s-BPDA)和56.96g NMP添加至p-PDA的溶液中,并搅拌预定时间以聚合聚酰胺酸,从而制备聚酰亚胺前体。此后,将0.187g(1.260mmol)邻苯二甲酸酐(PA)添加至聚酰胺酸溶液中,并搅拌预定时间以制备聚酰亚胺前体。
以使由反应制备的聚酰亚胺前体的固体浓度为12.8重量%的量添加有机溶剂以制备聚酰亚胺前体溶液。
<制备例6>聚酰亚胺BPDA-PMDA-pPDA(90:10:98.9)的聚合
以与制备例2中相同的方式制备聚酰亚胺前体溶液,不同之处在于改变BPDA-PMDA-pPDA的摩尔比使得二酐的当量比过量。
<制备例7>聚酰亚胺BPDA-pPDA-TFMB(100:88.9:10)的聚合
以与制备例3中相同的方式制备聚酰亚胺前体溶液,不同之处在于改变BPDA-pPDA-TFMB的摩尔比使得二酐的当量比过量。
<实验例1>
将制备例1至7中制备的各聚酰亚胺前体溶液旋涂在玻璃基底上。将涂覆有聚酰亚胺前体溶液的玻璃基底放在烘箱中,以6℃/分钟的速率加热,并在400℃下固化10分钟。在固化过程完成之后,将玻璃基底浸入水中以除去形成在玻璃基底上的膜,并在100℃的烘箱中干燥以制备厚度为6μm的聚酰亚胺膜。
如下测量所制备的聚酰亚胺膜的热膨胀系数(CTE)和热分解温度,并且结果示于下表1中。
<热膨胀系数的测量>
将膜切割成5mm×20mm以制备样品,然后通过使用附件将样品装载到TA公司的Q400仪器中。待实际测量的膜的长度等于16mm。将拉力设定为0.02N。从100℃至460℃以4℃/分钟的加热速率进行第一升温步骤,然后从460℃至100℃以5℃/分钟的冷却速率进行冷却,并从100℃至460℃以4℃/分钟的加热速率进行第二升温步骤。用TMA测量样品的热膨胀的变化。基于由加热引起的温度变化的样品尺寸变化示于图1a中,在该温度范围内测量的热膨胀系数示于下表1中。
<热分解温度的测量>
使用由TA仪器制造的Discovery TGA在氮气气氛中测量聚合物的重量损失为1%时的温度。
[表1]
从表1的结果可以看出,其中二胺相对于二酐过量的制备例1至3的聚酰亚胺膜具有为负值的CTE,而制备例4至7的膜具有为正值的CTE。在制备例4、6和7中,二酐相对于二胺过量。在制备例5中,二胺(pPDA)相对于二酐(BPDA)过量,但是添加了封端剂(PA),并因此酸组分的含量远高于二胺的含量。
<实施例1>
将制备例1中制备的聚酰亚胺前体溶液用溶剂稀释至固体内容物浓度为3重量%,然后将其旋涂在玻璃基底的一部分上。将涂覆有聚酰亚胺前体溶液的玻璃基底放在烘箱中,并以6℃/分钟的速率从室温加热(200℃、350℃和400℃),并在最终固化温度下保持10分钟以形成最终厚度为0.1μm的脱粘层。
为了形成柔性基底层,将制备例4的聚酰亚胺前体溶液旋涂以完全覆盖形成在玻璃基底上的脱粘层。将涂覆有聚酰亚胺前体溶液的玻璃基底放在烘箱中并以6℃/分钟的速率加热,在120℃下保持10分钟并在400℃下保持55分钟以形成厚度为10μm的柔性基底层,从而获得层合体。
<实施例2和3>
以与实施例1中相同的方式制备层合体,不同之处在于脱粘层分别由制备例2和3中制备的聚酰亚胺前体溶液形成。
<比较例1至4>
以与实施例1中相同的方式制备层合体,不同之处在于脱粘层分别由制备例4至7中制备的聚酰亚胺前体溶液形成。
<剥离力测试>
对于实施例和比较例中制备的层合体,将完全覆盖脱粘层的柔性基底层切割成宽度为10mm且长度为100mm的矩形形状,然后使用质构分析仪(TA,XT plus,稳定微***)在固定柔性基底的端部的情况下通过以50mm/分钟剥离样品来测量剥离力。结果示于表2中。
[表2]
根据以上结果,在最终固化温度为350℃或更高的情况下,与比较例的层合体不同,具有由通过使用当量比相对于二酐过量的二胺制备的聚酰亚胺前体形成的脱粘层的根据实施例的层合体表现出0.05N/cm或更小的低剥离力。此外,在比较例1的层合体中,由制备例4的聚酰亚胺前体组合物制成的脱粘层和柔性基底层二者即使在最终固化温度为350℃或更高时也保持显著高的粘合强度。由此,可以看出,当柔性基底层的涂覆面积大于脱粘层以完全覆盖脱粘层时,柔性基底层与支撑基底(玻璃基底)直接接触,使得即使在高热处理过程中,稳定的过程也是可能的,并且没有柔性基底层的分离。
虽然已经参照本发明的具体实施方案特别示出和描述了本发明,但是对于本领域技术人员明显的是,该具体描述仅是优选实施方案,并且本发明的范围不由此限制。因此,本发明的范围旨在由所附的权利要求书及其等同方案来限定。
Claims (15)
1.一种层合体,包括:
载体基底;
脱粘层,所述脱粘层形成在所述载体基底上并且包含在350℃或更高的温度下具有为负值的热膨胀系数(CTE)的聚酰亚胺;以及
形成在所述脱粘层上的柔性基底层。
2.根据权利要求1所述的层合体,其中所述脱粘层具有第一面积,以及所述柔性基底层具有大于所述第一面积的第二面积并且完全覆盖所述脱粘层。
3.根据权利要求1所述的层合体,其中所述脱粘层中包含的所述聚酰亚胺包含二胺和二酐在所述二胺的当量比相对于所述二酐过量的条件下聚合并固化的产物。
4.根据权利要求1所述的层合体,其中所述脱粘层包含含有联苯四羧酸二酐(BPDA)的二酐与含有苯二胺(PDA)的二胺聚合并固化的产物。
5.根据权利要求4所述的层合体,其中所述二酐还包含均苯四酸二酐(PMDA),以及所述二胺还包含2,3'-双(三氟甲基)联苯胺(TFMB)。
6.根据权利要求5所述的层合体,其中二酐和二胺的组合选自BPDA-PDA、BPDA-PMDA-PDA和BPDA-PDA-TFMB。
7.根据权利要求6所述的层合体,其中所述二酐和二胺的组合为BPDA-PDA-TFMB,并且TFMB的量为总的二胺的5mol%或更大。
8.根据权利要求6所述的层合体,其中所述二酐和二胺的组合为BPDA-PMDA-PDA,并且PMDA的量为总的二酐的5mol%或更大。
9.根据权利要求1所述的层合体,其中所述脱粘层的厚度为50nm或更大且1μm或更小。
10.根据权利要求1所述的层合体,其中所述柔性基底层包含在350℃或更高的温度下具有为正值的CTE的聚酰亚胺。
11.一种用于制造柔性显示器的方法,包括以下步骤:
在根据权利要求1至10中任一项所述的用于制造柔性显示器的层合体中包括的柔性基底层上形成器件;以及
将其上形成有所述器件的所述柔性基底层从脱粘层上剥离。
12.根据权利要求11所述的用于制造柔性显示器的方法,其中
在载体基底上形成所述脱粘层以具有第一面积,
所述柔性基底层形成为具有大于所述第一面积的第二面积并且完全覆盖所述脱粘层,以及
所述器件形成在所述柔性基底层上的所述脱粘层与所述柔性基底重叠的区域中。
13.根据权利要求12所述的用于制造柔性显示器的方法,其中剥离所述柔性基底层的步骤通过在所述脱粘层与所述柔性基底重叠的区域的内边缘处沿垂直于所述载体基底的方向切割以使所述柔性基底层从所述脱粘层分离来进行。
14.根据权利要求11所述的用于制造柔性显示器的方法,其中在所述剥离期间用于将所述柔性基底层从所述脱粘层上剥离的剥离强度为0.05N/cm或更小。
15.根据权利要求11所述的用于制造柔性显示器的方法,其中将聚酰亚胺基底层从其上形成有所述脱粘层的所述载体基底上的所述剥离不包括在所述脱粘层与所述柔性基底层之间引起化学或物理变化的过程。
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KR20200030016A (ko) | 2020-03-19 |
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