WO2013041017A1 - 预聚物、取向膜及其制备方法、液晶显示装置 - Google Patents

预聚物、取向膜及其制备方法、液晶显示装置 Download PDF

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WO2013041017A1
WO2013041017A1 PCT/CN2012/081578 CN2012081578W WO2013041017A1 WO 2013041017 A1 WO2013041017 A1 WO 2013041017A1 CN 2012081578 W CN2012081578 W CN 2012081578W WO 2013041017 A1 WO2013041017 A1 WO 2013041017A1
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liquid crystal
polyimide prepolymer
prepolymer
formula
polyimide
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PCT/CN2012/081578
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English (en)
French (fr)
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严巍
王丹
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京东方科技集团股份有限公司
北京京东方显示技术有限公司
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Priority to US13/704,149 priority Critical patent/US20140184997A1/en
Publication of WO2013041017A1 publication Critical patent/WO2013041017A1/zh

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    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—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
    • 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
    • C09K2323/0271—Polyimidfluoride

Definitions

  • the present invention relates to a fluorine-containing polyimide prepolymer, an alignment film made of a fluorine-containing polyimide prepolymer, a method for producing the same, and a liquid crystal display device comprising the alignment film, in particular It is suitable for liquid crystal display devices using the ADS (ADvanced Super Dimension Switch) display mode.
  • ADS ADvanced Super Dimension Switch
  • a liquid crystal display using a STN (Super Twisted Nematic) display mode has a problem that the viewing angle is small and the screen loses color when viewed from a large angle on the side, and the contrast and color performance are poor.
  • STN Super Twisted Nematic
  • ADS Advanced Super Dimension Switch
  • ADS Advanced Super Dimension Switch
  • Advanced super-dimensional field switching technology can improve the picture quality of TFT-LCD products, with high resolution, high transmittance, low power consumption, wide viewing angle, high aperture ratio, low chromatic aberration, push mura, etc. advantage.
  • the alignment of liquid crystal molecules is one of the keys to the production of liquid crystal display devices.
  • Rubbing orientation is a commonly used orientation method in the manufacture of liquid crystal display devices.
  • the action has a large influence on the transmittance of the entire liquid crystal display device. Therefore, the choice of oriented film is the key.
  • the most commonly used alignment film material is polyimide
  • the polyimide has the following advantages: 1) The film itself has a function of aligning liquid crystal molecules, 2) For all types of liquid crystals Both show good orientation effects, and 3) depending on the size of the substrate, spin coating, roll coating, dip coating, spray coating, sheet coating, etc., can be applied to the surface of the substrate. A uniform film, 4) complete orientation, can withstand 500. C, 5 minutes heat test.
  • the existing The polyimide material combined with the STN display mode requires a large pretilt angle, which makes it unsuitable for the ADS display mode.
  • the existing polyimide alignment film also has the disadvantage of being incapable of solvent resistance, and it is easy to slowly lose orientation property during the use of the liquid crystal display device in the process of preparing the liquid crystal display device and in the subsequent use of the liquid crystal display device. , causing the liquid crystal display device to fail.
  • the present invention provides a fluorine-containing polyimide prepolymer, an oriented film, a method for producing the same, and a liquid crystal display device, wherein the oriented film made of the fluorine-containing polyimide prepolymer has a good film formation. Performance, mechanical properties, solvent resistance, and better alignment of liquid crystal molecules, reducing the impact of changes in pretilt angle on the transmittance of liquid crystal display devices, especially reducing the transmittance in the dark state.
  • the present invention provides the following technical solutions:
  • Ar is selected from one of the structures represented by the following formula (2) or (3):
  • n is an integer from 3 to 8.
  • Ar is selected from the structures represented by the above formula (2) or formula (3), and n is 3, 5 or 8.
  • a method for preparing an oriented film comprising the steps of:
  • a liquid crystal display device comprising a color filter substrate and an array substrate, which further comprises the alignment film according to any one of [5].
  • the present invention can significantly improve the orientation of the alignment film to the liquid crystal molecules by introducing a fluorine atom in the form of a trifluoromethyl group in the polyimide prepolymer for preparing an alignment film and controlling the number of repeating units of the prepolymer.
  • the alignment performance reduces the repulsion between the dianhydride residue and the polar group of the liquid crystal molecule.
  • the pre-pretilt angle of the prepolymer of the invention is small, and the alignment film prepared therefrom can make the liquid crystal molecules more easily arranged along the rubbing direction, and the introduction of the cross-linkable phenylacetylene end group can further crosslink and solidify the oriented film, and enhance Take
  • the chemical stability of the film to the substance to be contacted improves its solvent resistance.
  • Fig. 1 is an infrared diagram of a polyimide prepolymer I prepared in Example 1.
  • Fig. 2 is an infrared diagram of the polyimide prepolymer II prepared in Example 2.
  • Fig. 3 is an infrared spectrum of a polyimide prepolymer III prepared in Example 3.
  • Fig. 4 is an infrared spectrum of the polyimide prepolymer IV prepared in Example 4.
  • the prepolymer of the present invention has a repeating unit formed of a specific diamine monomer having a trifluoromethyl group and an aromatic dianhydride monomer, and a phenylethynyl group as a terminal group, specifically,
  • the prepolymer of the present invention has a repeating unit represented by the formula (1) and is terminated by a blocking agent having a phenylacetylene group:
  • Ar is selected from one of the structures represented by the following formula (2) or (3): ⁇ -
  • n is an integer from 3 to 8.
  • the diamine monomer having a trifluoromethyl group used in the present invention is specifically 1,4-bis(4-amino-2-trifluorodecylphenoxy)-2-(3,-trifluorodecylphenyl) Benzene;
  • the dianhydride monomer of the Ar moiety having the structure represented by the formula (2) is 3,4,3,4,-diphenylether tetracarboxylic dianhydride (00?) having the formula (3)
  • Two of the Ar parts of the structure The anhydride monomer was 2,2,-bis(3,4-dicarboxybenzene)hexafluoropropane dianhydride (6FDA).
  • the alignment film can be remarkably improved by introducing a fluorine atom in the form of a trifluoromethyl group and selecting a suitable aromatic dianhydride monomer while controlling the number of repeating units of the formed polyimide prepolymer.
  • the orientation alignment property of the liquid crystal molecules reduces the repulsive force between the dianhydride residue and the polar group of the liquid crystal molecule, lowers the pretilt angle, and makes the liquid crystal molecules more easily aligned parallel to the surface of the alignment film.
  • the above two specific dianhydride monomers have good reactivity with the above diamine monomers, which is advantageous for the preparation of the polyimide prepolymer.
  • the number (n value) of the repeating units of the polyimide prepolymer of the present invention is preferably an integer of from 3 to 8, more preferably 3, 5 or 8.
  • n value is greater than or equal to 3
  • the repulsive force between the dianhydride residue and the liquid crystal molecule in the prepolymer can be remarkably lowered, which is very favorable for the orientation of the liquid crystal molecules; when the n value is less than or equal to 8, the prepolymer is formed.
  • the film properties are the best and the yield of the prepolymer is high.
  • the prepolymer of the present invention is blocked with a phenylacetylene group, and if the prepolymer of the present invention is blocked without using a phenylethynyl group, the prepolymer is easily soluble in various solvents and has poor solvent resistance.
  • the terminal blocking agent used in the present invention is not particularly limited as long as it is a terminal blocking agent capable of imparting a phenylethynyl group at the end of the prepolymer of the present invention, but is preferably 4-phenylacetylene-1 represented by the following formula. 8-naphthalenedihydride:
  • 4-Phenylacetylene-1,8-naphthalenedicarboxylic anhydride is used as a blocking agent.
  • the activity is higher when the blocking reaction is carried out, and the yield of the prepolymer can be improved.
  • 2,2,-bis(3,4-dicarboxybenzene)hexafluoropropane dianhydride (6FDA) having the structure represented by the formula (3) is preferred as the aromatic dianhydride monomer.
  • the monomer has an additional trifluoromethyl group and thus contributes to further reducing the repulsive force between the dianhydride residue and the liquid crystal molecules.
  • the prepolymer of the present invention may specifically be: Wherein Ar is selected from one of the structures represented by formula (2) or formula (3), and n is 3, 5 or 8. further, Ar is preferably a structure represented by the formula.
  • the prepolymer of the present invention can be produced by a usual method for producing a polyimide, for example, by a one-step method.
  • the one-step process is shown in the following reaction formula:
  • the one-step method is specifically: adding the above dianhydride monomer, the above diamine monomer and m-nonylphenol to a flask with a stirring and reflux condenser, stirring at room temperature for 8 to 12 hours under nitrogen, and controlling the raw material to be fed
  • the amount of the repeating unit of the produced polyimide prepolymer is controlled, and then the blocking agent and the diphenylbenzene are added, and the temperature is raised to reflux the diphenylbenzene with water for 3 to 4 hours, and then the diphenylbenzene is distilled off by heating. Further, isoquinoline was added, and the temperature was raised to 200 ° C to continue the reaction for 8-10 hours. After completion of the reaction, the mixture was cooled to room temperature, and poured slowly into stirred ethanol to obtain a prepolymer of the present invention, which was washed and dried to obtain a finished product.
  • the present invention provides an oriented film comprising the above prepolymer, which has the advantages of good solvent resistance and high mechanical strength, and has a small pretilt angle, and is suitable for a liquid crystal display device of an ADS display mode.
  • the present invention also provides a method for preparing the above oriented film, which comprises the following steps:
  • the above organic solvent is not particularly limited as long as it is a high-boiling aprotic solvent, and for example, N-mercaptopyrrolidone, DMAc (N,N-didecylacetamide), DMF (N,N-dimercaptoacetamide) can be used.
  • the coating method is not particularly limited, and may be, for example, spin coating, roll coating, brush coating, blade coating, dip coating, curtain coating, spray coating, IHJ sheet coating, or the like, and is preferably spin coating.
  • the drying can be carried out by a stage temperature increase in a vacuum oven (60 to 200 ° C).
  • the step of crosslinking the phenylacetylene group may specifically be carried out at 350 to 400 ° C for 2 hours under vacuum.
  • the present invention also provides a liquid crystal display device comprising the above alignment film.
  • Liquid crystal display device To include: LCD panels, LCD TVs, LCD devices, digital photo frames, electronic paper, mobile phones and other end products.
  • the use of the above-mentioned alignment film in the ADS type display device can remarkably improve the alignment alignment property of the alignment film to the liquid crystal molecules, and reduce the repulsion force between the dianhydride residue and the polar group of the liquid crystal molecule.
  • the pre-pretilt angle of the prepolymer of the invention is small, and when the rubbing orientation is used, the alignment film prepared therefrom can make the liquid crystal molecules more easily arranged along the rubbing direction, and the pretilt angle of the liquid crystal molecules is small, so that the ADS type display device is transparent. Higher rate and better display quality.
  • An ADS type display device includes a color filter substrate and an array substrate, wherein the array substrate is provided with a pixel electrode and a common electrode, and the pixel electrode and the common electrode are disposed on different layers of the array substrate, and the pixel electrode and An insulating layer is disposed between the common electrodes, the common electrode covers the entire pixel region, and the pixel electrode has a slit shape, and includes any one of the above-mentioned alignment films.
  • the introduction of the crosslinkable phenylacetylene end group can further crosslink and cure the alignment film, enhance the chemical stability of the alignment film to the contacted substance (such as liquid crystal), and improve its solvent resistance.
  • reaction temperature was controlled at 160-170 ° C for 4 hours, and finally discharged into distilled water, repeatedly washed with ethanol (AR, Beijing Chemical Plant) and deionized water, and dried in an oven at 120 ° C. In an hour, 96.16 g of a yellow powdery solid dinitro monomer as shown in the following chemical formula was obtained.
  • Trifluoromethylphenoxy)-2-(3,-trifluorodecylphenyl)benzene and 10 ml of m-nonylphenol (AR, Changzhou Xinhua Active Material Co., Ltd.), while stirring with nitrogen gas for 10 hours, Then, 0.2983 g of the above-prepared capping agent PENA and 10 ml of diphenylbenzene (AR, Beijing Chemical Reagent No. 1) were added, and the mixture was heated to 160 ° C for reflux for 3 hours, followed by the addition of 7 ml of isoquinoline (AR, Beijing Lianhua). Fine Chemical Co., Ltd.), the temperature was raised to 200 ° C to distill off the diphenylbenzene and continue to react for 10 hours.
  • AR Changzhou Xinhua Active Material Co., Ltd.
  • the three-necked flask was cooled to room temperature, and poured slowly into a well-stirred absolute ethanol (AR, Beijing Chemical Plant) to precipitate a yellow precipitate.
  • the yield was 57.6 wt% with respect to the starting materials ODPA, 1,4-bis(4-amino-2-trifluorodecylphenoxy)_2-(3,-trifluorodecylphenyl)benzene and PENA.
  • N-decylpyrrolidone (AR, Tianjin Dengfeng Chemical Reagent Factory) was used as a solvent, and refluxed at the boiling point for 24 hours, then cooled to room temperature, filtered, and further washed repeatedly with N-decylpyrrolidone, and dried under vacuum.
  • Example 3 The obtained polyimide prepolymer was analyzed by infrared analysis, and the results are shown in Fig. 2.
  • the solvent resistance was measured in the same manner as in Example 1 to be 99.7 wt%.
  • the yield was 62.3 wt% based on the starting materials ODPA, 1,4-bis(4-amino-2-trifluorodecylphenoxy)-2-(3,-trifluorodecylphenyl)benzene and PENA.
  • Example 4 The obtained polyimide prepolymer III was subjected to infrared analysis, and the results are shown in Fig. 3. The solvent resistance was measured in the same manner as in Example 1 to be 99.6 wt%.
  • Example 4 The solvent resistance was measured in the same manner as in Example 1 to be 99.6 wt%.
  • the yield was 59.7 wt% based on the starting materials ODPA, 1,4-bis(4-amino-2-trifluorodecylphenoxy)-2-(3,-trifluorodecylphenyl)benzene and PENA.
  • the yield was 50% by weight relative to the starting materials ODPA, 1,4-bis(4-amino-2-trifluorodecylphenoxy)-2-(3,-trifluorodecylphenyl)benzene and PENA. Its infrared spectrum is similar to the polyimide prepolymer prepared in the above examples. The solvent resistance was measured in the same manner as in Example 1 to be 92.3 wt%. Comparative example 2
  • the yield was 46.9 wt% based on the starting materials ODPA, 1,4-bis(4-amino-2-trifluorodecylphenoxy)-2-(3,-trifluorodecylphenyl)benzene and PENA. Its infrared spectrum is similar to the polyimide prepolymer prepared in the above examples. The solvent resistance was measured in the same manner as in Example 1 to be 90% by weight. Comparative example 3
  • the polyimide prepolymers lg obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were prepared, and dissolved in 10 ml of DMAc (AR, Tianjin Tiantai Fine Chemical Co., Ltd.), and stirred until they were completely dissolved.
  • a polyimide prepolymer dispersion was obtained, and the prepolymer dispersion was coated on a clean glass substrate (10 cm ⁇ 10 cm) by a spin coating method (MTI Spin coating, model VTC-100, spin coating parameter: 1000 r/min).
  • the temperature was raised to 180 ° ⁇ in a vacuum oven (heating at 401, 801, 1001, 1201 and 140 ° C for 1 hour, heating at 150 ° C for 30 minutes, and finally heating to 180 ° C) to remove the solvent and form a film. After the film formation was observed, it was again placed in a vacuum oven, and cured by crosslinking at 350 ° C for 2 hours under vacuum to obtain a crosslinked cured alignment film having a thickness of 44 ⁇ m.
  • the polyimide prepolymers of Examples 1 to 4 were easy to apply and form a film, and the film formability was good; and the polyimide prepolymers of Comparative Examples 1 and 2 had uneven film thickness at the time of film formation. There was a phenomenon such as impurities, and the polyimide prepolymer of Comparative Example 3 was incapable of being formed into a film and easily broken, and the film forming property was poor.
  • Example 6 Pretilt test
  • each of the glass substrates having the alignment films formed of the polyimide prepolymers of Examples 1 to 4 prepared in Example 5 was cut out of two pieces of 3 cm x 3 cm, respectively, using a friction machine (M).
  • the pre-tilt test of the obtained liquid crystal analog device was carried out, and the pretilt angles were 0.9°, 1.1°, 1.5 respectively. °, 1.2. , with traditional STN type polyimide oriented film 2 ⁇ 5. The pretilt angle is greatly improved.

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Abstract

提供一种聚酰亚胺预聚物、取向膜及其制备方法及液晶显示装置。所述聚酰亚胺预聚物具有式（1）所示的重复单元且被带有苯乙炔基团的封端剂封端。其中，Ar选自式（2）或（3）所示结构中的一种，n为3~8的整数。

Description

预聚物、 取向膜及其制备方法、 液晶显示装置
技术领域 本发明涉及含氟聚酰亚胺预聚物、 由含氟聚酰亚胺预聚物制得的取向膜、 它们的制备方法、 以及包括该取向膜液晶显示装置， 所述取向膜尤其适用于釆 用 ADS(ADvanced Super Dimension Switch)显示模式的液晶显示装置。
背景技术 以往的釆用 STN(Super Twisted Nematic)显示模式的液晶显示器存在可视 角度小、在侧面较大的角度观看时画面就会失色、对比度和颜色表现较差的问 题。 为了解决这一问题， 人们开发出了广视角技术。 ADS(ADvanced Super Dimension Switch), 即高级超维场转换技术， 通过同一平面内狭缝电极边缘所 产生的电场以及狭缝电极层与板状电极层间产生的电场形成多维电场，使液晶 盒内狭缝电极间、 电极正上方所有取向液晶分子都能够产生旋转，从而提高了 液晶工作效率并增大了透光效率。 高级超维场开关技术可以提高 TFT-LCD产 品的画面品质， 具有高分辨率、 高透过率、 低功耗、 宽视角、 高开口率、 低色 差、 无挤压水波紋 (push Mura)等优点。
液晶分子排列取向是制作液晶显示装置的关键之一， 摩擦 (Rubbing)取向 是目前液晶显示装置制造中常用的取向方法。在釆用 ADS技术的显示模式中， 釆用摩擦取向时， 希望液晶分子能平行于摩擦的方向排列， 而且液晶分子的预 倾角越小越好， 因为在 ADS显示模式中液晶分子在垂直方向上的动作对整个 液晶显示装置的透过率有很大的影响。 因此取向膜的选择成为关键。
在用于制备取向膜的材料中， 最常用的取向膜材料是聚酰亚胺， 聚酰亚胺 具有如下优点： 1)膜本身就有使液晶分子排列的功能， 2)对所有类型的液晶都 显示了良好的取向效果， 3)根据基片面积的大小， 可任意选用旋转涂布、 滚动 涂布、 浸渍涂布、 喷雾涂布、 板涂布等手段， 并能在基片表面涂布成均匀的 膜， 4)取向功能完全， 可以耐受 500。C、 5分钟的耐热试验。 但是， 现有的适 合于 STN显示模式的聚酰亚胺材料， 多要求较大的预倾角， 导致其并不适合 用于 ADS显示模式。
此外，现有的聚酰亚胺取向膜还存在不耐溶剂的缺点，在制备液晶显示装 置的过程中和以后的液晶显示装置的使用过程中， 在受到溶剂侵害时， 容易慢 慢失去取向性能， 导致液晶显示装置失效。
发明内容 针对上述问题， 经本发明人的深入研究发现，在聚酰亚胺中引入氟原子可 以有效的对预倾角进行控制， 进而完成了本发明。 即本发明提供一种含氟聚酰 亚胺预聚物、 取向膜及其制备方法、 以及液晶显示装置， 由所述含氟聚酰亚胺 预聚物制成的取向膜具有良好的成膜性能、机械性能、 耐溶剂性能， 并且可使 液晶分子更好地排列， 降低由于预倾角变化对液晶显示装置透过率的影响， 尤 其是降低对暗态下的透过率的影响。
具体而言， 本发明提供如下技术方案：
[1]一种聚酰亚胺预聚物， 其具有式 (1)所示的重复单元且被带有苯乙炔基 团的封端剂封端：
Figure imgf000004_0001
…式 (1);
其中， Ar选自下述式 (2)或 (3)所示结构中的一种:
Figure imgf000004_0002
式 (2)，
Figure imgf000004_0003
…式 (3);
n为 3~8的整数。 [2]如上述 1所述的聚酰亚胺预聚物， 所述带有苯乙炔基团的封端剂为 4- 苯乙炔 - 1 ,8-萘二酸酐 (PENA)。
[3]如上述 [1]或 [2]所述的聚酰亚胺预聚物， 所述聚酰亚胺预聚物具体为：
Figure imgf000005_0001
其中， Ar选自上述式 (2)或式 (3)所示结构， n为 3、 5或 8。
[4]如上述 [1卜[3]中任一项所述的聚酰亚胺预聚物， 其中 Ar选自上述式 (3) 所示结构。
[5]—种取向膜， 其包含上述 [1卜[4]中任一项所述的聚酰亚胺预聚物。
[6]如上述 [5]所述的取向膜， 其预倾角为 0~2°。
[7]如上述 [6]所述的取向膜， 所述预倾角为 0.5~1.5°。
[8]—种取向膜的制备方法， 其包括如下步骤：
1)将上述 [1卜 [4]中任一项所述的聚酰亚胺预聚物溶解于有机溶剂， 搅拌均 匀后涂布到玻璃基板上， 干燥除去溶剂并成膜；
2)升温至 350~400°C使苯乙炔基团交联。
[9]一种液晶显示装置， 包括彩膜基板和阵列基板， 其还包含上述 [5卜 [7] 中任一项所述的取向膜。
[10]如 [9]所述的液晶显示装置，所述阵列基板上设置有像素电极和公共电 极， 所述像素电极和所述公共电极设置在所述阵列基板的不同层， 所述像素电 极和所述公共电极之间设置有绝缘层， 所述公共电极覆盖整个像素区， 所述像 素电极的形状为狭缝状。 发明效果
本发明通过在用于制备取向膜的聚酰亚胺预聚物中以三氟曱基的形式引 入氟原子， 并控制预聚物的重复单元的数量， 可以显著改善取向膜对液晶分子 的取向排列性能， 降低二酐残基与液晶分子极性基团之间的排斥作用力。本发 明的预聚物预倾角很小，由其制备的取向膜可使液晶分子更容易沿着摩擦方向 排列， 同时可交联的苯乙炔端基的引入可以使取向膜进一步交联固化， 增强取 向膜对所接触物质 (如液晶）的化学稳定性， 提高其耐溶剂性。
附图说明 图 1为实施例 1制备的聚酰亚胺预聚物 I的红外语图。
图 2为实施例 2制备的聚酰亚胺预聚物 II的红外语图。
图 3为实施例 3制备的聚酰亚胺预聚物 III的红外谱图。
图 4为实施例 4制备的聚酰亚胺预聚物 IV的红外谱图。
具体实施方式 本发明的预聚物具有由特定的带有三氟曱基的二胺单体和芳香族二酐单 体形成的重复单元以及作为端部基团的苯乙炔基团， 具体而言， 本发明的预聚 物具有式 (1)所示重复单元且被带有苯乙炔基团的封端剂封端：
Figure imgf000006_0001
…式 (1);
其中， Ar选自下述式 (2)或 (3)所示结构中的一种: 丫-
\ 、
…式 (2),
CF-÷
' " fY
-义 ^
…式 (3)，
n为 3~ 8的整数。
本发明中所用的带有三氟曱基的二胺单体具体为 1,4-二 (4-氨基 -2-三氟曱 基苯氧基) -2-(3， -三氟曱基苯基)苯； 所用的具有式 (2)所示结构的 Ar部分的二 酐单体为 3,4,3，,4，-二苯醚四酸二酐(00? )，具有式 (3)所示结构的 Ar部分的二 酐单体为 2,2，-双 (3,4-二羧基苯)六氟丙烷二酐 (6FDA)。
本发明人发现，通过以三氟曱基的形式引入氟原子并选择合适的芳香族二 酐单体， 同时控制所形成的聚酰亚胺预聚物的重复单元的数量， 可以显著改善 取向膜对液晶分子的取向排列性能，降低二酐残基与液晶分子极性基团之间的 排斥作用力， 降低预倾角， 使液晶分子更为容易地平行于取向膜表面排列。 上 述两种特定的二酐单体与上述二胺单体的反应性良好，有利于聚酰亚胺预聚物 的制备。
本发明的聚酰亚胺预聚物的重复单元的数量 (n值)优选为 3~8的整数， 更 优选为 3、 5或 8。 当 n值大于等于 3时， 可显著降低预聚物中的二酐残基与 液晶分子之间的排斥力， 非常有利于液晶分子的取向； 当 n值小于等于 8时， 预聚物的成膜性最好， 且预聚物的产率较高。
本发明的预聚物被苯乙炔基团封端，如果不釆用苯乙炔基团对本发明的预 聚物进行封端， 则该预聚物会易溶于各种溶剂， 耐溶剂性差。 本发明中使用的 封端剂只要是可赋予本发明的预聚物端部苯乙炔基团的封端剂，就没有特别的 限制， 但优选为如下式所示的 4-苯乙炔 -1,8-萘二酸酐：
Figure imgf000007_0001
以 4-苯乙炔 -1,8-萘二酸酐作为封端剂， 在制备本发明的预聚物时， 进行封端反 应时活性更高， 可以提高预聚物的收率。
在上述二酐中， 优选具有式 (3)所示结构的 2,2，-双 (3,4-二羧基苯)六氟丙烷 二酐 (6FDA)作为芳香族二酐单体。 该单体具有额外的三氟曱基， 因此有助于 进一步降低二酐残基与液晶分子之间的排斥力。
本发明的所述预聚物具体可以为：
Figure imgf000007_0002
其中， Ar选自式 (2)或式 (3)所示结构中的一种， n为 3、 5或 8。 进一步地， Ar优选为式 所示结构。
本发明的预聚物可以通过用于制备聚酰亚胺常用的方法制备，例如可以通 过一步法制备。 一步法的流程如下述反应式所示：
Figure imgf000008_0001
所述一步法具体为： 将上述二酐单体、上述二胺单体和间曱酚加入到带有搅拌 和回流冷凝管的烧瓶中， 氮气下室温搅拌 8~12小时， 通过控制原料投料摩尔 比控制所生成的聚酰亚胺预聚物的重复单元的数量， 然后加入封端剂和二曱 苯，升温以使二曱苯带水回流 3~4小时，之后加热蒸出二曱苯，再加入异喹啉, 升温到 200 °C继续反应 8-10小时。 反应结束后冷却至室温， 緩慢地倒入搅拌 的乙醇中， 得到本发明的预聚物， 洗涤、 干燥即可得到成品。
另外， 本发明还提供包含上述预聚物的取向膜， 其具有耐溶剂性好、机械 强度高的优点， 同时预倾角小， 适合用于 ADS显示模式的液晶显示器件。
另外， 本发明还提供上述取向膜的制备方法， 该方法包括如下步骤：
1)将上述聚酰亚胺预聚物溶解于有机溶剂， 搅拌均勾后涂布到玻璃基板 上， 干燥除去溶剂并成膜；
2)升温至 350~400°C使苯乙炔基团交联。
上述有机溶剂只要是高沸点非质子性溶剂就没有特别的限制，例如可以使 用 N-曱基吡咯烷酮、 DMAc(N,N-二曱基乙酰胺)、 DMF(N,N-二曱基曱酰胺)等。 上述涂布方法没有特别限制， 例如可以为旋涂、 辊涂、 刷涂、 刮刀涂布、 浸渍 涂布、 幕涂、 喷雾涂布、 IHJ板涂布等， 优选为旋涂。 所述干燥可以在真空烘箱 内通过阶段升温而进行 (60~200。C )。 所述使苯乙炔基团交联的步骤具体可以为 在 350~400°C、 在真空条件下交联 2小时。
进一步， 本发明还提供包含上述取向膜的液晶显示装置。 液晶显示装置可 以包括： 液晶面板、 液晶电视、 液晶显示器件、 数码相框、 电子纸、 手机等终 端产品。 尤其是在 ADS型显示装置中釆用上述取向膜， 可以显著改善取向膜 对液晶分子的取向排列性能，降低二酐残基与液晶分子极性基团之间的排斥作 用力。 本发明的预聚物预倾角很小， 釆用摩擦取向时， 由其制备的取向膜可使 液晶分子更容易沿着摩擦方向排列， 而且液晶分子的预倾角很小， 使得 ADS 型显示装置透过率更高， 显示质量更好。 ADS 型显示装置， 包括彩膜基板和 阵列基板， 所述阵列基板上设置有像素电极和公共电极， 所述像素电极和所述 公共电极设置在所述阵列基板的不同层，所述像素电极和所述公共电极之间设 置有绝缘层， 所述公共电极覆盖整个像素区， 所述像素电极的形状为狭缝状， 其包含上述所述的任一种取向膜。同时因为可交联的苯乙炔端基的引入可以使 取向膜进一步交联固化， 增强取向膜对所接触物质 (如液晶）的化学稳定性， 提 高其耐溶剂性。
实施例 以下，通过实施例来进一步阐述本发明，但本发明的保护范围不受限于下 述实施例。
制备例 1 : PENA的制备
向 250ml的带有氮气通口、 温度计、机械搅拌、 回流冷凝管的三颈烧瓶中 加入用二曱苯 (AR, 北京化学试剂一厂）重结晶过的 4-溴 -1, 8-萘酐 (AR,鞍山市 惠丰化学有限责任公司） 10g、苯乙炔 5.5g(6ml)(AR, 西格玛奥德里奇公司）、三 苯基碑 0.1956g(CP, 上海试剂一厂）、 碘化亚铜 0.0657g(AR, 西格玛奥德里奇 公司）、 三苯基膦二氯化钯 0.0322g(AR, 西格玛奥德里奇公司）， 50ml 蒸馏过 的三乙胺 (AR, 天津化学试剂二厂）、 100ml曱苯 (AR, 北京化学试剂一厂）， 反 应混合物在通入氮气的条件下， 用油浴锅緩慢加热回流 6.5小时， 同时保持氮 气通畅。 可观察到反应瓶壁有黄白色固体析出， 冷却过滤， 得到黄色固体。 之 后用蒸馏水洗掉催化剂和反应产生的无机盐， 再在 120°C干燥 2小时， 用曱苯 重结晶后得到 13.2g黄色针状固体 PENA。 制备例 2:二胺单体 1,4-二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基) 苯的制备
实施例中所用的 1,4-二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯 根据下述化学式制备， 具体步骤如下所述。
二硝基单体的制备： 向 1000ml 带有机械搅拌、 氮气通口、 带水器 (Dean-Stark trap)、 回流冷凝管的三颈烧瓶中加入三氟曱基双酚 0.2mol(50.84g)(根据文献： Liu BJ, Wang GB, Hu W, Jin YH, Chen CH, Jiang ZH, et al. J Polym Sci Part A Polym Chem 2002; 40:3392所记载的方法制备)、 2-氯 -5- 硝基 -3-三氟曱苯 0.4mol(90.22g)(AR, 上海善岛化工有限公司）、 无水碳酸钾 0.24mol(33.12g)(AR, 天津化学试剂厂）、 DMF 500ml(AR, 天津天泰精细化学 品有限公司）和曱苯 70ml, 加热以使曱苯回流 4小时， 回流温度控制在 130°C , 然后升温至 150°C蒸除曱苯并继续反应 8 小时。 进一步将反应温度控制在 160~170°C继续反应 4小时， 最后出料到蒸馏水中， 经乙醇 (AR, 北京化工厂） 和去离子水反复洗涤， 并在烘箱内于 120°C下干燥 12小时， 得到 96.16g如下 述化学式所示的黄色粉末状固体二硝基单体。
二胺单体的制备： 将上述合成好的二硝基单体 0.02mol(12.65g)、 铁粉
0.24mol(13.44g)(AR, 北京化学试剂厂）、 60ml体积分数为 50%的乙醇水溶液置 于 250ml三颈烧瓶中回流， 回流过程中滴入 0.704ml浓盐酸溶液 (AR, 北京化学 试剂厂， 36.5% (体积))， 及 10mL体积分数为 50%的乙醇水溶液， 继续回流反应 3小时后加入 0.366g NaOH, 中和多余未反应的盐酸后对该混合溶液进行热过 滤， 滤液在氮气保护条件下冷却至二胺单体析出， 然后用乙醇重结晶得到 8.5g 二胺单体 1 ,4-二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯。
Figure imgf000010_0001
实施例 1
向带有磁力搅拌器、 氮气通口、 回流冷凝管的 100ml 三口烧瓶中加入 0.4653g ODPA(AR, 西格玛奥德里奇公司）、 1.1448g上述制备的 1,4-二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯以及 10ml间曱酚 (AR, 常州市新华 活性材料有限公司）， 一边通入氮气， 一边搅拌 10小时， 然后加入 0.2983g上 述制备的封端剂 PENA和 10ml二曱苯 (AR,北京化学试剂一厂），加热至 160 °C 进行带水回流 3小时，之后加入 7ml异喹啉 (AR,北京联华精细化工有限公司）， 升温到 200 °C蒸除二曱苯并继续反应 10小时。 反应结束后将三口烧瓶冷却至 室温， 緩慢地倒入充分搅拌的无水乙醇 (AR, 北京化工厂）中， 析出黄色沉淀。 将该黄色沉淀水洗多次后抽滤， 120°C干燥， 得到 1.10g聚酰亚胺预聚物 I , 其重复单元数量 n=3。 相对于原料 ODPA、 1,4-二 (4-氨基 -2-三氟曱基苯氧 基 )_2-(3，-三氟曱基苯基)苯和 PENA, 产率为 57.6wt%。
对所得到的聚酰亚胺预聚物 I进行红外分析 (Nicolet Impat 410 型傅里叶 变换红外光语仪）， 结果如图 1所示， 其中 1780 cnT1 1726 cm 处的吸收峰对 应 C=0; 1363 cm"1处的吸收峰对应 C-N; 1320 cm"1 , 1136 cm"1处的吸收峰对 应 -CF; 而 2215cm-1处的特征吸收峰证明苯乙炔封端反应顺利进行， 从图中还 可以看出在 3200-3600cm-1范围内没有胺基的吸收峰， 说明聚合物扣环非常完 全。
称取 0.3g聚酰亚胺预聚物 I , 在真空烘箱中、 在 350°C下保持 2小时， 使 苯乙炔基团交联， 然后将交联固化后的样品置于带有回流冷凝管的烧瓶中， 以 N-曱基吡咯烷酮 (AR,天津登峰化学试剂厂)为溶剂、在其沸点下回流 24小时， 然后冷却至室温， 过滤后进一步用 N-曱基吡咯烷酮反复洗涤， 真空干燥至恒 重，计算剩余样品相比于初始样品的质量百分数作为其耐溶剂性的评定，质量 百分数越大证明溶剂对其溶解作用越小。 该聚酰亚胺预聚物 I的耐溶剂性为 99.6%。 实施例 2
除了将上述 ODPA替换为等摩尔的 6FDA作为二酐成分以外，与实施例 1 同样地进行操作， 得到 1.16g聚酰亚胺预聚物 Π , 其重复单元数量 n=3。 相对 于原料 6FDA、 1,4-二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯和 PENA, 产率为 55.2wt%。
对所得到的聚酰亚胺预聚物 Π进行红外分析， 结果如图 2所示。用与实施 例 1相同的方法测定其耐溶剂性， 为 99.7wt%。 实施例 3
除了将上述 0.4653g ODPA、 1.1448g 1,4-二 (4-氨基 -2-三氟曱基苯氧 基) -2-(3，-三氟曱基苯基)苯分别替换为 0.7755g ODPA、1.7172g 1,4-二 (4-氨基 -2- 三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯之外， 与实施例 1 同样地进行操作， 得到 1.74g聚酰亚胺预聚物 III, 其重复单元数量 n=5。 相对于原料 ODPA、 1,4- 二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基）苯和 PENA , 产率为 62.3wt%。
对所得到的聚酰亚胺预聚物 III进行红外分析， 结果如图 3所示。用与实施 例 1相同的方法测定其耐溶剂性， 为 99.6wt%。 实施例 4
除了将上述 0.4653g ODPA、 1.1448g 1,4-二 (4-氨基 -2-三氟曱基苯氧 基 )_2-(3，-三氟曱基苯基)苯分别替换为 1.2408g ODPA、2.5758g 1,4-二 (4-氨基 -2- 三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯之外， 与实施例 1 同样地进行操作， 得到 2.46g聚酰亚胺预聚物 IV , 其重复单元数量 n=8。 相对于原料 ODPA、 1,4- 二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基）苯和 PENA , 产率为 59.7wt%。
对所得到的聚酰亚胺预聚物 IV进行红外分析， 结果如图 4所示。用与实施 例 1相同的方法测定其耐溶剂性， 为 99.3wt%。 比较例 1
除了将上述 0.4653g ODPA、 1.1448g 1,4-二 (4-氨基 -2-三氟曱基苯氧 基 )_2-(3，-三氟曱基苯基)苯分别替换为 1.5510g ODPA、3.1482g 1,4-二 (4-氨基 -2- 三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯之外， 与实施例 1 同样地进行操作， 得到 2.5g聚酰亚胺预聚物 V , 其重复单元数量 n=10。 相对于原料 ODPA、 1,4- 二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯和 PENA,产率为 50wt%。 其红外谱图与上述实施例中制备的聚酰亚胺预聚物类似。用与实施例 1相同的 方法测定其耐溶剂性， 为 92.3wt%。 比较例 2
除了将上述 0.4653g ODPA、 1.1448g 1,4-二 (4-氨基 -2-三氟曱基苯氧 基 )_2-(3，-三氟曱基苯基)苯分别替换为 1.8612g ODPA、3.7206g 1,4-二 (4-氨基 -2- 三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯之外， 与实施例 1 同样地进行操作， 得到 2.76g聚酰亚胺预聚物 VI,其重复单元数量 n=12。相对于原料 ODPA、 1,4- 二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基）苯和 PENA , 产率为 46.9wt%。 其红外谱图与上述实施例中制备的聚酰亚胺预聚物类似。 用与实施 例 1相同的方法测定其耐溶剂性， 为 90wt%。 比较例 3
除了将上述 0.4653g ODPA、 1.1448g 1,4-二 (4-氨基 -2-三氟曱基苯氧 基 )_2-(3，-三氟曱基苯基)苯分别替换为 0.3102g ODPA、0.8586g 1,4-二 (4-氨基 -2- 三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯之外， 与实施例 1 同样地进行操作， 得到 0.55g聚酰亚胺预聚物 W, 其重复单元数量 n=2。 相比于原料 ODPA、 1,4- 二 (4-氨基 -2-三氟曱基苯氧基) -2-(3，-三氟曱基苯基)苯和 PENA,产率为 37.4%。 其红外谱图与上述实施例中制备的聚酰亚胺预聚物类似。用与实施例 1相同的 方法测定其耐溶剂性， 为 68wt%。 实施例 5(成膜性）
分别准备实施例 1~4和比较例 1~3所得的聚酰亚胺预聚物 lg, 将其溶解 于 10ml的 DMAc(AR, 天津天泰精细化学品有限公司）中， 搅拌直至其完全溶 解，得到聚酰亚胺预聚物分散液，通过旋涂法 (MTI Spin coating,型号 VTC-100, 旋涂参数： 1000r/分钟)将预聚物分散液涂布在清洁玻璃基板 (lOcmxlOcm)上， 在真空烘箱内通过阶段升温至 180°〇（分别在401、801、1001、1201和 140°C 下加热 1小时， 在 150°C加热 30分钟， 最后升温至 180 °C)去除溶剂并成膜， 观察成膜情况后， 再次置入真空烘箱中， 在 350°C、 真空条件下固化交联 2小 时， 得到交联固化后的取向膜， 其厚度为 44μπι。
其中， 实施例 1~4的聚酰亚胺预聚物易于涂布和成膜， 成膜性良好； 而比 较例 1和 2的聚酰亚胺预聚物在成膜时存在膜厚不均、有杂质等现象， 比较例 3的聚酰亚胺预聚物存在无法成膜、 易于碎裂的现象， 成膜性差。 实施例 6: 预倾角测试
首先制作液晶模拟器件：分别从实施例 5制备的带有由实施例 1~4聚酰亚 胺预聚物形成的取向膜的玻璃基板上， 各自裁出 3cmx3cm的两块， 用摩擦机 (M-2000 型摩擦机， 河北宣化试验机厂)对取向膜进行同向平行摩擦， 之后以 使取向膜相对的方式、 用封框胶 (S-WB21 型， 积水化学株式会社)沿玻璃基板 的三边将两块玻璃板粘接成盒， 对封框胶先使用 UV (紫外光)固化 60秒钟， 然 后在 120°C下热固化 1小时， 保证封框胶将两玻璃基板完全粘牢， 最后注入液 晶 (MAT-09-1284型， 默克液晶公司）0.03mg, 并再次用少量封框胶封口并重复 上述固化封框胶的步骤， 制成一个完整可用于测试的液晶模拟器件。
釆用 PAT20型预倾角测试仪 (长春联诚仪器有限公司） (测量误差为 ±0. 1°), 分别对所得液晶模拟器件进行预倾角测试， 其预倾角分别为 0.9°、 1.1°、 1.5°、 1.2。， 与传统 STN型聚酰亚胺取向膜 2~5。的预倾角相比有很大改善。

Claims

权 利 要 求 书
1. 一种聚酰亚胺预聚物， 其特征在于， 其具有式 (1)所示的重复单元且被
Figure imgf000015_0001
…式 (1);
其中， Ar选自下述式 (2)或 (3)所示结构中的一种:
-^
式 (2)，
Figure imgf000015_0002
…式 (3);
n为 3~8的整数。
2. 如权利要求 1所述的聚酰亚胺预聚物， 其特征在于， 所述带有苯乙炔 基团的封端剂为 4-苯乙炔 -1,8-萘二酸酐。
3. 如权利要求 1或 2所述的聚酰亚胺预聚物， 其特征在于， 所述聚酰亚 胺预聚物具体为：
Figure imgf000015_0003
其中， Ar选自上述式 (2)或式 (3)所示结构中的一种， n为 3、 5或 8。
4. 如权利要求 3所述的聚酰亚胺预聚物， 其特征在于， Ar选自上述式 (3) 所示结构。
5. 一种取向膜， 其包含上述权利要求 1~4中任一项所述的聚酰亚胺预聚 物。
6. 如权利要求 5所述的取向膜， 其特征在于， 其预倾角为 0~2°。
7. 如权利要求 6所述的取向膜， 其特征在于， 所述预倾角为 0.5~1.5°。
8. 一种取向膜的制备方法， 其包括如下步骤：
1)将权利要求 1~4中任一项所述的聚酰亚胺预聚物溶解于有机溶剂，搅拌 均匀后涂布到玻璃基板上， 干燥除去溶剂以成膜；
2)升温至 350~400°C使苯乙炔基团交联。
9. 一种液晶显示装置， 包括彩膜基板和阵列基板， 其特征在于， 其包含 权利要求 5~7中任一项所述的取向膜。
10. 如权利要求 9所述的液晶显示装置， 其特征在于， 所述阵列基板上设 置有像素电极和公共电极，所述像素电极和所述公共电极设置在所述阵列基板 的不同层， 所述像素电极和所述公共电极之间设置有绝缘层， 所述公共电极覆 盖整个像素区， 所述像素电极的形状为狭缝状。
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