WO2019200646A1 - 液晶介质混合物、液晶显示面板及液晶显示面板的制备方法 - Google Patents

液晶介质混合物、液晶显示面板及液晶显示面板的制备方法 Download PDF

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WO2019200646A1
WO2019200646A1 PCT/CN2018/087311 CN2018087311W WO2019200646A1 WO 2019200646 A1 WO2019200646 A1 WO 2019200646A1 CN 2018087311 W CN2018087311 W CN 2018087311W WO 2019200646 A1 WO2019200646 A1 WO 2019200646A1
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liquid crystal
group
vertical alignment
display panel
substrate
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PCT/CN2018/087311
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English (en)
French (fr)
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蓝松
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深圳市华星光电半导体显示技术有限公司
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Priority to US16/045,077 priority Critical patent/US20190322938A1/en
Publication of WO2019200646A1 publication Critical patent/WO2019200646A1/zh

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    • 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
    • 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
    • G02F1/1303—Apparatus specially adapted to the manufacture of LCDs

Definitions

  • the present invention relates to the field of liquid crystal display technology, and in particular, to a liquid crystal medium mixture, a liquid crystal display panel, and a method for preparing a liquid crystal display panel.
  • the structure of the liquid crystal display panel is mainly composed of a thin film transistor array (TFT Array) substrate, a color filter (CF) substrate, and a liquid crystal layer (Liquid Crystal Layer) disposed between the two substrates.
  • TFT Array thin film transistor array
  • CF color filter
  • Liquid Crystal Layer Liquid Crystal Layer
  • the upper and lower substrate surfaces of the liquid crystal display panel need to be sprayed with a layer of polyimide (PI) alignment material, which is mainly used to guide the ordering of liquid crystal molecules, but the PI alignment material has the following disadvantages: (1) the PI The alignment material is expensive, and the associated equipment for spraying the PI alignment material is also expensive, resulting in an increase in production cost; (2) the PI alignment material usually uses N-methylpyrrolidone (NMP) as a solvent, but the NMP solvent is not environmentally friendly. It is easy to cause harm to the human body; (3) The PI alignment material is easy to lose the product yield due to problems such as uniformity of coating, non-stickiness and foreign matter during the spraying process, so that the product cost is improved. Therefore, display panels that do not print polyimide alignment materials (i.e., vertical alignment liquid crystal material display panels) have gradually become research hotspots.
  • NMP N-methylpyrrolidone
  • the upper and lower substrates of the vertical alignment liquid crystal display panel eliminate the printing process of the PI alignment material, and the function of guiding the alignment of the liquid crystals by adding a material having a vertical alignment function to the liquid crystal medium mixture; wherein, the liquid crystal medium
  • the mixture includes liquid crystal molecules, a vertical alignment agent, and a reactive monomer (RM).
  • the vertical alignment liquid crystal material display panel in which the liquid crystal layer is prepared by the conventional vertical alignment agent has the following problems: on the one hand, the ability of the vertical alignment agent to be anchored to the substrate surface of the liquid crystal display panel needs to be improved, and it is necessary to increase the liquid crystal diffusivity to further reduce the occurrence of chromatic aberration. Probability; on the other hand, the polymer particles formed by the vertical alignment agent are large and uneven, which tends to cause poor alignment stability of the liquid crystal, resulting in a dark state of light leakage of the liquid crystal display panel, which makes the liquid crystal display panel less reliable.
  • the technical problem to be solved by the embodiments of the present invention is to provide a liquid crystal medium mixture, a liquid crystal display panel, and a method for preparing the liquid crystal display panel, which are formed by improving the anchoring ability of the vertical alignment agent in the liquid crystal layer and the polymerization reaction under UV irradiation.
  • the uniformity of the polymer particles is used to improve the alignment stability of the liquid crystal to avoid the phenomenon that the liquid crystal display panel is dark and easy to leak light, and the reliability of the liquid crystal display panel is improved.
  • an embodiment of the present invention provides a liquid crystal medium mixture disposed in a liquid crystal layer of a liquid crystal display panel, including liquid crystal molecules, a reactive monomer, and a vertical alignment agent, wherein the vertical alignment agent includes a head base and a middle a group, a tail group, a polymerizable group, and a polymerization inhibiting functional group;
  • the structural formula of the vertical alignment agent is One of them; among them,
  • A refers to a head group for anchoring a surface of a substrate of the liquid crystal display panel to achieve vertical alignment of the liquid crystal molecules, and the structure is represented as a composition containing a plurality of oxygen atoms;
  • P refers to a polymerizable group for forming a polymer particle film layer under ultraviolet light irradiation so that the liquid crystal molecules produce a pretilt angle, and the structure is expressed as Any combination of them;
  • L refers to a polymerization inhibiting functional group for reducing the reactivity of the polymerizable group P to make the polymer particle size distribution formed under ultraviolet light irradiation uniform and further enhancing the surface ability of the substrate of the liquid crystal display panel.
  • Group its structure is expressed as phenols, the specific structural formula is Wherein, the value of n is 1 to 2; R' represents: a linear or branched alkane of 1 to 5 C atoms, wherein any one of R' carbon atoms may be -O-, -CO-, -COO-, -O-CO- substitution.
  • the mass percentage relationship of the liquid crystal molecules, the reactive monomer and the vertical alignment agent is 0.2 to 0.5%: 0.2 to 5.0%: 94.5 to 99.6%.
  • the structure of the vertical alignment agent is one or more of the following compounds:
  • the embodiment of the present invention further provides a liquid crystal display panel, including a TFT array substrate, a color filter substrate, and a liquid crystal layer disposed between the TFT array substrate and the color filter substrate; wherein the liquid crystal layer Filled with a mixture of liquid crystal media;
  • the liquid crystal medium mixture includes liquid crystal molecules, a reactive monomer, and a vertical alignment agent, and the vertical alignment agent includes a head group, an intermediate group, a tail group, a polymerizable group, and a polymerization inhibiting functional group;
  • the structural formula of the vertical alignment agent is One of them; among them,
  • A refers to a head group for anchoring a surface of a substrate of the liquid crystal display panel to achieve vertical alignment of the liquid crystal molecules, and the structure is represented as a composition containing a plurality of oxygen atoms;
  • P refers to a polymerizable group for forming a polymer particle film layer under ultraviolet light irradiation so that the liquid crystal molecules produce a pretilt angle, and the structure is expressed as Any combination of them;
  • L refers to a polymerization inhibiting functional group for reducing the reactivity of the polymerizable group P to make the polymer particle size distribution formed under ultraviolet light irradiation uniform and further enhancing the surface ability of the substrate of the liquid crystal display panel.
  • Group its structure is expressed as phenols, the specific structural formula is Wherein, the value of n is 1 to 2; R' represents: a linear or branched alkane of 1 to 5 C atoms, wherein any one of R' carbon atoms may be -O-, -CO-, -COO-, -O-CO- substitution.
  • the mass percentage relationship of the liquid crystal molecules, the reactive monomer and the vertical alignment agent is 0.2 to 0.5%: 0.2 to 5.0%: 94.5 to 99.6%.
  • the structure of the vertical alignment agent is one or more of the following compounds:
  • the embodiment of the invention further provides a method for preparing a liquid crystal display panel, the method comprising the following steps:
  • Step S1 providing a TFT array substrate, a color filter substrate, and a liquid crystal medium mixture; wherein the liquid crystal medium mixture includes liquid crystal molecules, a reactive monomer, and a vertical alignment agent, and the vertical alignment agent includes a head group, an intermediate group, a tail group, a polymerizable group, and a polymerization inhibiting functional group;
  • the structural formula of the vertical alignment agent is One of them; among them,
  • A refers to a head group for anchoring a surface of a substrate of the liquid crystal display panel to achieve vertical alignment of the liquid crystal molecules, and the structure is represented as a composition containing a plurality of oxygen atoms;
  • P refers to a polymerizable group for forming a polymer particle film layer under ultraviolet light irradiation so that the liquid crystal molecules produce a pretilt angle, and the structure is expressed as Any combination of them;
  • L refers to a polymerization inhibiting functional group for reducing the reactivity of the polymerizable group P to make the polymer particle size distribution formed under ultraviolet light irradiation uniform and further enhancing the surface ability of the substrate of the liquid crystal display panel.
  • Group its structure is expressed as phenols, the specific structural formula is Wherein, the value of n is 1 to 2; R' represents: a linear or branched alkane of 1 to 5 C atoms, wherein any one of R' carbon atoms may be -O-, -CO-, -COO-, -O-CO-substituted;
  • Step S2 selecting, in the TFT array substrate or the color filter substrate, a substrate to be injected into the liquid crystal medium mixture, and injecting the liquid crystal medium mixture into the selected substrate;
  • Step S3 applying a sealant on the surface of the selected substrate to form a plastic frame enclosing the liquid crystal medium mixture in a semi-closed shape, and coating a surface of the selected substrate with a conductive adhesive on a surface other than the plastic frame;
  • Step S4 the TFT array substrate or the color filter substrate is assembled in a vacuum environment, and the sealant of the plastic frame is cured, so that the liquid crystal medium mixture in the plastic frame is formed to be located at the a liquid crystal layer between the TFT array substrate or the color filter substrate; wherein a portion of the vertical alignment agent in the liquid crystal medium mixture is adsorbed on the surface of the TFT array substrate or the color filter substrate by its own head base And vertically aligned with the surface of the TFT array substrate or the color filter substrate to guide the vertical alignment of the liquid crystal molecules, and another portion of the vertical alignment agent in the liquid crystal medium mixture is filled in the liquid crystal layer;
  • Step S5 applying a certain voltage to the liquid crystal layer, causing liquid crystal molecules in the liquid crystal medium mixture to be deflected, and irradiating the liquid crystal layer whose liquid crystal molecules have been deflected by ultraviolet light for a certain time while continuously applying a voltage,
  • the vertical alignment agent filled in the liquid crystal layer is polymerized with the active monomer, a particle size is formed on the surface of the TFT array substrate and the color filter substrate by using its own polymerization inhibiting functional group. a uniformly distributed polymer film;
  • Step S6 removing the continuously applied voltage, and continuing to irradiate the liquid crystal layer of the polymer film having a uniform particle size distribution to ultraviolet light for a period of time, so that the TFT array substrate and the color filter substrate remain.
  • the surface vertical alignment agent reacts with the active monomer, and further forms a polymer film having a uniform particle size distribution on the surface of the TFT array substrate and the color filter substrate by using its own polymerization inhibiting functional group.
  • a liquid crystal display panel was prepared.
  • the mass percentage relationship of the liquid crystal molecules, the reactive monomer and the vertical alignment agent in the liquid crystal medium mixture is 0.2 to 0.5%: 0.2 to 5.0%: 94.5 to 99.6%.
  • the sealant of the plastic frame is cured by thermal curing or ultraviolet light irradiation.
  • the voltage applied to the liquid crystal layer is 13 to 25 V, and the intensity of ultraviolet light irradiation is 85 to 100 mW/cm 2 , and the irradiation time is 20 to 100 s.
  • the ultraviolet light irradiation time used is 90 to 120 minutes.
  • the embodiment of the present invention has the following beneficial effects: since a polymerization inhibiting functional group is used in the vertical alignment agent to reduce the reactivity of the polymerizable group, the polymer particle size distribution formed by the polymerization under UV irradiation is uniform, Moreover, the surface capability of the substrate of the liquid crystal display panel is enhanced, thereby improving the alignment stability of the liquid crystal to avoid the phenomenon that the liquid crystal display panel is dark and easy to leak light, and the reliability of the liquid crystal display panel is improved.
  • FIG. 1 is a schematic structural view of a liquid crystal medium mixture according to Embodiment 1 of the present invention.
  • FIG. 2 is a flowchart of a method for fabricating a liquid crystal display panel according to Embodiment 3 of the present invention
  • FIG. 3 is a view showing an application scenario of a method for preparing a liquid crystal display panel according to Embodiment 3 of the present invention; wherein, a1-color film substrate, a2-vertical alignment agent, a3-active monomer RM, a4-liquid crystal molecule, a5-ITO Film layer, a6-TFT array substrate, a7-polymer film layer;
  • FIG. 4 is a comparative diagram of a polymer film layer formed by preparing a liquid crystal layer using different vertical alignment agents in a method for fabricating a liquid crystal display panel according to a third embodiment of the present invention.
  • a liquid crystal medium mixture is disposed in a liquid crystal layer of a liquid crystal display panel, including liquid crystal molecules 1, an active monomer 2, and a vertical alignment agent 3, the vertical orientation.
  • Agent 3 includes a head group, an intermediate group, a tail group, a polymerizable group, and a polymerization inhibiting functional group;
  • the structural formula of the vertical alignment agent 3 is One of them; among them,
  • A refers to a head group for anchoring the surface of the substrate of the liquid crystal display panel to achieve vertical alignment of the liquid crystal molecules 1, and the structure thereof is represented as a composition containing a plurality of oxygen atoms; for example, the structural formula of A may preferably be
  • P refers to a polymerizable group which forms a polymer particle film layer under ultraviolet light irradiation so that the liquid crystal molecule 1 produces a pretilt angle, and its structure is expressed as Any combination of them;
  • L refers to a polymerization inhibiting functional group for reducing the reactivity of the polymerizable group P to make the polymer particle size distribution formed under ultraviolet light irradiation uniform and further enhancing the surface ability of the substrate of the anchor liquid crystal display panel, the structure thereof Expressed as phenols, the specific structural formula is Wherein, the value of n is 1 to 2; R' represents: a linear or branched alkane of 1 to 5 C atoms, wherein any one of R' carbon atoms may be -O-, -CO-, -COO-, -O-CO- substitution.
  • the polymerization inhibiting functional group L can lower the reactivity of the polymerizable group P to make the polymer particle size distribution formed by the polymerization under UV irradiation uniform, and enhance the substrate surface ability of the anchor liquid crystal display panel,
  • the use amount of the vertical alignment agent 3 is lowered, the alignment stability of the liquid crystal is improved, the dark state of the liquid crystal display panel is avoided, and the reliability of the liquid crystal display panel is improved.
  • the structure of the polymerization inhibiting functional group L is preferably One of them, the polymerization mechanism is:
  • the structure of the vertical alignment agent 3 is one or more of the following compounds:
  • the mass percentage relationship between the liquid crystal molecule 1, the reactive monomer 2 and the vertical alignment agent 3 is 0.2 to 0.5%: 0.2 to 5.0%: 94.5 to 99.6%, which can improve the alignment stability of the liquid crystal. It is more effective to avoid the phenomenon that the liquid crystal display panel is dark and easy to leak light.
  • the second embodiment of the present invention further provides a liquid crystal display panel, including a TFT array substrate, a color filter substrate, and the TFT array substrate and the color filter substrate.
  • a liquid crystal layer in between; the liquid crystal layer is filled with the liquid crystal medium mixture in the first embodiment of the present invention.
  • the liquid crystal medium mixture in the second embodiment of the present invention has the same structure and connection relationship as the liquid crystal medium mixture in the first embodiment of the present invention. For details, please refer to the related content of the liquid crystal medium mixture in the first embodiment of the present invention. Repeat them one by one.
  • a method for fabricating a liquid crystal display panel includes the following steps:
  • Step S1 providing a TFT array substrate, a color filter substrate, and a liquid crystal medium mixture; wherein the liquid crystal medium mixture includes liquid crystal molecules, a reactive monomer, and a vertical alignment agent, and the vertical alignment agent includes a head group, an intermediate group, a tail group, a polymerizable group, and a polymerization inhibiting functional group;
  • the structural formula of the vertical alignment agent is One of them; among them,
  • A refers to a head group for anchoring a surface of a substrate of the liquid crystal display panel to achieve vertical alignment of the liquid crystal molecules, and the structure is represented as a composition containing a plurality of oxygen atoms;
  • P refers to a polymerizable group for forming a polymer particle film layer under ultraviolet light irradiation so that the liquid crystal molecules produce a pretilt angle, and the structure is expressed as Any combination of them;
  • L refers to a polymerization inhibiting functional group for reducing the reactivity of the polymerizable group P to make the polymer particle size distribution formed under ultraviolet light irradiation uniform and further enhancing the surface ability of the substrate of the liquid crystal display panel.
  • Group its structure is expressed as phenols, the specific structural formula is Wherein, the value of n is 1 to 2; R' represents: a linear or branched alkane of 1 to 5 C atoms, wherein any one of R' carbon atoms may be -O-, -CO-, -COO-, -O-CO-substituted;
  • Step S2 selecting, in the TFT array substrate or the color filter substrate, a substrate to be injected into the liquid crystal medium mixture, and injecting the liquid crystal medium mixture into the selected substrate;
  • Step S3 applying a sealant on the surface of the selected substrate to form a plastic frame enclosing the liquid crystal medium mixture in a semi-closed shape, and coating a surface of the selected substrate with a conductive adhesive on a surface other than the plastic frame;
  • Step S4 the TFT array substrate or the color filter substrate is assembled in a vacuum environment, and the sealant of the plastic frame is cured, so that the liquid crystal medium mixture in the plastic frame is formed to be located at the a liquid crystal layer between the TFT array substrate or the color filter substrate; wherein a portion of the vertical alignment agent in the liquid crystal medium mixture is adsorbed on the surface of the TFT array substrate or the color filter substrate by its own head base And vertically aligned with the surface of the TFT array substrate or the color filter substrate to guide the vertical alignment of the liquid crystal molecules, and another portion of the vertical alignment agent in the liquid crystal medium mixture is filled in the liquid crystal layer;
  • Step S5 applying a certain voltage to the liquid crystal layer, causing liquid crystal molecules in the liquid crystal medium mixture to be deflected, and irradiating the liquid crystal layer whose liquid crystal molecules have been deflected by ultraviolet light for a certain time while continuously applying a voltage,
  • the vertical alignment agent filled in the liquid crystal layer is polymerized with the active monomer, a particle size is formed on the surface of the TFT array substrate and the color filter substrate by using its own polymerization inhibiting functional group. a uniformly distributed polymer film;
  • Step S6 removing the continuously applied voltage, and continuing to irradiate the liquid crystal layer of the polymer film having a uniform particle size distribution to ultraviolet light for a period of time, so that the TFT array substrate and the color filter substrate remain.
  • the surface vertical alignment agent reacts with the active monomer, and further forms a polymer film having a uniform particle size distribution on the surface of the TFT array substrate and the color filter substrate by using its own polymerization inhibiting functional group.
  • a liquid crystal display panel was prepared.
  • step S1 the TFT array substrate and the CF substrate without the coated PI film are provided, and the mass percentage relationship of the liquid crystal molecules, the reactive monomer, and the vertical alignment agent in the liquid crystal medium mixture is set to 0.2 to 0.5%: 0.2 to 5.0%: 94.5 to 99.6%.
  • step S2 any one of the TFT array substrate or the color filter substrate is used as a substrate for injecting a liquid crystal medium mixture, and a liquid crystal medium mixture having the above mass ratio relationship is injected into the selected substrate by an ODF process.
  • step S3 a sealant is applied on the surface of the selected substrate to form a semi-closed plastic frame, the inner region of the plastic frame is used to fill the liquid crystal medium mixture, and the surface of the outer portion of the plastic frame is coated with conductive adhesive. In order to ensure the electrical conductivity of the TFT array substrate and the color film substrate assembly.
  • step S4 the TFT array substrate and the CF substrate are bonded together in a vacuum environment, and the sealant is cured, and the curing method is performed by thermal curing or UV curing, thereby obtaining liquid crystal between the TFT array substrate and the CF substrate.
  • the vertical alignment agent is adsorbed on the surface of the TFT array substrate or the color filter substrate by its own head base, and is arranged perpendicular to the surface of the TFT array substrate or the color filter substrate to guide the vertical alignment of the liquid crystal molecules. Another portion is filled in the liquid crystal layer as shown by 3a in FIG.
  • step S5 the voltage applied to the liquid crystal layer is 13 to 25 V, so that liquid crystal molecules are deflected, as shown by 3b in FIG.
  • ultraviolet light having an irradiation intensity of 85 to 100 mW/cm 2 and an irradiation time of 20 to 100 s is irradiated to the liquid crystal layer in which the liquid crystal molecules have been deflected, so that the vertical alignment agent filled in the liquid crystal layer is irradiated.
  • a polymer film having a uniform particle size distribution is formed on the surface of the TFT array substrate and the color filter substrate by using its own polymerization inhibiting functional group, as shown by 3c in FIG.
  • step S6 the above-mentioned continuously applied voltage of 13 to 25 V is removed, and the liquid crystal layer is further irradiated with ultraviolet light for 90 to 120 minutes (intensity of 85 to 100 mW/cm 2 ) so that the surface of the TFT array substrate and the color filter substrate are vertical.
  • the alignment agent reacts with the active monomer, and further forms a polymer film having a uniform particle size distribution on the surface of the TFT array substrate and the color filter substrate by using its own polymerization inhibiting functional group, thereby preparing a liquid crystal display panel. As shown in 3d in Figure 3.
  • the structures, amounts, and orientation effects of the vertical alignment agents used in the liquid crystal molecules are as follows:
  • the structure of the vertical alignment agent when a liquid crystal layer having an area of 10*10 cm is prepared by the method for preparing a liquid crystal display panel according to the third embodiment of the present invention, the structure of the vertical alignment agent is Moreover, the structure contains a polymerization inhibiting functional group, so that the polymer formed by the UV reaction of the liquid crystal layer has a small and uniform particle size, as shown by 4a in FIG. 4; and the structure using the vertical alignment agent is Moreover, the structure does not have a polymerization inhibiting functional group, so that the polymer formed by the UV reaction of the liquid crystal layer has a large particle size and is uneven, as shown by 4b in FIG.
  • the practice of the present invention has the following beneficial effects: a polymer formed by polymerization under UV irradiation due to the use of a polymerization inhibiting functional group in the vertical alignment agent to reduce the reactivity of the polymerizable group.
  • the particle size distribution is uniform, and the surface capability of the substrate of the liquid crystal display panel is enhanced, thereby improving the alignment stability of the liquid crystal to avoid the phenomenon that the liquid crystal display panel is dark and easy to leak light, and the reliability of the liquid crystal display panel is improved.

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Abstract

一种液晶介质混合物，包括液晶分子(a4)、活性单体(a3)和垂直取向剂(a2)，垂直取向剂(a2)包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；其中，头基锚定液晶显示面板的基板表面来实现对液晶分子(a4)起到垂直配向作用，中间基团和尾基引导液晶分子(a4)排列，聚合性基团在紫外光照射下形成聚合物颗粒膜层来使得液晶分子(a4)产生预倾角，而阻聚功能基团通过降低聚合性基团的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀，减少了碎亮点发生，以及增强锚定液晶显示面板的基板表面能力。液晶介质混合物能改善液晶层中垂直取向剂(a2)的锚定能力及其在UV照射下聚合反应形成的聚合物颗粒的均匀性，用以提升液晶配向稳定性来避免暗态易漏光的现象出现。

Description

液晶介质混合物、液晶显示面板及液晶显示面板的制备方法
本申请要求于2018年4月20日提交中国专利局、申请号为201810362206.7、发明名称为“液晶介质混合物、液晶显示面板及液晶显示面板的制备方法”的中国专利申请的优先权，上述专利的全部内容通过引用结合在本申请中。
技术领域
本发明涉及液晶显示技术领域，尤其涉及一种液晶介质混合物、液晶显示面板及液晶显示面板的制备方法。
背景技术
液晶显示面板的结构主要是由一薄膜晶体管阵列(Thin Film Transistor Array，TFT Array)基板、一彩色滤光片(Color Filter，CF)基板、以及配置于两基板间的液晶层(Liquid Crystal Layer)所构成，其工作原理是通过在两片玻璃基板上施加驱动电压来控制液晶层的液晶分子LC的旋转，将背光模组的光线折射出来产生画面。
通常，液晶显示面板的上下基板表面都需要喷涂一层聚酰亚胺(PI)配向材料，主要是用来引导液晶分子有序排列，但是PI配向材料具有以下几点劣势：(1)该PI配向材料价格昂贵，且相关喷涂该PI配向材料的配套设备价格也昂贵，导致生产成本提高；(2)该PI配向材料通常使用N-甲基吡咯烷酮(NMP)作为溶剂，但因NMP溶剂不环保而易对人体造成危害；(3)该PI配向材料在喷涂过程中由于存在涂布均匀性、不粘以及异物等问题，容易对产品良率造成损失，使得产品成本提高。因此，不喷印聚酰亚胺配向 材料的显示面板(即垂直取向液晶材料显示面板)逐渐成为研究热点。
在制作工艺上，垂直取向液晶材料显示面板的上下基板省去PI配向材料的印刷工艺，通过在液晶介质混合物里添加具备垂直取向功能的材料实现引导液晶有序排列配向的功能；其中，液晶介质混合物包括液晶分子、垂直取向剂及活性单体(RM)。
然而，由传统垂直取向剂制备液晶层的垂直取向液晶材料显示面板存在以下问题：一方面、垂直取向剂锚定在液晶显示面板的基板表面能力有待提高，需要增加液晶扩散性来进一步降低色差出现概率；另一方面、垂直取向剂形成的聚合物颗粒较大且不均匀，容易造成液晶配向稳定性较差，导致液晶显示面板出现暗态易漏光的现象，使得液晶显示面板信赖性较低。
发明内容
本发明实施例所要解决的技术问题在于，提供一种液晶介质混合物、液晶显示面板及液晶显示面板的制备方法，通过改善液晶层中垂直取向剂的锚定能力及其在UV照射下聚合反应形成的聚合物颗粒的均匀性，用以提高液晶配向稳定性来避免液晶显示面板出现暗态易漏光的现象，提升了液晶显示面板信赖性。
为了解决上述技术问题，本发明实施例提供了一种液晶介质混合物，设置于液晶显示面板的液晶层中，包括液晶分子、活性单体和垂直取向剂，所述垂直取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
其中，所述垂直取向剂的结构通式为
Figure PCTCN2018087311-appb-000001
Figure PCTCN2018087311-appb-000002
之中一种；其中，
A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；
R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生 预倾角的聚合性基团，其结构表示为
Figure PCTCN2018087311-appb-000003
之中的任意一种组合；
L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
Figure PCTCN2018087311-appb-000004
其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代。
其中，所述阻聚功能基团的结构表示为
Figure PCTCN2018087311-appb-000005
Figure PCTCN2018087311-appb-000006
之中一种。
其中，所述液晶分子、活性单体和垂直取向剂的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％。
其中，所述垂直取向剂的结构为以下化合物中的一种或多种：
Figure PCTCN2018087311-appb-000007
Figure PCTCN2018087311-appb-000008
相应于，本发明实施例还提供了一种液晶显示面板，包括TFT阵列基板、彩膜基板以及设置于所述TFT阵列基板和所述彩膜基板之间的液晶层；其中，所述液晶层中填充有液晶介质混合物；
所述液晶介质混合物包括液晶分子、活性单体和垂直取向剂，所述垂直取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
其中，所述垂直取向剂的结构通式为
Figure PCTCN2018087311-appb-000009
Figure PCTCN2018087311-appb-000010
之中一种；其中，
A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为 -(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；
R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生预倾角的聚合性基团，其结构表示为
Figure PCTCN2018087311-appb-000011
之中的任意一种组合；
L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
Figure PCTCN2018087311-appb-000012
其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代。
其中，所述阻聚功能基团的结构表示为
Figure PCTCN2018087311-appb-000013
Figure PCTCN2018087311-appb-000014
之中一种。
其中，所述液晶分子、活性单体和垂直取向剂的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％。
其中，所述垂直取向剂的结构为以下化合物中的一种或多种：
Figure PCTCN2018087311-appb-000015
Figure PCTCN2018087311-appb-000016
相应于，本发明实施例又提供了一种液晶显示面板的制备方法，所述方法包括以下步骤：
步骤S1、提供一TFT阵列基板、一彩膜基板以及液晶介质混合物；其中，所述液晶介质混合物包括液晶分子、活性单体和垂直取向剂，所述垂直 取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
其中，所述垂直取向剂的结构通式为
Figure PCTCN2018087311-appb-000017
Figure PCTCN2018087311-appb-000018
之中一种；其中，
A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；
R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、 环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生预倾角的聚合性基团，其结构表示为
Figure PCTCN2018087311-appb-000019
之中的任意一种组合；
L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
Figure PCTCN2018087311-appb-000020
其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代；
步骤S2、在所述TFT阵列基板或所述彩膜基板中，选出待注入所述液晶介质混合物的基板，并在所选基板注入所述液晶介质混合物；
步骤S3、在所选基板的表面涂布密封胶形成将所述液晶介质混合物围成半封闭状的胶框，且在所选基板除胶框之外区域的表面涂有导电胶；
步骤S4、将所述TFT阵列基板或所述彩膜基板在真空环境下组立贴合，并对所述胶框的密封胶进行固化，使得所述胶框内的液晶介质混合物形成为 位于所述TFT阵列基板或所述彩膜基板之间的液晶层；其中，所述液晶介质混合物中垂直取向剂的一部分依靠其自身的头基吸附在所述TFT阵列基板或所述彩膜基板的表面上，并垂直于所述TFT阵列基板或所述彩膜基板的表面排列来引导所述液晶分子垂直配向排列，所述液晶介质混合物中垂直取向剂的另一部分填充在所述液晶层中；
步骤S5、对所述液晶层施加一定电压，使得所述液晶介质混合物中的液晶分子发生偏转，并在持续施加电压的同时对所述液晶分子已发生偏转的液晶层进行紫外光照射一定时间，使得填充在所述液晶层中的垂直取向剂在与活性单体发生聚合时，利用其自身的阻聚功能基团会在所述TFT阵列基板和所述彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜；
步骤S6、去除所述持续施加的电压，再继续对所述已形成颗粒大小分布均匀的聚合物薄膜的液晶层进行紫外光照射一段时间，使得残存在所述TFT阵列基板和所述彩膜基板表面的垂直取向剂与活性单体全部反应，也会利用其自身的阻聚功能基团进一步在所述TFT阵列基板和所述彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜，从而制备出液晶显示面板。
其中，所述步骤S1中，所述液晶介质混合物中液晶分子、活性单体和垂直取向剂的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％。
其中，所述步骤S4中，对所述胶框的密封胶采用热固化或紫外光照射 固化。
其中，所述步骤S5中，对所述液晶层施加的电压为13～25V，且采用的紫外光照射的强度为85～100mW/cm2，照射时间为20～100s。
其中，所述步骤S6中，采用的紫外光照射时间为90～120min。
实施本发明实施例，具有如下有益效果：由于垂直取向剂中采用了阻聚功能基团，用以降低聚合性基团的反应活性来使得UV照射下聚合反应形成的聚合物颗粒大小分布均匀，并且增强锚定液晶显示面板的基板表面能力，从而提高了液晶配向稳定性来避免液晶显示面板出现暗态易漏光的现象，提升了液晶显示面板信赖性。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例一提供的液晶介质混合物的结构示意图；
图2为本发明实施例三提供的液晶显示面板的制备方法的流程图；
图3为本发明实施例三提供的液晶显示面板的制备方法的应用场景图；其中，a1-彩膜基板、a2-垂直取向剂、a3-活性单体RM、a4-液晶分子、a5-ITO膜层、a6-TFT阵列基板、a7-聚合物膜层；
图4为本发明实施例三提供的液晶显示面板的制备方法中液晶层采用不同垂直取向剂制备后所形成聚合物膜层的对比图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发 明作进一步地详细描述。
如图1所示，为本发明实施例一中，提供的一种液晶介质混合物，设置于液晶显示面板的液晶层中，包括液晶分子1、活性单体2和垂直取向剂3，该垂直取向剂3包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
其中，垂直取向剂3的结构通式为
Figure PCTCN2018087311-appb-000021
Figure PCTCN2018087311-appb-000022
之中一种；其中，
A指的是用于锚定液晶显示面板的基板表面来实现对液晶分子1起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；例如，A的结构式可以优选为
Figure PCTCN2018087311-appb-000023
Sp指的是用于引导液晶分子1排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
Z指的是用于引导液晶分子1排列的中间基团，其结构表示为[A]m，m 的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；例如，A为苯环时，优选为
Figure PCTCN2018087311-appb-000024
R指的是用于引导液晶分子3排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
P指的是用于紫外光照射下形成聚合物颗粒膜层使得液晶分子1产生预倾角的聚合性基团，其结构表示为
Figure PCTCN2018087311-appb-000025
之中的任意一种组合；
L指的是用于降低聚合性基团P的反应活性来使得紫外光照射下形成 的聚合物颗粒大小分布均匀以及进一步增强锚定液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
Figure PCTCN2018087311-appb-000026
其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代。
应当说明的是，由于阻聚功能基团L可以降低聚合性基团P的反应活性来使得UV照射下聚合反应形成的聚合物颗粒大小分布均匀，并且增强锚定液晶显示面板的基板表面能力，降低垂直取向剂3的使用量，提高了液晶配向稳定性，避免了液晶显示面板出现暗态易漏光的现象，提升了液晶显示面板信赖性。
在本发明实施例一中，阻聚功能基团L的结构优选为
Figure PCTCN2018087311-appb-000027
Figure PCTCN2018087311-appb-000028
之中一种，其阻聚合机理为：
Figure PCTCN2018087311-appb-000029
Figure PCTCN2018087311-appb-000030
从而使得垂直取向剂3的结构为以下化合物中的一种或多种：
Figure PCTCN2018087311-appb-000031
Figure PCTCN2018087311-appb-000032
在本发明实施例一中，液晶分子1、活性单体2和垂直取向剂3的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％，可以使得液晶配向稳定性得到提高，更有效的避免液晶显示面板出现暗态易漏光的现象。
相应于本发明实施例一中提供的液晶介质混合物，本发明实施例二还提供了一种液晶显示面板，包括TFT阵列基板、彩膜基板以及设置于所述TFT阵列基板和所述彩膜基板之间的液晶层；其中，该液晶层中填充有本发明实施例一中的液晶介质混合物。由于本发明实施例二中的液晶介质混合物与本发明实施例一中的液晶介质混合物具有相同的结构及连接关系，具体请参见本发明实施例一中的液晶介质混合物的相关内容，在此不再一一赘述。
如图2所示，为本发明实施例三中，提供的一种液晶显示面板的制备方法，所述方法包括以下步骤：
步骤S1、提供一TFT阵列基板、一彩膜基板以及液晶介质混合物；其中，所述液晶介质混合物包括液晶分子、活性单体和垂直取向剂，所述垂直取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
其中，所述垂直取向剂的结构通式为
Figure PCTCN2018087311-appb-000033
Figure PCTCN2018087311-appb-000034
之中一种；其中，
A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；
R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H 原子还可以被F、Cl基团取代；
P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生预倾角的聚合性基团，其结构表示为
Figure PCTCN2018087311-appb-000035
之中的任意一种组合；
L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
Figure PCTCN2018087311-appb-000036
其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代；
步骤S2、在所述TFT阵列基板或所述彩膜基板中，选出待注入所述液晶介质混合物的基板，并在所选基板注入所述液晶介质混合物；
步骤S3、在所选基板的表面涂布密封胶形成将所述液晶介质混合物围成半封闭状的胶框，且在所选基板除胶框之外区域的表面涂有导电胶；
步骤S4、将所述TFT阵列基板或所述彩膜基板在真空环境下组立贴合，并对所述胶框的密封胶进行固化，使得所述胶框内的液晶介质混合物形成为位于所述TFT阵列基板或所述彩膜基板之间的液晶层；其中，所述液晶介质 混合物中垂直取向剂的一部分依靠其自身的头基吸附在所述TFT阵列基板或所述彩膜基板的表面上，并垂直于所述TFT阵列基板或所述彩膜基板的表面排列来引导所述液晶分子垂直配向排列，所述液晶介质混合物中垂直取向剂的另一部分填充在所述液晶层中；
步骤S5、对所述液晶层施加一定电压，使得所述液晶介质混合物中的液晶分子发生偏转，并在持续施加电压的同时对所述液晶分子已发生偏转的液晶层进行紫外光照射一定时间，使得填充在所述液晶层中的垂直取向剂在与活性单体发生聚合时，利用其自身的阻聚功能基团会在所述TFT阵列基板和所述彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜；
步骤S6、去除所述持续施加的电压，再继续对所述已形成颗粒大小分布均匀的聚合物薄膜的液晶层进行紫外光照射一段时间，使得残存在所述TFT阵列基板和所述彩膜基板表面的垂直取向剂与活性单体全部反应，也会利用其自身的阻聚功能基团进一步在所述TFT阵列基板和所述彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜，从而制备出液晶显示面板。
具体过程为，在步骤S1中，提供无涂布PI膜的TFT阵列基板和CF基板，并将液晶介质混合物中液晶分子、活性单体和垂直取向剂的质量百分比关系设置为0.2～0.5％：0.2～5.0％：94.5～99.6％。
在步骤S2中，TFT阵列基板或彩膜基板中任选一个作为注入液晶介质 混合物的基板，并通过ODF制程方式在所选基板注入具有上述质量配比关系的液晶介质混合物。
在步骤S3中，在所选基板的表面涂布密封胶形成半封闭状的胶框，该胶框内部区域用于填充上述液晶介质混合物，同时在胶框外部区域的表面涂有导电胶，用以保证TFT阵列基板和彩膜基板组立贴合后的导电性能。
在步骤S4中，真空环境下，将TFT阵列基板和CF基板贴合在一起，并对密封胶进行固化，固化方式采用热固化或UV固化，从而得到位于TFT阵列基板和CF基板之间的液晶层。应当说明的是，垂直取向剂的一部分依靠其自身的头基吸附在TFT阵列基板或彩膜基板的表面上，并垂直于TFT阵列基板或彩膜基板的表面排列来引导液晶分子垂直配向排列，另一部分填充在所述液晶层中，如图3中3a所示。
在步骤S5中，对液晶层施加的电压为13～25V，使得液晶分子发生偏转，如图3中3b所示。此时，在持续施加电压的同时采用照射强度为85～100mW/cm2，照射时间为20～100s的紫外光对液晶分子已发生偏转的液晶层进行照射，使得填充在液晶层中的垂直取向剂在与活性单体发生聚合时，利用其自身的阻聚功能基团会在TFT阵列基板和彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜，如图3中3c所示。
在步骤S6中，去除上述持续施加的13～25V电压，再继续对液晶层进行紫外光照射90～120min(强度为85～100mW/cm2)，使得残存在TFT阵列 基板和彩膜基板表面的垂直取向剂与活性单体全部反应，也会利用其自身的阻聚功能基团进一步在TFT阵列基板和彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜，从而制备出液晶显示面板，如图3中3d所示。
在一个实施例中，通过本发明实施例三中的液晶显示面板的制备方法制备出面积大小为10*10cm的液晶层时，液晶分子中所用垂直取向剂的结构、用量和取向效果对比如下：
Figure PCTCN2018087311-appb-000037
在另一个实施例中，通过本发明实施例三中的液晶显示面板的制备方法制备出面积大小为10*10cm的液晶层时，因采用的垂直取向剂的结构为
Figure PCTCN2018087311-appb-000038
且该结构中含有阻聚功能基团，故使得液晶层经过UV反应后所形成的聚合物粒径较小且均匀，如图4中4a所示；而采用垂直取向剂的结构为
Figure PCTCN2018087311-appb-000039
且该结构中不带阻聚功能基团，故使得液晶层经过UV反应后所形成的聚合物粒径大且不均匀，如图4中4b所示。
综上所述，实施本发明实施例，具有如下有益效果：由于垂直取向剂中采用了阻聚功能基团，用以降低聚合性基团的反应活性来使得UV照射下聚合反应形成的聚合物颗粒大小分布均匀，并且增强锚定液晶显示面板的基板表面能力，从而提高了液晶配向稳定性来避免液晶显示面板出现暗态易漏光的现象，提升了液晶显示面板信赖性。
以上所揭露的仅为本发明一种较佳实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明权利要求所作的等同变化，仍属本发明所涵盖的范围。

Claims (13)

  1. 一种液晶介质混合物，设置于液晶显示面板的液晶层中，其中，包括液晶分子、活性单体和垂直取向剂，所述垂直取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
    其中，所述垂直取向剂的结构通式为
    Figure PCTCN2018087311-appb-100001
    Figure PCTCN2018087311-appb-100002
    之中一种；其中，
    A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
    Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
    Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取 代；
    R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
    P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生预倾角的聚合性基团，其结构表示为
    Figure PCTCN2018087311-appb-100003
    之中的任意一种组合；
    L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
    Figure PCTCN2018087311-appb-100004
    其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代。
  2. 如权利要求1所述的液晶介质混合物，其中，所述阻聚功能基团的结构表示为
    Figure PCTCN2018087311-appb-100005
    之 中一种。
  3. 如权利要求1所述的液晶介质混合物，其中，所述液晶分子、活性单体和垂直取向剂的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％。
  4. 如权利要求1所述的液晶介质混合物，其中，所述垂直取向剂的结构为以下化合物中的一种或多种：
    Figure PCTCN2018087311-appb-100006
    Figure PCTCN2018087311-appb-100007
  5. 一种液晶显示面板，其中，包括TFT阵列基板、彩膜基板以及设置于所述TFT阵列基板和所述彩膜基板之间的液晶层；其中，所述液晶层中填充有液晶介质混合物；
    所述液晶介质混合物包括液晶分子、活性单体和垂直取向剂，所述垂直取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
    其中，所述垂直取向剂的结构通式为
    Figure PCTCN2018087311-appb-100008
    Figure PCTCN2018087311-appb-100009
    之中一种；其中，
    A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
    Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-，-CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
    Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；
    R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
    P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生 预倾角的聚合性基团，其结构表示为
    Figure PCTCN2018087311-appb-100010
    之中的任意一种组合；
    L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
    Figure PCTCN2018087311-appb-100011
    其中，n的值为1～2；R’表示为：1～5个C原子的直链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代。
  6. 如权利要求5所述的液晶显示面板，其中，所述阻聚功能基团的结构表示为
    Figure PCTCN2018087311-appb-100012
    之中一种。
  7. 如权利要求5所述的液晶显示面板，其中，所述液晶分子、活性单体和垂直取向剂的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％。
  8. 如权利要求5所述的液晶显示面板，其中，所述垂直取向剂的结构为以下化合物中的一种或多种：
    Figure PCTCN2018087311-appb-100013
    Figure PCTCN2018087311-appb-100014
  9. 一种液晶显示面板的制备方法，其中，所述方法包括以下步骤：
    步骤S1、提供一TFT阵列基板、一彩膜基板以及液晶介质混合物；其中，所述液晶介质混合物包括液晶分子、活性单体和垂直取向剂，所述垂直取向剂包括头基、中间基团、尾基、聚合性基团和阻聚功能基团；
    其中，所述垂直取向剂的结构通式为
    Figure PCTCN2018087311-appb-100015
    Figure PCTCN2018087311-appb-100016
    之中一种；其中，
    A指的是用于锚定所述液晶显示面板的基板表面来实现对所述液晶分子起到垂直配向作用的头基，其结构表示为含有多个氧原子的组合物；
    Sp指的是用于引导所述液晶分子排列的刚性链路，其结构表示为-(CH 2)i-，i的值为1～8；其中，Sp任意一个中末端的CH 2可以被-O-，-S-， -CO-，-CO-O-，-O-CO-，-O-CO-O-，-OCH 2-，-CH 2O-，-CH＝CH-，-CF＝CF-，-CH＝CH-COO-，-OCO-CH＝CH-取代；
    Z指的是用于引导所述液晶分子排列的中间基团，其结构表示为[A]m，m的值为大于1的正整数；其中，A表示为苯环或环烷烃，且苯环或环烷烃的环上一个或多个H原子还可以被F、Cl、Br、I、-CN、-NO 2、-C(＝O)H取代；
    R指的是用于引导所述液晶分子排列的尾基，其结构表示为具有5～20个C原子的直链或支链化的烷烃；其中，R的任意一个CH 2基团可以被苯基、环烷基、-CONH-、-COO-、-O-CO-、-S-、-CO-、-CH＝CH-基团取代，且H原子还可以被F、Cl基团取代；
    P指的是用于紫外光照射下形成聚合物颗粒膜层使得所述液晶分子产生预倾角的聚合性基团，其结构表示为
    Figure PCTCN2018087311-appb-100017
    之中的任意一种组合；
    L指的是用于降低所述聚合性基团P的反应活性来使得紫外光照射下形成的聚合物颗粒大小分布均匀以及进一步增强锚定所述液晶显示面板的基板表面能力的阻聚功能基团，其结构表示为苯酚类，具体结构通式为
    Figure PCTCN2018087311-appb-100018
    其中，n的值为1～2；R’表示为：1～5个C原子的直 链或支链化的烷烃，其中，R’的任意一个碳原子可以被-O-、-CO-、-COO-、-O-CO-取代；
    步骤S2、在所述TFT阵列基板或所述彩膜基板中，选出待注入所述液晶介质混合物的基板，并在所选基板注入所述液晶介质混合物；
    步骤S3、在所选基板的表面涂布密封胶形成将所述液晶介质混合物围成半封闭状的胶框，且在所选基板除胶框之外区域的表面涂有导电胶；
    步骤S4、将所述TFT阵列基板或所述彩膜基板在真空环境下组立贴合，并对所述胶框的密封胶进行固化，使得所述胶框内的液晶介质混合物形成为位于所述TFT阵列基板或所述彩膜基板之间的液晶层；其中，所述液晶介质混合物中垂直取向剂的一部分依靠其自身的头基吸附在所述TFT阵列基板或所述彩膜基板的表面上，并垂直于所述TFT阵列基板或所述彩膜基板的表面排列来引导所述液晶分子垂直配向排列，所述液晶介质混合物中垂直取向剂的另一部分填充在所述液晶层中；
    步骤S5、对所述液晶层施加一定电压，使得所述液晶介质混合物中的液晶分子发生偏转，并在持续施加电压的同时对所述液晶分子已发生偏转的液晶层进行紫外光照射一定时间，使得填充在所述液晶层中的垂直取向剂在与活性单体发生聚合时，利用其自身的阻聚功能基团会在所述TFT阵列基板和所述彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜；
    步骤S6、去除所述持续施加的电压，再继续对所述已形成颗粒大小分 布均匀的聚合物薄膜的液晶层进行紫外光照射一段时间，使得残存在所述TFT阵列基板和所述彩膜基板表面的垂直取向剂与活性单体全部反应，也会利用其自身的阻聚功能基团进一步在所述TFT阵列基板和所述彩膜基板的表面分别形成有颗粒大小分布均匀的聚合物薄膜，从而制备出液晶显示面板。
  10. 如权利要求9所述的液晶显示面板的制备方法，其中，所述步骤S1中，所述液晶介质混合物中液晶分子、活性单体和垂直取向剂的质量百分比关系为0.2～0.5％：0.2～5.0％：94.5～99.6％。
  11. 如权利要求10所述的液晶显示面板的制备方法，其中，所述步骤S4中，对所述胶框的密封胶采用热固化或紫外光照射固化。
  12. 如权利要求11所述的液晶显示面板的制备方法，其中，所述步骤S5中，对所述液晶层施加的电压为13～25V，且采用的紫外光照射的强度为85～100mW/cm2，照射时间为20～100s。
  13. 如权利要求12所述的液晶显示面板的制备方法，其中，所述步骤S6中，采用的紫外光照射时间为90～120min。
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