WO2014190673A1 - 取向膜及其制备方法、含所述取向膜的液晶显示装置 - Google Patents

取向膜及其制备方法、含所述取向膜的液晶显示装置 Download PDF

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WO2014190673A1
WO2014190673A1 PCT/CN2013/086970 CN2013086970W WO2014190673A1 WO 2014190673 A1 WO2014190673 A1 WO 2014190673A1 CN 2013086970 W CN2013086970 W CN 2013086970W WO 2014190673 A1 WO2014190673 A1 WO 2014190673A1
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formula
polyimide
alignment film
alignment layer
crystal display
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肖昂
汪姗姗
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BOE Technology Group Co Ltd
Beijing BOE Optoelectronics Technology Co Ltd
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BOE Technology Group Co Ltd
Beijing BOE Optoelectronics Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C09K2323/027—Polyimide

Definitions

  • Embodiments of the present invention relate to an alignment film, a method of fabricating the same, and a liquid crystal display including the alignment film
  • TFT-LCD Thin Film Transistor Liquid
  • an alignment film i.e., an oriented polyimide film
  • an alignment film is usually used to cause the liquid crystal molecules to be aligned in a uniform direction on the surface of the film, thereby achieving alignment of the liquid crystal molecules. Since light is partially absorbed by the polyimide film as it passes through the polyimide film, the high transmittance polyimide film plays an important role in producing a liquid crystal display panel with low power consumption and high contrast.
  • Ar may be a phenyl group, a tea group, a benzophenone group, a dibenzoyl group, a diphenyl ether group or a diphenylsulfonyl group.
  • the optical transmittance of the conventional polyimide film is generally about 70% to 75%.
  • An embodiment of the present invention provides an alignment film, wherein the alignment film is composed of polyimide, and the polyimide 4 shows:
  • R is a strong electron withdrawing group
  • R 2 is each independently methyl, ethyl, propyl, isopropyl, methyl tt, ethoxy, propyl or isopropoxy.
  • the 1 is 8, 0, S0 2 , CC1 2 or CF 2 .
  • the polyimide is obtained by reacting 1,4,5,8-naphthalenetetracarboxylic dianhydride represented by the formula -1 with the bridged diphenylenediamine represented by the formula -2,
  • a method for preparing an oriented film comprising:
  • the R in the formula -2 is a strong electron withdrawing group, and each independently is a methyl group, an ethyl group, a propyl group, an isopropyl group, a methyl group, an ethoxy group, a propyl group or an isopropyl group;
  • the 1 is 8, 0, S0 2 , CC1 2 or CF 2 .
  • the step (1) can be carried out at room temperature.
  • the heating process in the step (2) comprises: first heating at 90-100 ° C for 3-6 min, Heat at 220-250 ° C for another 40-80 min.
  • the orientation process in the step (3) is a rubbing alignment process.
  • a liquid crystal display device having an alignment film as described above on an array substrate or a color filter substrate of the liquid crystal display device.
  • the polyimide film of the embodiment of the present invention is composed of polyimide, and the polyimide is represented by 1,4,5,8-naphthalenetetracarboxylic dianhydride represented by Formula-1 and Formula-2.
  • R may be a strong electron withdrawing group such as S, 0, S0 2 , CC1 2 or CF 2 ; and may be a methyl group, an ethyl group, a propyl group or an isopropyl group.
  • R 2 may be methyl, ethyl, propyl, isopropyl, tt, tt, tt, isopropyloxy base.
  • Step 1 adding bridged diphenylenediamine to N-methylpyrrolidone (NMP), and then adding 1,4,5,8-naphthalenetetracarboxylic dianhydride to carry out a reaction, and filtering the reaction liquid to obtain a liquid polyamic acid;
  • NMP N-methylpyrrolidone
  • Step 2 Dissolving the liquid polyamic acid in NMP to obtain a solution, applying the solution to the surface of the substrate and heating to obtain a polyimide film. Thereafter, an orientation process was performed on the polyimide film to obtain an oriented polyimide film, that is, an alignment film.
  • the orientation process employed may be an orientation process commonly used in the art, such as a rubbing alignment process, in which the polyimide film is oriented in the rubbing direction under the action of a high speed rotating friction roller.
  • the molar ratio of the reaction raw material bridged diphenylenediamine to 1,4,5,8-naphthalenetetracarboxylic dianhydride may be 1:1, but in actual operation, one of them may be excessive, for example, the ratio of the two may be It is 1:1 - 1:1.1, or 1:1 - 1.1:1.
  • the bridge R in the diamine is a strong electron withdrawing group, so that the CH bond length on the diamine aromatic ring can be reduced, thereby reducing Harmonic vibration absorption of CH, ultimately reducing the absorption rate of light by polyimide film, and increasing polyimide Optical transmission of the film.
  • the oriented film of the embodiment of the present invention is prepared according to the above-described method for preparing an oriented film, and the specific steps are as follows: Step S1: 0.05 mol of bridged diphenylenediamine is added to 200 ml of dry N-methylpyrrolidone (NMP) at room temperature. In the solvent, 0.05 mol of 1,4,5,8-naphthalenetetracarboxylic dianhydride was slowly added thereto while stirring well, and after stirring for 24 hours, it was allowed to stand and filtered to obtain a liquid polyamic acid.
  • the liquid polyamic acid has a number average molecular weight of from 4000 to 6000, and the structural formula and IR spectrum data are as follows:
  • the bridged diphenylenediamine may be 3,3,-dimethyl-4,4,-diphenyl sulfoxide, that is, R in the formula-2 is S0 2 , and both are methyl groups.
  • R, and the bridged diphenylenediamine of other groups listed in the present invention may also be prepared according to the steps described in the step S2 of the present invention: Dissolving the liquid polyamic acid obtained in the step 1 In N-methylpyrrolidone, a clear liquid is obtained, and the obtained clear liquid is uniformly applied to the surface of the transparent glass substrate to have a film thickness of about 100 nm, and heated at 100 ° C for 5 minutes to remove a part of the residual solvent (ie, N).
  • the number average molecular weight of the polyimide is from 4000 to 6000, and the structural formula of the polyimide and the IR optical data are as follows: (form-4);
  • the temperature during the initial heating may be 90-110 ° C, and the heating time may be 3-6 min, in order to remove a small portion of the solvent (ie N-decyl pyrrolidone), so that the surface of the polyimide (PI) film is flat .
  • the temperature for subsequent heating may be 220-250 ° C, and the heating time may be 40-80 min as long as the heating completely removes the solvent and forms a polyimide film. Thereafter, an orientation process commonly used in the art is carried out on the polyimide film to obtain an oriented polyimide film.
  • Examples 1-15 were prepared by the above preparation methods, and then optical transmittances of these examples and comparative examples at different wavelengths were measured by an EZ-COM optical measuring system, and the results are shown in Table 1.
  • the structure of the comparative example is as shown in the formula -A in the background art, wherein Ar is a tea group.
  • Example 12 83.6 83.8 84.2 basis 0 isopropyl methoxy
  • Example 15 82.0 81.1 82.1 Base « - Comparative Example CH 2 HH 72.8 74.9 74.2 From the measurement results shown in Table 1, it is understood that the optical transmittance of the polyimide film of the embodiment of the present invention at each wavelength is higher than that of the comparative example. It is about 7%-16% higher.
  • the reason why the polyimide film of the embodiment of the present invention has a relatively good optical transmittance is that the light absorption rate of the polyimide film mainly depends on the density of the CH bond in the structure of the polyimide film and the bridge in the diamine.
  • the action of the bond R when R is a strong electron withdrawing group, reduces the CH bond length on the diamine aromatic ring, thereby reducing the harmonic vibration absorption of the CH, ultimately reducing the absorption rate of the film and increasing the optical transmittance of the film.
  • the embodiment of the present invention further provides a liquid crystal display device having an alignment film as described above, that is, the polyimide film after orientation, on the array substrate or the color filter substrate of the liquid crystal display device.
  • polyimide is obtained by the method described above.

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Abstract

一种取向膜及其制备方法、含所述取向膜的液晶显示装置。所述取向膜为取向后的聚酰亚胺膜。取向膜的制备方法包括：将桥连二苯二胺加入到 N- 甲基吡咯烷酮中，再加入1，4，5，8-萘四甲酸二酐进行反应，过滤反应液得到液体状聚酰胺酸；将所述液体状聚酰胺酸溶解于 N-甲基吡咯烷酮，得到一溶液，将所述溶液涂覆到基板表面并加热，得到聚酰亚胺膜；再通过取向工艺得到取向膜；其中，聚酰亚胺的结构式如式-4所示：式-4，其中，R为强吸电子基团，R1和R2各自独立地为甲基、乙基、丙基、异丙基、甲氧基、乙氧基、丙氧基或异丙氧基。所述聚酰亚胺膜具有较好的光学透射率。

Description

取向膜及其制备方法、 含所述取向膜的液晶显示装置 技术领域
本发明实施例涉及一种取向膜及其制备方法、 含所述取向膜的液晶显示
背景技术
在制作薄膜晶体管液晶显示器（TFT-LCD, Thin Film Transistor Liquid
Crystal Display )时， 通常使用取向膜（即取向后的聚酰亚胺膜）来使液晶^ 子在膜表面达到均一定向的排列， 从而实现液晶分子的定向排列。 由于光在 透过聚酰亚胺膜时会被聚酰亚胺膜部分吸收， 因此高透射率的聚酰亚胺膜对 于制作低功耗和高对比度的液晶显示面板有着非常重要的作用。
一种传统聚酰亚胺膜：
Figure imgf000003_0001
(式 -A );
其中， Ar可以为苯基、 茶基、 二苯酮基、 二苯甲烷基、 二苯醚基或二苯 磺酰基等。 该传统聚酰亚胺膜的光学透射率一般在 70%~75%左右。 发明内容
本发明实施例提供一种取向膜， 所述取向膜由聚酰亚胺构成， 所述聚酰 亚胺 -4所示：
Figure imgf000003_0002
式 -4， 其中， R为强吸电子基团， 和 R2各自独立地为甲基、 乙基、 丙基、 异丙基、 甲 tt、 乙氧基、 丙 或异丙氧基。
例如， 所述 1 为8、 0、 S02、 CC12或 CF2。
所述聚酰亚胺是由式 -1所示的 1,4,5,8-萘四甲酸二酐与式 -2所示的桥连 二苯二胺反应得到的，
Figure imgf000004_0001
一种取向膜的制备方法， 包括：
( 1 )将式 -2所示的桥连二苯二胺加入到 N-甲基吡咯烷酮中， 再加入式 .1所示的 1,4,5,8-萘四甲酸二酐进行反应， 过滤反应液得到液体状聚酰胺酸，
Figure imgf000004_0002
式. 式 -2,
所述式 -2中的 R为强吸电子基团， 和 各自独立地为甲基、 乙基、 丙基、 异丙基、 甲 tt、 乙氧基、 丙 或异丙 tt;
( 2 )将所述液体状聚酰胺酸溶解于 N-甲基吡咯烷酮， 得到一溶液， 将 所述溶液涂覆到基板表面并加热， 得到聚酰亚胺膜；
( 3 )通过取向工艺对所述聚酰亚胺膜进行取向， 得到取向膜，
亚胺的结构式如式 -4所示：
Figure imgf000004_0003
式 -4。
所述 1 为8、 0、 S02、 CC12或 CF2。
例如， 所述步骤（1 )均可在室温下进行反应。
例如， 所述步骤（2 ) 中的加热过程包括： 先在 90-100 °C下加热 3-6min, 再在 220-250°C加热 40-80min。
例如， 所述步骤（3 ) 中的取向工艺为摩擦取向工艺。
一种液晶显示装置， 所述液晶显示装置的阵列基板或彩膜基板上具有如 上所述的取向膜。 具体实施方式
本发明实施例的聚酰亚胺膜由聚酰亚胺构成， 所述聚酰亚胺由式 -1所示 的 1,4,5,8-萘四甲酸二酐与式 -2所示的桥连二苯二胺聚合生成：
Figure imgf000005_0001
(式 -1 ); (式 -2 )。
式 -2所示的桥连二苯二胺中， R可以为 S、 0、 S02、 CC12或 CF2等强吸 电子基团； 可以为甲基、 乙基、 丙基、 异丙基、 甲^ J^、 乙^ J^、 丙^ J^、 异丙氧基； R2可以为甲基、 乙基、 丙基、 异丙基、 甲 tt、 乙 tt、 丙 tt、 异丙氧基。
本发明实施例取向膜的制备方法， 包括：
步骤 1: 将桥连二苯二胺加入到 N-甲基吡咯烷酮 （NMP ) 中， 再加入 1,4,5,8-萘四甲酸二酐进行反应， 过滤反应液得到液体状聚酰胺酸；
步骤 2: 将所述液体状聚酰胺酸溶解于 NMP, 得到一溶液， 将所述溶液 涂覆到基板表面并加热， 得到聚酰亚胺膜。 之后， 对聚酰亚胺膜实施取向工 艺， 得到取向后的聚酰亚胺膜， 即取向膜。 其中， 所采用的取向工艺可以是 本领域中常用的取向工艺， 如摩擦取向工艺， 将聚酰亚胺膜在高速旋转的摩 擦辊的作用下沿摩擦方向取向。
其中， 反应原料桥连二苯二胺与 1,4,5,8-萘四甲酸二酐的摩尔比可以是 1:1 , 但实际操作中可以将其中之一过量， 如两者的比例可为 1:1 - 1:1.1 , 或 1:1 - 1.1:1。
由上述公开内容可以看出， 在本发明实施例的聚酰亚胺的结构中， 二胺 中的桥键 R为强吸电子基团，所以能够减少二胺芳香环上 C-H键长，从而减 少 C-H的谐波振动吸收， 最终减少聚酰亚胺膜对光的吸收率， 提高聚酰亚胺 膜的光学透射率。
提供了下述实施例来阐述所述聚酰亚胺取向膜的制备过程， 所述实施例 仅仅是描述性的， 并非限定本发明的范围。
实施例
根据上述取向膜的制备方法准备本发明实施例的取向膜，具体步骤如下： 步骤 S1: 在室温下， 将 0.05mol的桥连二苯二胺加入到 200ml干燥的 N-甲基吡咯烷酮 （NMP ) 溶剂中， 在充分搅拌的状态下向其中緩慢加入 0.05mol的 1,4,5,8-萘四甲酸二酐，搅拌 24小时后静置并过滤，得到液体状聚 酰胺酸。 该液体状聚酰胺酸的数均分子量为 4000-6000, 结构式以及 IR光谱 数据如下所示：
Figure imgf000006_0001
(式 -3 );
IR ( KBr ): 1660cm—1, 1720cm—1, 3260-3270cm"1„
作为一个例子， 桥连二苯二胺可以为 3,3，-二甲基 -4,4，-二 二苯亚砜， 即式 -2中的 R为 S02, 和 均为甲基。 应当理解， R、 和 为本发明 所列其他基团的桥连二苯二胺也可以按照所述步骤来制备本发明的聚酰亚胺 步骤 S2: 将步骤 1得到的液体状聚酰胺酸溶解于 N-甲基吡咯烷酮中， 得到澄清液， 将得到的澄清液均匀地涂覆到透明玻璃基板表面， 使其膜厚约 为 lOOnm, 在 100°C下加热 5min, 去除部分残留溶剂（即 N-甲基吡咯烷酮）， 然后在 250°C下加热 lhr, 完全固化后， 得到聚酰亚胺膜。 该聚酰亚胺的数均 分子量为 4000~6000, 且聚酰亚胺的结构式及 IR光语数据如下所示：
Figure imgf000007_0001
(式 -4 );
IR (KBr) : 1360-1370cm"1 0
其中， 初步加热时的温度可以为 90- 110 °C , 且加热时间可以为 3-6min , 目的是去除少部分溶剂 （即 N-曱基吡咯烷酮）， 使得聚酰亚胺（PI )膜表面 平整。 后续加热时的温度可以为 220-250°C , 且加热时间可以为 40-80min, 只要该加热能完全去除溶剂并形成聚酰亚胺膜。 之后， 对聚酰亚胺膜实施本 领域常用的取向工艺， 得到取向后的聚酰亚胺膜。
通过上述制备方法制备实施例 1-15 ,然后用 EZ-COM光学测量系统测量 这些实施例以及比较例在不同波长下的光学透射率， 结果示于表 1中。
比较例的结构如背景技术中的式 -A所示， 其中， Ar为茶基。
表 1 本发明实例 1-15以及比较例的光学透射率 聚酰亚胺 光学透射率 (％)
膜 R i 350~400nm 400~550nm 550~700nm 实施例 1 0 曱基 曱基 81.2 80.3 81.9 实施例 2 0 乙基 乙基 80.8 84.3 80.7 实施例 3 0 甲基 乙基 85.3 82.2 86.4 实施例 4 so2 曱基 甲基 81.5 85.4 83.8 实施例 5 S 甲基 甲基 83.3 85.2 85.1 实施例 6 CF2 曱基 甲基 82.4 81.2 81.1
CC12 丙基 异丙
实施例 7 83.2 82.5 81.3 基
实施例 8 CC12 曱基 乙基 82.4 83.5 83.7
CC12 甲氧 乙氧
实施例 9 83.5 83.8 84.2 基 基
0 乙基 乙氧
实施例 10 81.5 81.6 81.7 基
0 丙基 异丙
实施例 11 80.5 80.8 82.8 基
s 异丙 丙氧
实施例 12 83.6 83.8 84.2 基 0 异丙 甲氧
实施例 13 81.8 81.7 82.5 基 基
0 乙氧 丙基
实施例 14 81.7 81.9 81.3 基
0 丙氧 异丙
实施例 15 82.0 81.1 82.1 基 « - 比较例 CH2 H H 72.8 74.9 74.2 由表 1显示的测量结果可知， 各波长下本发明实施例的聚酰亚胺膜的光 学透射率比比较例的光学透射率高约 7%-16%。
本发明实施例的聚酰亚胺膜具有比较好的光学透射率的原因是： 聚酰亚 胺膜的光吸收率主要取决于聚酰亚胺膜结构中的 C-H键密度和二胺中的桥键 R作用， 当 R为强吸电子基团时会减少二胺芳香环上 C-H键长， 从而减少 C-H的谐波振动吸收， 最终减少膜对光的吸收率， 提高膜的光学透射率。
本发明实施例还提供了一种液晶显示装置， 该液晶显示装置的阵列基板 或彩膜基板上具有如前所述的取向膜， 也即取向后的所述聚酰亚胺膜。
其中， 聚酰亚胺由前面所述的方法制得。
以上所述， 仅为本发明的较佳实施例而已， 并非用于限定本发明的保护 范围。

Claims

权利要求书
1、 一种取向膜， 所述取向膜由聚酰亚胺构成， 其中， 所述聚酰亚胺的结 构式 -4所示：
Figure imgf000009_0001
式 -4,
其中， R为强吸电子基团， 和 R2各自独立地为甲基、 乙
异丙基、 甲 tt、 乙氧基、 丙 或异丙氧基。
2、 根据权利要求 1所述的取向膜， 其中， 所述 1 为 8、 0、 S02、 CC1: 或 CF2。
3、 根据权利要求 1或 2所述的取向膜， 其中， 所述聚酰亚胺是由式 -1 所示的 1,4,5,8-萘四甲酸二酐与式 -2所示的桥连二苯二胺反应得到的，
Figure imgf000009_0002
式 -2c
4、 一种取向膜的制备方法， 包括：
( 1 )将式 -2所示的桥连二苯二胺加入到 N-甲基吡咯烷酮中， 再加入式 .1所示的 1,4,5,8-萘四甲酸二酐进行反应， 过滤反应液得到液体状聚酰胺酸，
Figure imgf000009_0003
式 -2,
所述式 -2中的 R为强吸电子基团， 和 各自独立地为甲基、 乙基、 丙基、 异丙基、 甲 tt、 乙氧基、 丙 或异丙 tt;
( 2 )将所述液体状聚酰胺酸溶解于 N-甲基吡咯烷酮， 得到一溶液， 将 所述溶液涂覆到基板表面并加热， 得到聚酰亚胺膜；
( 3 )通过取向工艺对所述聚酰亚胺膜进行取向， 得到取向膜；
亚胺的结构式如式 -4所示：
Figure imgf000010_0001
式 -4
5、 根据权利要求 4所述的取向膜的制备方法， 其中， 所述 1 为8、 0、 S02、 CC12或 CF2。
6、 根据权利要求 4所述的取向膜的制备方法， 其中， 所述步骤（1 ) 均 在室温下进行反应。
7、 根据权利要求 4所述取向膜的制备方法， 其中， 所述步骤（2 ) 中的 加热过程包括：先在 90-100 °C下加热 3-6min,再在 220-250°C加热 40-80min。
8、 根据权利要求 4所述的取向膜的制备方法， 其中， 所述步骤（3 ) 中 的取向工艺为摩擦取向工艺。
9、一种液晶显示装置， 其中， 所述液晶显示装置的阵列基板或彩膜基板 上具有权利要求 1、 2或 3所述的取向膜。
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